pt q

Q 3 20 1 9

P E T R O L E U M T E C H N O L O G Y QU AR T E R L Y

R E F IN IN G
G AS P R O C E SSI N G
P E T R O C H E M I C AL S

O P T I M I S I NG MAKING RECIPS
FCC PRETREAT
M O R E R E L IA B L E

IMO 2020 FIELDBUS

S H I F T I NG T H E F O C U S O U T O F F A S H I O N?

cover q1 copy 2.indd 1 11/06/2019 19:53

 www.uop.com

honeywell.indd 1 13/06/2019 10:09

 ptq
3 What about the hydrogen?
Chris Cunningham

5 ptq&a

19 Fundamentals of refinery safety

Norman Lieberman Process Improvement Engineering

PETROLEUM TECHNOLOGY QUARTERLY 23 Digitalisation is transforming KPI setting

Duncan Micklem KBC (A Yokogawa Company)

29 Optimising desalter control

Andrew Shaw and Neil Murch Tracerco
Q3 (Jul, Aug, Sep) 2019
w w w . e p t q . c om 33 Simulating and optimising an FCC naphtha post-treater
Pedro Rojas Bryan Research & Engineering, LLC

41 Eliminating phosphorus from cooling treatment

Renate Ruitenberg and Emregul Cetin
Nalco Champion, an Ecolab Company

45 Piston design method makes recips more reliable

Andreas Brandl, Bruce Hermonat and John Ladd
Hoerbiger

57 The origins and fates of chlorides in hydroprocessing units

Steven A Treese Becht Engineering

67 Fieldbus – is interest fading?

Meghdut Manna Technical Advisor

73 Racing to meet IMO 2020 regulations

Victor Scalco and Maggie Vidal
General Atomics Electromagnetic Systems

79 Process schemes to solve the fuels/chemicals imbalance

John J Murphy and Clyde F Payn
The Catalyst Group

83 Sustainable technology for cleaning a crude preheat exchanger network

Yoshinori Kanno JX Nippon Oil & Energy Corporation
Guiqing Xu Softard Industries
Ian Baxter Cat Tech International

89 Residuum hydrocracking: chemistry and catalysis

Julie Chabot and Woody Shiflett
Advanced Refining Technology and Chevron Lummus Global

99 Best practice for refinery flowsheets

Jitendra Chellani and Asma Al Sariyahi
KBC

107 Preventative maintenance of piping systems

Shirish Lal
Piping Technology & Products

111 Technology in Action

Cover
Equinor’s gas liquefaction plant in Hammerfest, Norway, built by Linde Engineering, produces 4.3 million t/y of LNG.

Photo: Linde Engineering

©2019. The entire content of this publication is protected by copyright full details of which are available from the publishers. All rights
reserved. No part of this publication may be reproduced, stored in a retrieval system or transmitted in any form or by any means – electronic,
mechanical, photocopying, recording or otherwise – without the prior permission of the copyright owner.
The opinions and views expressed by the authors in this publication are not necessarily those of the editor or publisher and while every care
has been taken in the preparation of all material included in Petroleum Technology Quarterly and its supplements the publisher cannot be held
responsible for any statements, opinions or views or for any inaccuracies.

ed com copy 19.indd 1 17/06/2019 07:35

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013071_Q3_PTQ_Volume_Ad_Mech.indd 1 6/5/19 9:52 AM
 ptqPETROLEUM TECHNOLOGY QUARTERLY
What about the
hydrogen?
Vol 24 No 4
Q3 (Jul, Aug, Sep) 2019

T
here is no doubt about the big topics for discussion at our international
refining conference, efining India 201 , when the gathering gets under
Editor way in New Delhi this September. There is the matter of how best to
Chris Cunningham configure refineries for tighter regulations on transportation fuels in India, the
editor@petroleumtechnology.com BS-VI regulations which apply nationwide from April 2020. More pressing for
the world at large as well as India’s refiners is the anuary deadline for sea
Production Editor based transport that delivers the crude feedstocks for refiners, the IMO 2020
Rachel Storry
production@petroleumtechnology.com
regulations on bunker fuels. But, as the International nergy Agency highlights
in a new report, The Future of Hydrogen, hitting these new sulphur removal
Graphics Editor targets as economically as possible is much more than about having the right
Rob Fris process line-up and juggling changes to the product slate.
graphics@petroleumtechnology.com efinery consumption of hydrogen as feedstock, reagent and energy source for
hydrotreating and hydrocracking adds up to 38 million t/y, which corresponds
Editorial roughly to half of global demand for the pure form of the gas.
tel +44 844 5888 773
fax +44 844 5888 667
To meet the IMO 2020 bunker fuel specifications, refineries will need to remove
approaching 80 of the sulphur that arrives in crude feedstocks, up from about
Business Development Director 70 , so that hydrogen consumption in refineries will rise accordingly.
Paul Mason Byproduct hydrogen, chiefly from catalytic naphtha reforming, accounts for
sales@petroleumtechnology.com roughly a third of a site’s total requirement so the balance needs to be made up
either by internal dedicated hydrogen production or through purchases from
Advertising Sales Office merchant suppliers.
tel +44 844 5888 771
fax +44 844 5888 662
Hydrogen supply is an important element in a refiner’s operating expenditure
and can have a significant impact on margin and competition. Dedicated
Managing Director hydrogen production mostly comes from steam methane reforming based on
Richard Watts natural gas supplies. egions with a deficit of natural gas, India and China
richard.watts@emap.com in particular, rely heavily on partial oxidation of extra-heavy feedstocks,
including petroleum coke and coal. Bought-in supplies of hydrogen are chiefly
Consultant
a realistic option only in the major refining hubs, in particular the US Gulf Coast
Nic Allen
consultant@crambethallen.com
and otterdam-centred western urope, where su cient hydrogen pipeline
infrastructure is in place.
Circulation Consuming natural gas and coal in hydrogen production for refining
Fran Havard processes results in 230 million t/y of carbon dioxide emissions, according
circulation@petroleumtechnology.com to the I A. This is equivalent to around 20 of all emissions of CO2 by the
refining sector. With all of that extra desulphurisation in prospect, to reduce
emap, 10th Floor, Southern House, or eliminate emissions refineries will need to equip their hydrogen production
Wellesley Grove, Croydon CR0 1XG
tel +44 208 253 8695
with equipment for carbon capture to meet shrinking targets. Alternatively, they
could use electrolytic hydrogen from renewable energy sources. A few major
refining sites such as Shell Pernis have carbon capture equipment in place, but
Register to receive your regular copy of at present refiners are not running electrolysers to generate hydrogen.
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 ptq&a
Q Can you suggest a catalyst scheme for hydrotreating
middle distillates when hydrogen availability is limited?
A Amit Kelkar, Global Distillate Application Manager, Shell
Catalysts & Technologies, amit.kelkar@shell.com
Upgrading mid-distillates to ultra low sulphur die-
sel (ULSD) requires desulphurisation of sterically hin-
dered, substituted dibenzothiophenes which tend to
have slow reaction rates. Removal of sulphur from
these refractory species can occur via two reaction
pathways. The first one is through direct hydrogeno-
lysis of the carbon-sulphur bonds and is termed direct
hydrodesulphurisation (HDS). The second pathway
involves hydrogenation of one of the aromatic rings fol-
lowed by carbon-sulphur bond hydrogenolysis. This is
called indirect HDS and has a significantly higher reac-
tion rate compared to direct HDS (see Figure 1).
Cobalt molybdenum (Co-Mo) catalysts exhibit a
higher intrinsic activity for direct HDS reactions com-
pared to nickel molybdenum (Ni-Mo) catalysts. On the
other hand, Ni-Mo catalysts have superior hydrode-
nitrogenation (HDN) and aromatic saturation (HDA)
activity. Complex nitrogen compounds often present
in cracked feeds such as light cycle oil (LCO) and light
coker gasoil (LCGO) inhibit HDS and saturation reac-
tions. Faster conversion of these nitrogen molecules
results in a synergistic HDS benefit. Hence, NiMo cata-
lysts tend to outperform CoMo catalysts when process-
ing high end-point, refractory feeds under conditions
favourable for hydrogenation.
Detailed analysis of the HDS and HDN profile across
a catalyst bed provides insights into the design of an
optimum catalyst system for maximising HDS activity
in a H2 constrained unit. Relatively easy HDS reactions,
which are catalyst independent, occur in the top 20-30%
of the reactor. Deeper into the catalyst bed, the organic
nitrogen level is much lower for the NiMo catalyst com-
pared to the CoMo catalyst. Reducing the nitrogen level
sooner means more of the catalyst is operating in a low
inhibition environment with the resulting HDS boost.
The aromatic saturation reaction rate increases rapidly
once a low organic nitrogen level is achieved and hence
Direct HDS
k1 mechanism kD
R R1
k2
S
k4
R R1 k3
4,6-DMDBT S
R R1
R R1
Indirect HDS
kI >> kD mechanism kI
Figure 1 Direct and indirect HDS pathways
www.eptq.com
Q&A copy 36.indd 1
it is higher for NiMo compared to CoMo (see Figure 2).
This study highlights that deep HDS and HDA reac-
tions are strongly dependent on nitrogen removal.
Greater HDN results in higher HDS and HDA activ-
ity and thus more H2 consumption. Managing H2 con-
sumption is an exercise in optimising the HDN activity
to get the synergistic HDS benefit without excess con-
sumption. In practical terms, this involves using a
NiMo catalyst in the middle of the reactor and a CoMo
catalyst in the bottom. This configuration takes advan-
tage of the higher HDN activity of the NiMo to boost
the HDS activity of the bottom CoMo. Use of CoMo
in the bottom also reduces the H2 consumption. Shell
Catalysts & Technologies has applied this ‘sandwich’
concept in a wide variety of feed and operating condi-
tions, combining the best of CoMo and NiMo catalysts.
A Michael Martinez, Technical Service Manager, Porocel,
mmartinez@porocel.com
When hydrogen is limited, refiners can work with cat-
alyst vendors to design a catalyst load that maximises
desulphurisation while controlling hydrogenation
activity. Strategic use of Excel rejuvenated catalysts
can help refiners achieve this goal. In general, CoMo
catalysts have less hydrogenation activity compared
to NiMo catalysts, which corresponds to lower lev-
els of hydrogen consumption. In low pressure units,
xcel rejuvenated CoMo is often a good fit for high
HDS performance with the lowest hydrogen con-
sumption. However, in units processing more severe
feeds especially at higher pressures, the optimum cata-
lyst design may be a combination of NiMo and CoMo
to balance overall HDS and HDN activity while mini-
mising hydrogen consumption. Porocel works closely
with refiners to create designs using the right balance of
Excel rejuvenated catalysts to maximise desulphurisa-
tion activity while minimising hydrogen consumption.
A Per Zeuthen, Fellow, Haldor Topsoe, pz@topsoe.com
The simple answer is to choose CoMo catalyst rather
than NiMo catalyst. This exercise is about avoiding
saturation of aromatics and if you are willing to trade
100000
Sulphur and nitrogen
Deep HDN accelerates HDS CoMo S
10000
NiMo S
1000 CoMo N
NiMo N
levels, ppm
100
10
NiMo product N<10 ppm
1
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Position in catalyst bed
Figure 2 Sulphur and nitrogen profile in catalyst bed
PTQ Q3 2019 5
13/06/2019 14:52
 off some cycle length, product density, and yield, then
other tricks can be considered as well. You can choose
a less active catalyst, which is also cheaper, and run at
higher reactor temperature at start-of-run. It favours a
lower H2 consumption. You can also choose larger cat-
alyst pellets and at the same time get a credit for lower
power consumption.
Q What performance gains can we expect from using
fouling resistant trays in sour water stripping?
A Marcello Ferrara, Chairman, ITW, mferrara@itw
technologies.com; Cristina Ferrara, Process Engineer, ITW,
cferrara@itwtechnologies.com
While the equipment designed for mitigating fouling
can work based on the process/design, it has no impact
on the chemical mechanism of fouling formation.
Therefore fouling will deposit and cleaning will be nec-
essary at some point.
In particular, the sour water stripper (SWS) is a
very critical unit as it can directly impact the produc-
tion of the entire site should the outlet water be out of
spec (due to fouling deposition). At this point, capacity
reduction or mechanical cleaning is a must.
While capacity reduction will impact the production
of the site, mechanical cleaning has a limited amount of
time to be implemented while the units providing feed
to the SWS are running.
Generally, during mechanical cleaning, the water will
be routed to the feed tank, which can store a defined
quantity of water (normally up to three days’ produc-
tion). There is therefore a limited time for cleaning the
SWS, which is usually not long enough to perform a
complete clean.
In SWS units processing phenolic water, the fouling is
mostly of a polymeric nature. ITW Online Cleaning can
effectively address the cleaning of polymeric deposits
in any equipment in the oil and gas industry. It is a pat-
ented cleaning technology based on cleaning process
equipment in a closed loop. An entire production unit
can be cleaned in as little as 24 hours on a feed-out/
feed-in basis. The cleaning process includes:
• Patented method and process steps
• Patented chemicals
• Patented monitoring system.
ITW Online Cleaning can be used in the preparation
of a turnaround, during the shutdown phase, or proac-
tively during a unit run. In a turnaround application,
downtime will be dramatically reduced as mechani-
cal cleaning can be pulled out of the turnaround scope.
During a run, the unit will resume production under
clean conditions thereby achieving immediate value out
of the delta performance.
A Celso Pajaro, Head Engineered Solutions Refinery, Sulzer
Chemtech, Celso.Pajaro@Sulzer.com
If the sour water stripper is experiencing fouling, the
use of fouling resistant trays will increase the run
length of the unit. As an example, a sour water unit was
being shut down every year to perform chemical clean-
6 PTQ Q3 2019
Q&A copy 36.indd 2
ing in order to regain capacity. The column had round
floating valve trays and the majority of the fouling was
happening on the feed tray. This tray was replaced with
an anti-fouling tray and the unit operated for more than
three years without cleaning.
Not all sour water stripping columns experience foul-
ing problems; typically, a sour water stripper will run
without problems if the refinery uses demineralised
water for process needs. Fouling typically happens
when processing desalter water, or when cooling water
leaks into the sour water (low pressure condensers with
tube failures that allow cooling water into the process).
The presence of calcium and magnesium carbonates in
the sour water will make it foul by precipitating once
the temperature exceeds 180°F (82°C).
It is a good design practice to use antifouling trays in
sour water strippers even though the water is not foul-
ing; a small failure in the overhead condenser of the
crude unit, FCC, delayed coker, or any main fraction-
ator will leak cooling water into the sour water that
will foul the sour water stripping system, reducing its
capacity and eventually forcing a shutdown to clean
the unit.
Q What are the likely principal sources of fouling in the
feed exchangers to our naphtha hydrotreater, and how can we
best reduce them?
A Berthold Otzisk, Senior Product Manager – Process
Chemicals, Kurita Europe, berthold.otzisk@kurita.eu
When fouling is observed in the feed exchangers to
your naphtha hydrotreater (NHT), a root cause analy-
sis is always a very useful tool to determine the reasons
for the fouling. The NHT feed material is mainly naph-
tha from the CDU or coker. Additionally, the bottom
product of a Sats gas plant splitter (for instance, butane)
is often routed into the naphtha tank. Coker feed con-
tains very reactive materials like olefins, carbonyls, and
amines. Peroxide free radicals formed by oxygen may
initiate polymer formation. The injection of a high per-
forming antioxidant such as Kurita AO-7208 is the clas-
sical treatment, with direct injection into the naphtha
tank which will block polymer formation.
But it is also possible that, in addition to polymer
deposits, iron salts or other inorganic foulants are trans-
ported with the feed material to the NHT. Vaporised
naphtha and hydrogen are heated in a fired heater
to the required reactor inlet temperature. This also
increases the risk that coke particles are formed, which
may clog the feed heat exchanger tubes.
Sometimes the presence of ammonium chloride salts
is not noticed in the NHT feed, even though the crude
oil also contains organic chlorides. Many organic chlo-
rides are stable at temperatures below 350°C and
decompose only in the NHT under the influence of
the catalyst and hydrogen. Hydrochloric acid (HCl) is
formed, which can react in the compressor with excess
hydrogen by forming ammonium salts, which enter
the feed stream again and can cause salt fouling before
the reactor.
www.eptq.com
17/06/2019 10:11
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 For prevention of fouling caused by organic and inor-
ganic foulants, typically chemical programmes with
multiple functions are used. Kurita AP-2103 is an anti-
foulant that stabilises asphaltenes, disperses coke parti-
cles and thereby keeps them small (particle size limiter).
It also prevents the reaction of polynuclear aromatic
condensation reactions.
A Matthew Lane, Antifoulants Technical Support Specialist,
Baker Hughes, a GE company, Matthew.Lane@bhge.com
Fouling in feed exchangers is comprised of organic and
inorganic materials from the feed. On the feed side of
the feed/e uent exchangers, inorganic fouling is usu-
ally caused by iron sulphide from upstream operations.
This type of fouling can be mitigated by:
• Implementing source control and maintaining a
robust corrosion control programme
• Filtering the feedstock going to the unit
• Dispersing the inorganic material to maintain a small
particle size. Dispersant antifoulants are commonly
used to treat fouling of this nature and are available
from Baker Hughes.
These methods should help minimise the amount of
iron that interacts with the heated surfaces, thus min-
imising the amount of inorganic fouling in the feed
exchangers to the naphtha hydrotreater.
Organic fouling is typically the result of poly-
mer chain formation that occurs before the hydro-
treater or in the feed e uent exchangers. This can be
accomplished by limiting the amount of free radical
polymerisation that occurs and limiting the size of the
polymer chains that do form. Typical mitigation strate-
gies include:
• Eliminating intermediate storage or removing oxygen
from intermediate storage
• Filtering the feedstock going to the unit
• Using an oxygen scavenger to control peroxide
induced polymer formation
• Using a polymerisation inhibitor.
Fouling can also occur on the e uent side of the
exchanger, typically in the form of ammonium chloride.
Minimising the accumulation of salts is key to avoiding
pressure drop concerns and potential corrosion issues.
This type of fouling can be mitigated by:
• Installing chloride traps in the hydrogen feed
• Performing water washes – continuous or intermit-
tent – if ammonium chloride is already present
• Using salt dispersants to break up existing deposits
and minimise deposition of additional salts.
A Xiomara Price, Senior Product Analytics/Support
Manager, SUEZ – Water Technologies & Solutions, xiomara.
price@suez.com
The charge of naphtha hydrotreaters can be composed
of multiple feed streams. Each one of those streams can
contain fouling precursors that when present in high
enough quantities can lead to fouling in the preheat sys-
tem. Straight run feed typically comes from the crude
unit. Corrosion by-products and/or corrosive materials
such as amine salts are generally the most common con-
tributors to fouling in these streams. Although olefins
8 PTQ Q3 2019
Q&A copy 36.indd 3
are generally not a concern for straight run material,
carbonyls can be present and could contribute to the
formation of polymer when other species are present
and the proper conditions exist. Cracked stock can orig-
inate from either the coker, FCC or visbreaker units and
can contain various levels of olefins, carbonyls, and pyr-
role nitrogen which can polymerise and contribute to
fouling. Purchased feed by nature is very variable, and
contains inorganic and organic foulants. This feed can
also be problematic because it can contain oxygen that
could have built up during transportation, and oxygen
acts as a catalyst during the polymerisation reaction.
Various strategies can be implemented to aid in the
reduction of fouling in naphtha hydrotreaters depend-
ing on the primary fouling mechanism:
• Addressing the root cause of the corrosion upstream
of the unit is key when corrosion by-products are
the primary contribution to the fouling. This can be
achieved by things such as improved desalting, amine
extraction, use of lower salting amines, process changes,
and so on. The right approach will be dependent on the
specific situation.
• Feed filtration will help remove filterable solids that
Various strategies can be
implemented to aid in the
reduction of fouling in naphtha
hydrotreaters depending on the
primary fouling mechanism
are present in the various feeds. Having the right size
filters and operating them properly is essential.
• Directly feeding material from unit to unit with-
out going to tankage is always best when dealing with
polymerisation precursors. The direct feed eliminates
the potential for oxygen intrusion or any other contami-
nation from tankage.
• If the unstable feed must be sent to tankage, nitrogen
blanketing the tank is recommended to keep oxygen out
of the system. The system must be reliable.
• Proper tank draining to keep water from being emul-
sified into the feed or biological growth from occurring
is also important.
• If implementation of the different strategies above is
not su cient to achieve desirable run lengths, a chemi-
cal treatment programme can be used. Chemistries exist
to disperse existing material and/or to inhibit the for-
mation of polymerisation.
A Marcello Ferrara, Chairman, ITW, mferrara@itw
technologies.com; Cristina Ferrara, Process Engineer, ITW,
cferrara@itwtechnologies.com
Naphtha fouling generates from naphtha degradation
processes. The fouling is normally a brownish solid,
which is of the polymeric type. Some fouling preven-
tion treatment can be implemented to reduce foul-
ing formation, but fouling will deposit in any case
www.eptq.com
13/06/2019 14:52
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exxon.indd 1 13/06/2019 10:08

 and performance will inevitably decay. A refinery will
normally tolerate this decay, because it is less costly
than a shutdown with related production loss and
mechanical cleaning.
By cleaning an entire production unit in as little as 24
hours on a feed-out/feed-in basis, ITW Online Cleaning
gives an alternative to refineries, which can evaluate
the costs of running the unit under reduced perfor-
mance vs achievable recovery, rather than tolerating the
costs only.
ITW Online Cleaning can effectively address the
cleaning of organic deposits of heat exchangers, as well
as any other equipment in the oil and gas industry. It is
a patented cleaning technology based on cleaning heat
exchangers and/or process equipment in a closed loop.
A proprietary chemistry is used to dissolve the poly-
meric deposits. The dissolved material is fully stable
and can be fully reused/reprocessed.
A Francesco Ragone, Product Manager, Process Development
& Marketing, CHIMEC, fragone@chimec.it
The main impurities removed in a naphtha hydrotreater
are:
• Sulphur, present in mercaptans, sulphides, disulphi-
des, polysulphides, and thiophenes
• Nitrogen
• Oxygen, dissolved or present in the form of com-
pounds such as phenols or peroxides
• Olefins, according to the feed type
• Metals, present in sediments, corrosion by-products
and molecules that once hydrotreated are released and
deposited on the catalyst.
The operating conditions are a function of type of
feed, desulphurisation levels desired in the treated
product, olefin content, and so on.
Together with the high temperature reached in the
preheat exchangers, the impurities listed above can be,
separately or in combinations, sources of fouling, which
then can be organic, inorganic or both, according to
the case.
The organic fouling may result from:
• Gums already present precipitation, for instance
formed in a storage tank due to oxygen contamination
• Polymerisation reactions, triggered by free radicals
formed by thermal decomposition, peroxides formed
by the reaction of olefins with molecular oxygen, met-
als can lead to the formation of free radical hence to free
radical polymerisation, which in turn lead to gums for-
mation and precipitation
• Thermal cracking to polyaromatic hydrocarbons
(PAH), which can interact by means of pi-pi stacking to
form micelles that become insoluble in the medium and
then precipitate.
On the other hand, the typical inorganic fouling is
iron sulphide, dragged from other processes.
According to the dimensions of the fouling parti-
cles’ precursors, the dominant deposition mechanism
spans from Brownian motion to turbulent diffu-
sion. Once deposited on the metal surface, the fouling
layer becomes thicker and undergoes thermal aging,
turning harder with time both physically speak-
10 PTQ Q3 2019
Q&A copy 36.indd 4
ing and from the point of view of an eventual online
chemical remediation.
This is why Chimec suggests, first of all, to proceed
with a risk based assessment (RBA) to understand
which are the causes of fouling deposition in the sys-
tem, starting from the feed analyses, historical process
data evaluation and, when possible, fouling collection
and detailed chemical analyses.
The result of the RBA leads to the best chemical solu-
tion(s) for hydroprocessing units, available in the
Chimec portfolio:
• Inorganic dispersants, for FeS
• Organic dispersants, for gums and polymers
• Stabilisers, especially when reactive feeds are pro-
cessed, i.e. pyrolytic or FCC gasoline
• Multifunctional products in different proportions.
The chemical treatments briefly introduced can be
both set as low dosage, continuous chemical treat-
ments, to avoid fouling build-up, or as shock treatments
for online remediation – Chimec Reactor Plus, which
should be performed as soon as possible after the crit-
icality occurred.
It is worth noting that on the reactor e uent, ammo-
nium chloride and ammonium bisulphide formed
after the reaction between ammonia (from denitrifica-
tion reactions) and hydrogen chloride (present as an
impurity in the hydrogen) or hydrogen sulphide (from
desulphurisation) respectively are the cause of inor-
ganic fouling, mainly in the heat exchangers located
between the reactor and the high pressure separator
vessel, where the salt point is reached. The salts formed
add to the fouling related issues, loss of heat transfer
and section flow reduction, and the risk of acidic under-
deposit corrosion. Water washes are often ineffective.
For the reactor e uent, Chimec Salt Dispersant can
help to reduce the opex while keeping the system safer.
A Behzad Yasini, Senior Principal Tech. Service Engineer,
Haldor Topsoe, beya@topsoe.com
Fouling in the reactor feed-e uent heat exchangers
of naphtha hydrotreater units is often reported on the
feed side. The presence of cracked material is the main
cause of fouling. Fouling at the last shell where the feed
is completely vaporised is more severe than in other
shells. Gum also could be formed at the top bed of the
reactor. However, to find the root cause of fouling, an
analysis of the scales is recommended.
Good technical practice for processing cracked naph-
tha is to feed the cracked feed directly and avoid any
contact with air. Also, imported feeds are a source of
oxygen, so if there is no oxygen stripping upstream of
the feed pump such streams could cause fouling. If,
considering all the above mentioned points, the fouling
rate cannot be managed, diolefins may be the cause. It
will require a dedicated reactor to saturate the diolefins.
There are other reasons for fouling which are less
likely compared to feeding cracked streams, such as
poor performance of a feed filter and high water con-
tent in feed. After each shutdown or start-up, scales are
released due to thermal shock and cause problems not
only for the heat exchangers but also for the reactor.
www.eptq.com
13/06/2019 14:52
grace.indd 1 16/06/2019 07:52
 A Kevin Carlson, Global Application Manager – CFH & NHT,
Shell Catalysts & Technologies, Kevin.Carlson@shell.com
Fouling issues in hydroprocessing units can be a trou-
blesome problem resulting in reduced throughputs,
increased risk of corrosion, increased energy cost, and
unplanned shutdowns. Several different types of foul-
ing commonly occur in hydroprocessing units, with
each type having its own characteristics and deposi-
tion locations. Diagnosis of the type of fouling and the
underlying deposition mechanism is essential to solve
a fouling problem. NHT units can be susceptible to a
number of these mechanisms, however the most com-
mon two would be metal sulphide deposition and
polymerisation lay-down.
When observed in feed exchangers, metal sulphide
deposition, iron oxide (FeO, Fe2O3), and iron sulphide
(FeS) scale can be generated as corrosion products in
upstream units and intermediate storage facilities,
which can then settle and agglomerate in the lower
velocity sections of upstream piping and exchang-
ers. This not only causes issues in the affected process
equipment but can also lead to catalyst bed fouling
if process upsets dislodge foulant deposits, sending
them into the reactor. Diagnoses include assessment
of upstream corrosion monitoring, feed analysis, and
deposit analysis, with the best mitigation options being
corrosion monitoring and management. Reactor inter-
nal fouling can be mitigated through the use of grading
systems or the Shell Gas Phase Settling Tray technolo-
gies, which can be effective in capturing these metal
sulphide particles prior to entering the catalyst bed.
When processing cracked naphtha feeds, diole-
fins in the feed can polymerise to form gums or coke.
This polymerisation process tends to start at tempera-
tures above 3 0°F (200°C) and is greatly accelerated in
the presence of oxygen. In addition to upstream foul-
ing, due to the high reactivity of diolefins when con-
tacted with the catalyst, gum formation can occur in
the first catalyst bed, leading to a top layer crust caus-
ing increased pressure drop. Avoiding oxygen ingress
is the best mitigation method available when process-
ing cracked naphtha. The most common oxygen ingress
point is through intermediate air breathing tanks or
poor performing tank blanking systems, and these
should be verified for good operation.
Q What are the latest advances in catalyst technology for
FCC pretreat?
A Michael Tinning T Schmidt, Product Line Director, Haldor
Topsoe, mtp@topsoe.com
The research and development of new hydrotreat-
ing catalysts for FCC pretreat has historically been
driven by the fuel specifications for particularly sul-
phur. As legislation for sulphur content has required 50
wtppm, and later on 10 wtppm sulphur fuels in many
countries, the demand for FCC pretreat catalysts with
the highest activity for sulphur removal (HDS) has
grown. Traditionally, these catalysts have been of the
CoMo type for low to medium pressure units, where
12 PTQ Q3 2019
Q&A copy 36.indd 5
maximum HDS is focused with minimum hydrogen
consumption. Topsoe has for more than 15 years engi-
neered catalysts for this refinery segment with the
range of BRIM technology catalysts. These products
fulfil exactly the target of high HDS activity combined
with remarkable stability.
In recent years, some parts of the world have enjoyed
a much lower cost of hydrogen, making it possible
and attractive to increase H2 consumption in the pre-
treat step. By doing so, refiners benefit from the volume
swell of the product since more barrels of liquid prod-
uct are obtained when hydrogen is used to hydroge-
nate the feed and saturate the aromatics. Furthermore,
a growing trend in the industry is that high severity
hydrotreating and H2 consumption in the pretreat step
make the FCC feed behave much better in the FCC
unit. A hydrotreated FCC feed with reduced nitro-
gen (HDN), fewer aromatics (HDA), and more added
hydrogen enables the FCC catalyst to produce more
gasoline, and in particular it can enable production of
many more olefins, in particular propylene. This type
of severe hydrotreating is typically only possible in
medium to high pressure units and the prerequisite is
a top tier NiMo hydrotreating catalyst with extraordi-
nary hydrogenation functionality. When Topsoe com-
mercialised several NiMo catalysts based on HyB IM
technology, it opened up exactly this possibility due to
the significant step change in these catalysts’ hydroge-
nation function, and significantly reducing the aromat-
ics in the FCC feed. arlier it had not been possible to
achieve such a degree of HDN and HDA with a con-
ventional alumina based catalyst. With the 201 devel-
opment of TK-5 4 HyB IM, a catalyst specifically
designed to provide HDS and maximum hydrogena-
tion at low to medium pressure, refiners have a com-
plete portfolio of BRIM and HyBRIM catalysts to choose
from, covering all aspects of modern FCC pretreat-
ing. And, indeed, more severe FCC pretreating will be
needed as more FCC units are turning towards propyl-
ene production.
A Kevin Carlson, Global Application Manager – CFH & NHT,
Shell Catalysts & Technologies, Kevin.Carlson@shell.com
Building on the proven capability and reliability of
the Centera technology platform, Shell Catalysts &
Technologies is now delivering the Centera GT level
of performance. In the FCC pretreat application, per-
formance is measured by many metrics, and success is
achieved through the application of a custom designed
catalyst system. nabling continued FCC-PT perfor-
mance gains, three new products have been devel-
oped providing top tier performance in HDS, HDN,
and AroSat while maintaining the proven stability and
contaminant tolerance Shell Catalyst & Technologies
FCCPT catalysts have been known for.
Centera GT DN-3 55, a step-out Type II nickel-mo-
lybdenum catalyst for FCC feed pretreatment (FCC-PT),
provides significant nitrogen removal (HDN) and sul-
phur removal (HDS) improvements over the previous
generation. It is especially well suited to high qual-
ity FCC feed production in moderate to high pressure
www.eptq.com
13/06/2019 14:52
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Our INTERCATTM Fluid Catalytic Cracking (FCC) additives

offer the refiner the ability to tailor the selectivity of the
FCC, boost LPG yield, improve and maintain catalyst
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Contact us to find out how our technology

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matthey.indd 16/10/2017 10:12
13/06/2019 09:48
 units processing di cult feeds, where nitrogen removal
and hydrogenation reactions are valued to improve
FCC conversion levels. The increased HDS activity of
DN-3 55 can also help refiners meet ultra low sulphur
gasoline sulphur specifications. Centera GT DN-3 55
provides these significant increases in nitrogen, aromat-
ics, and sulphur removal activities while maintaining
stability and reliability.
Centera GT DC-2655 and DC-2656 are the new Type
II Co-Mo with Ni promoter catalysts for FCC-PT ser-
vice providing step-out gains in performance from pre-
vious generations. Again providing kinetic capability
with enhanced stability and metals tolerance, the per-
formance characteristics of these two products pro-
vide custom catalyst system designing that can dial in
performance requirements within unit operating con-
straints and run length objectives. Centera GT DC-2655
enhances FCC pretreat performance and stability across
a broad range of scenarios, particularly in lower pres-
sure applications that require very high HDS activity
and stability. DC-2656, with the same high level of HDS
but near NiMo level of HDN performance, is especially
suited for high quality FCC feed production in moder-
ate-to-high pressure units where both high desulphuri-
sation (HDS) and denitrification (HDN) are required.
Either by themselves or combined within a cus-
tomised catalyst system, Centera GT provides high
FCC feed quality across a broad range of operating
objectives.
Q Can you suggest ways of reducing catalyst bed plugging
in our hydrotreaters?
A Celso Pajaro, Head Engineered Solutions Refinery, Sulzer
Chemtech, Celso.Pajaro@Sulzer.com
Catalyst beds are excellent filters. To reduce bed plug-
ging, you should reduce the fouling material going to
the reactor. Some refineries install large capacity filters
to remove the solids; others take a different approach
by reducing solid generation (corrosion products, or
polymer formation).
The type of hydrotreater feed (naphtha, diesel, or
VGO) will determine the approach to reducing solids
generation:
Naphtha hydrotreater
Naphtha coming directly from the crude column can
have a lot of corrosion products if the column is suf-
fering from chloride salts attack. Changing the trays
from carbon steel to high alloy and adding a corro-
sion prevention treatment programme (which could
include water wash) will reduce the corrosion product
generation.
VGO hydrotreater
One example of a fouling mechanism is corrosion in the
vacuum column packing section (HVGO) and the asso-
ciated pipes due to naphthenic acids. A refinery pro-
cessing heavy crudes had to skim the top reactor bed
every two years. Once the structured packing material
14 PTQ Q3 2019
Q&A copy 36.indd 6
was upgraded to 317L and the pipes were replaced to
high alloy, the VGO reactor’s run length was increased
from two (due to pressure drop) to three years (due to
catalyst activity).
In one dramatic case, a facility running high acid
crudes was skimming the top of the catalyst bed every
six months. They finally had to replace the hot piping to
stainless steel.
Diesel hydrotreater
Similar to the VGO hydrotreater, sulphur and naph-
thenic acids can produce corrosion in the crude col-
umn. If carbon steel trays are used, the corrosion rate
is higher and more solids will be generated. The refiner
may request the trays in seven gauge to last longer, but
this means more material available for corrosion. The
situation is similar with piping; the end result is solids
going to the diesel hydrotreater reactor which need to
be removed.
Processing cracked material
Many refineries process cracked material with straight
run in their hydrotreaters and need special consider-
ation to keep oxygen out. Oxygen will initiate polymer-
isation reactions with olefins. Oxygen can get into the
streams from storage tanks that do not have nitrogen
or fuel gas (make sure it does not have oxygen) blan-
keting. Also, processing streams from other facilities
can contain oxygen. Polymers will start fouling the heat
exchangers before fouling the catalyst bed, so continu-
ous monitoring of the feed heat exchanger’s pressure
drop is needed to identify the presence of polymers in
the feed in a timely manner.
A Marcello Ferrara, Chairman, ITW, mferrara@itw
technologies.com; Cristina Ferrara, Process Engineer, ITW,
cferrara@itwtechnologies.com
Catalyst bed plugging can be differentiated as one
occurring in the top layer and one underneath. In the
top layer, plugging is normally made up of two compo-
nents, an inorganic one (usually iron sulphide) and an
organic one, while in the layer underneath plugging is
normally of the organic type only.
The top layer works as a filter for the solids (normally
corrosion products) generated during the run. This
is particularly true for the guard reactors/beds. In the
layer underneath, plugging is generated by feed degra-
dation and is of the polymeric type; this shows up as a
carbonaceous material.
ITW has developed a proprietary chemistry that can
dissolve the carbonaceous material which binds the cat-
alyst and creates the plugging. Application of ITW pro-
prietary chemistry is a tool to prevent or to release delta
P on hydrotreaters’ reactors.
A Xiomara Price, Senior Product Analytics/Support
Manager, SUEZ – Water Technologies & Solutions, xiomara.
price@suez.com
Reactor catalyst bed plugging can occur from depo-
sition of organic and/or inorganic materials. As
described in question three, various fouling precur-
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17/06/2019 10:12
 sors can be present in the different types of feeds. The
same applies to diesel, kerosene, or gasoil hydrotreat-
ers. In addition to the mitigation strategies outlined in
question three, you should ensure the hydrogen to feed
ratio is adequate and check if there is any potential for
sodium intrusion.
A Matthew Lane, Antifoulants Technical Support Specialist,
Baker Hughes, a GE company, Matthew.Lane@bhge.com
Similar to exchanger fouling, bed plugging is typically
caused by either organic or inorganic materials or both.
In order to reduce catalyst bed plugging, consider:
• Implementing source control to reduce the corrosion
that is the source of the iron in the hydrotreater feed
• Injecting a dispersant into the feed charge pump to
break down fouling inorganics into smaller particles,
which will help with reactor bed plugging
• Installing traps at the top of the reactor bed to pre-
vent polymerisation and the resulting increase in pres-
sure drop
• Purge with an inert gas or inject an inhibitor to pre-
vent oxygen from reacting with olefins to form free
radicals.
Additives are available from Baker Hughes for all
of these issues. Catalyst bed plugging may result from
a variety of causes, so a combination of the aforemen-
tioned suggestions may be needed to help reduce cata-
lytic bed plugging.
A Roberta Cenni, Senior Product Line Manager, Haldor
Topsoe, roc@topsoe.com
Strategies to mitigate bed plugging in hydrotreaters
vary, depending upon the root cause of the problem.
Correctly functioning reactor internals may solve oper-
ational issues in most cases.
As a starting point, a visual inspection of the bed
should be conducted, and samples of catalyst and
deposits should be collected for further analysis. These
activities are important to assess the nature of the prob-
lem and envisage the right corrective measures. When
bed plugging is caused by coking in the catalyst bed,
one common reason is local hydrogen starvation. Often,
this is the result of inhomogeneous distribution. In
this case, the design of the distribution tray(s) should
be assessed.
Bed plugging is also often caused by the deposi-
tion of foreign material in the interstices between cat-
alyst and grading particles. The material is typically
generated elsewhere in the plant: certain corrosion
mechanisms, malfunctioning of upstream equipment,
additives may create particulates. Topsoe’s preferred
solution in this situation is a combination of mechan-
ical equipment and grading. Scale catchers are excep-
tionally versatile and e cient to capture even tiny
particulates. This type of equipment is positioned in
the reactor head, performing its function in a space
that is under-utilised. The catalyst volume is not
adversely influenced by the presence of scale catchers.
On the contrary, in some situations scale catchers free
grading space to the benefit of catalyst. Below the scale
catcher, grading ensures that any tiny particles that
www.eptq.com
Q&A copy 36.indd 7
escape the mechanical equipment are retained prior to
reaching the catalyst layer
Q Is an add-in unit available for reducing the SO2 content
of flue gases?
A Kim Christensen, Senior Product Line Manager, Haldor
Topsoe, kich@topsoe.com
A Topsoe SNO process can be added to an existing
flue gas stream for removal of not only SOx but also
NOx, Hg, and other particulates. The SNO process has
shown to be competitive with conventional scrubbing
solutions within the refinery, carbon black, and power
industries.
The process is simple to operate with no waste
streams but producing commercial grade sulphuric
acid as a revenue source while avoiding purchase of
absorbents and eliminating waste treatment and dis-
posal costs as seen with conventional wet scrubbing
solutions. The Topsoe SNO process also provides an
option to recycle hot combustion air back to the boilers,
improving overall energy e ciency resulting in lower
CO2 emissions.
The first SNO plant was started up in 1 1 and
since then several companies have adopted the technol-
ogy, such as OMV in Austria, Agip in Italy, Vattenfall in
Denmark, and Petrobras in Bra il.
Q Hydrate blockages are slowing our FCC off-gas flow. Is
there some way of avoiding/reducing the problem?
A Melissa Clough Mastry, Technology Manager, BASF,
Melissa.mastry@basf.com
Hydrates in FCC off-gas are formed when small hydro-
carbons and small molecules such as H2S come into
contact with liquid water. Other small molecules can
also be triggers, including methane, ethane, and CO2.
Formation is especially possible at low temperatures, so
care must be taken during the winter period. To avoid
or reduce this problem, reduce the probability of this
reaction by reducing sulphur content in the FCC, espe-
cially during winter, by avoiding the introduction of
water, and by keeping the off-gas temperature high.
The high temperature is needed because the reaction to
form hydrates only happens when liquid water is pres-
ent, so higher temperatures keep any H2O in gaseous
form, avoiding condensation. educing sulphur content
can be done by either working together with planning
to schedule the processing of sour crudes for hotter
periods or, if an FCC pretreater is available, to monitor
pretreater severity to keep FCC feed sulphur to a min-
imum. High temperatures in the FCC off-gas can be
maintained by minimising the heat loss of the system,
which can be done by an external heater if available.
Q We are trying to blend our diesel product with biodiesel,
but the cold flow properties are not really good enough. How
can we improve matters?
PTQ Q3 2019 15
13/06/2019 14:52
 Process Notes

Vacuum tower cutpoint delivers profits

Cutpoint Concerns poorly designed heaters may experience coking with

COT below 700°F (370°C).
Crude unit vacuum tower performance is often critical
to a refiner’s bottom line. The vacuum tower bottoms Flash zone pressure is set by vacuum system
stream is valued far below the gas oil cuts, so most performance and column pressure drop. Lower flash
refineries look to minimize it. Many vacuum columns zone pressure increases cutpoint until the tower shell
are also designed or revamped to produce a diesel cut, C-factor limit is reached, at which point the packed
recovering diesel slipped from the atmospheric column beds begin to flood. Vacuum producing systems are
that would otherwise be downgraded to VGO product. mysterious to many in the industry, so a large number
of refiners unnecessarily accept poor vacuum system
Good vacuum column performance can maximize the
performance. With technical understanding and a good
profitability of downstream units by removing distillate
field survey, the root causes of high tower operating
hydrotreater feed (diesel) from FCCU or hydrocracker
pressure can be identified and remedied.
feed (VGO) and removing VGO from coker feed (resid).
In columns with stripping trays, stripping steam rate
One important measure of vacuum column
and tray performance are important. Stripping steam
performance is VGO/resid cutpoint. The cutpoint is the
rate is limited by vacuum column diameter (C-factor)
temperature on the crude TBP curve that corresponds
and vacuum system capacity. Any steam injected into
to the vacuum tower resid yield.
the bottom of the tower will act as load to the vacuum
system, so vacuum system size, tower operating
Vacuum column cutpoint depends on three variables:
pressure, and stripping steam rate must be optimized
1. Flash zone temperature
together. Depending on the design, a stripping section
2. Flash zone pressure
with 6 stripping trays can provide between zero and
3. Stripping section performance (if present)
two theoretical stages of fractionation, which can drive
Flash zone temperature is driven by vacuum heater coil a big improvement in VGO yield.
outlet temperature (COT). Increasing COT increases
Although the variables for maximizing vacuum tower
cutpoint. Vacuum heater outlet temperature is typically
cutpoint are simple, manipulating them to maximize
maximized against firing or coking limits. When
cutpoint without sacrificing unit reliability is not.
processing relatively stable crudes, vacuum heaters
Contact Process Consulting Services, Inc. to learn how
with better designs and optimized coil steam can avoid
to maximize the performance of your vacuum unit.
coking even at very high COT (800°F+, 425°C), but

3400 Bissonnet St. +1 (713) 665-7046

Suite 130 info@revamps.com
Houston, TX 77005, USA www.revamps.com

pcs cutpoint.indd 1 16/12/2018 14:52

 A Don Wolfe, Fuel Additives SME, Baker Hughes, a GE
company, Don.Wolfe@bhge.com
Blending of biodiesel stocks with petrodiesel stocks to
consistently produce fit for purpose D 75 or D74 7 fuels
can be challenging. Compounding this challenge is that
the inherent cold flow characteristics of most B100 blend
materials are significantly poorer than the petrodiesel
material that they are blended with, and that the biodiesel
has a higher density. There are a number of factors that
should be considered as they may potentially impact the
final cold flow characteristics of your final diesel blend.
Characteristics of B100 blend stock
The feedstock used to produce B100 can have a signif-
icant impact upon the base cold flow characteristics
(and the resulting blends) – the more highly saturated
the feedstock used to produce B100, the poorer the cold
flow properties. Additionally, saturated monoglycerides
(SMG) have been shown to precipitate out of solution
– the SMG crystals change over time and become resis-
tant to resolubilisation. Heat and agitation can help to
minimise the impacts of SMG crystallisation. Currently,
it is not possible to effectively manage B100 low tem-
perature performance with the use of additives alone.
One option that may prove useful for more reliable cold
weather characteristics in B100 is to utilise the No. 1-B
grade of B100 that has stricter limits imposed on cold
soak filterability testing and SMG content.
Storage of B100 blend stock
Storage of B100 can be demanding. It is generally rec-
ommended that the storage tank, as well as all injec-
tion/blending equipment, be designed such that B100
is maintained at least 10°F warmer than the cloud point
to minimise the formation of precipitant. Blending
B100 below the cloud point of the blend into the petr-
odiesel will likely produce a final blend with a higher
cloud point than expected. While outside the scope of
this question, it should also be understood that elevated
temperatures can accelerate the instability/degradation
of B100. Additives can mitigate/extend the storage sta-
bility life of B100.
Petrodiesel properties
Understand your base fuel cold flow characteristics and
specifications, as well as how they respond to commer-
cial cold flow improvers (pour point depressants, fil-
terability products such as CFPP, and so on). The cold
flow improvers for the final blend should be added to
the petro-component, and the temperature of the petr-
odiesel should (like B100 storage) be at least 10°F above
the natural cloud point of the oil.
Method of blending
B100 should be blended with the petrodiesel as soon
as practical, to limit any storage related issues (SMG
precipitation, oxidation stability issues, microbiologi-
cal contamination). In-line blending is preferred over
splash blending for a number of reasons, including both
a potential for less e cient mixing (stratification of the
heavier biodiesel component) as well as shock precipi-
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Q&A copy 36.indd 8
tation of biodiesel constituents when it contacts a cold
tanker wall. Loading procedures may be implemented
that may improve splash blending operations. In-line
blending of biodiesel and petrodiesel is the preferred
method to ensure thorough mixing, producing a homo-
geneous blend and minimising any cold wall impacts.
Again, all blending and storage should be designed to
ensure that the temperature of the blend is at least 10°F
above the cloud point of the blend.
A Tatiana Barbosa, Lead Sales Operations Specialist, SUEZ
– Water Technologies & Solutions, tatiana.barbosa@suez.com
First of all, you can mix biodiesel from different sources
to help in the cold flow properties. Usually vegetable oil
has a lower CFPP than tallow oil. For example, when
biodiesel is made from tallow oil, around 30% of soy oil
needs to be added just to get a CFPP around 8°C. The
biodiesel from 100% tallow oil has a CFPP of 14-15°C (it
is solid in many regions).
The second solution is to apply cold flow additives to
help decrease CFPP or pour point. You can add addi-
tives to change the crystallisation structure of the bio-
diesel or diesel. This can reduce the CFPP by a few
degrees, and when done in combination with applying
a blend of vegetable oil it could reduce CFPP by 5-10°C.
There are many additives in the market that can be
tested in a lab to achieve the best combination between
additive dosages vs cold flow properties changes.
Dosages of additives are usually 2000-5000 ppm.
The third solution is to distil the biodiesel in the vac-
uum tower and use only lighters in the blend. These
solutions will also help with any colour issues. A vac-
uum distillation process will help to complete the dry-
ing of the biodiesel and separate a side stream of a
higher quality product with no colour that is lighter
than the bottom product. The bottom product will be
concentrated in heavies and higher cold flow improv-
ers. The light stream will have lower cold flow proper-
ties. Simulation in pilot plants can be done to achieve
the best conditions for the distillation process and will
depend on each biodiesel source.
A Torkil Ottesen Hansen, Technology Director, Haldor
Topsoe, tih@topsoe.com
Biodiesel derived from the FAME process has poor cold
flow properties and this limits its blending ability. The
recommended solution for blending more bio derived
feed into the diesel pool is to hydrotreat the bio mate-
rial. This renewables stream can then be further catalyt-
ically dewaxed with low yield loss to provide excellent
cold flow properties. A Topsoe Hydroflex unit is an
example of such a solution.
A Patrick Truesdale, Principal Consultant, Emerson
Automation Solutions, Patrick.Truesdale@emerson.com
This is a typical challenge. It depends on the cold flow
properties – is it CFPP or pour point? There are addi-
tives that can be added, but then they vary according
to the type of biodiesel component. Additive injection
would need to be carefully controlled, as these addi-
tives are expensive and have a non-linear response.
PTQ Q3 2019 17
13/06/2019 14:52
 Pr o ce ss Not e s
Avoid Fired Heater Coking
For many refiners, heater coking in Crude and Vacuum
Distillation Units (CDU/VDUs) is a common occurrence.
Many units around the world are shut down every two
years, every year, or even every six months to deal
with chronic heater coking. However, with the right
design features driven by a solid understanding of
heater coking mechanisms, fired heater run length can
be extended beyond five years, even with relatively
challenging crudes.
The two primary drivers of heater tube coking in CDU/
VDU services are oil film temperature and residence
time. Secondary factors such as crude coking tendency,
solids content, and blend instability can further
accelerate heater tube coking. So, which heater design
parameters will maximize heater run length and avoid
shutdowns for high heater tube metal temperature or
high heater pass pressure drop?
MASS FLUX IS KING
Mass flux (lb/s/ft2 or kg/s/m2) is found by dividing the
mass flow through a heater tube by the tube’s cross-
sectional area. High mass flux begets high velocity and
suppresses coking in several important ways. First,
high mass flux means that the fluid moves through
the tube faster, minimizing residence time. Second,
high velocity results in high heat transfer coefficient,
which minimizes internal oil film temperature. Finally,
high mass flux creates high wall shear inside the tube,
minimizing build-up of solids or asphaltenes.
3400 Bissonnet St.
Suite 130
Houston, TX 77005, USA
pcs avoid.indd 1
Heater coking is not inevitable
HEAT FLUX CAN SURPRISE
Heat flux (BTU/hr/ft2 or kcal/hr/m2) measures the
amount of heat absorbed through a given outside
surface area of a heater tube. High heat flux raises tube
metal temperature and causes high oil film temperature
inside the tube. Popular fired heater design programs
use a well-stirred firebox model and calculate peak
heat flux by applying a simple multiplier to the average
heat flux. In reality, heater design parameters such as
firebox height/width ratio, burner type, burner sizing,
burner placement, and air/flue gas flow patterns can
result in actual peak heat fluxes that are much higher
than the “calculated” peak heat flux on the heater
datasheet. Localized areas with very high heat flux will
coke and suffer from high tube metal temperature.
Of course there are many other variables that must
be considered, such as pass arrangement, vertical or
horizontal tubes, cylindrical or box or cabin, coil steam,
etc. Problems stemming from blend instability are
becoming more common as refiners are increasingly
mixing light shale crudes with heavy crudes. As the
crude begins to vaporize, asphaltenes can precipitate
out of unstable mixtures and coat the heater tubes,
forming coke and creating hot spots.
Even with challenging crudes, refiners have achieved
Crude Heater and Vacuum Heater run length goals
through careful design and respect for the basics of
coking. Contact Process Consulting Services, Inc. to
learn more.
+1 (713) 665-7046
info@revamps.com
www.revamps.com
16/12/2018 14:53
 Fundamentals of refinery safety
A study of process safety considerations arising from a raffinate
splitter explosion
NORMAN LIEBERMAN
Process Improvement Engineering
R
efinery safety relies upon two
questions:
1. Is the process design intrinsi-
cally dangerous
2. Do shift operators understand
how their instruments function
Safety in refineries is not a matter
of attitude. Safety is a product of the
knowledge of process engineer and
console operators. The explosion at
Texas City was related to three fac-
tors: relief valve location, level indi-
cation, and flow measurement.
Location of relief valve
eferring to Figure 1, we have
shown two possible locations for
the tower pressure relief valve.
Which is correct
The correct choice is position 1.
If the tower floods, the liquid head
pressure in the vapour line will
cause the relief valve at position 2
to open, due to the static head of liq-
uid in the vapour line, even though
tower pressure is not excessive.
arge volumes of liquid will then
flow into the relief valve header sys-
tem, which hopefully is connected to
the flare and not to an atmospheric
vent, as discussed below.
Level indication
iquid levels are not measured
directly. They are indirectly meas-
ured by means of a level-trol’
(see Figure 2). The pressure differ-
ence (DP) between P1 and P2 (psi)
is measured, and then converted
into inches of level (DH) by use of
Equation 1:
DH = (DP) (28) ÷ (SG) (1)
where SG specific gravity of the
liquid
www.eptq.com
q3 lieberman.indd 1
Flare
1
Flare
2 DP
Figure 1 The correct location for the relief
valve is position 1
The specific gravity used is called
the calibration specific gravity’. It
is not typically adjusted for months
or years, that is, until the instrument
technician recalibrates the level-trol.
If the fluid in the level-trol becomes
less dense than normal, the indi-
cated level on the panel, relative
to the real level in the vessel, will
decline, as discussed.
Flow measurement
Flows are indirectly measured by
use of a flow orifice plate. The DP
across the orifice plate is measured
and then converted to flow using
Equation 2 (see Figure 2):
Flow ∝ (K • ΔP)½ (2)
where K orifice coe cient
The factor that many operators
do not know is how to correct a
flow for a meter being off- ero. et
us say the meter on the instrument
is reading a flow of A. The meter is
then bypassed so that the observed
flow should drop to ero, but it only
drops to B. To calculate the correct
flow, use Equation 3:
P2
Level
output
P1
Level-trol
Figure 2 Level is a function of specific
gravity x differential pressure
Corrected Flow = [(A2 – B2)]½ (3)
In the 1 0s, when flows were indi-
cated on a strip chart recorder, we
made this correction with a pencil,
as the paper strip was already cali-
brated for the square root function.
With a digital display, this correction
must be made with Equation 3.
Raffinate splitter explosion
– Texas City
The following story relates to an
incident that was a combination of
operators not understanding how
level and flow instruments worked,
and process engineers not adhering
to good design practices.
In 1 74, I was waiting for the ele-
vator in the Amoco Oil Building in
Chicago with Gary lmer. Norm,
Gary said, if Amoco is in such a
rush to get the xylene splitter at
Texas City built, they should pay
me overtime. How about filling out
some data sheets to help me for a
few days
So, to a minor extent, I participated
in the design of the xylene split-
ter. After the isomerisation unit at
PTQ Q3 2019 19
13/06/2019 17:09

P1
Relief
valve
Blowdown
Loop
seal
3 psig To condenser
Figure 3 Raffinate splitter at Texas City
Texas City was built, the tower was
transformed into a ra nate splitter,
which became the most famous dis-
tillation tower in America.
In 2005, the tower’s relief valve
opened as a consequence of a high
liquid level. A cloud of naphtha
vapour formed because the relief
valve was not connected to the
flare. It vented indirectly to the
atmosphere. The naphtha vapours
were ignited by a truck engine and
exploded. Fifteen contractors were
crushed to death in a trailer and 180
injured. The price of gasoline rose
by 10 cents a gallon in the US, as the
refinery was the largest producer of
gasoline in America.
The understanding in the indus-
try is that this was a consequence
of connecting the relief valve vent
to the atmosphere, rather than to
the refinery flare. The real story is
more complex.
Background
The author worked as an operat-
ing supervisor in Texas City, and
as a process engineer in Chicago
for Amoco Oil between 1965 and
1981, and designed 7% of the pro-
cess equipment in Texas City (cok-
ers, sulphur recovery, light ends
fractionation, amine system, fuel
gas treating). For the distillation
towers, the author supervised the
debutaniser, butane splitter, depro-
paniser and butane-pentane splitter.
20 PTQ Q3 2019
q3 lieberman.indd 2
Vapour line
50 psig
(1)
Raffinate
splitter
Feed
flow
(15) Open
P2
(30)
No
flow
Closed
All the relief valves were located at
the top of the towers. All relieved
directly to the atmosphere. The rea-
son the author did not object to this
design was because it was that way
when he had assumed supervision
of the process. Also, the towers had
been commissioned in 1958 and
nothing had happened yet. What
would result if a tower flooded due
to a high liquid level, and the relief
valve opened, was not a question
that was considered.
Fundamental causes of raffinate
splitter explosion
The documented, industry-accepted
causes of the ra nate splitter failure
are:
• Relief valve not connected to
plant flare
• Operator laxity.
However, there are a number of
other errors that have not been fully
explained (see Figure 3):
1. Design of the loop seal draining
the blowdown tower to the three
psig (3#) condensate collection
system
2. Elevation of the splitter relief
valves relative to the top of the tower
3. Lack of technical support during
start-up operations
4. Operators not understanding the
relationship between tower bottom
temperature and tower bottoms
indicated level
5. Operators not understanding
the concept of a level-trol being
‘tapped-out’.
6. Failure to check liquid head pres-
sure at the bottom of the tower.
How levels are measured
We do not directly measure levels in
process units. We measure the pres-
sure difference between the top and
bottom level taps (see Figure 2). To
convert from a differential pressure
to level, we use the specific gravity
of the liquid (see Equation 2). For a
given differential pressure, the indi-
cated level that operators observe on
the control panel will:
• Go down, as the liquid becomes
less dense
• Go up, as the liquid becomes more
dense.
This occurs even though the
actual liquid level in the tower has
never changed.
During the ra nate splitter
start-up, the liquid in the bottom
of the tower was less dense than
normal. Thus, the indicated level
observed on the control panel
was lower than the actual level.
Unfortunately, when the liquid fills
the space between the lower and
upper level taps, the differential
pressure measured between the level
taps remains constant, regardless of
how high the liquid level becomes
(see Figure 2). This is called being
tapped-out’. If the specific gravity of
the liquid is 10% higher than normal,
the indicated level on the panel will
read 110 . But, if the specific gravity
of the liquid is 10% lower than nor-
mal, the indicated level on the panel
will read 90%. As the level rises by
10 ft, or even 100 ft, above the top
level connection, the indicated level
will remain at 90%. Which is exactly
what happened at Texas City.
Temperature vs specific gravity
The operators did suspect that they
had a high level. However, they
then commissioned the splitter feed
preheat exchanger. This resulted
in the tower bottom temperature
increasing. This reduced the specific
gravity of the liquid, which reduced
the indicated level. This led the
operators to draw the false conclu-
sion that their tower’s bottom level,
which they had begun to suspect
was too high, was actually OK.
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13/06/2019 17:09
 The hourly shift operators, who
were later terminated, testified
to the above, as the reason they
allowed the tower to overflow. They
testified that this was proof that the
cause of overfilling the tower was
not their negligence but a faulty
level indicator.
The operators were victorious in
their litigation (possibly because the
above principle was not explained
during the proceedings).
Was the splitter pressure excessive?
Apparently, the tower pressure itself
never became excessive. The oper-
ators were bringing in more feed to
the splitter than they were drawing
off from the bottoms product outlet.
It was not that the tower
over-pressurised, it was that it over-
flowed. If the pressure relief valve
had been located at the top of the
splitter (as was the case in the towers
the author operated in Texas City in
the 1 70s), overfilling would not nec-
essarily have caused the relief valve
to open. But, if the relief valve is
located (as in the case of the ra nate
splitter) many feet beneath the top of
the tower (see Figure 3), then a head
of liquid would exert a head pres-
sure on the relief valve, which then
could cause the relief valve to open.
Certainly, it was the large vol-
ume of saturated liquid, and not just
vapour, that blew out of the relief
valve and into the blowdown tower.
False bottom flow indication
The operators had closed off the
normal bottoms product out-
let level control valve. But why
Because they thought it was leak-
ing through. The valve was likely
not leaking. But the flow transmitter
was off- ero. Very often, flow trans-
mitters are off- ero. For example, let
us say that the indicated flow is 8
b/h. The instrument is checked and
found to be off- ero. The eroed
flow is 4 b/h. Flow meters read as
a function of the square root of the
measured pressure drop through
the flow orifice plate. Therefore, the
corrected flow (compensating for
the meter reading off- ero) is (see
Equation 3):
(8)2 – (4)2 = 64 – 16 = 48
(48)½ = 7 B/H
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q3 lieberman.indd 3
The meter was reading 1 b/h too
high. But if the control valve is shut,
and the real flow falls to ero, the
operators will see a flow of 4 b/h.
Apparently, the operators in
Texas City mistook a meter being
off- ero for a large flow through the
ra nate splitter’s bottom level con-
trol valve. As they were bringing
in feed continuously, and the indi-
cated level on their panel was not
increasing (although the real level
was increasing), they blocked in the
splitter bottom’s level control valve.
Loop seal
The blowdown stack loop seal is
shown in Figure 3. The liquid from
the blowdown stack flowed into a
slightly pressurised (about 3 psig)
hydrocarbon liquid collection sys-
tem, rather than into an open
sewer. To prevent hydrocarbon
vapours from continuously back-
ing out of this collection system into
the atmospheric blowdown stack,
there was an intervening loop seal.
Unfortunately, as the liquid in the
blowdown stack flowed upwards
in the vertical portion of this loop,
the liquid lost head pressure due
to its increased elevation. As this
liquid was naphtha at its saturated
liquid bubble point, it partly vapor-
ised. The expanding vapour choked
off the liquid flow. The result was
vapour lock.
Vapour lock stopped the flow of
naphtha draining from the blow-
down stack. The liquid level in the
stack backed up over the inlet no -
le. The vapour flowing through
the inlet no le blew the naphtha
up the stack. The naphtha ignited
reportedly by a running truck
engine.
Probably, a high point vent on
the top of the loop seal – which is a
common feature of loop seals used
in water plumbing systems could
have prevented the vapour lock. But
then, what would be the disposition
of this vapour
The ultimate question
We can hope that refiners would
have learned a lesson from this
incident. But that is not the ques-
tion. Would the author have made
the same mistake if he had been
present Hopefully, he would
have noted that the input flow
measurement exceeded the out-
put flow measurement. Then, he
would have calculated that the
level in the splitter must be increas-
ing. Had the unit’s technical ser-
vice engineer been involved in the
tower’s start-up, he or she should
have interceded with operat-
ing personnel based on the above
material balance.
But there is another, more fun-
damental action, that the author
would certainly have taken to pre-
vent this explosion. In 1 84, he
was involved in an alkylation unit
depropaniser start-up at the Good
Hope refinery. No one was sure of
the liquid level. The level gauge
glasses were largely useless as
the process fluid was water white
(not yellow), and the glasses old
and scratched.
The author placed a pressure
gauge (see Figure 3) at the top vent
of the level glass (P-2) and then
checked the head pressure (P-1).
This is the pressure difference
between the top vapour line and top
of the gauge glass. To convert this
DP to feet:
Feet = (DP) (2.3) ÷ Specific gravity of butane (4)
At Good Hope, the measurement
indicated we had 40 ft of liquid
above the top of the gauge glass. We
were tapped-out. The liquid level
was pumped down until the indi-
cated level on the panel declined
from a straight line of exactly 80 to
a slightly fluctuating 70 .
In 1 74, the author demonstrated
this method of finding levels on
start-up to his operators in Texas
City. But by 200 , this simple step to
enhance operational safety during
start-up operations had been sub-
merged in the flood of bureaucracy,
to the detriment of refinery safety.
Norman Lieberman is a field troubleshooter
for refinery delayed coker, alkylation, crude
and vacuum system process problems, and
has been instructing refinery troubleshooting
seminars since 1983. His company provides
retrofit designs for refinery vacuum systems.
He graduated with a degree in chemical
engineering from Cooper Union for the
Advancement of Science and Art in New York.
Email: norm@lieberman-eng.com
PTQ Q3 2019 21
13/06/2019 17:09
 Your valves are talking to you.
Are you listening?
Because details matter.

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metso.indd 1 16/12/2018 14:58

 Digitalisation is transforming KPI setting

Digitalisation means turning numbers on a dashboard into profit on

your income statement

DUNCAN MICKLEM
KBC (A Yokogawa Company)

C
alculating and reporting key
performance indicators (KPI)
is a routine practice in the

uncertainty reduced
refining and chemicals industries.

Losses due to
It is key to helping decision mak- Business
ers act, and to helping managers management
oversee performance. Digitalisation
tools like Business Intelligence Production
management
(BI) and dashboards are helping to
increase the visibility and timeliness

Decision value
of KPIs, break down organisational Operations
management
silos, and drive consistency across
organisations. However, this is not
enough in itself. Automation
The challenges of poor underlying
data, di culties of setting targets
rs

es

s
Se OW

es

rs

s
s

s
s

nd

ay
nd

th
th

ay

ou

ou
and the interactions between con-
ut

ut

on
on

D
D

co

N
co
in

in
H

M
M

M
Se

flicting KPIs mean that, all too often,

KPIs are not effective in delivering Decision making Decision impact
any true improvement in perfor- Time horizon Time horizon

mance. At the same time, digital-

isation is changing organisational
responsibilities, and predictive
analytics are changing information
from being about the past to being
about the future.
In this article, we reprise the basic
principles and objectives of KPIs
with regard to achieving opera-
tional excellence, discuss some
of the root causes of ineffective
KPIs, and then explain how vari-
ous digitalisation technologies and
approaches can transform the effec-
tiveness of KPIs in your business.
Purpose and principles of KPIs
KPIs are an important ingredient
in achieving operational excellence.
KBC believes the two facets of oper-
ational excellence are:
• Making better decisions, faster
• Perfect execution of those deci-
sions, every time.
Within the first, leading KPIs pro-
vide timely decision support infor-
Figure 1 KPIs can be applied on a number of different timescales and at all levels in
an organisation
mation to support people to make
the right decisions in a timely way.
In the second area, lagging KPIs
measure the effectiveness of the
entire process (both decision mak-
ing and execution) to allow fine
tuning or modification of the work
processes, physical processes or
organisation to take place.
Given that leading KPIs are
intended to support decision mak-
ing, it is essential to understand
how people make decisions. In par-
ticular, how people make decisions
in environments where there is lim-
ited time and limited information,
such as most refining and chemicals
facilities.
In this type of environment, deci-
sions are typically made via rec-
ognition primed decision ( PD)
making, which is fast, natural
and intuitive, and effective when
deployed by experts. The typical
process is as follows:
1. Situational awareness
• Based on visual information
about the situation, the expert
makes a mental ‘pattern match’ to
determine what is happening.
• The expert interprets the mean-
ing of the event, and then makes
a mental simulation of what will
happen next.
2. Identify options
• Determine the root cause of the
issue.
• Search for solutions, typically
from experience.
• As solutions are found, check
if they will su ce to solve the
problem.

www.eptq.com PTQ Q3 2019 23

q3 kbc.indd 1 15/06/2019 07:36

 3. Implement the first su cient’
solution, then stop searching for
more solutions.
Leading KPIs play an important
role in this process by providing a
top level of situational awareness,
by flagging up and highlighting
issues, and potentially providing a
simple overview of all the possible
issues that need to be considered.
KPIs can help provide situational
awareness to less expert people,
by explicitly identifying the most
important factors rather than hop-
ing it will be spotted amongst the
weeds of many data points.
Current simple digitalisation tech-
nologies such as data integration
and dashboards greatly enhance the
power of situational awareness KPIs.
Data visualisation such as col-
our coding changes the KPI from a
number on a screen somewhere to
something highlighting action may
be required.
Data aggregation, to bring
together data from multiple sources,
can allow KPIs to be viewed in com-
parison to each other, and makes
decision makers aware of situations
outside their direct silo. This can
make decision making more holistic
without needing meetings or calls to
exchange information.
KPIs can be applied on a number
of different timescales and at all lev-
els in an organisation. Some of the
decision timescales are illustrated in
Figure 1.
So, for instance, top level busi-
ness financial results (lagging KPI)
are reported quarterly or annually,
whereas operational decision mak-
ing takes place on a timescale of
days, hours or minutes.
One of the ways digitalisation
adds value to an organisation is
compressing the decision timescales,
thus reducing losses due to uncer-
tainty. This is key to understanding
how digitalisation changes KPI man-
agement, as will be discussed later.
KPI pitfalls
Having established the theory behind
KPIs, we will now examine some of
the things that make KPIs ineffective.
Rubbish in, rubbish out
KPIs and the situational awareness
they bring are only as good as the
24 PTQ Q3 2019
q3 kbc.indd 2
data being used to calculate them.
It is commonplace for experienced
operators to ignore or reject data
when they ‘know’ (either rightly
or wrongly) a certain meter might
be wrong. The entire system is
dependent on the inputs being cor-
rect, and being able to detect and
highlight errors in the data.
Target setting
To make KPIs effective requires
some sort of measurable target, or
target range, to be set. There are
various interlocking issues that
make target setting a challenge:
• Motivational risks: set a target too
high and people become demoti-
vated, too low, and they become
complacent. Put a target on some-
one that is not within their realm
of control and they will feel perse-
cuted. Even targets that are appro-
One of the ways
digitalisation
adds value to an
organisation is
compressing the
decision timescales,
thus reducing losses
due to uncertainty
priate can be perceived as top down
micromanagement rather than
useful ‘situational awareness’ to
empower the decision maker.
• Conflicting targets: particularly in
the refining and chemicals indus-
tries there are many trade-offs
between competing priorities. For
instance, improvements in energy
e ciency may compromise process
yield; pushing up throughput can
compromise reliability and mainte-
nance costs. Targets set in isolation
can drive narrow improvements
that make things worse from a
holistic perspective.
• Volatile external environment:
what is best today may not be
best tomorrow as operating strat-
egies can change, and the relative
value of different objections is not
fixed. Targets need to be smart
enough to adapt to changing
circumstances.
• Keeping the key in KPI: in very
complex environments, there are
a lot of things to pay attention to,
therefore there is a general tendency
to have too many KPIs on too many
dashboards, which starts to erode
the very purpose of the system.
Research shows that human cog-
nitive capacity can only cope with
about seven things (+/-3) at any
one time, so large numbers of KPIs,
however important, are cognitively
di cult to process.
Lack of action
Many KPIs are regarded with a ‘so
what?’ attitude by the users. Correct
data and targets do not necessarily
result in corrective action. Training
is the common method of solving
this with simple steps to solve the
typical out-of-target KPIs. However,
the method is limited when trying to
consider the complex environments
with multiple variables acting on the
KPI; this results in either additional
time and effort spent in trouble-
shooting the issue or disregard of the
KPI as a lower priority when com-
pared to KPIs that return to ‘normal’
when the known action is applied.
How deeper digitalisation can help
As discussed previously, ‘shallow’
digitalisation can move data around
and get KPIs displayed to the right
people at the right time. However,
this type of digitalisation does not
address the fact that the KPIs and
targets themselves may be weak. A
‘deeper’ level of digitalisation, uti-
lising digital twins and data analyt-
ics, can address many of the pitfalls
of KPI setting.
To illustrate the philosophy of
digitally transformed KPIs, we will
consider the example of furnace
coil inlet temperature. This is an
example of an energy KPI. The KPI
is intended to indicate to mainte-
nance or engineering if the pre-
heat exchangers are performing as
expected, and triggers actions such
as exchanger cleaning. Some of
the challenges associated with this
KPI are:
• The coil inlet temperature will
decrease due to fouling in the
exchangers, but is also affected by
www.eptq.com
15/06/2019 07:36
 Information for Reliability and Instrumentation Engineers

INTELLIGENT
machine monitoring

The profit:
Return On
Investment
of condition
monitoring
prognost.com/profit
bbb
How to select a
Condition Monitoring System
monitoringguide.com

prognost.indd 1 13/03/2019 10:07

 Raw T. flow Engineering Wider unit Economics Predictive
lab data data (geometry) simulation analytics

Cleaning impact
Data assurance Data upgrade simulation Economic analysis Predictive analytics

Unit level data Calculate Individual Cleaning Best exchanger(s)

rec utility higher value exchanger payback and to clean in
engineering cleaning benefit cost benefit future
Hot monitor KPIs
thermal data Combined Best exchanger(s) Turns a lagging
reconciliation Normalise for cleaning benefit to clean NOW KPI into a leading
flow, crude type, KPI
Data quality etc. Simulation Economic KPIs
KPIs (D Ps) performance directly compared
Visualise trends KPIs (MPIs) to other
possible actions

Figure 2 Managing the exchanger cleaning decision

factors such as the type of feedstock,
production rate and product mix.
This means the KPI itself is ‘noisy’
and needs to be normalised
• The reduction in temperature
implies heat exchangers need clean-
ing, but does not indicate which
exchanger should be cleaned
• The temperature only reduces
after fouling has occurred, so while
the KPI is intended as a leading
indicator it is really a lagging indi-
cator of performance
• The KPI may suggest that clean-
ing is required, but this is still some-
what qualitative, and the action is
competing with many other possi-
ble maintenance activities.
We propose a more robust philos-
ophy for managing the exchanger
cleaning decision making process
(see Figure 2).
The first step in the process is
data assurance. This eliminates the
‘rubbish in, rubbish out’ problem
by monitoring data quality and
reconciling via a first principles
digital twin. Using a physics based
model rather than purely statistical
data reconciliation forces the data
to obey physical and chemical laws
such as the conservation of mass
and energy and fluid behaviour.
The digital twin can thus pick up
data errors and to a certain extent
patch in missing data. The digi-
tal twin, in turn, generates a new
set of KPIs around data quality
(KBC refers to these as data quality
parameters, DQP) which are then
used to trigger instrumentation
checks or maintenance.
The second step is using engineer-
ing simulation in the digital twin to
calculate higher value engineering
parameters. Whereas the original
KPI was a directly measured tem-
perature, the digital twin calculates
parameters such as fouling factor.
The fouling factor normalises out the
changes in flow rate, fluid type, and
so on, and provides a pure indication
of fouling rather than an indicator
muddied by external factors. In this
example, fouling factor is the higher
value parameter, but similar exam-
ples for other applications include
equipment e ciencies, distillation
tray flooding, and catalyst activities.
The third step is automated sim-
ulations of alternate futures, in
this case the technical impacts of
cleaning different exchangers in
the network. This changes the KPI
from a vague indication that foul-
ing has occurred to a detailed pin-
point of the impact of fouling in
each exchanger. The simulation
model also has KPIs governing
its performance (KBC refers to
these as model performance indi-
cators, MPI), which are then used
to trigger engineering checks to
recalibrate and update the model
when necessary.
The fourth step adds economics to
the analysis and calculates the costs/
benefits of cleaning each exchanger.
This economic analysis allows
exchanger maintenance to be eval-
uated in a risk based work selec-

Crude Preheat Train HXs

HX Monitor

E1 Time to clean  E2 Time to clean  E3 Time to clean  E4 Time to clean 

HX Ok HX Ok HX Ok HX Ok
£1 Payback minus time since last £2 Payback minus time since last £3 Payback minus time since last £4 Payback minus time since last
clean clean clean clean

E5 Time to Clean E6 Time to Clean E7 Time to Clean E8 Time to Clean

Clean in 30 days Clean in 30 days Clean in 30 days Clean Now
£5 Payback minus time since last £6 Payback minus time since last £7 Payback minus time since last £8 Payback minus time since last
clean clean clean clean

Figure 3 Simple dashboard for frontline staff

26 PTQ Q3 2019 www.eptq.com

q3 kbc.indd 3 15/06/2019 07:36

 and prescriptive
cyclohexane. maintenance
Remarkably, techniques.
the selectivity ratio This is key
of mono- was not enou
tion process alongside any other flagged maintenance
because
borylated these technologies
versus diborylated have huge products
methane potential isacross 15:1 system. In the
activities.
thewithsector,
the offering
heterogeneous a bettercatalyst.
alternative In to the traditional
comparison, the a 20% higher
The fifth step adds predictive analytics to predict
calendar
homogeneous based approach
catalyst gives to asset maintenance. methane
a monoborylated outlet oil temp
the evolution of fouling in future, and thus indicate
yield
With of this only 5.6%. Thus,
approach, the the focus heterogeneous
is analysingcatalyst issues in the previou
upcoming requirements for cleaning. Predictive ana-
exhibits
known to both
causehigher a problem yieldsuch andasselectivity
vibration for in amono-pump nisms were in
lytics turns a lagging indicator into a leading indicator
orborylated
compressor. methane
Sonic monitorsthan thecanhomogeneousbe added to the catalyst.
device process safety
and Importantly,
allows actionthe to be taken
team before
found thatlossesMOF areUiO-67-Mix
incurred.
and when vibration exceeds a certain level, alerts can be The system
The final step
without iridium is adding
had nothat AI or knowledge
effect on methane based ana-
sent to advise operators remedial actionborylation.
is needed. and, because
lytics The
that can generate
team analytics
also carried correct advice taking in all ele-
Prescriptive addsout a newdetailed layeroptimisation
of sophisti- oil supply and
ments of the
of theto catalyticsituation and then
reaction conditions provide clear actions
usinga UiO-67- to
cation the methodology, moving it from product in different mo
resolve
Mix-Ir it. This action may require human intervention
based to as the catalyst
a broader process by based
screening severalIndifferent
approach. deliver- • High temper
or, where
C-H the process
inert solvents. isUsing
trusted, C6D thenasautomated,
thebesolvent auto-
led to furnaces run p
ing prescriptive analytics, there has to
12 a recognition
matic maintenance
bis(pinacolborane) requests.
conversion of 19%
that processes, activities and systems usedand in the a muchplant ble of supplyi
This
lower work yield process
of 3.3% addsfora monoborylated
large amount of data
methane. system could
are interconnected. Prescriptive analytics looks at data
processing
Conversely,
streams
and these,
acrosswhen
calculations,
the
andcommon
and solvent
pinpoints
generates a large
tetrahydrofu-
sophisticated signa- ing three bitu
amount
tures and patterns of data that are happening initadvance
ran of
was additional
employed, information.
98% conversion However,
of the does
borylation duction lines,
notofreagent
increase
an event. was the achieved;
number of KPIs for
however, thefrontline
major product staff. heater in wint
Thiswas processborylated is entirely automated,
tetrahydrofuran,
Critically, too, the approach also tells the operator and
with the
only data
3.8% and
yield • Normal tem
model of performance
monoborylated KPIs only
methane.
the root cause of the problem. It can inform them not need Among to be addressed
the solvents tem is capable
byonly
exception.
tested, theThe
that dodecane frontline
compressor gave the isstaff best
going areto presented
results:
fail but a also withthataits
conversion required for th
simple
impending failure is directly linked to the leakage (see
of dashboard
>99%, turnover that has
number extremely of 67, clear
a actions
monoborylated of liq- heater
Figure
uidmethane
3). theyield
into gas of lines19.5%,
at a and certain no concentration
detectable amount or even of • The furnac
diborylated
This requires methane
no expert or borylated
training
just a slow change in the pressure recorded. That effec- or dodecane
implicit (<1%),
knowl- as long as th
which
edge
tively is amounts
to interpret.
the prescriptive to an
This extraordinarily
automated
element work high selectivity
of the process
approach. lever-
It not between the fu
ages ofmany
>99%aspects for theof monoborylated
digitalisation: product.
only highlights the impending problem, it also high- Hot oil hea
Experiment
• Multiple data that strongly
sources (processsuggests data, that
price the UiO-67-
lights actions can be taken to avoid it. Itdata,
is stillengi-in its
Mix-Ir
neering data) structure
are with metal-organic
aggregated together framework allows
infancy today, but over the course of 2019 we expect to One of th
bis(pinacolborane)
• First principles process and digital
methane twin molecules
reconciles to thereact
see the level of interest and excitement around it gather-
data, inside the pores to yield monoborylated methane
ing simulates
pace all thethe time.scenarios, and calculates the value
and nota
while preventing the formation of the thermodynam-
of cleaning
• Dataically more favoured the
analytics diborylated methane.
changesInthe the
Scoping out the predicts
results future and redesigne
next
process phase
from reactive of our research, the team plans to activate
Ultimately, though,toprescriptive
proactive analytics is just one
methane with
• Dashboards are the same
used to chemistry,
visualise but will substitute line place
example, albeit an important one,the of end results
the drive toin an
digital
Earth-abundant
accessible way. metals such as iron, cobalt, nickel and
across theforoiliridium,
and gaswhich sector. In terms of outcomes, we
We copper
believe
see three keythis trends type is rare
of digitalisation
playing
and
out across the
expensive.
willsector greatly
as the inlet and
reduce
march theto number
digital of
gathers KPIs.
pace. Since
First, decisions
the nature will
of be
work
Platinum-containing
increasingly made by catalystintelligence,
artificial for functionalisationand execu-
will change. As refinery and asset tasks become more
ofofnitro-aromatics
tion
autonomousthose decisions and AI will
assisted,be automated,
significant there is no collector and
Catalysis with hydrogen (hydrogenation) isproductivity
a key pro-
longer
gain any need to provide decision support KPIs for tank coils, pr
cesscan be expected.
in refining, amongIndividuals
other industries. and the businesses
In particular,
routine
they operation. Instead there will be KPIs monitor- heaters.
the work for need toofunderstand
hydrogenation functionalised that the requirement
nitro-aromatics
ingfortheworkers
performance of the analytics
willtoevolve. Organisations and data and to ensure
people will
is employed manufacture aromatic amines (ani-
theneed
system is
to retrain operating correctly.
lines), which themselves.
are important to the agrochemical, pig- Orifice design
We also
ment, and expect to see 2019 witness
pharmaceutical industries. the continuing
Nitro-aromatic roll- Previously, at
out
Conclusionof a new consist
compounds trend which of at least we term one nitrohere: group
‘networks (NOof ) oil flow resu
KPIs are a key
industry
attached to element
co-opetition’.
an aromatic to The
decision support in
opportunity
ring. Typically, the
totheir refin-
seamlessly
hydro-
2
the storage ta
ingconnect
and
genationchemicals
elementshas industries.
of the value
required Digitalisation
use chain will give
of catalysts cancompetitive
address
containing tomers. As th
many of
advantage the issues that have
precious metals such as platinum, palladium, and
to companies which compromised
recognise KPI
that effec-
or rho-can the furnaces
tiveness
take in
advantage the past.
of theWe see
opportunity
dium. Other researchers have reported that changinga future to evolving
build business where alli- flowing throu
routine
the operation
ances across the has
supported value very
Pt sites chain. fewMuch
from KPIs due
as to thetohas
Amazon
nanoparticles highly done
highly ally decreases
autonomous
with consumer nature of
goods operations.
shipping
dispersed clusters or single-atom catalytic sites in Instead
and KPIs
delivery will be a
supply furnace outlet
focused
chains, on identifying
process exceptions
manufacturers
Pt catalyst with iron oxide (FeOx) support resulted willand do anomalies.
to react to KPIs
market the required
will inbeunprecedented
opportunitysmart, and with targets
manufacturing
reactivity adapting to variable
andenhanced
and pricing challenges. situ-
selectivity diameter of th
ations Theoptimised
for final key by
hydrogenation trend rigorous
ofacross modelling.
this sectortoKPIs
nitro-aromatics will
thebe willaround
aromatic be 100mm. Then,
increasingly
organisational
amines. However, future facing,
change. the low leveraging
Knowledge
surface area predictive
automating
of this system ana- and throughout th
lytics rather
powerful
limits than
theprovision
numberretrospectively
of data
accessibleandmeasuring
models
catalyticacross what refining
surface wentsites. fice diameters
wrong. This willwill
A promising
organisations require
alternative changes
democratise would in be
the culture
to use anda organ-
decision-making support pro- pressure. In th
isation
cess. to get
material
The the most
composed
people whoout of aofhigh-surface
embrace thethisnew willinformation,
area oxide,
make themselvesand
such system, even
rigorous
more and instead
as silica,
employable robust while technology
of iron theoxide. to calculate
The problem
organisations the correct
who is that
embrace effectively. In
course willofbe
it because action.
of itsable
most lowtoacidity
achieveand weak
digital interaction, SiO
transformation in 2a tion thickness
meaningful way and compete in 2019 and beyond. from 50mm to
Duncan Micklem is Executive Vice President, Strategy and Marketing
with www.eptq.com
KBC (A Yokogawa Company).
www.eptq.com 88 PTQ Q2 2019 PTQ Q1 2019 13
www.eptq.com PTQ Q3 2019 27

q4 argonne.indd 3 14/09/2018 09:35

outlook .indd 7 q2 tupras.indd 2 17/12/2018 13:12

q3 kbc.indd 4 15/06/2019 07:36

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magnetrol.indd 1 13/06/2019 10:12

 Optimising desalter control
Analysing desalter performance and improving crude blending capacity with
multi-phase instrumentation and control
ANDREW SHAW and NEIL MURCH
Tracerco
N
ot all refineries are the same
and, as such, the challenges
with blending crude feed-
stocks vary between facilities.
Fluctuation in crude supply can be
beneficial, however it can also bring
significant operational challenges
during the desalting process that
can have an impact further down-
stream into other parts of the distil-
lation unit.
Crude blending
Opportunity crudes are becoming
a more attractive option for refiners
looking to improve flexibility, max-
imise operating margins, increase
distillate yields or convert high sul-
phur fuel into diesel and gasoline,
but they are not without their dif-
ficulties. Whether it be oil sands,
shale or condensate, higher total acid
number (TAN) or increased levels of
elemental impurities and contami-
nants such as waxes, solids, iron and
vanadium all of these characteristics
can lead to processing issues. The
e cient removal of these impurities
along with salts and water (BS W)
from crude feedstock is imperative to
maintain reliable operations, prevent
unplanned shutdowns and outages,
and reduce corrosion and fouling.
Foremost of these challenges is to
monitor and manage the position
and quality of process fluids, includ-
ing emulsion, upstream of the dis-
tillation tower; namely, the desalter.
Whether the process involves inline
or intermediate blending, the use of
accurate and reliable level or inter-
face control devices ( IC) in the
desalter can reduce and in some
cases eliminate process problems
resulting from unwanted carryover
or carry under.
www.eptq.com
q3 tracerco.indd 1
Reliable control
Introducing these crude blends
creates some variable processing
conditions with respect to instru-
mentation and control, so it is
important by design that devices can
reliably manage fluctuations. There
are several technologies that can be
employed for level and interface
control that look at differential pres-
sure, volume percentage of water or
electro-magnetic pulses, for exam-
ple. Changes in operating condi-
tions such as temperature, pressure
or even the type of feedstock can
also affect the accuracy and relia-
bility of these devices. Being able to
monitor and adapt to these variable
conditions can optimise separation
to improve feedstock flexibility.
Mixing can be increased to maxim-
ise wash water contact, thus remov-
ing more undesirable materials and
contaminants from the crude.
Not being able to accurately
control the interface is a common
occurrence. By providing a high res-
olution measurement around the
oil-water interface layer, the ten-
dency or lack of control leading to
incursions of conductive process
fluids to the electrostatic grids and
overdosing of chemicals such as
demulsifiers is reduced. This ena-
bles refiners to reduce costs asso-
ciated with unplanned trips or
upsets, ensure the correct amount of
chemical dosing, all while enhanc-
ing safety. There are also associated
environmental benefits from having
accurate control over process inter-
faces with respect to brine or e uent
discharge and recirculation as part of
wash water recharge. By visualising
and monitoring the water level posi-
tion, it is possible to reduce hydro-
carbon carry under or oil in water,
which reduces demand on filtration
and chemical treatment, improving
operational e ciency and environ-
mental compliance of the wastewa-
ter treatment plant.
Process review
Tracerco was approached by a
refinery to help understand and
diagnose the root cause of various
process issues on its crude desalting
unit. During a recent turnaround,
significant damage was found
within various distillation towers,
mainly involving corrosion and
tray positioning or quality. It was
believed that the issues could have
been caused by poorly performing
desalters. Tracerco worked with the
refinery to carry out some of their
process diagnostic techniques and
services on the crude unit, including
a neutron backscatter scan (NBS).
This technique offers a non-con-
tact solution that can be quickly
deployed. It is used while the ves-
sel is online to assess the various
liquid levels and interfaces as well
as analyse the process condition to
ascertain the failure modes of the
distillation tower damage.
Neutron backscatter technology
Accurate measurement of levels and
interfaces in separators is vital for
process control and process inves-
tigation. The Tracerco Diagnostics
neutron backscatter scan, developed
in the 1 50s, responds specifically
to hydrogenous materials such as
hydrocarbons, aqueous liquids and
petrochemicals to quickly locate lev-
els and interfaces and facilitate cali-
bration of equipment or optimise
process changes (see Figure 1).
PTQ Q3 2019 29
13/06/2019 17:13
 The technology works as the
nucleus of the hydrogen atom is
more e cient than any other at
slowing down high energy neu-
trons, therefore turning ‘fast’ neu-
trons into ‘slow’ neutrons. A probe
consisting of a source of fast neu-
trons adjacent to a detector sensi-
tive only to slow neutrons is held
against the vessel wall. Fast neu-
trons penetrate the vessel and inter-
act with the contents (see Figure 1).
If the fluids are hydrogenous, slow
neutrons diffuse out and are scat-
tered back to the detector. The sig-
nal level or intensity at the detector
fluctuates very rapidly when the
hydrogen concentration behind the
vessel wall changes, which is at the
interfaces: vapour/liquid, liquid/
liquid and liquid/solid.
Process review findings
The NBS scans were carried out on
both desalter vessels in the paral-
lel train at previous running con-
ditions. Additionally, as part of
the study, Tracerco scanned sev-
Figure 2 Typical neutron backscatter results
Figure 3 Results indicating poor oil water separation
30 PTQ Q3 2019
q3 tracerco.indd 2
Figure 1 Neutron backscatter signal
interacting with hydrogenous content
eral operating conditions, which
included variations in crude blend
and wash water rates to look at
the effects on the interface level.
Typical NBS results are shown in
Figure 2, where the signal change
between hydrogenous layers are
clearly defined. This is an indication
that the vessel is working as per
the design conditions; however, the
actual results from the study indi-
cated that there was not a clear oil/
water interface. Figure 3 illustrates
the recorded results, which sug-
gested that the unit was not oper-
ating as per design due to a large
amount of emulsion present, result-
ing in not having a clear interface.
The existing differential pres-
sure level transmitter was showing
a steady oil/water interface at the
expected set point but, as the results
suggested, this was incorrect, mean-
ing the operator had been running
for some time effectively without
any level control. As a result, the
malfunctioning level transmitter
led to carryover of emulsion (H2O,
NaCl) in the oil stream to the distil-
lation columns, in turn corroding
overheads due to increased chlo-
rides. There was also carry under
of oil in water, affecting wash
water purity and environmental
non-conformances.
The solution
Following the analysis of the results
and in consultation with the refiner,
The Tracerco Profiler (see Figure 4)
was chosen to replace the existing
desalter instrumentation as a sin-
gle, integrated interface, control and
monitoring device. Using gamma
ray absorption to measure process
fluid density and position by the
change in radiation intensity, the
instrument provides an accurate
measurement of the process fluid
distribution within the desalter,
offering continuous high resolution
imaging and control of each phase.
The Tracerco Profiler typically
comprises a two or three dip pipe
assembly, installed into a vessel
through a single nozzle. A nar-
row dip pipe holds a chain of low
energy gamma sources, while the
remaining dip pipe(s) hold an array
of gamma detectors (Geiger-Müller
tubes). Typically, each source is
directed using a collimating rod onto
two detectors above and below the
plane of the source. This collimation
reduces the number of low energy
gamma sources used, and stops radi-
ation in all directions except that of
the detector. This creates a continu-
ous measurement range by directing
each radiation beam up or down.
Measuring density change in this
way allows for the most e cient
operating conditions to be main-
tained, as well as monitoring the
effectiveness of chemical additive
and mud washing regimes. As part
www.eptq.com
13/06/2019 17:13
 of the analysis of the desalter unit,
Tracerco also provided its Hyperion
density gauge in conjunction with
flow and volume measurements
on the crude feed line to moni-
tor the density of blended crude
charge as part of its ratio control
optimisation. With repeatable, accu-
rate and reliable real-time process
measurements, the Profiler pro-
vided the client with the confidence
to correctly control operating levels,
enhancing separation.
Conclusion
In the months subsequent to the
installation of the Profiler on the
first stage desalter, a number of key
and measurable benefits were real-
ised that enhanced the unit’s per-
formance and reliability. Due to the
industry leading vertical resolution
of 30mm, the client’s confidence in
the interface level was increased.
This led to optimising the interface
for maximum wash water contact,
reducing emulsion breaker chem-
ical dosing by 50 . In relation to
its crude quality, the refiner noted
a 44 reduction in BS W and an
improvement in the salt removal
e ciency (S ) of the unit, with a
reduction in chlorides by 50 .
The demand on the atmospheric
distillation tower preheat furnace
was reduced due to eliminating
excess water on the dehydrated
crude to provide a more favourable
approach temperature. This also had
an impact on reducing the corrosion
of condensing overheads and tow-
ers from hydrochloric acid due to
excess chlorides in the heated stream
being removed more effectively.
Coupled with the enhanced instru-
Figure 5 The Tracerco Profiler HMI trend screen (15 minutes)
www.eptq.com
q3 tracerco.indd 3
Figure 4 The Tracerco Profiler
ment accuracy, the unit did not have
any process trips resulting from lack
of control or upsets due to interface
incursions to the lower grid, which
equated to an increase of 2.5 opera-
tional days per month.
Tracerco provides proprietary soft-
ware with its measurement and con-
trol solution which is a ready-made
graphical user interface providing
a clear insight into separation qual-
ity whilst enabling e cient opera-
tion and control of the instrument.
The display options available from
the HMI provided the refiner with
a window into the vessel, allowing
the operators to visualise the pro-
cess density distribution and uti-
lise the diagnostic data. The HMI
offered easy access to the process
and instrument status in real-time
(see Figure 6), as well as trend data
(see Figure 5). This allows adjust-
ments to the process to be monitored
and changed on the run, enabling
Figure 6 The Tracerco Profiler HMI live view screen
decisions to be made faster, analysis
easier to understand, and a greater
depth of optimisation. The instru-
ment has now been fully integrated
into the refiner’s distributed control
system (DCS).
The Tracerco Profiler is field-
proven in over 500 installations from
subsea to refining and acts as the
interface control solution for millions
of barrels of oil processed every day.
Andrew Shaw is Business Development
Manager, responsible for all of Tracerco’s
process diagnostic activities in the EMEAA
region. He is an oil and gas industry professional
with more than 18 years’ experience in a wide
variety of roles in the industry.
Neil Murch is Business Development Manager
for EMEA with Tracerco. An instrumentation
and control systems professional with more
than 10 years’ experience in the oil and gas,
manufacturing and automation industries,
he has a global technical advisory role for
Tracerco’s instrumentation systems.
PTQ Q3 2019 31
13/06/2019 17:13
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 Simulating and optimising an FCC
naphtha post-treater
A model integrates sections of an FCC naphtha post-treater for evaluating plant
operating conditions to maximise octane-barrel at varying levels of desulphurisation
PEDRO ROJAS
Bryan Research & Engineering, LLC
F
luid catalytic cracking (FCC)
naphtha remains one of the
largest contributors by volume
to the gasoline pool (30-40%). Since
Tier 3 regulations impose a maxi-
mum sulphur limit of 10 ppm in the
final gasoline product, and more
than 90% of the sulphur in gaso-
line comes from FCC naphtha, pro-
cess technologists have improved
catalyst formulations and process
configurations over the years to pro-
duce low sulphur cracked naphtha
while minimising the loss of octane
due to olefin saturation.
Feeding FCC naphtha to a con-
ventional hydrotreater may reduce
sulphur to acceptable levels, but it
would also result in excessive olefin
saturation, which is detrimental for
the cracked naphtha octane-barrel.
The good news is that olefin and
sulphur concentrations are not dis-
tributed uniformly along the boil-
ing range of an FCC naphtha. The
lighter portion has a higher concen-
tration of olefins and lower sulphur
content in the form of mercaptans,
compared to the heavier fraction,
which has a lower olefin concen-
tration and higher sulphur, mostly
thiophenic refractory type species.
FCC naphtha post-treating technol-
ogies take advantage of this uneven
molecular spread to separate the
full boiling range naphtha (FBRN)
into two or three fractions with dif-
ferent treatment options.
In the simplified process config-
uration shown in Figure 1, FB N is
fed to a splitter to obtain an olefin
rich light cracked naphtha (LCN)
stream and a heavy cracked naph-
tha (HCN) stream that contains
most of the thiophenic sulphur.
The LCN is sent to a caustic treater
www.eptq.com
q3 bre.indd 1
sulphur FBRN before being sent to
Caustic
the gasoline pool. The advantage
treater of this set-up is that olefins in the
CN do not get saturated, hydrogen
Light cracked Naphtha
naphtha splitter consumption is lower compared to
a conventional hydrotreater, and
FBR
Combined octane loss is minimised.
low sulphur
naphtha
FBR naphtha A simulation model that inte-
grates the different sections of an
Heavy cracked
naphtha FCC naphtha post-treater (splitter,
caustic treater, SHDS unit) using
SHDS ProMax simulation software is pre-
sented. The SHDS reactor beds
are modelled using the ProMax
Figure 1 Post-treater configuration AutoKinetic reactors. The model is
used to evaluate different scenarios
unit where light mercaptans are with the objective of attaining a low
extracted with NaOH in a liquid- sulphur product while minimising
liquid contactor. There is no olefin octane loss, maximising octane-
consumption in this unit, therefore barrel, and staying within the
olefins in the CN are preserved. bounds of plant operational con-
The HCN is sent to a selective straints. The optimum operation
point is determined for two case
The first step for studies. In case 1, the target final
product sulphur for the combined
creating a successful treated naphtha streams is 30 ppm.
The effect of changing the cut point
simulation is to of the naphtha splitter on the caustic
treater and SHDS unit are studied.
properly characterise In case 2, the final product sulphur
is reduced to 10 ppm. The use of this
the feed by selecting simulation model will help deter-
a species set that can mine if the same plant configura-
tion of case 1 is able to achieve the
allow modelling of the more restrictive sulphur specifica-
tion, and if the required increased
physical and chemical severity will allow the reactor to
remain within the limits of opera-
transformations tion constraints.
hydrodesulphurisation (SHDS) unit Post-treater model and process
where catalyst formulation is such description
that hydrodesulphurisation (HDS) Feed composition
is performed while minimising ole- The first step for creating a success-
fin saturation. After treatment, CN ful simulation is to properly charac-
and HCN can be combined as a low terise the feed by selecting a species
PTQ Q3 2019 33
14/06/2019 09:33
 is a key parameter, since caustic
Condenser treatment does not remove thio-
phene in the LCN.
Reflux Reflux
pump splitter Caustic treater
1 To caustic The separated LCN stream is sent
LCN
Feed to a liquid-liquid extractor (see
heater Q-2 Figure 3), where it is contacted with
Oil
speciation FBR
25
Naphtha a caustic solution in counter-current
naphtha splitter operation to remove light mercap-
E-2 tans in the naphtha. Low sulphur
50
LCN exits at the top of the extractor
Diolefins with its olefin content intact, and
Reboiler Bottom Reactor reactor mercaptide rich caustic comes out
splitter Mixer heater
HCN
at the bottom. The exiting caustic
E-3
solution is mixed with air and sent
Naphtha
pump to an oxidiser reactor where mer-
Q-4 Q-3
captans are oxidised to disulphides
Hydrogen To HDS
and water in the presence of catalyst
that is suspended in the caustic. The
Figure 2 ProMax naphtha splitter model and diolefins reactor majority of the disulphide organic
phase is no longer soluble in the
set that can allow modelling of the naphthenes and aromatic fractions aqueous phase and is separated
physical and chemical transforma- (PONA), elemental sulphur, and out of the caustic in a three-phase
tions relevant to the process plant. nitrogen, the Oil Speciation block separator. Regenerated caustic is
Different types of species in the adjusts species composition to recycled back to the column after
ProMax simulation environment are match laboratory data. fresh caustic and catalyst is added
considered to model feed and prod- to replace losses. The model uses an
uct streams for the FCC post-treater: Naphtha splitter electrolytic caustic thermodynamic
para ns, olefins, naphthenes, aro- After the FBRN is speciated, it is fed package to account for the disso-
matics, mercaptans, sulphides, to the naphtha splitter (see Figure ciation in a solution of light mer-
disulphides, thiophenes, benzothio- 2). The column is modelled with a captans and caustic. The oxidiser
phenes, pyridines, and so on. total condenser and thermosiphon reactor is modelled as a three-phase,
Feed stream composition is esti- reboiler. The two product streams adiabatic, equilibrium Gibbs mini-
mated using the Oil Speciation are an LCN stream with sulphur misation type reactor.
block. Starting with a basic char- species that are mostly mercaptans,
acterisation of the feed naphtha and an HCN stream that contains Selective HDS and scrubber
in terms of distillation curve data, the majority of the thiophenic sul- Naphtha and dissolved hydrogen in
API gravity, bulk para n, olefin, phur. The distribution of thiophene the liquid phase are passed through
a fixed bed, adiabatic diolefins reac-
tor to selectively saturate diolefins
Low sulphur while minimising olefin saturation
light naphtha
(see Figure 2). Diolefins can polym-
Caustic to column erise at SHDS reactor conditions
1
Recycle and foul the catalyst bed, increas-
ing pressure drop. It is also detri-
Feed Extractor mental to have diolefins in the final
exchanger
From 2
gasoline product because of the
Naphtha potential for deposits or gum for-
Splitter Heater
Light Pump
Mixer Spent mation. After the diolefins reactor,
air
naphtha Q-1
Q-3 HCN is combined with treating gas,
which is make-up hydrogen mixed
Dry air Saturator Disulphide
oil with scrubbed compressed recy-
Oxidiser
Separator cle gas (see Figure 4). The hydrogen
Water Recycle hydrocarbon mixture is heated to
Regen. caustic
caustic
reaction temperature and sent to
Recycle a two-bed reactor with inter stage
pump quenching to control temperature
Q-4
rise. The beds are modelled as fixed
bed, plug flow, gas phase, adiabatic
Figure 3 ProMax caustic treater unit model reactors.

34 PTQ Q3 2019 www.eptq.com

q3 bre.indd 2 14/06/2019 09:33

 The reactor outlet is sent to a
separator after cooling and water From
Scrubber
Q-4 Q-3

washing to prevent ammonium K-1

bisulphide salts from precipitat- C-1 duty

K-2
Recycle
ing. The separator gas is treated in E-4 E-5
gas Recycle gas
C-2 duty loop
Makeup
an amine scrubber to remove H2S gas
(see Figure 5). The amine scrubber Feed Gas
mix
is simulated using an electrolytic From
pump Treating gas
Diolefins T+Q
thermodynamic package to model Reactor
HCN Fuel
Feed Quench
H2S dissociation and reactions that P-duty mix
Quench
H2 split
gas

occur in the presence of an aqueous To

Preheater
Reactor
Condenser

amine solution. Treated gas is com- Separator feed

pressed and recycled back to the Q-2

Q-5
reactor. The separator liquid is sent HDS bed 1 Water
S1
to a stabiliser to remove light com- Reactor
effluent Bed 1 outlet
Tops
Reflux
1
ponents. Finally, the SHDS heavy Quench tray
E-1

naphtha from the stabiliser is mixed Bed 2 feed

12 Distillate

with CN to form a final FB N des- Stabiliser

HDS bed 2
ulphurised product.
The principal desired type of reac- From
Separator
tion in a SHDS reactor is hydrodes- 28

ulphurisation, where organic Bottoms

Q-7
Low sulphur Product
sulphur species are contacted with HCN S2
hydrogen to remove sulphur in the
form of H2S (see Figure 6). Olefin From
Low sulphur
FBRN
Caustic
saturation is an undesired reaction Low sulphur
LCN
that lowers the octane of the final
product. Additionally, recombina- Figure 4 ProMax SHDS unit model: reactor beds and stabiliser
tion reactions of H2S with olefins to
produce mercaptans are detrimen- Sweet gas to
tal and also present due to signifi- Lean
Compressor
cant olefin concentration in the feed. amine 1

Once the simulation environment

Scrubber
is populated with relevant species,
the AutoKinetic reactors automat- 7
ically load the reactions described Rich
above, rate expressions, and kinetic amine

parameters. Off gas

Purge split
Furthermore, kinetic parameters
Wash Q-5
are tuned to match relative reac- water
Q-4
Sour gas
Separator
tion rates of different types of sul- From To
phur species. In general, sulphides HDS reactor Stabiliser
Wash water E-2 E-3
and disulphides react faster than mixer Sour water
thiophenes and benzothiophenes.
Species adsorption on the catalyst
surface is also taken into account Figure 5 ProMax SHDS unit model: separator and scrubber
to model the effects of HDS inhibi-
tion by H2S. Increasing the amount Sul ide desulph risation
of H2S in the recycle gas requires
higher weighted average bed Disul ide desulph risation
temperatures (WABT) to reach a
Thiol desulph risation
fixed target final product sulphur
because of inhibition effects (see
Benzothiophene desulph risation
Figure 7). Higher temperatures
increase olefin saturation, hydro-
gen consumption, decrease catalyst
Recombination
life, and generate higher octane
losses for the HCN.
Alkene hydrogenation
HDS selectivity is an important
catalyst performance parameter in
post-treating. It relates to the level Figure 6 Relevant reactions in SHDS

www.eptq.com PTQ Q3 2019 35

q3 bre.indd 3 14/06/2019 09:33

 3.5 620 Base case conditions for 30 ppm FBRN
Octane loss
product sulphur
610
3.0 WABT
600 Operating condition Value
2.5 590 Splitter cut point, °F 158
H2/Hydrocarbon ratio, scf/bbl 1000
2.0 580
HDS reactor P, psig 340
HCN octane loss

570 HDS reactor inlet T, °F 527

1.5 560
LHSV, h-1 4.2

1.0 550 Specification Feed Product

WABT, ºF
540 FBR naphtha sulphur, ppm 740 30
0.5 Olefins, wt% 19 13
530 Octane loss 2.0
0 520 RVP, psi 2.90 2.94
50 2500 4980 7480
Recycle gas sulphur, ppm mole Table 1

are a wide variety of catalysts in the

Figure 7 Effect of H2S on SHDS reactor and post-treater product market, kinetic parameters in the
AutoKinetic reactors can be tuned
(with the use of the ProMax Kinetic
100
Model Calibrator) to match HDS selectiv-
90
Data set 1 ities from different catalyst formu-
80 Data set 2 lations, as well as different levels of
70 olefin saturation, aromatic hydro-
Olefin saturation, wt%

60 genation (if present), hydrodenitro-

genation, and inhibition by H2S and
50
organic nitrogen species.
40
30 Case study 1: optimised conditions
20 for 30 ppm sulphur
10 Table 1 shows base case conditions
0
for a product sulphur of 30 ppm.
60 70 80 90 100 The naphtha splitter cut point will
Desulphurisation, wt% be changed to increase the LCN
flow rate. Necessary adjustments
Figure 8 Selectivity of HDS in the caustic treater and SHDS
units to achieve 30 ppm sulphur in
the final combined desulphurised
100 cracked naphtha are presented.
90 Selection of the optimised operation
point is subject to:
80
• Maintaining the caustic to feed
70
volumetric ratio between 10-25% in
60 the caustic treater
Recovery in LCN, %

C3 mercaptans
50 Olefins • Temperature rise in each SHDS
40 C4 mercaptans bed lower than 38°F (21.1°C)
30 Thiophene • Reactor unitary pressure drop
lower than 1.5 psi/ft.
20
10 Naphtha splitter recoveries: olefins,
0 mercaptans, thiophenes
150 155 160 165 170 175 180
As the cut point increases, the recov-
Cut point, ºF
ery of olefins in the CN fraction
steadily rises (see Figure 9). Likewise,
Figure 9 Naphtha splitter recoveries in light naphtha C3 mercaptans, C4 mercaptans and
thiophene recovery in the light naph-
of desulphurisation and olefin sat- the case studies, at higher desul- tha also go up. Thiophene increases
uration in the SHDS reactor. Model phurisation levels such as those rapidly when the cut point is higher
kinetic parameters are adjusted required by Tier 3 specifications, than 175°F (80°C). As an example,
to reproduce selectivity behav- olefin saturation becomes more pro- a thiophene recovery of 37% in the
iour from experimental data.1,2 For nounced (see Figure 8). Since there LCN is equivalent to 59 ppm sul-

36 PTQ Q3 2019 www.eptq.com

q3 bre.indd 4 14/06/2019 09:33

 phur that will not be removed by
caustic treatment. There is no appre- 52
ciable amount of C5+ mercaptans in
the light naphtha under the condi-
tions of this study. 51

Light naphtha sulphur in

LCN sulphur, ppm

50
caustic extraction
As the caustic/feed ratio increases
in the extractor, contact between
49
aqueous and hydrocarbon phases is
improved. This favours extraction
of low molecular weight mercap- 48
tans from the oil phase, and sulphur 0 5 10 15 20 25
in the LCN decreases up to a cer- Caustic/feed, vol%
tain point (see Figure 10). Caustic is
regenerated by sending it to an oxi- Figure 10 Caustic extractor outlet light naphtha sulphur at cut point = 158°F (70°C)
diser and separator after the extrac-
tor. The caustic that comes out of the
separator will have a small amount Light and heavy naphtha sulphur to achieve 30 ppm final product sulphur for
different scenarios
of entrained disulphides that are sent
back to the extractor. Disulphides are
% of FBRN to light Caustic treater Required HCN
soluble in the hydrocarbon phase, naphtha LCN sulphur, ppm sulphur, ppm
so any disulphides entering with 6 49 28
the caustic exit in the LCN stream; 9 43 28
this is called re-entry sulphur. 12 40 28
14 45 26
Continued increase of caustic/feed 17 57 24
ratio will end up increasing sulphur 19 79 19
in the CN due to re-entry sulphur.
There is an optimum caustic/feed Table 2
ratio that minimises sulphur in the
LCN (see Figure 10). When look- but as HDS takes place and H2S is end point out of the naphtha
ing at naphtha feed composition, produced, the recombination reac- splitter increases the amount of
lower sulphur levels in the caustic tion will favour production of mer- olefins sent to the caustic treater
treater are constrained by the molec- captans and the concentrations of that do not undergo saturation.
ular weight of mercaptans and non- C3-C4 mercaptans increase. The result is that when the oper-
extractable thiophenes in the feed. ation of SHDS is not as severe,
e-entry sulphur can be decreased Product octane-barrel and the octane-barrel of the final
by using a naphtha wash before the octane loss product increases and octane
separator. The use of a naphtha wash At different hydrogen to hydro- loss decreases (see Figure 12).
will be presented in case study 2. carbon ratios, increasing the LCN However, with further cut point
As higher amounts of non-extract-
able sulphur remain in the LCN
after caustic treatment, there will 8
be a lower sulphur requirement for 2-propanethiol
7
the HCN to achieve a combined 1-propanethiol
naphtha product of 30 ppm (see 6 2-butanethiol
Table 2). A more severe operation 1-butanethiol
of the SHDS unit will be required to 5
remove sulphur from HCN. 4
Mole fraction, ppm

Recombination along the 3

SHDS reactor 2
Reaching low sulphur levels in
SHDS is limited by recombination. 1
As an example, in the first bed of
0
the SHDS reactor, C3-C4 mercap- 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
tans are initially consumed, as
Flowline fractional length, fraction
evidenced by decreasing mole frac-
tions (see Figure 11). Close to the
inlet, H2S concentrations are low, Figure 11 Concentration of light mercaptans along the reactor

www.eptq.com PTQ Q3 2019 37

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Octane-barrel, Mbbl/d
Octane loss
Figure 12 Octane-barrel and octane loss as a function of naphtha splitter cut point
Maximum octane barrel at different H2/HC ratios for 30 ppm final product sulphur
H2/HC ratio,
scf/bbl
1000
1500
2000
Table 3
increase, the amount of non-ex-
tractable sulphur such as thio-
phenes in the LCN also increases,
requiring lower HCN sulphur to
compensate and maintain 30 ppm
sulphur in the final combined
naphtha product. After a certain
point, as the cut point is increased,
the octane loss becomes higher
and the octane-barrel decreases
because olefin saturation and
cracking become significant at
higher SHDS reactor tempera-
tures. The benefit gained from
sending more olefins in the CN
is lost because of increased SHDS
severity to maintain product sul-
phur specification. Operation
at higher severity also increases
hydrogen consumption and short-
ens catalyst life for the SHDS
reactor.
38 PTQ Q3 2019
q3 bre.indd 6
therefore, increasing the amount of
2300 hydrogen through the reactor beds
1000 scfH2/bbl requires higher WABT to achieve
2290 1500 scfH2/bbl
30 ppm sulphur. When seeking
2000 scfH2/bbl
2280 the optimum point of operation,
some variables to be considered
2270 are: profits obtained by operat-
ing at the highest octane barrel; or
2260
lowest octane loss versus the cost
2250 of catalyst replacement or regen-
155 165 175 eration due to shorter run cycles
Cut point, ºF and hydrogen consumption. While
octane demand is high, even small
or moderate octane increases can
generate significant revenues.3 For
this specific situation, it is desira-
2 ble to operate at a higher hydro-
gen to hydrocarbon ratio than
the base case, provided that plant
1 1000 scfH2/bbl equipment, in particular the recy-
1500 scfH2/bbl cle compression system, can handle
2000 scfH2/bbl increased recycle hydrogen capac-
155 165 175
ity. Between 1500 and 2000 scf/bbl,
Cut point, ºF
there is no significant gain in octane
barrel. A higher WABT is needed
at 2000 scf/bbl, which is detrimen-
tal to catalyst life, so the optimum
operation point to reach 30 ppm
sulphur is the one that produces an
octane loss of 1.1 at 1500 scf treating
hydrogen/bbl feed.
Octane-barrel, Recycle ratio, WABT, H2 consumption,
Mbbl/d scf/bbl °F scf/bbl
Case study 2: optimised conditions
2279 1417 546 79 for 10 ppm sulphur
2284 1926 550 77 The new target for combined prod-
2284 2479 555 76 uct sulphur is 10 ppm for the same
feed, plant configuration, reactor
geometry, and catalyst, subject to
the same operational constraints as
Maximum octane-barrel at different case 1.
H2/HC ratios (30 ppm)
The operation points with lowest Naphtha wash
octane loss for each treating gas With the caustic treater config-
uration of case 1, there is a sul-
phur removal limit associated
While octane with disulphide entrainment in
demand is high, even the caustic aqueous phase of the
oxidiser e uent. To reduce the
small or moderate amount of re-entry sulphur, a
naphtha stream is injected and
octane increases can mixed with the oxidiser outlet
before the separator. The disul-
generate significant phides will preferentially trans-
fer to the organic phase, reducing
revenues the amount of re-entry sulphur in
the regenerated caustic and in the
LCN. The outlet naphtha wash
hydrogen to hydrocarbon ratios stream can be sent to a hydro-
are presented in Table 3. Excess treater for further processing.
hydrogen absorbs some of the heat The reduction in LCN sulphur
of reaction in the catalytic beds, when using a naphtha wash is in
www.eptq.com
14/06/2019 09:33
 the order of 30-60% for the scenar-
ios in case study 2. Before using a 50
naphtha wash, to obtain 10 ppm

Bed 1 temperature increase, ºF

Without wash
sulphur as a final product sulphur With wash
45
meant exceeding the maximum
allowable temperature increase
in SHDS reactor beds (see Figure 40
13). A higher delta T can lead to
the formation of dangerous hot 35
spots in the catalytic bed if there
is flow maldistribution, as well as 30
increased olefin saturation, and the
potential for runaway reactions.
25
Lowering LCN sulphur means that 158 166 172 175 177
SHDS unit operation to achieve 10 Cut point, ºF
ppm final product sulphur is less
severe. This is evidenced by lower Figure 13 Effect of caustic treater naphtha wash on SHDS reactor delta T for 10 ppm
SHDS reactor temperature increases product sulphur
in Figure 13. All case 2 scenarios use
a naphtha wash. Maximum octane barrel at different H2/HC ratios for 10 ppm final product sulphur

Maximum octane-barrel at
H2/HC ratio, Octane loss Delta T Bed 1, Delta T Bed 2, Unitary P drop,
different H2/HC ratios (10 ppm) scf/bbl °F °F psi/ft
The behaviour of product 1500 1.7 39 23 1.1
octane-barrel and octane loss as 2000 1.6 35 21 1.4
a function of cut point for dif- 2500 1.6 32 20 1.7
ferent hydrogen to hydrocarbon
ratios is similar to case 1. For each Table 4
hydrogen to hydrocarbon ratio,
octane-barrel goes through a max-
Case studies results
imum and octane loss through a
minimum.
Table 4 presents the minimum Operating condition 30 ppm product 10 ppm product
Splitter cut point, °F 175 175
octane loss for each hydrogen to H2/hydrocarbon ratio, scf/bbl 1500 2000
hydrocarbon ratio. Higher hydro- WABT, °F 550 599
gen to hydrocarbon ratios produce H2 consumption, scf/bbl 77 113
lower octane loss to achieve 10
Product specification 30 ppm product 10 ppm product
ppm sulphur. At 2500 scf/bbl, the Olefins, wt% 14.5 12.3
unitary pressure drop of 1.7 psi/ft Octane-barrel, Mbbl/d 2284 2262
is higher than the allowable max- Octane loss 1.1 1.6
imum, and at lower H2/HC ratios RVP, psi 3.0 3.0
the temperature increase in the
first bed of 3 °F is higher than the Table 5
maximum allowed. The interme-
diate point at 2000 scf/bbl satisfies Conclusion References
both constraints. However, there is By performing an integrated simu- 1 Meyers R A, Handbook of Petroleum Refining
only a small window of flexibility lation of the naphtha splitter, caustic Processes, 3rd edition, McGraw-Hill 2004.
to account for changes in opera- treater and selective hydrotreater, 2 Ghosh P, Andrews A T, Quann R J, Halbert
tion. If significant variability in feed it was possible to observe how T R, Detailed kinetic model for the hydro-
desulphurization of FCC naphtha, Energy &
composition is expected, switch- changes upstream elicit changes
Fuels, 12.23, 2009, 5743-5759.
ing to a more selective catalyst or to downstream sections when the
3 Fifadara J, Producing ultra low sulphur
converting to a configuration with final product sulphur specification gasoline with octane retention, Catalysis 2018,
inter-stage H2S stripping might was fixed. Starting from a base case, www.digitalrefining.com/article/1001488.
be necessary. optimised cases were determined
ProMax, and AutoKinetic are registered
Table 5 shows a summary of with a lower octane loss for 30 ppm trademarks of BRE Group, Ltd. Oil Speciation
results for both case studies. To and 10 ppm product sulphur. The is trademark of BRE Group, Ltd.
achieve lower sulphur levels, the use of simulation software helped Pedro Rojas is a Development Engineer with
WABT in the reactor and hydrogen realise the need for changes to plant Bryan Research & Engineering, LLC. His work
consumption are higher, while the base case configuration so that oper- focuses on petrochemical processes and
olefin content of the final product is ating conditions at 10 ppm sulphur refinery hydroprocessing. He holds a PhD from
lower, for a constant VP. are well below plant constraints. Texas A&M University. Email: p.rojas@bre.com

www.eptq.com PTQ Q3 2019 39

q3 bre.indd 7 14/06/2019 09:33


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 Eliminating phosphorus from
cooling treatment
Non-phosphorus programmes for corrosion and scale control in water cooling
systems reduce environmental impact and operating costs
RENATE RUITENBERG and EMREGUL CETIN
Nalco Champion, an Ecolab Company
T
he water footprint of a refin-
ery or petrochemical plant
is in large part made up of
the water used for process cooling.
Typically, most of the treatment
programmes contain phosphorous
(P) as a key component in corrosion
or scale control. These P based pro-
grammes raise concerns of eutroph-
ication in sensitive water bodies
receiving the cooling water blow-
down. Although surface run-off
and sewage disposal are the main
sources of eutrophication,1 indus-
trial producers have started to seek
more environmentally friendly
treatment solutions, both to comply
with the changing legislations and
achieve their performance targets.
Innovation is needed to deliver on
both the environmental and perfor-
mance goals.
Two new non-P programmes
were developed by Nalco
Champion: one for good corrosion
control in severe water matrices
and another for superior scaling
control in seawater. This article
describes the development and
application of these two different
non-P cooling water treatment pro-
grammes, and the operational and
economical improvements they
can bring. Examples in industrial
cooling systems are given to high-
light that environmental protection
and cost control are not necessarily
mutually exclusive
P based cooling water treatment
Common examples of phosphorous
containing chemistries in cooling
treatment are:
• Ortho- or polyphosphates as key
corrosion inhibition actives
• Phosphonates for scale control,
www.eptq.com
q3 nalco.indd 1
for instance in all organic cooling
programmes.
Legislation has tightened signif-
icantly in countries such as China
that have been impacted by the neg-
ative effects of algal blooms. The
main challenges associated with
phosphorous are:
• Algal blooms in the receiving sen-
sitive water bodies
• Tricalcium phosphate scaling
potential at high heat flux
• High levels of phosphate if recy-
cled wastewater is used
• Variable background levels caus-
ing control issues.
Existing non-P/low-P treatment
programmes have limitations, par-
ticularly if process control is not
stringent.2 Mild steel corrosion pro-
tection is challenging in high stress
water containing high chlorides and
sulphates, soft water with low hard-
ness to aid inhibition mechanisms
and low buffering. The long holding
time index (HTI) at high cycles can
increase the risk of tricalcium phos-
phate scaling.
Two separate non-P solutions
developed by Nalco Champion
R&D are presented, one that elim-
inates the above corrosion control
issues, and one for seawater scale
control. They can both reduce total
cost of operation at an increased
level of environmental protection.
Non-P scale inhibition for seawater
cooling towers
Seawater cooling towers commonly
used for temperature control of pet-
rochemical production processes in
the Middle East utilise up to 28%
of a site’s total electrical energy.
Due to the high salinity of seawa-
ter, typical cycles of concentration
are low, hence the seawater intake
is high, resulting in high water fees
as well as high electricity costs. The
high scaling potential results in lim-
ited cycles of concentration when P
based antiscalants are used, leav-
ing room for total cost of operation
improvement.3 The goal of safe-
guarding production while reduc-
ing the water and energy footprint
can be achieved by increasing the
cycles, provided that biofouling and
scaling are kept under control.
Biofouling is the key challenge
in these climates and has a much
higher impact on heat transfer than
scaling does. Therefore biofouling
needs to be under control if cycles
increase is to be implemented. At
one of the largest seawater cooling
systems in the Middle East, Purate
technology was introduced to pro-
duce ClO2 on site from chlorate,
improving biofouling control while
improving safety through 68%
reduction in chemical handling and
improved process monitoring and
control. The new e cient treatment
eliminated 2-3 cleaning events per
year as well as throughput restric-
tion in the warmest months. The
service plan in place identified
additional operational savings by
increasing the tower cycles while
the cleaner system allowed reduc-
ing the amount of cooling tower
pumps and fans in operation.
Purate technology is a cost-effec-
tive programme for large systems;
annual operational savings include:
• $900 000 in cleaning and chemical
spend
• >$1.1 million in annual seawater
cost savings through cycles increase
from 1.12 to 1.25, reducing seawater
intake by around 70 000 m3/h.
PTQ Q3 2019 41
14/06/2019 09:38
 4

Total savings $M per annum

3

0
0 1.2 1.4 1.6 1.8 2.0 2.2 2.4
Cycles of concentration

Figure 1 Projected non-P enabled savings from cycles increase in a large seawater
cooling tower

• $1.25 million in electricity savings chemistries cannot be analysed reli-

by turning fans and recirculation ably in the seawater matrix by tra-
pumps off, saving 2 million kWh ditional wet chemical methods, the
annually, equating to 20 000 tons of non-P seawater offering uses fluo-
CO2 carbon footprint reduction. rescence for on-line detection of the
The largest benefit of running dose rate as well as inhibitor con-
with a cleaner system is improved sumption; a fluorescent tag embed-
heat transfer in the summer months, ded in the chemistry allows 3D
when removing excess process heat Trasar control for system assurance.
via the closed cooling system can Full scale implementation at a sis-
limit production throughput. The ter site confirmed the ability of the
closed cooling water temperature new non-P treatment to maintain
was reduced by 1.4ºC to 2.1ºC dur- excellent heat transfer conditions,
ing une through August, improv- even in the hotter months.
ing process temperature control.
This debottlenecking is estimated to Non-P corrosion control in a soft
have resulted in at least 10 million water cooling tower
in increased production value. Cooling systems running on soft
To enable the next step in opera- or high chloride water suffer from
tional optimisation, a new non-P high corrosion stress. xisting
PRESSURE VESSELS scale inhibitor and dispersant was low-P cooling water treatment pro-
developed by the global Nalco grammes have limitations in that
HEAT EXCHANGERS Champion D teams and trailed operational window.
at the pilot cooling towers at King The non-P cooling water treat-
PROCESS Abdullah University of Science and ment programme developed by
Technology in Kuwait. This effec- Nalco Champion consists of a blend
TECHNOLOGY
tive and sustainable solution was of proprietary scale and corrosion
shown to allow cycles of 1.8 to 2.2, inhibitors to overcome those limi-
VALVES unlocking higher cost saving poten- tations. This new programme pro-
tial than is achievable with the P vides high cathodic and anodic
BALL VALVES
based scale inhibitors. corrosion inhibition in mild steel in
To accurately predict scaling ten- various challenging water matrices
dency in the seawater matrix, a sea- (soft water, high chloride water),
water scaling modelling tool was widening the operational window
www.borsig.de developed, as seawater cycling up with better calcium carbonate scale
is outside the scope of conventional inhibition and eliminating calcium
BORSIG GmbH models, which are based on fresh phosphate scaling.
Phone: + 49 (0)30 4301-01 water chemistry. With this tool, the
Fax: + 49 (0)30 4301-2236 total cost savings from reduced sea- Case history background
E-mail: info@borsig.de
Egellsstrasse 21
water pumping and extraction fees A major petrochemical and refining
13507 Berlin were calculated (see Figure 1). corporation in Greater China aimed
Germany While traditional antiscalant to improve its cooling water treat-

www.eptq.com

BORSIG Q3-2019.indd 1 28.02.2019 16:03:05

q3 nalco.indd 2 14/06/2019 09:38

 4.0 14
Corrosion
Non-P started pH 13
3.5
12
3.0

11

Mild steel corrosion, mpy

2.5
10
Corrosion target 2 mpy
2.0
9
1.5
8
Figure 2 Mild steel coupons before and 1.0 7
after the treatment programme
0.5 6
ment both to comply with the Total Transition

pH
0 5
P legislation (<0.5 ppm P as total

7 ar
14 Apr
21 Apr
28 Apr
5 pr
y
y
My
2 ay
9 n
16 Jun
23 Jun
30 Jun

7 n
14 Jul
21 Jul
28 Jul
4 Jul
11 Aug
18 Aug
25 Aug
g
phosphate) and to achieve better

12 a
19 Ma
26 a

Ju

Ju

Au
M

A
M

corrosion results. With the make-up
source alternating between river
water and soft ground water with
high chlorides, the corrosion rates
were causing lower life span of
assets and high maintenance costs.
A low-P treatment programme
had been used since the plant
started operation. The high chlo-
rides and high HTI are challenging
and compromised the robustness
of this treatment programme. The
corrosion rate control targets of <2
mils per year (mpy) were not con-
sistently met when the plant needed
to change the make-up water source
from river water to low hardness,
low alkalinity well water. Manual
pH and blowdown control could
not reliably keep the fluctuating
water quality in the system’s oper-
ational window. The strict e uent
limits did not allow for a robust
conventional programme to be
used, therefore the company had to
accept high corrosion rates and the
associated maintenance costs. The
blowdown from the cooling towers
had to be routed through the waste-
water treatment facilities, incurring
considerable extra cost.
Case history solution and results
The new Nalco Champion non-P
cooling water treatment programme
developed to address these chal-
lenges comprises two key innova-
tive components:
• Scale inhibition and dispersion
• Corrosion protection and inhibi-
tor stabilisation.
The synergistic effect brings in
improved corrosion control, extend-
ing the application window also to
M
31
Figure 3 Online mild steel corrosion vs pH
more corrosive water matrices such • Reduce maintenance costs and
as soft water and high chloride/ extend asset life.
high sulphate water. The new non-P treatment pro-
The critical component of the gramme tolerates the pH swings
program is 3D Trasar technology and the fluctuations in water qual-
for cooling as a stress management ity changes due to make-up source
system. This technology controls change, giving more robust corro-
the key parameters in the cooling sion control in challenging opera-
system using online monitoring and tional conditions.
automation of product feed. The
chemical feed is responding to the References
changes in the system stress, ensur- 1 Chislock M F, et al, Eutrophication: Causes,
ing excellent operational reliability Consequences, and Controls in Aquatic
in high stress heat exchangers under Ecosystems, Nature Education Knowledge,
2013.
low flow or high heat flux.
2 Townsend G, et al, Corrosion Challenges of
Since starting up the new non-P
Desalinated Water as Cooling Tower Make-Up
programme, mild steel corrosion under Control with Dual Cathodic Inhibition:
rates were much improved in both MECC Bahrain, 8-11 Feb 2016.
corrosion coupon (see Figure 2) and 3 Peabody G A, et al, Bringing About A Sea
online probe readings (see Figure 3). Change: Climate Control Middle East online
The average corrosion readings on article 31 Oct 2011.
the 3D Trasar controller fell from
1.88 mpy to 0.63 mpy. 3D TRASAR is a trademark of Nalco Champion,
With the new non-P treatment an Ecolab Company.
programme, the plant was able to:
Renate Ruitenberg is a Senior Marketing
• Fully comply with total phospho-
Manager with Nalco Champion, focusing
rus discharge limits
on global water treatment innovation. She
• Reduce wastewater treatment worked as a process engineer before joining
costs by $480 000 Nalco Water R&D in 2003. She holds a MSc
in engineering form Delft University of
Technology, The Netherlands.
Water challenges
Emregul Cetin is a Senior Marketing Manager
Water challenges Value with Nalco Champion in the Global Innovation
Chlorides 300 ppm Cl
Effluent P limit <0.5 ppm P
Marketing Team. She worked in various sales
Holding time Index >200 h
positions in Nalco Champion for 17 years prior
to joining the Innovation Marketing team with
MU Ca hardness 20-25 ppm CaCO3
field experience in industrial water treatment
Low alkalinity in MU 30-35 ppm CaCO3
Silica scaling risk 115 ppm SiO2 in heavy, refining and petrochemical industries.
Alternating water source Fluctuations She holds a BSc in environmental engineering
from Middle East Technical University, Ankara,
Table 1 Turkey.

www.eptq.com PTQ Q3 2019 43

q3 nalco.indd 3 14/06/2019 09:38

 O U R S P IR IT O F INNOVATIO N DRIVES
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©2019 Zeeco Inc. All rights reserved.

zeeco.indd 1 13/06/2019 10:32

19_PTQ_060719_FlareGuardian.indd 1 6/7/19 4:55 PM
 Piston design method makes recips
more reliable
Gas leaking past piston rings and rider bands is a significant problem for many
reciprocating compressors
ANDREAS BRANDL, BRUCE HERMONAT and JOHN LADD
Hoerbiger
L
eakage of gas past piston rings
and rider bands – otherwise
known as slippage or blow-by
is a significant issue for up to one
in three reciprocating compressors
in process gas service. For new or
recently serviced compressors, pis-
ton leakage is rarely a problem. As
time goes by, however, ring wear
can give rise to serious leakage,
especially in cylinders with bores
smaller than 10 in (250 mm), high
pressure applications, and non-
lubricated compressors.
Cylinder leakage can have three
consequences, depending on the
setup of the individual compressor:
• eakage may cause unaccept-
ably high cylinder discharge
temperatures
• eakage can significantly reduce
compressor capacity
• The rider bands and piston rings
may wear quickly or fail altogether,
necessitating frequent maintenance
shutdowns.
xtensive field experience at
Hoerbiger suggests that 30 of
compressors have at least one cyl-
inder where after a year of oper-
ation the additional temperature
rise due to piston blow-by is at least
20°F (11°C). Depending on the com-
pressor, a rise of 30°F (17°C) will
typically trigger a high temperature
alarm.
One study1 suggests that of
compressor damage reports relate
to piston rings and a further to
rider bands. The combined figure of
18 makes cylinder rings the sec-
ond most frequent cause of failure
for reciprocating compressors, after
valve failures.
The fact that cylinder leakage is
so common, and often so harmful,
www.eptq.com
q3 hoerbiger.indd 1
Figure 1 A piston with two piston rings
and two rider bands
implies a problem with the rules of
thumb traditionally used to decide
the type and number of piston
rings and rider bands (also known
collectively as cylinder rings).
Clearly, we need a more rigorous
engineering approach.
It turns out that modelling gas
leakage to an acceptable degree of
accuracy is not di cult. For a given
compressor geometry and operating
condition, we can approximate the
leakage path as a series of orifices of
known si e. Combined with empir-
ical models of the rate at which the
piston rings wear, this allows us to
predict which cylinders will be vul-
nerable to the effects of leakage, and
to optimise the configuration of pis-
ton rings and rider bands so as to
reduce leakage.
In this article, we explain how
piston leakage occurs, what the
consequences are, and how the
new leakage model works. We also
present several examples of how
redesigned configurations of pis-
ton rings and rider bands have
reduced previously serious leakage
to acceptable levels.
In recent years, the scientific
study of compressor valves has
greatly increased the performance
and reliability of recips. We believe
that in turning our attention to cyl-
inder rings we can bring a similar
level of benefits, for both new com-
pressor designs and retrofits.
Why leakage happens
Piston ring leakage occurs when the
ring’s end gap opens up as a conse-
quence of circumferential wear.
The job of the piston rings is to
seal the compression chamber. In
a typical double-acting compres-
sor, the piston rings maintain a
seal between the two ends of each
cylinder (see Figure 1), while the
rod packing stops gas escaping to
the environment.
Piston rings fit into grooves in the
piston and press outwards to create
a sliding seal against the cylinder
wall. Depending on the application,
the number of piston rings is gen-
erally between two and eight. They
are generally made from PTF or
P K based wear materials.
In normal operation, the outer
surface of the piston ring wears
away through contact with the
cylinder liner; this can happen
especially quickly in unlubricated
cylinders. To accommodate this
wear, and to allow the rings to be
fitted and removed, each ring has
a narrow gap in its circumference.
Various designs exist (see Figure
2a-f), but the general principle is
the same. When the ring is new,
the end gap is designed to be as
small as possible, consistent with
thermal expansion and the need
to prevent the two ends of the ring
from touching (which can lead to
premature failure).
As Figure 2 shows, both pis-
ton rings and rider bands can be
PTQ Q3 2019 45
13/06/2019 19:19
 equipped with grooves for pressure
control. On piston rings, these are
called pressure balancing grooves
(see Figure 2d). Their purpose is not
to eliminate differential pressure
(which would defeat the purpose of
the ring) but to reduce the contact
pressure on the cylinder liner and
hence the wear rate. On rider bands,
they are known as pressure relief
grooves (see Figure 2i and j), since
they are added to eliminate differ-
ential pressure (see below).
More complex piston ring designs
exist with a view to reducing leak-
age. One example is the so-called
-type (US) or twin ( uropean) ring
(see Figure 2e and f). Here a plain
ring and a second ring of -shaped
cross-section fit together so that each
ring covers the gap in the other.
These designs are only suitable for
single-acting cylinders, however.
In addition, complex designs (and
this even includes the step-cut ring
shown in Figure 2c) are not always
reliable: they have narrow cross-
sections prone to breakage and
uneven wear, and corners that can
act as stress concentrators.2 A fur-
ther di culty is that because these
designs are novel they are generally
unfamiliar to operators and even
repair shops, so repairs are more
di cult and time consuming.
To handle realistic wear rates,
piston rings are normally rather
deep in cross-section. On a large
compressor, for instance, the rings
can typically wear by up to 0.25 in
( .3 mm) before they need to be
replaced. The problem is that as a
worn piston ring expands to main-
tain its contact with the cylinder
wall, the gap in the ring opens up
(see Figure 3).
For 0.25 in ( .3 mm) of radial
wear, the si e of the end gap
increases by 2 0.25 1.57 in (3 .
mm). Assuming a gap si e of 0.1 in
(2.5 mm) to begin with, and a clear-
ance of 0.0 in (1.5 mm) to the cylin-
der wall, the resulting leakage area
is 0.1 in2 ( 3. mm2), equivalent to
the area of a circular hole 0.3 in ( .0
mm) in diameter. It is no wonder
piston leakage can be a problem.
specially at risk are non-lube
machines, because oil helps to
seal gaps as well as reducing ring
wear. High operating pressures
46 PTQ Q3 2019
q3 hoerbiger.indd 2
the worst effects of piston leakage.
This is because for a given amount
of radial wear on the piston rings,
the si e of the end gap and hence
the mass flow rate of gas lost to
leakage is relatively independent
of the cylinder diameter, assuming
a constant clearance between pis-
A B ton and cylinder. A certain leakage
Straight-cut Angle-cut rate might account for just 0.5 of
piston ring piston ring
the capacity of a 25 in ( 35 mm) cyl-
inder, for instance, but 20 of the
capacity of a 4 in (100 mm) cylinder.
Leakage can cause excessive
temperatures
Depending on the compressor and
the application, an undesirable
C D
Step-cut Angle-cut piston increase in discharge temperature is
piston ring ring with the first problem that may be expe-
pressure-balancing
grooves
rienced as a result of leakage across
piston rings.
We can approximate the leakage of
gas past a piston ring as an isenthal-
pic throttling process, during which
the temperature of an ideal gas does
not change. This means that gas
at the discharge temperature ends
up on the low pressure side before
E F
L-type piston ring L-type piston ring
being compressed and heated
with cam with peg again. The net result is an increase in
the discharge temperature.
High operating temperatures
are bad for compressors for rea-
sons of reliability and safety. High
temperatures can degrade lubri-
cating oil, weaken valve plates and
increase wear on other components.
G H Accordingly, API 18 limits dis-
Solid shrunk-on Angle-cut charge temperatures for each stage
rider band rider band to 275°F (135°C) for hydrogen and
300°F (14 °C) for other gases.
API compressors are designed to
run at 40°F (22°C) below the alarm
temperature, so even a modest tem-
perature rise due to leakage can
cause problems. In practice, severe
leakage can increase discharge
I J temperatures by 0°F (33°C). This
Angle-cut Angle-cut is usually above the safe operat-
rider band with rider band with
side reliefs side and face reliefs ing temperature, and so will force
a shutdown.
Suction pressures above 300 psig
Figure 2 Different styles of piston rings (21 barg) and compression ratios
and rider bands as provided by all major above 2.5 are more likely to lead to
suppliers of compressor components temperature problems.
and speeds also tend to wear out Loss of capacity
rings faster. Other compressors are constrained
Small-diameter cylinders 10 in by capacity rather than discharge
(250 mm) and below tend to suffer temperatures. On a maxed-out
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13/06/2019 19:19
 hydrogen feed compressor, for
instance, losing just 5% of the
hydrogen supply could reduce the
throughput of the entire unit.
In practice, capacity loss can be up
to 20% for a badly leaking compres-
sor. In most cases, this is unaccept-
able. And even if the compressor
has capacity to spare, the energy
wasted has a financial cost.
Reduced reliability
Lack of reliability is the third issue
that may result from piston leakage.
Wear and extrusion of rider bands
and piston rings, and subsequent
ring breakage, are the main prob-
lems in this case.
These reliability issues can affect
compressors both large and small
over the entire pressure range. This
is in contrast to the high tempera-
tures and lost capacity that relate
mainly to small and medium-sized
machines and those operating at
higher pressures.
The job of the rider bands is to
support the weight of the piston
and centralise it within the cylin-
der. Compared to piston rings, rider
bands are usually wider and shal-
lower. They are typically designed
to accommodate just 0.04–0.1 in of
radial wear.
Since rider bands have so little
allowance for wear, it is crucial that
they should see the lowest possible
contact pressures. This means lim-
iting the load to the weight of the
piston (5–10 psi, 35–70 kPa) and
avoiding extra loads imposed by
the gas pressure. So-called ‘combo’
rings – combined piston and rider
rings – perform badly in this
respect, because their radial wear
allowance is no greater than for
standard rider bands, yet the con-
tact pressure is much higher. As a
result, combo rings are now consid-
ered obsolete.
Many rider bands are closed rings
that are shrunk onto the piston (see
Figure 2g). This design is immune to
gas pressure differences, but such
rings are di cult to fit and there is
a risk of damage during the fitting
process if repair procedures are not
followed closely.
Other rider bands have a gap (see
Figure 2, bottom, second from left).
As far as the gas is concerned, they
www.eptq.com
q3 hoerbiger.indd 3
Cylinder bore
A
Ring leakage area
Increased gap width
due to wear
C Worn ring
Radial wear
Figure 3 (a) Leakage gap on straight-cut piston rings, with (b) cross-sectional view and
(c) the effect of wear
appear no different from piston
rings. In this case, gas pressure in
the gap and beneath the rider band
forces the rider band against the
cylinder wall, turning it from a pas-
sive to an active component. Rider
band activation causes rapid wear
Since rider bands
have so little
allowance for wear,
it is crucial that they
should see the lowest
possible contact
pressures
and even complete failure, leading
to shutdown.
A better solution is often to incor-
porate relief grooves in the edges
and/or faces of the rider band to
allow free passage to the gas leak-
ing past the piston rings (see Figure
2i and j). This eliminates gas dif-
ferential pressure across the rider
band. Although it increases pres-
sure drops and wear rates at the
piston rings, the extended life of
the rider band more than makes up
for this.
Ring standout
B
Ring gap width
Original ring size
Depending on the application and
industry, the MTBF of piston rings
and rider bands should normally
be somewhere between two and
five years. More frequent replace-
ment may indicate a problem with
the design of the piston or the
cylinder rings.
Problems may be misattributed
A further di culty related to piston
leakage is that the symptoms may
be hard to spot.
When valves fail, the valve cov-
ers get hot. If the rod packing fails,
packing leakage rates increase.
Operators can usually identify these
problems and relate them to the
observed loss of performance.
Piston ring leakage and rider
band wear, in contrast, are harder
to identify. In fact, without dis-
mantling the compressor they can
only be confirmed using special-
ist data acquisition equipment. As
a result, excessive temperatures
and loss of capacity may be attrib-
uted to the wrong causes and thus
not addressed.
Building a better model
Pistons can be quite complex
designs, typically incorporating two
rider bands and up to eight piston
rings or even more.
PTQ Q3 2019 47
13/06/2019 19:19
Anz-PTQ Hydrogen 1-seitig
neuman esser.indd 1 2019-05.indd 1 05.06.19 09:11
13/06/2019 10:24
 At present, designers use rules
of thumb to decide the number
and arrangement of the rings.
Compressor manufacturers have
tables that might say, for instance,
that a non-lube compressor with
a discharge pressure up to 500 psi
and a gas molecular weight below
10 requires three piston rings. A
lubricated compressor in the same
service could get away with two
rings, whereas a heavier gas would
require four, and so on.
Hoerbiger’s experience of the
frequency and severity of piston
leakage suggests that these rules
of thumb are inadequate, at least
for the more di cult cases: smaller
bores, higher pressures and non-
lube designs. We therefore set out
to develop a mathematical model
of cylinder ring leakage that can be
used to optimise the selection and
arrangement of piston rings and
rider bands.
The model views the ring end
gaps as a series of interconnected
orifices that create a flow path from
one end of the piston to the other.
The pressures at each end of the
cylinder are calculated from stand-
ard compressor
models, while an
empirical correlation provides the
rates of ring wear. The result is a
model that is actually fairly simple
and suitable for routine use, but
which predicts cylinder leakage
accurately enough to make a real
difference when specifying ring
configurations.
Researchers have used parts of
this model for many years to study
piston leakage in both compressors
and engines. However, as far as we
know, the model has never been
used in compressor application
engineering, and incorporating a
wear equation is new. The follow-
ing sections explain the model in
more detail.
The compression chamber model
Our starting point for the leak-
age model is to calculate the cyl-
inder pressures and temperatures
in both chambers (head end and
crank end) as a function of crank
angle. This is done using the stand-
ard equations for pressure and
density changes in reciprocating
compressors.3
www.eptq.com
q3 hoerbiger.indd 4
Leakage across a single orifice
To calculate the leakage past a sin-
gle piston ring or rider band we
assume a perfect seal wherever
the ring touches the piston and the
cylinder liner, so that the end gap
is the only leak path (see Figure 3).
The reference by Feistel justifies this
assumption. Assuming isenthalpic
flow:
./-
𝑚𝑚 = 𝜙𝜙  2𝑝𝑝' 𝜌𝜌'
𝜅𝜅 − 1
1−
𝑝𝑝-
𝜅𝜅 𝑝𝑝'
where m is the mass flow through
the orifice, is the effective leakage
area, p is pressure, is density, is
the isentropic exponent (for exam-
ple, 1.4 for an ideal diatomic gas),
and the subscripts 0 and 1 represent
upstream and downstream condi-
tions, respectively.
The effective flow area is
derived by multiplying the geomet-
ric flow area by an empirical dis-
charge coe cient Cd that depends
on the ring style (for example,
angle-cut or step-cut):
𝑑𝑑$%&'()*+ − 𝑑𝑑-'./0(
𝜙𝜙 =  𝑔𝑔 𝐶𝐶)
2 1
where g is the width of the end
gap. For non-lubricated straight-cut
rings, we used a discharge coe -
cient of 0.65.4
According to Liu and Yongzhang,
cylinder lubrication reduces ring
leakage by 30–35% compared to the
non-lubricated case.5 For lubricated
compressors, we therefore reduce
the effective flow area accordingly.
We neglect any pressure loss due
to tangential flow, which occurs in
the common case where the end
gaps of neighbouring piston rings
are not aligned. According to Ruddy
et al, this is an acceptable assump-
tion for bores smaller than 20 in
(500 mm), while the finished model
shows that piston ring leakage is
unlikely to have a significant impact
on bores larger than 15 in (380 mm).6
Modelling wear
A properly fitted piston ring or
rider band has only a very small
end gap when it is new, so leakage
will be negligible. Leakage becomes
important only once radial wear
(wradial) has opened up the end gap g:
𝑔𝑔 = 𝑔𝑔#$#%#&' + 2𝜋𝜋 𝑤𝑤-&.#&' (3)
The amount of wear depends on
the contact pressure, relative veloc-
ity, time, and an empirical wear
coe cient k:
𝑤𝑤 = 𝑘𝑘 𝑝𝑝  𝑣𝑣  𝑡𝑡 (4)
"#$%#& +,-.#+. "0&#.%10
Typical wear coe cients for
non-lubricated applications are
around 1–16 m3/Nm.4
.
(1) Orifices in series
To calculate the leakage past the
complete set of piston rings and
rider bands we use the well-estab-
lished orifice and volume’ model.6,7
This views the ring end gaps as a
series of orifices connected by fixed
volumes, similar to a labyrinth seal.
The calculation of pressures,
temperatures and gas densities in
between the piston rings is similar
to the approach used to model the
compression chambers, with the
exception that the change in vol-
ume is zero. The governing equa-
tions derive from a mass balance, an
energy balance and the ideal gas law:
(2)
(5)
𝑑𝑑𝜌𝜌# = (𝑑𝑑 𝑚𝑚 − 𝑑𝑑( 𝑚𝑚#, )
𝑉𝑉# ( *#
𝑑𝑑𝑝𝑝# = 𝜅𝜅
𝑝𝑝&
𝑑𝑑 𝑚𝑚 − 𝜅𝜅
𝑝𝑝#
𝑑𝑑 𝑚𝑚 +
𝜅𝜅 − 1
𝑑𝑑) 𝑄𝑄#
𝜌𝜌& 𝑉𝑉# ) &# 𝜌𝜌# 𝑉𝑉# ) #, 𝑉𝑉#
(6)
If necessary, we can modify
Equations 5 and 6 to account for
heat transfer.8 The resulting changes
in pressure and temperature feed
back to Equation 1 via the pressure
and density terms.
Figure 4 summarises the complete
leakage model for a piston with two
rider bands and four piston rings.
Case study: curing rapid rider
band failure
One compressor we examined came
down every six months due to rider
band failures on the first stage.
• Speed: 507 rpm
Lubricated
• Rated power: 500 hp (373 kW)
• First stage cylinder bore: 17.5 in
(444 mm)
• Second stage cylinder bore: 9.5 in
(241 mm)
• Stroke: 9 in (229 mm)
• Rod diameter: 2.25 in (57 mm)
• Isentropic exponent: 1.1 7
PTQ Q3 2019 49
13/06/2019 19:19
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 • Molar mass: 45 kg/kmol
• First stage suction pressure: 10 Suction Head-end Discharge
psig (0.7 barg) valve compression chamber valve
• First stage discharge pressure: 75
psig (5.2 barg).
The first stage piston was fitted
with two angle-cut piston rings and
two angle-cut rider bands, without
relief grooves, mounted outboard of
the piston rings. We wanted to see Volumes
whether adding face and side relief between
cylinders
grooves to the rider bands would Suction Discharge
improve reliability. manifold manifold
Figure 5 shows the simulated Piston rings
pressure trends for the original ring and rider
layout. It is clear that the total pres- bands
sure drop is divided fairly evenly
between the two piston rings and the
two rider bands. This is not surpris-
ing because the leakage area of the
Crank-end
rider bands is comparable to that of compression chamber
the piston rings, and to the gas the
two types of ring look very similar. Figure 4 The corresponding piston leakage model
The pressure drop across each
rider band is of the order of 15 psi.
This is much greater than the 5 psi
Ambience0
for which these unlubricated rider Chamber pressure
Ambience1
rings are designed. The extra load
CE
presses the rider bands against the 6
HE
cylinder liner and creates excessive vol0
5
wear. As a result, the rider bands vol1
were failing prematurely. 4 vol2
Pressure, bar

Figure 6 shows the simulated

pressure trends using rider bands 3
with relief grooves. The grooves 2
effectively eliminate any pressure
drop across the rider bands, so they 1
1.5 1.6 1.7 1.8 1.9 2.0
should now perform as designed.
Time, s
The pressure drops across the two
piston rings have increased. This will
accelerate wear on the piston rings, Figure 5 Simulated pressure trends in the compression chambers and the spaces between
but this is acceptable since their wear the cylinder rings (original rider band design, no relief grooves)
allowance is an order of magnitude
larger than that of the rider bands.
The rider rings with relief grooves
were fitted and the run time Chamber pressure Ambience0
Ambience1
increased by a factor of three.
CE
6
HE
Case study: avoiding high discharge
5 vol0
temperatures vol1
In this example, both stages of a 4 vol2
Pressure, bar

two-throw non-lube hydrogen

compressor suffered from critically 3
high discharge temperatures within
2
six months of operation. For stage
1, the measured temperature was 1
280°F (138°C), which is 54°F (30°C) 1.5 1.6 1.7 1.8 1.9 2.0
higher than its isentropic value. For Time, s
stage 2, the measured temperature
was 225°F (107°C) to 35°F (1 °C) Figure 6 Simulated pressure trends in the compression chambers and the spaces
higher than its isentropic value. between the cylinder rings (recommended rider band design, with relief grooves)

www.eptq.com PTQ Q3 2019 51

q3 hoerbiger.indd 5 13/06/2019 19:19

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man.indd 1 1 10.04.19 10:04
13/06/2019 10:23
 The compression ratios on both
stages were moderate (2.25 on stage
1 and 1.65 on stage 2) and the valve
losses were low. Most of the irre-
versibility causing the temperature
increase could therefore be attrib-
uted to piston leakage.
• Speed: 412 rpm
• Rated power: 250 hp (186 kW)
• First stage cylinder bore: 5.75 in 0 100 20 30 40 50 60 70 80 90 100
(146 mm) Swept volume, %
• Second stage cylinder bore: 4.25
in (108 mm) Figure 7 Measured pV diagram for stage 1 (head end chamber in blue, crank end
• Stroke: 9 in (229 mm) chamber in red)
• Rod diameter: 2 in (51 mm)
• Gas: hydrogen

Discharge temperature, stage 1,

300
• Isentropic exponent: 1.4
• Molar mass: 2 kg/kmol
280
• First stage suction pressure:
405 psig (27.9 barg)
260
• First stage discharge pressure:
929 psig (64.1 barg) 240
• Second stage discharge pressure:
1534 psig (105.8 barg) 220
Detailed pressure data confirmed
severe piston leakage on both stages; 200
Figure 7 shows this for stage 1.
Comparison of the measured (solid) 150
ºF

0 500 1000 1500 2000 2500 3000 3500 4000

and ideal (dotted) pressure curves
Operating time, h 4 rings, piston OD: 5.6 in
reveals a typical piston leakage pat-
tern: compared to the theoretical
curve, the actual cylinder pressure Figure 8 Simulation results showing discharge temperature as a function of time for
rises faster at the beginning of the stage 1
compression stroke and slower at the
end of the compression stroke. temperature after a certain run time. rider rings and a liner-to-piston gap
The existing first stage piston On this basis, we chose for the first of 0.065 in (1.65 mm) to give a maxi-
had four piston rings and the sec- stage a design with six pressure-bal- mum discharge temperature of 250°F
ond stage piston had six. Each pis- anced piston rings, two outboard (121°C) after one year of operation.
ton had two rider bands mounted
inboard of the piston rings.
Applying our model to the exist- Capacity
ing pistons showed an expected 6 rings, gap 0.50 mm PB 6 rings, gap 0.50 mm
temperature increase after 4000 6 rings, gap 1.00 mm PB 6 rings, gap 1.00 mm
hours of operation of 60°F (33°C) on 6 rings, gap 1.50 mm PB 6 rings, gap 1.50 mm
stage 1 (see Figure 8) and about 35°F 6 rings, gap 1.65 mm PB 6 rings, gap 1.65 mm
(1 °C) on stage 2. These figures cor- 320 18000
respond excellently with the meas- 310 16000
ured values of 54°F (30°C) and 35°F 300
290 14000
(19°C), respectively.
280 12000
The model was then used to eval-
270 10000
uate different piston designs (see
260
Figure 9). The thick blue line gives 8000
250
the discharge temperature as a func-
Run time, h

240 6000
tion of the piston ring end-gap flow 230 4000
area. The other lines, each of which
Tdis, ºF

220
represents a different piston design, 210 2000
show the flow area as a function of 200 0
the run time. 0 0.05 0.10 0.15 0.20 0.25
These graphs make it possible to Eff flow area ring, cm2
select the best piston design based
on the maximum allowed discharge Figure 9 Temperature increase over time for different piston designs (stage 1)

www.eptq.com PTQ Q3 2019 53

q3 hoerbiger.indd 6 13/06/2019 19:19

 was shut down to replace the wear
components. A snapshot analysis
revealed high piston leakage.
• Speed: 412 rpm
• Rated power: 170 hp (127 kW)
• Cylinder bore: 6.5 in (165 mm)
• Stroke: 9 in (229 mm)
• Rod diameter: 2 in (51 mm)
• Gas: hydrogen
Figure 10 The new first stage piston Figure 11 The new second stage piston • Isentropic exponent: 1.4
• Molar mass: 2 kg/kmol
• Suction pressure: 395 psig
100 18000 (27.2 barg)
95 16000 • Discharge pressure: 810 psig
90 (55.8 barg)
14000
The original piston design had
85
12000 four standard angle-cut piston
80
1000 rings and two rider bands. Figure
75 12 shows the corresponding sim-
8000
70 ulation. After 8000 hours of opera-
Capacity, %

6000 tion, the expected effective leakage

Run time, h
65
60 4000 area is 0.02 in2 (0.125 cm2), which
Capacity
2000
corresponds to a capacity loss of
55
4 rings, gap 1.9 mm almost 15%.
50 0 Figure 13 shows the simulation
0 0.02 0.04 0.06 0.08 0.10 0.12 0.14
Eff flow area ring, cm2 results for four new piston designs.
Each has six pressure-balanced
rings and two rider bands, but
Figure 12 Performance simulation for the original piston design the liner-to-piston gap varies. For
the upgrade, a liner-to-piston gap
of 0.055 in (1.4 mm) was chosen,
100 18000 resulting in an expected capacity
95 16000 loss of just 3% after 8000 hours.
90 14000 The new piston was installed in
85 2016 and reduced capacity losses as
12000
80 expected. Its sister machine has been
1000 similarly upgraded in the meantime.
75
8000
70 Capacity Conclusion
Capacity, %

6000
Run time, h

65 6 rings, gap 0.50 mm PB Field analysis of hundreds of recip-

60
55
50
0 0.02
Eff flow area ring, cm2
Figure 13 Performance simulation for the new piston design with a choice of four liner-
to-piston gap sizes
On the second stage, an eight-ring
piston with a liner-to-piston gap of
0.060 in (1.5 mm) was chosen to give
a maximum expected discharge
temperature of 210°F (99°C) after
one year.
Figures 10 and 11 show the new
pistons as manufactured. They
were installed in August 2015
and have performed as expected,
with significantly lower discharge
temperatures. Piston leakage is
6 rings, gap 1.00 mm PB 4000
rocating compressors has shown that
6 rings, gap 1.40 mm PB
2000 up to 30% of process gas compressors
6 rings, gap 1.90 mm PB
0 are at risk of excessive gas discharge
0.04 0.06 0.08 0.10 0.12 0.14 temperatures, serious capacity loss
or mechanical breakdown because of
cylinder ring leakage. Especially at
risk are:
• Non-lube machines
• Cylinder diameters below 10 in
no longer the bottleneck on this (250 mm)
compressor. • Suction pressures above 300 psig
(21 barg)
Case study: fixing a • Compression ratios greater than
capacity problem 2.5.
In a third case study, the capacity A new piston performance mod-
of a single stage non-lube hydro- elling technique is straightforward
gen compressor decreased over to carry out and yields results that
time. The recycle valve (the primary match field measurements with
capacity control system on this good accuracy. It is simple enough
unit) had to be closed gradually, to include in everyday engineering
until at zero recycle the compressor work and can replace traditional

54 PTQ Q3 2019 www.eptq.com

q3 hoerbiger.indd 7 13/06/2019 19:19

 The PIONA characterisation and
kinetic approach used in this work A
allow for the ability to predict the 2.5
Ease JEA
reactivityof
stream ebutane buys of
uipmentpetcoke
a wide
operation/start-up/shutdown suchprimarily
range of from
vac- when
as the two areas relative to field gas quality differs. Gas and the otherthreats
formation standardofin aging
insoluble marine safety
sulphide
mixed
Conditioning Conference case involves
(LRGCC), Norman, Conditioning Conference areas
(LRGCC), calculated
Norman, to that
K, Materials
value calculated
by increasing by amine the
the non-ideal
units,
destruc-
NACE
Bad
nearby
uum
unit weather/extreme
refineries
residues. This located
would environmen-
along
mean the
not processing equipment capable Toof requirements add to the complexity
4800and b/dthe h drotreater and* ini- salts ofoforganic
Wmagnesium and calcium,
Oklahoma, Feb 1995. Oklahoma, Feb 2015. Corrosion Conference & Expo, 2013.
phase discharge, slurry and
oil the product non-ideal 365 by blethe energy idealsources. gas method.
2.0 Millions Checking dol- 4isentropic
of CDU tion
Minyard F,expansion
Woodson sulphur T S, method.
compounds
Upgrade The
FCC
tal
US
only
3 rules
tiateAPI conditions
GulfthatofCoast
Recommended
the optimisation
corrosionthumb may
andPractice
c inrequire
coal
cle. from
studies(APIrapid
applications
945
The RP 945 handling
both
can
also MDEA
i Nassef
12 reference well
A S, solventfluids of with
Banazadeh-Neshabouri varying of
19 safety
N, IMechE
which Daughtryresults management
J,in: Teletzke and
E, 7, emer-
Controlling
isentropic expansion coe cient both =idealchamber and non-ideal
upstream theisentropic
considered direct integration
Conference
method
Transactions (Vol
provides201-

Reactivity index
days * Avoiding
shutdown
$2.0/ b/d
of thest,
= $ 3.5 million/y lars in revenue to India’s oil and (COS
slurry oil
andwith
CS ) at lower
chemical settling
operating
aids, World
US
be andare
carried international
out blend to FLNG suppliers.
of feeds, facility.
JEA
differ- in conditions will add to facility cost, gency response 2 procedures of such
(R2008): Environmental Cracking Formulated
Keller M W, MDEA
Roberts reference
K P, Rybicki Analyser
solvent
E F, Iski E V, 212).
corrosion: case studies from amine plant
that
affect
method the is known
catal
not cause
which
recommendedSimulated problems
results for expansion
gas sector
chamber
methods
are being may
lost need
daily to
with- be •
the Reduced
Refining,Professional
mostNov/Dec1999. heat
conservative transfer
Engineering
in
results heaters,
Publishing,1998.
anda
Thus,
procures
ent
Amine floating
operating
Units, petcoke
Apr 2008. liquefaction
and
conditions, coals facilities
scalingboth on
up, equipment
Jefftreat
Shirazi Desalter
S Ultra
A, Comparison1.5
count, and
Desalter
of erosion temperatures
resistance 55facilities.
operational operation,
Liu Y, Yongzhang Laurance (<220°C).Reid Gas
Y,K,Prediction It also has
Conditioning
for the sealing
in inmore
this practice.
case. freOverall,uent need upset for ends catal
j
st considered
= considered
1 even
chamber
for relief2 ofcases with causing
may bemore fuelNorman,
recommended consumption for impor- and
cases
U,these examples Motaghi M, Shree Krishnamurthy S, Anode
The only meaningful process of cost koutiron considering the impact of envi- low pressure drop, which
are
spot
and
4 De
change generally
socargo
Piston on),
Waard
out. and
C, considered
but Lotzshort-
modelling also for
toallows
implies
Prediction benign
mid-term
poten- CO2 complexity.
the
of carbonate
= chamber protective
downstream layer
the Thecoke
with characteristics
Conference
higher
grade potential
cost
(LRGCC),
fromof piston forringsloss
traditional of iscontain-
Oklahoma,
ofcrudes, PTQ, Q2Feb
a reciprocating
show
for the thatof ancarbon
electrostaticn value derived
separator from
is for69 Z factors
ronmental close waste tochamber
1.0.and vs. the cost involving
of compressor,
tant
2016.as the SCOT aInternational
twoprocess phase operates region or at
waters.
fixed
corrosion
tial price
monetary Liquefaction
basis, taking process
steel, advantage
paper trains
no. calcium carbonate 1.0 particles sand, Society mentHotmust also be addressed Compressor when
Psaving by reducing the considered
designer
reventative to choose
actions the
that data arenumber,
tarecy-
could en of For
2010.
• spots in heating tubes, which
plotting
recycle
presented the
flow.
at NACE Forversus
1993. this scale, the wlost =cases
revenue
Petroleumwear (m) with
from Zthe
Engineers factors
bottom close
SPE-188531-MS,of the to Engineering
other
near gas or
atmospheric vapour
Conference, relief
pressure
Purdue cases. and
University, an
are
of
need most
markettotherun edistillation
arbitragecient when
cracking to reduce
experiments. operatedoper- 6considering hull offabrication. A and cat-
H2S in treated gas

Elliott J D, Impact feed properties

be type
inside
5 cle more
flow and Erate F,arrangement
accurate would betower
relative 2 vol% of and
to piston
that
ofFCCU in Safety
the 1.0,
gbarrel. theAnalyser
Indirect
atthe
Analyser
integration
effort to become method self- 1986.reduces their operational life
Ehmke
continuously
ating costs.
Polysulphide
with very
stops
infrequent
presented
Design
Crude = leakage
and
the gap
operation
Abu
(m) Dhabi
of the
International
FLNG excessive
astrophic
operating pressure
tank
parameters failure
on drop
delayed can
could
coker require
result
petcoke
therings
derived overhead
effluent, and
from rider
Simulated
or demandsEquation
100 stem Julbands
b/d. do 3.not
At that
replace
Moreover,
$1.0/ will and
b/d, the
dsufficient, non-ideal 0.5(m) isentropic
increased and refinery methodmar- • educed flow D,rates which PofN,over-
corrosion,
shutdowns.
Cleco
give
References
Hydro.
air
Power’s
acceptable
Proc.,
However,
1981,
Brame
leakage an
149-155.
increase
Energy
perfor-
Petroleum
facilities
oil= diameter Exhibition
present a set of
Conference,
safety chal- more
in
Ruddy
Abu 6quality,
Robert air
BJames
presented
subsequent blower
L, Dowson is the
at duty
Vice
large
Economou
ERTC in
President
2008
scale the sulphur
Coking
discharge
The
Global
and
the
plotting
6 this need
Ehmke, toversus
costEPF,is:
upsetUse remove
starts
ammonium thepolysulphide
could ma imum
eliminate to result
kgins
Dhabi,
Wash
= in about
alone
UAE, wear Nov will 1notdifference
coefficient
2017. sustain the
(m 3
/Nm) in ris- loads
the Gasification
prediction
Marketing,
recovery
References pumping
of Oilpressures units,
& Gas/Refining
unit
Conference. within
(SRU) making
the ring them
packs
with Pall Canada.
to wouldmaintain
in G lenges =ascontactbelow:
stopoperational
Center’s Madison saltinterruptions Unit 3,from should
located of LNG into thePart sea. This be
1 mance
Liang X, over Yan W,aThomsen
defined K,operating
Kontogeorgis life.
amount
the need of for content
estimating n using the discharge
ping cost of areas.
R,crude 0 refining.
pressure This
(N/m ) difference
efficiency of
Including lesslargeeEnergycient
bore diesel engines, Proceedings of
2
corrosion and hydrogen blistering, paper 13 waterJames Arshad A, High 71With
Eq. 2over
of 35
API years
520 ofAdministration,
I,experience
Eighth with
Edition, Pall
Dec
be
in
M, Applied
On expected
Boyce,
petroleum to offshore,
ouisiana,
troublesome
fluid characterizationand
USA,
compres- this
withis • Potentially
contact
large inventories of flow.
U.S.
followed by
Information
a rapid phase transition,
India
crude
100 b/d
no.
Equation59, oil3,before
NACE at
recycle leastit* in
Corrosion/81, enters
365 some* $1.0/
Ontario,the
cases. crude
Canada, v
b/d = essentially
the = sliding
relativeinstallation
contaminant
Phase hydrocarbon
velocity
reduces
removal of
of thetoGES ring
improves against
zero new liner •
the
whenVR Ministry
to exist- and Blockages
IMechE
Corporation
2008.
density Journal
in
of Petroleum in tubes
fluid of Mechanical
separation
& Natural which
Gas, Oillowers
andEngineering
clarification
& Gas
will
another
thesors
distillation
6-10
$ 36 adversely
Apr500 example
it 1981.
PC-SAFT results equation
unit. in:impact
ofof an state,operational
open Fluid mar-
existing
ing (m/s)
refineries sweetening refrigerants
Desalterand control
processes,
those with (such
roomLaurance
failing as Science,
which
their could
a23(6),
Eq. 8capacities
across broadAPI295-304,cause
range and serious
of1981.
e
heavy ciencies. structural
industries,
Edition,heDec has
the non-ideal B isentropic method 2
Journal,
Green-
of
FGE.
M, and
520 Part
brownfield
I, Eighth
benefits
eket ciency.
Equilibria,
7 •NACE
2014, 375, 254-268.
Substantially
PetroPower
(National Associationplant lower (see of discharge
Figure
Corrosion 6). propane)
t
Reid = time
Gas represent
(s)
Conditioning a hazard
Conference which
(LRGCC), 78damage
Eweisinvolved
been to the
Reibungs- in offshore
und
the facility,
Undichtigkeitsverluste
development of with
many
2 The saltCharacterization
content of crude oils var- Optimised desalting processes
mechanical filtration could 2008.
Paraskos J, Scalco V, Optimize value from
Conclusion of uses
CD the n value derived fromeffec- plot- anCompared with 5 arealoss. currently applied
Riazi M, and properties 2.5
Thetemperatures
660 MWe
Engineers) standard plant consists
MR-0175/ISO two may
of15156, Norman, require
= Oklahoma,
discharge adding
coefficient
Feb 2017. to energy
safety miti- possible 3, 4,stability
Kolbenringen,
3leading-edge
FCC Eqs.bottoms, and Forschungshefte
application
Hydrocarbon Prevention
solutions
respectively des
Processing, to Vereins
Eqs.advance of
B-13,
Apr
ies
The with
Ignoring
sizing origin, the
calculation the
labour
petroleum fractions, ASTM international, 2005, water
results and content
formate-
the tively
ting the increase
isentropic India’s P versus sup-
data are inevitable
combination
Deutscher Ingenieure, of to
No. guarantee
catalyst
371, 1935. and mini-
amine
330• Increased
CorrosionMWe
Availability Sumitomo
Cracking unit capacity
Resistant SHI FW
materials CFBs CE
for Oil gation
14 Fontana =
incrank
terms end
M G, of separation
Greene N D, Corrosionor fire such
plant and
2013.
B-14, an
and occurrence
C-9process
of API is
performance.
520 Part a I, key He safety
Eight holds
Edition, a
in the
Volrial
three emulsion
50. costs
relief ofexamples
tank and the
cleaning, amount
presented consider of along
in ply, =1reduce
Figure
HE the
head relief
Arrangementend environmental
path. NY,Plotting
waste
NY, 1967. this 8requirement
of salt-in-crude oil mum
solvent
Disconzi shutdowns
FinP,engineering
TGT
Deschamps and
line-ups,C maintenance
J, Pereira existing
E L,
The •
coupled
Field Greater
process
Equipment.to a MTBF
technology
single 660 for
options
MWe wear
cho-
steam walls.
Engineering, McGraw-Hill,
2.0 bachelor
Dec 2008. of of offshore
degree designs.
from McGill
3 the cost
emulsion-forming of landfill for
particles the insludge
the and35 create a more efficiency in ofcrude of
this Eq.those refiner Partunits that canben- be
Njiarticle
G, 0Svrcek suggest W, Yarrantonthe following.
H, Satyro M, data
analysers improves
in40 45the
desalter accuracy the Development
8 components.
sen
turbine for the
Friedman B,5 Craig10
FLNG
generator facility
that
B, 15
isshould
20
connected
Understanding 25
takethe 30•15 Process
Lagad V related
V, Cayard 50
accidental
M S, Srinivasan refineries
hydro-S, correlation
The
4 use
C2 ofof
University. and
concrete
Email:
API 520 gas
of an in-cylinder
I,plants
for
robert_h_james@pall.com heat
the
Eighth cantransfer
hull
Edition, pro-
Dec

Reactivity index
removed.
crude
The of oils,
ideal Assuming
like
gas sizing polar landfill
resins
method is $1.0/
and oil production. n value affected.
sourpro- gas estimated and shows the 2008;
Characterization of heavy oils and bitumens. 1. References Victor M for
Scalco reciprocating
III is Global compressors,
Commercial
basics
into account corrosion
maintaining in sweet Time,
and
the highest
minutes Prediction and assessment
(both of of rich amine efit from P0 is pressure reduced at theoperating
of costs,
inlet to the nozzle,
to Lb,
vides
Vapor the
asphaltenes.the Entergy
treatingessentially
pressure costand To
plants, Laurance
power
is: critical
prevent
theReid same
grid.
corrosion,
constant
Gas
Behind
relief dis-
prediction
Conditioning it carbon
1 Goebelreleases
content
isentropic
corrosion and
under expansion
D, emulsion
1.5Reciprocating
simulated
refrigerants
profile
refinery properties vides
As
verify- International
compressor
conditions, Strategic
lower
Ali Arshad
fluid
benefits
the cost
Business
emissions,
density is
inof the
Compressor
Senior
at
Development
throat
storage
desalting
improved
Director
where – depends
Engineering
cross
cryo-
Manager,
oper-
Technology/
sectional
availability
each
is CFB
Nomenclature
essential for boiler possible.
toresilience
pre-process Sometimes
is a CFB the polishing this
crude and
& Figure
will partially
suction6 Cleco’s processed
660-MWe natural
Madison gas genic
Unit 3 is aGulftronic fluids
multi-fuel Electrostatic
Conference,
primaril CFB
Purdue as
on crude it retains
power plant
University,
oil its
that
2012. structural
typically
ualitcapacity.
, refin-
NACEiffre uentl fluctuate according
t
method heavy hydrocarbons, Energy and discharge valve monitoring, Separators with
charge
Conference areas (LRGCC), for gas
Norman, or vapour
Oklahoma, withFeb ing the
Corrosion path involves
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 The origins and fates of chlorides in
hydroprocessing units
A step-by-step roadmap to identifying and managing the negative effects of
chlorides in hydroprocessing units
STEVEN A TREESE
Becht Engineering
T
his article in three parts
explores the impacts chlo-
rides may have on hydropro-
cessing units (hydrotreaters and
hydrocrackers). It will provide a
methodical approach to identify-
ing the typical effects that point
toward chlorides, the sources of
chlorides in process feed streams,
Part 1: Recognising the problem
Problems caused by chlorides are
often missed or misdiagnosed in a
refinery. They impact not only the
hydroprocessing units, but other
units as well. Sometimes the meth-
ods used to manage chlorides in
upstream units, such as corrosion
inhibitors, merely move the prob-
lem on downstream. Partial solu-
tions in hydroprocessing units may,
in turn, just pass problems on to
other units. Comprehensive solu-
tions require a wider understanding
of the problem.
Locating a chloride root source
is made more di cult if a prob-
lem has gone unrecognised or has
been allowed to persist for a few
months. The chlorides will propa-
gate throughout a refinery in mul-
tiple streams and in multiple forms
to obscure the original source. There
may be multiple sources. Someone
may have introduced the chlorides
into a system without realising it or
without realising the impacts.
The amount of material required
to create a significant chloride
problem is often very small. To get
1 wppm chloride from perchloro-
ethylene (P C) contamination in
a 50 000 barrels of naphtha hydro-
treater feed, you only need about 1
www.eptq.com
q3 becht.indd 1
chloride induced failure mecha-
nisms, methods for identifying
chlorides, strategies for chloride
control, and a step-by-step process
outline for dealing with a prob-
lem. Some of the approaches and
impacts here can also be applied
to other halogens in hydrotreaters,
such as fluoride.
gallon of P C in the feed (0.0055
vol of the stream). Introducing
a barrel of P C into the naphtha
stream can contaminate it for sev-
eral days.
So how can you approach a chlo-
ride problem Methodical applica-
tion of the steps below is suggested.
The balance of this article provides
the background to execute the steps:
1. Recognise the problem Recognise
the chloride problem from the
impacts observed in the plant.
Where is the problem Are other
units seeing problems
2. How big is the problem? How
much material are you looking for
Calculate or estimate the amount.
3. Identify the source(s) Identify
potential sources for the chlorides,
both organic and inorganic. ook
especially at reformers and isom-
erisation units where concentrated
organic chlorides are present. Use
analyses to narrow down the pos-
sible sources. For organic chlorides,
determine specifically what chloride
compound(s) you are looking for
(speciation). If all you find is P C,
for instance, then you need to sus-
pect the reformer, the isomerisation
unit, or solvent dumping.
4. Manage the chlorides This may
The first part of the article will
focus on recognising a chloride
problem in a hydroprocessing unit.
In the second part, we will tackle
how to identify the magnitude and
source of the problem.
Part three of the article will focus
on ways to address the chloride
issues.
include physical changes or correct-
ing practices and procedures. You
may need to use higher metallurgy
in some equipment. You may need
to adopt a coping strategy rather
than a complete solution.
Chlorides and/or their effects can
be successfully controlled, once they
are identified and understood.
We will begin by looking at how
to recognise a problem rooted in
chlorides.
Step 1: Recognise the problem
Chloride as a possible issue can be
identified from its typical effects on
hydroprocessing units. There will
likely be impacts in other units also
which can serve to support your
identification.
Figure 1 illustrates several areas
to look for indications of chloride
impacts in a hydroprocessing unit.
Impacts are sometimes seen in other
units of the refinery.
Referring to Figure 1, the most
common issues indicative of chlo-
rides include:
• Deposition of salts in reactor
preheat exchangers and charge
heater (A) Deposits of white salt in
exchangers when opened often indi-
cate a chloride problem. This is seen
PTQ Q3 2019 57
14/06/2019 09:58

Hydrogen F Recycle
C
make-up
Feed surge
drum Charge
heater
Feed
stock Feed/effluent
A A
B
Charge
pump
Chloride-impact areas
Location Impact
A Preheat exch. salt fouling/deposits
B Effluent NH4Cl deposits, corrosion
C Metals and salts deposits in catalyst beds
D Corrosion in upper trays and shell HCI
E REAC salt and FeS fouling
F Compressor fouling valves/blades
G Overhead condenser corrosion HCI
H FeS fouling
NH4Cl(s) NH3(g) + HCl(g)
2 HCl(aq) + Fe(s) FeCl2(aq) + H2(g)
FeCl2(aq) + H2S FeS(s ) + 2HCl(g)
Figure 1 Locations of typical hydroprocessing unit chloride problems
in cokers and crude units, as well
as hydroprocessing units. If there is
any entrained water in the hydro-
processing unit feed or chloride
salts above saturation are present,
there will be fouling of the feed pre-
heat exchangers. The salts will sim-
ply lie down on the exchanger tubes
as their solubility dictates. If the
tubes are austenitic stainless steel,
stress corrosion cracking may occur.
Under-deposit corrosion is also a
likely result. In any event, there
would be a loss of heat transfer and,
eventually, high pressure drop.
• Reactor fouling (C) Chloride con-
taining salts that reach the reactors
will decompose or hydrolyse at
reaction conditions, releasing HCl
and leaving metals fouling the cat-
alyst. If, somehow, sodium chlo-
ride is present in the feed, it will
deposit directly in the catalyst bed
without decomposing, forming a
hard rind and causing high pres-
sure drop. Fortunately, most cat-
alysts today are fairly resistant to
poisoning, so the metals may not
hurt much. The HCl probably does
58 PTQ Q3 2019
q3 becht.indd 2
F
compressor
Reactor
Wash water
B E REAC
Separator
SW
Effluent stripper
Stripper
feed
feed
G vate a chloride problem. Once
D increases pressure drop, reduces
Accumulator
Product
stripper
H
Reboiler
H impacts, but ammonia is not as sol-
not harm the catalyst and, in the
case of hydrocracking, may even
help catalyst activity a little. More
importantly, the HCl moves into
the e uent train.
• Reactor effluent fouling and cor-
rosion (B, E) Heat exchanger tube
and shell thinning or pitting, espe-
cially in reactor e uent exchangers,
is often seen. The most common
corrosion location of concern is the
reactor e uent side of the feed/
e uent exchangers where ammo-
nium chloride salts (NH4Cl) deposit
in the exchangers, especially when
wash water practices are inade-
quate. If austenitic stainless steel is
present, chloride stress corrosion
cracking presents an additional
metallurgical challenge.
Fouling or high pressure drop in
e uent exchangers at higher tem-
peratures than ammonium bisul-
phide laydown occurs (say over
250°F, 120°C) also points toward
ammonium chloride deposition.
In the reactor e uent train,
ammonium chloride will deposit
below the temperature indicated by:
TDep = 523 * EXP(0.0507 * Ln(Ksp)).
Ksp = PNH3 * PHCl
Where TDep = deposition tempera-
ture, °F
PNH3 = ammonia partial pressure,
psi
PHCl = Hydrochloric acid partial
pressure, psi.4
Note that the feed nitrogen is
just as important in this equa-
tion as the chlorides. The use of
amines upstream to control corro-
sion or scavenge H2S will aggra-
Off gas deposited, the ammonium chloride
heat transfer, and causes tube dam-
age by under-deposit corrosion.
This effect is intensified as water
SW
begins to condense in the reactor
e uent. The first drop of water
Reflux will be rich in acid gas and very
pump corrosive. Ammonia generated
from feed nitrogen or injected with
Stripped wash water can help reduce the pH
product
uble at high temperatures as HCl, so
the HCl tends to control the pH.
• Stripper/fractionator feed pre-
heat (A) Some of the most di cult
exchanger conditions are presented
when fractionator or stripper feed is
preheated by high pressure reactor
e uent. The fractionator feed has a
small amount of residual free water
that is carried into the fractiona-
tor preheat exchangers. This water
contains dissolved ammonium
chloride. As the stream is heated,
the water eventually evaporates,
leaving ammonium chloride salt
deposits on the tubes where it evap-
orates. The exchanger where you
can expect trouble can be identified
using flash calculations, if you can
estimate the water slip out of the
upstream separators.
The deposit insulates the tubes,
raising the temperature on the
underside of the deposit until the
ammonium chloride breaks down
into ammonia and hydrochloric
acid. The presence of trace amounts
of water in the hygroscopic ammo-
nium chloride deposit promotes
acid attack of the tubes in the form
of pitting.
Dry attack under deposits is also
www.eptq.com
14/06/2019 09:58

possible as a corrosion cell is set up
between the clean and the fouled
metal surfaces. Attack is, again, in
the form of pitting.
• Stripping and fractionation
impacts (D, G, H) Corrosion of the
upper trays in a hydroprocessing
unit stripper or fractionator may
indicate a problem. Crude units will
see essentially the same effects from
chlorides. Wet H2S can also show a
similar effect. Testing for corrosion
products and pH wherever water
collects downstream of a suspected
problem may help. Deposits of iron
sulphide will be observed in prod-
uct rundown coolers and tanks
when chloride is active in a system.
The metallurgist frequently helps
sort out these effects.
In the fractionation system, chlo-
rides will follow the water and
ammonia, just as they do in the
crude units. Expect to see corro-
sion anywhere a liquid water phase
may be present. Problem areas fre-
quently include upper trays, tower
walls, and overhead condensers.
Chloride salt deposition in draw
lines and exchangers has also been
Part 2: Magnitude and source(s) of the problem
Part 1 introduced the symptoms
of a chloride problem in a hydro-
processing unit. In this part, we
will explore how to interpret the
symptoms by determining how
much chloride containing material
we are looking for and identifying
the possible or likely source(s) for
this amount of material, embod-
ied in steps 2 and 3 of the problem
analysis.
Step 2: How big is the problem?
It is very helpful to know the mag-
nitude and type of the chloride
problem before you go looking for
a possible source. Start by chemi-
cally analysing selected streams for
chlorides. Be sure your operators
use good industrial hygiene prac-
tices (for instance, chemical gloves)
in sampling streams for chlorides
since most chloride compounds are
hazardous, even in the low concen-
trations we are testing.
www.eptq.com
q3 becht.indd 3
F
Hydrogen F Recycle
C
make-up compressor
observed. This laydown follows the sion are issues. These are believed Reactor
equation presented above, although to be active
Feed surge in promoting corrosion Wash water
application of the equation is dif- of the drumfuel gas piping. Charge
ficult because it is hard to deter- ■ Reformer water/chloride heater balance B E REAC
mine partial pressures for ammonia Feedproblems Reformers that do not
stock Feed/effluent
and acid. need chloride make-up to maintain Separator
• Compressor issues (F) Make-up a residual are probably getting chlo-
hydrogen compressors and recycle rides through the feed. ThisAmay or A
B
compressors will experience chlo- may not be a problem, depending
Charge
S
ride salt deposition on machine sur- on the unit.pump
faces. In reciprocating compressors, As aChloride-impact
general comment,
areas chloride Efflue
Stripper
valve deposits form, resulting in issues
Location are often missed because evi-
Impact feed
A Preheat exch. salt fouling/deposits
high valve failure rates. Centrifugal dence may
B Effluent NHcome in the form of iron
4Cl deposits, corrosion
G
compressors will experience loss in sulphide
C Metals and(FeS) deposits
salts deposits in equip-
in catalyst beds
e ciency. ment, which
D Corrosion maytrays
in upper beandattributed
shell HCI to
D
E REAC salt and FeS fouling
• Impacts observable in other sys- sulphidic
F Compressorcorrosion. The FeS may
fouling valves/blades
tems and units: actually
G Overheadcome
condenser from wetHCINH4Cl
corrosion
Ac
■ Amine systems Several hydro-
H FeS fouling
under-deposit corrosion via the
treating units have high pressure reaction route shown below: Product
stripper
amine scrubbers to remove H2S
from recycle gas. These scrubbers NH4Cl(s) NH3(g) + HCl(g) H
also effectively remove chloride Reboiler
2 HCl(aq) + Fe(s) FeCl2(aq) + H2(g)
from the gas. While the hydro-
treater may not have problems, the FeCl2(aq) + H2S FeS(s ) + 2HCl(g)
amine regenerator tower and over- H
head system may suffer accelerated Once you realise you have a
corrosion. chloride issue, you need to deter-
■ Fuel gas systems Chlorides mine the magnitude and find the
have been detected in fuel gas source(s) of the chlorides. These are
streams where fouling and corro- the subjects addressed in Part 2.
Analyse the hydroprocessing organic chlorides can be determined
unit feed by water washing the feed. Then
Determine the total chloride content analyse the wash water and the
of the feed and the split between remaining oil for chloride separately.
inorganic and organic chlorides. • Detailed speciation of the organic
There are multiple methods availa- chlorides is available. This is a huge
ble for determining feed chlorides: help in finding or eliminating possi-
• X-rays can be used to determine ble sources. This service is available
the chloride content of most hydro- from several of the common third-
carbon streams down to less than 3 party labs.
ppm. This method is useful and fast • Analyse the feed for bottom sed-
for normal chloride analyses. iment and water (BS&W) to get an
• Wet chemical methods based on idea of how much inorganic salts
potentiometric titration with meth- may be entering.
anol and ion chromatography are
also available. These are accurate to Analyse the sour wash water
less than 1 ppm, but require consid- Determine the chloride content of
erably longer to run than the x-ray. the spent sour wash water from
• Newer instrumental analysis the high pressure separator and the
methods are continually improving stripper overhead, if used.
chloride determination. Methods
for determining individual chloride Analyse the chlorides in the
compounds down to less than 0.01 crude unit
ppm in feedstocks are available. Crude assays indicate salt content
• The split between inorganic and of the crude in pounds per thou-
PTQ Q3 2019 59
14/06/2019 09:58
 sand barrels. This is a good starting can estimate the amount of chloride easily using the concentration of
point. The crude salts are usually coming into the hydroprocessing chlorides (usually in volppm) and
sis indicatesbythat
determined increasing
a simple devicecrude
like efforts at the refinery.
unit. Consider a 50 000 Actual
b/d refin-
diesel ProCorr
the make-up Consulting
gas rate. Services
If you has have
TAN by 0.1 should have
the ‘Nalcometer’ based on little effect
conduc- ery operating data (temperatures
hydrotreater with a 40°API feed con- been able to develop
1.5 volppm chloride in 700 a useful modelscf/
on corrosion
tivity rates and reference.
using a calibration that cor- and
taining stream
5 ppmcompositions)
organic chloride. can The
be for naphthenic
bbl reformer hydrogenacid make-up
corrosion.at
rosion rates might even
For more detail, look at the decrease.
inor- used to estimate past corrosion.
total incoming organic chloride is: By Because
50 000 bpd, the Tancorr
the make-up modelhydrogen
is also
ganic and organic chloridesreading
Caution should be used in in the comparing the expected actual cor- easy to use
is bringing in: and only requires read-
too much
crude beforeinto
and small changes
after the desalters.up rosion
50 000 bpdrates withlb/bbl
x 288.6 the xbasis
5x10-6 used to=
parts Cl ily available input data, there are a
72 lb/day chloride
or down in corrosion predictions.
Look at the chloride contents of any set the inspection intervals, deci- number
50 000 bpd ofx 700
ways it can
scf/bbl be -6used
x 1.5x10 to =
ppm HCl
Between the inherent accuracy lim- sions can be made on whether help refineries optimise their high
slops or recovered oil streams sent Using the spent wash water anal- 52.5 scf/day chloride
its of the model and limited ability inspection intervals should be TAN crude processing capabilities.
to the crude unit. Detailed organic yses, suppose you have 50 gal/min
to accurately measure corrosion in shortened or can be increased. This This model÷is379.45 a critical new tool for =
chloride speciation and analysing wash water (once through) to our 52.5 scf/day scf/mol x 35.5 lb/mol
the field, actually seeing small dif- capability is particularly useful refineries seeking to improve profit-
4.9 lb/day chloride
for sodium, calcium, and magne- 50 000 b/d diesel hydrotreater. The
ferences in corrosion rate will nor- when crude slates vary widely or ability through processing increas-
sium may help here. If the chlo- concentration expected in the spent For deposits of chlorides in
mally be very hard to do. the refinery has made a step change ing amounts of opportunity crudes.
ride problem is in a specific boiling wash water would be about: exchangers or the reactors, you
Another way Tancorr can be used shift in crude sulphur and TAN.
range, you can make a rough heart- can estimate the mass of chloride
is to check the corrosivity of actual (72Finally,
lb/day Cl)Tancorr
/ (50 gal/minpredictions canx
x 1440 min/day References
cut of that boiling range of the
crude blends that come out of the be
8.34used
lb/gal)in
x 10conjunction
6
= 120 wppm with actual
Cl in water 1inCraig
theHdeposits from the
L Jr, Temperature andanalyses.
velocity
crude and look
refinery’s at theIf chlorides
P model. appropriate in piping condition data to develop You inthen
effects can make
naphthenic some Corrosion
acid corrosion, assump-
that cut specifically.
sulphur and TAN ranges have been If you sulphur
allowable recycle and water TAN forranges
phase tions
96, about
Paper No. 603. how much mass of
developed and those ranges have control or use stripped
which ensure that minimum desired sour water, 2deposit
Jin P, et al,that represents.
Mechanism Note that
of high temperature
Analyse theinto
been built chlorides
the P in model,
the then you need
piping to account
life targets for any This
are achieved. chlo- for ammonium
corrosion chloride
by model naphthenic deposits,
acids, Corrosion
make-up hydrogen
this use of Tancorr may have little ride coming in with
approach can also be used when the water when bothPaper
2016, the7302.
chloride and nitrogen are
3 Vetters E, Clarida D, Maintaining reliability
Test for IfHCl
value. in the analysis
rigorous make-uphas hydro-
not amaking
refinerythe is above calculations.
looking to processYou needed. So, for instance, if you have
when processing opportunity crudes, PTQ, Q4
gen. Normally, this is done
been done to set sulphur and TAN using a could also get an estimate
increasing amounts of opportunity of how a naphtha with 5 ppm chloride, but
2013.
Dräger tube or similar test
ranges, then this approach can be method. much material
crudes over time you are looking
without for
initiating only 1 ppm nitrogen, the amount
This maycheck
an easy not to
beensure
accurate
that if your
specific by taking the 72 lb/day
a major metallurgy upgrade project. chloride of deposit possible is limited by the
chloride adsorbers
crude blends will are
not saturated,
cause exces- in and approach
This assuming has it was PERC. been
previously This nitrogen, not the chloride; 1 wppm
which case you Tancorr
sive corrosion. need to can
usebe
another
easily would imply
described a PERC
in more contamination
detail. 3 nitrogen can make, at most, 3.8
Eric Vetters is President of ProCorr Consulting
method
linked withto look for organic
P output chlo-
data to auto- of about 6.2 gal/day. ppm NH Cl deposit before running
Services LLC in4 Owasso, Oklahoma. He has over
rides (or, calculation
mate the better yet,process.
change your Looking
Conclusion at the hydrogen out
35 of of
years nitrogen.
experienceIn in fact,
processyou will not
engineering
adsorbents).
Tancorr can also be used to sup- make-up
By analysing stream analyses,
literature data usingyou getcorrosion
and even atthat much
Phillips 66 andasas adeposition
consultant.
Fromrisk
port the feed
basedanalysis results( and
inspection BI) can estimateabout
knowledge howthe much chloride
mechanism, occurs
Email: and partial pressures drop.
ewvetters@yahoo.com
known or estimated flow rates, you is entering from this source fairly The excess chloride will go on to

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60 PTQ Q3 2019 www.eptq.com

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q3q2becht.indd 4 5
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20:38
 lower the pH of any e uent water.
You get some e uent fouling,
along with a corrosion bonus.
From observations and expe-
rience, the density of the fouling
deposits tends to be in the order of
20-30 lb/ft3, regardless of what the
foulant is. Suppose we have our
diesel hydrotreater with 72 lb/day
of chloride and it has more than
enough nitrogen for all the chloride
to deposit as a NH4Cl in the e u-
ent. The amount of deposit expected
would then be about:
72 lb Cl/day x 53.5 lb NH4Cl / 35.5 lb Cl ÷ 25
lb/cft (avg) = 4.3 cft/day of NH4Cl deposits
Another approach to determin-
ing the amount of material you are
looking for is to perform chloride
balances around the upstream units.
This can be one of the best tools for
identifying the source and magni-
tude of a chloride problem at the
same time. Pay particular attention
to the desalters and reforming and
isomerisation units. Develop a good
material balance and sample all
streams for chlorides. With atten-
tion to detail, an acceptable ( /-2 )
chloride balance is achievable.
Once you have an idea of how
much chloride you are looking for,
you can begin considering possible
sources for the material.
Step 3: Identify the sources
As you could surmise from the ana-
lytical testing above, chlorides in
hydroprocessing units enter gener-
ally via two routes:
• Feedstock
• eformer hydrogen make-up.
We now have an idea of how
much material we are looking for,
so we can start looking at the pos-
sible sources in more detail. From
experience, the most common
source(s) for chloride problems are
Chemical Perchloroethylene
Nickname PERC
Formula C2Cl4
Molecular weight 165.8
Boiling point, °F 250
Density, g/cm3 1.622
Density, lb/gal 13.5
Solubility in water 0.15 g/L
Wt% chlorine 85.6
Health effects Toxicity moderate to low
NFPA ratings, H-F-R 2-0-0
Table 1
into a hydroprocessing unit liquid
feed from one of these units. We
will talk later about the reformer
hydrogen route.
Chloriding agents are used to
provide the necessary chloride to a
reformer or isomerisation unit. The
agents are mixed with naphtha and
injected into the unit. Agents which
have been used include trichloro-
ethylene (TC , C2HCl3), perchloro-
ethylene (P C, C2Cl4), and carbon
tetrachloride (CCl4). P C is most
common and carbon tetrachloride
is no longer used due to toxicity.
P C has also been used for dry
cleaning and equipment cleaning.
These materials normally convert
completely to yield HCl in pro-
cesses. Key properties of some of
these chemicals are listed in Table 1.
Chloriding agents can enter
hydroprocessing unit feedstocks
by several, unintended routes.
Observed contamination routes
from reformer and isomerisation
operations have included:
• eaks or drainings from chlorid-
ing agent storage drums or systems
100
90
80
Properties of chloriding agents
Trichloroethylene Carbon Tetrachloride
TCE or Trike
C2HCl3 CCl4
131.4 153.8
189 170
1.46 1.5867
12.2 13.2
1.28 g/L 0.81 g/L (25°C)
81.1 92.3
Carcinogenic Very toxic
2-1-0 3-0-1
• Overflow of chloriding agent
drums to sewer or flare
• Poor chloriding agent receiving
practices (such as draining resid-
ual material from a truck into the
sewer).
The agents that reach the sewer or
flare end up in the slops or recov-
ered oil systems and are charged
back to the crude unit. They then
normally distill into the naphtha
heading to the reformer pretreater.
Crude oil
Salt is a natural part of crude oil. A
certain amount of brine is co-pro-
duced with crude. The brine is sep-
arated in the field and the relatively
dry crude oil is sent to the refinery.
Chloride introduced into a well
during a workover or well stimu-
lation effort will also appear in the
produced crude. During transporta-
tion, brine can enter crude oil from
seawater. egardless of the origin,
the crude salts can be a source of
chlorides in hydroprocessing unit
feeds. The salts consist primarily of
sodium, magnesium, and calcium

internal to a refinery. Outside crude

Chloride hydrolysed, %

70
contamination can still occur occa- 60
Magnesium chloride
sionally, however, so do not rule it 50
Calcium chloride
out too early. 40
30
Feedstock chloride sources 20
Naphtha reforming and 10
isomerisation units
0
Chloride is used in both reformers 200 300 400 500 600 700 800
and isomerisation units to maintain Temperature, ºF
catalyst activity. We are going to
focus here on how chloride can get Figure 2 Decomposition of crude oil chlorides during processing

www.eptq.com PTQ Q3 2019 61

20:38 q3 becht.indd 5 14/06/2019 09:58

 chlorides. As a rule, the less polar
the salt, the less soluble it will be
in water and the more soluble it is
in the crude. The crude will tend to
hang on to magnesium and calcium
chlorides, even through desalting.
Sodium salt removal by desalting
is usually complete. Fortunately,
the normal levels of magnesium
and calcium chlorides in crudes
are low. But some crude have more
than others.
As crude is processed through the
primary crude unit, vacuum unit,
and coker, residual magnesium
or calcium chlorides will begin to
hydrolyse in the presence of trace
water, releasing HCl.1,2 The hydrol-
ysis relationship to temperature
is illustrated in Figure 2, with data
published by Petrolite.3 Sodium
chloride will not decompose to any
significant extent. HCl generated
from the magnesium and calcium
salts will move upward in the distil-
lation columns until it finds ammo-
nia or amines to combine with, or
until a liquid water phase forms,
or until the HCl gets drawn into a
product. There the chlorides effects
will be evident in the columns or
exchangers for the crude, vacuum,
and/or coker units.
A key control on crude unit inor-
ganic chlorides is desalting e -
ciency. Most desalters can remove
90-95% of the salts from the incom-
ing crude in a single stage. This salt
will mostly be sodium chloride. A
lot of the magnesium and calcium
chlorides stay in the desalted crude.
For a crude with 20 lb per thousand
barrels salt, the product salt will be
less than 2 lb per thousand barrels.
This is not really a problem level.
If the crude salt level rises to 200 lb
per thousand barrels, however, and
the crude has more magnesium and
calcium salts, the desalter may only
produce 20 lb per thousand barrels
product. This is a lot of salt to leave
in the crude unit charge, even when
only some is Mg and Ca.
Organic chlorides are not natu-
rally present in crude oils. A crude
organic chloride source that has
been frequently observed is the
blending of organic solvents (for
instance, PERC dry cleaning sol-
vent) into the crude for disposal.
This is often di cult to trace back to
62 PTQ Q3 2019
q3 becht.indd 6
a specific crude source. Some refin-
ers have set specifications for maxi-
mum organic chlorides in crude (or
in the naphtha fraction of crude)
that they are willing to purchase.
Such solvents would usually distill
into the naphtha streams and react
in the naphtha hydrotreaters to
release HCl.
Other upstream units
Residual chlorides from upstream
units often end up in hydroprocess-
ing unit feeds. For instance, chlo-
rides in a coker fractionator will be
present in every product stream.
Depending on the operating condi-
tions for a given column, chlorides
will distribute across the full range
of distillation products. A chloride
balance around each upstream unit,
although di cult, helps indicate
where a problem condition exists.
These chlorides may include various
organic compounds resulting from
the reaction of HCl with olefins.
Water and nitrogen play roles in
determining where chlorides come
out of fractionation units. Most chlo-
rides are very soluble in water, so
any chloride formed by decomposi-
tion in a still will move up a column
until liquid water forms. Some of the
chloride will partition to the oil, in
equilibrium with the water phase.
While we might usually ignore
HCl dissolved in oil, when you are
worried about parts per million of
chloride, the solubility is impor-
tant. Nitrogen compounds, such
as amines, also hold on to chloride,
acting as bases. Some nitrogen com-
pounds are specifically designed to
pull inorganics into the oil phase.
Crudes high in nitrogen will tend
to produce gasoils high in nitrogen,
which will carry chloride into down-
stream hydroprocessing systems.
Even within the upstream units,
operating conditions for columns
can increase or decrease chloride
contents of streams. Manipulating
column pressures, temperatures,
and reflux rates can greatly affect
how the chlorides will partition
among the product streams.
In some instances, very heavy
crudes may be charged directly to
a coker. These heavy crudes are
generally not desalted and have
not been separated well from pro-
duction brines. Crude chlorides are
thus introduced directly into the
coker, often at the fractionator. The
resulting coker products have con-
centrations of chloride and will even
contain organic chlorides formed
from reactions between HCl and ole-
fins in the coker products.
Potentially major sources (or
accumulation locations) for organic
chlorides within a refinery are the
recovered oil and slops systems.
These streams are often charged to
the crude unit to save the hydrocar-
bon value of the streams. Organic
chlorides can enter these systems
from many sources, including:
• Reformer or isomerisation unit
chloriding agents as previously
described
• Skimmings from the sour water
drums or tanks from a contaminated
system
• Spent maintenance solvents sent
into the system
• Receiving solvents from an out-
side source for disposal
• Wastewater treatment plant recov-
ered oil or sludge.
When recovered or slop oil con-
taminated with organic chlorides
is re-run in the crude unit, the
organic chlorides distribute into the
products according to their boiling
points. It can be extremely di cult
to identify the source(s).
Contamination of a refinery sewer
system with organic chlorides can
be a particularly di cult issue to
identify. Because the compounds
involved are not very water solu-
ble, are only mildly volatile, and are
heavier than water, they can lay in
the sewer seal boxes and other low
point, quiescent locations until high
flow rates entrain the material out
of the low points or a hydrocarbon
dissolves them out. They may then
show up all at once or in spikes.
Similar issues can make identifying
a chloride source di cult when the
materials are moving through the
sour water or flare systems.
Reformer hydrogen make-up
The most common gaseous source
of chloride in hydroprocessing
units is naphtha reformer hydrogen.
There is always a trace of chloride
(as HCl) in any naphtha reformer
or isomerisation unit net hydrogen
www.eptq.com
14/06/2019 09:58
 production. When this cessing. Chlorides do get
Checklist for hydroprocessing unit feed chloride sources
offgas is introduced into through FCC feed pretreat-
a hydroprocessing unit as ers and end up in the FCC
General
make-up hydrogen, the  Verify the chloride analyses are accurate with alternate lab
slurry and cycle oils, for
chloride goes too.  Perform speciation of chlorides so you know what to look for instance. Coker streams
The chloride level in almost always have some
reformer hydrogen is nor- Crude unit sources chlorides. The levels in
 MgCl2 and CaCl2 changes in crude slate
mally very low – about  Poor desalter performance or upset
these streams are gener-
1-3 volppm. It is often  Organic chloride disposal into crude (inside or outside refinery) ally low, but they can be
managed by passing  HCl in wet crude tower reflux elevated if there is a prob-
the net reformer hydro-  Organic chloride in reprocessed recovered oil or slops lem. Consider all feed
 Organic chloride in desalter make-up water
gen through a chloride  Cracked stocks fed back to crude unit
and recovered oil streams
adsorber. When the adsor-  High H2S scavenger or corrosion inhibitor levels in crude when looking for chloride
bent is spent, it will allow sources.
chloride to slip, but the Reforming/isomerisation units Table 2 provides a check-
 Spent chloride adsorbent on net gas (reformer hydrogen)
resulting material released  Poor net gas scrubber operation (isom)
list for many of the possible
is an organic chloride  Poor chloride/water balance in reformer chloride sources in feeds to
polymer (‘green oil’, not  Poor reformer catalyst activity a hydroprocessing unit. It
HCl). This was alluded to  Poor chloriding agent receiving practices contains the most common
 Chloride agent drained to process sewer or sour water
in the analytical discus-  Chloride agent sent to slops, recovered oil, or flare
sources people have seen,
sion above. as well as a few less com-
An isomerisation unit Miscellaneous mon ones. Is it all inclu-
maintains a higher level of  Organic chloride in hydrocarbons recovered from sour water sive? Probably not; you
 Maintenance cleaning solvents dumped to slops
HCl in the treat gas than  Maintenance cleaning solvents dumped to effluent water treating
have to think through your
a reformer; but the small  Reaction of HCl with olefins where they may mix specific case, but the table
amount of purged net gas  Chloride salts in recycled stripped sour water used in wash water is a starting point.
leaving the isomerisation  Other unidentified sources or practices? You can systematically
unit is treated in a caustic work your way through
absorber so that almost Table 2 the list. Be sure to actually
no chloride escapes. If the consider and prove or dis-
absorber is mismanaged, of course, a liquid feed. Suppose we have a prove each possible source. From
chloride can get out. 50 000 b/d naphtha hydrotreater experience, most locations that have
For perspective, it is helpful to and we run once-through reformer had a problem that they thought
consider the potential magnitudes hydrogen at 500 scf/day rate. One was from an outside source, actu-
of the different chloride sources and volppm chloride in the gas will be ally had internal problems they did
their impacts. We often worry about about 2 lb/day of chloride, whereas not recognise. Do not make assump-
chlorides from the reformer hydro- 1 wtppm chloride in the feed will be tions and eliminate sources too
gen make-up because we know about 13 lb/day. We need to be a lot quickly or without proof. Be sure
it always contains chloride (with- more concerned about feed chloride you understand the actual practices
out an adsorber), but compare the content than make-up hydrogen being used in handling any chloride
amount of chloride introduced into chloride, in general. chemicals, not just what the refin-
a hydrotreater from the reformer Also, do not assume chlorides ery has on paper. Verify procedure
gas with the impact of chloride in are eliminated by upstream pro- against practice.

Part 3: Managing the chlorides

Parts 1 and 2 of this article provided
a methodical approach to identifying
a chloride problem in a hydropro-
cessing unit, determining the size of
the problem and narrowing it down
to a likely source or sources. This
final part will address approaches to
dealing with the source(s).
Step 4: Manage the chlorides
Now that you have a clue about the
magnitude of chlorides present and
where they might be coming from,
you can address the problems.
There are three fundamental strate-
gies or options for controlling chlo-
rides in a hydroprocessing unit:
• Keep chlorides out
• Intercept what gets through
• Design and monitor for chlorides.
By the application of these strate-
gies, individually and in combina-
tion, chlorides have been effectively
controlled in many units.
Keeping chlorides out
As a general rule, target to have
much less than 2-3 ppm chlorides
in feed and less than 0.5 ppm in
make-up reformer hydrogen to a
hydroprocessing unit. In eliminat-
ing chlorides from the feeds, con-
sider the following:
• What potential sources were
implicated using the Table 2 check-
list? Run the sources to ground.
• If possible, select crudes that have

www.eptq.com PTQ Q3 2019 63

q3 becht.indd 7 14/06/2019 09:58

 hat the tem- low salt content, or at least a salt content within a
daily by 1°C
the previous
SERVICE range you can tolerate. Eliminate any crude source
that has demonstrated high organic chloride con-
plaints, were tents or penalise that crude’s value consistent with
its impacts. Crude pricing may make this option
the system, di cult to implement.
r equipment • Dry the crude as much as possible before it
reaches the crude unit. Keep the crude warm in
clearly seen tankage to maximise water separation. Water draw
almost equal the crude tanks regularly. Consider using one of
ot oil flow. the materials marketed by treatment chemical sup-
pliers to accelerate separation.
• Pay attention to desalter performance and con-
imed to heat sider a second stage of desalting. Where single
es, two sales stage desalting removes 90-95% of the salts; two
itumen tem- stage desalting will remove 98-99% of the salts.
f the system, The second stage targets the magnesium and cal-
erations, was cium chlorides more. This may be enough to avoid
problems.
m, complaints • Caustic can be injected into the desalted crude to
erature were neutralise HCl released in the crude unit by hydrol-
was clearly ysis. This can help reduce crude unit corrosion and
ning the tem- intermediate product chloride levels; however,
with a total caustic may negatively affect the vacuum and coker
C, as well as units downstream.
uction lines, • Run designed experiments on your crude, vac-
o sales lines, uum, and coker towers to identify the operating
conditions that minimise chlorides in the hydropro-
s of the stor- cessing feeds.
rformance of • Dry hydroprocessing unit feeds are essential.
aily increase Upstream systems should ensure good water sep-
il circulating aration and feed tanks should be regularly water-
performance drawn to keep salts out of processing units. It is a
ove 85 . The good practice to use swing-line draws from your
king up 20 tanks where possible. Dry stripping (reboiling)
e enough for feeds is preferable to steam stripping (which guar-
uench drum
d in cost and SERVICE antees a wet feed).
• For chlorides present in reformer hydrogen,
installation of a cold chloride adsorbent (alumina)
e equivalent
ons, and the
YOUR PROFITS bed ahead of the make-up hydrogen compressors
will eliminate most of the chloride. Alumina beds
can take up, perhaps, 10-15% chloride. This is a
ed by seven proven technology. If you already have a chlo-
ride adsorber on make-up gas, be sure it is work-
Tailor-made performance begins by putting ing correctly. Calculate the expected bed capacity
your needs center stage. Services offered by and life. Change the bed when you calculate that
it would be spent; do not wait until you detect
HOERBIGER provide long-term improvements
the Production breakthrough.
. Her refining
in reliability, efficiency and environmental
ot oil units, and soundness. The goal: to make your plant run Intercept what gets through
tions. She holds even more profitably. Your second line of defence against chlorides is to
key. control what gets through into the hydroprocessing
px.hoerbiger.com unit feed. One ppm of chlorides in 50 000 b/d gas-
oil is about 16 lb/day or about 3 t/y. Options for
tendent in the
controlling the chloride slip within a unit include:
ery, Turkey. His
• Wash the e uent exchangers with condensate.
nks and hot oil
production and Meet the same rate, water quality, and design con-
n electrical and figuration requirements defined in API P 32,7 as
kır, Turkey. applied to an ammonium chloride case. Inject con-
densate upstream of the first exchanger where chlo-
rides may deposit as determined by the equations

PTQ Q2 2019 91
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q3 becht.indd 8 14/06/2019 09:58
 presented earlier. There must be
enough condensate for about 25
to remain free liquid at the injec-
tion point. Allow enough down-
stream piping for the condensate
to mix well (perhaps 30 diameters)
or install an inline mixer (which
will not block flow if it fails); other-
wise, the condensate droplets will
damage the downstream piping or
exchanger by erosion or erosion/
corrosion.
• If the chloride and nitrogen levels
in the feed are low enough, conden-
sate injection can be intermittent.
This frequently works in naphtha
and jet hydrotreaters. It may even
be worth dropping unit pressure
and temperature for a good, inter-
mittent wash every few months.
Sample and analyse the wash water
to determine the length and fre-
quency of washing. The required
time is longer than you might think.
You cannot leave any salt deposit
or it will be more corrosive. Wash
water pH can be moderated by
ammonia or non-volatile amine
injection, but avoid contaminating
the product with nitrogen if it is
reformer feed.
• Where chloride deposits in frac-
tionation towers or draw systems,
periodic or continuous water wash
is also useful. Water washing for
4-12 hours every 2- months has
been used to remove deposits with
success. Again, be sure all the salts
are removed during the water wash.
• For fractionator preheat
exchanger problems, the quality
of water separation ahead of the
exchangers is crucial. To aid in
separation, keep your high pres-
sure separator temperature above
0°F (32°C), but not over 105-110°F
(40-43°C). Separation of water and
oil must be better than e -
cient. You need to remove enough
water so that all the remaining
water evaporates in a relatively cool
exchanger, thereby reducing the
risk of corrosion.
• You may be able to simply raise
separator oil level and help your-
self. A review of residence times
and separator configurations, along
with a water balance, should indi-
cate if improvements are needed
here. ate increases over time often
defeat a separator that used to be
www.eptq.com
q3 becht.indd 9
adequate at lower rates. Water coa-
lescing and separation seem to be as
much art as science. A combination
of coalescing pads and hori ontal
plate separators have been fairly
effective in di cult cases.
Design and monitor for chlorides
If you cannot keep the chlorides
out and you cannot make them go
where you want, you will have to
otherwise cope with their presence.
A few techniques that have been
successful are:
• xpect increased corrosion in
the areas described earlier. Plan to
increase metallurgical inspection,
and plan on more frequent retubes
and replacements of bundles and
shells.
• Select metallurgies that are
resistant to chloride attack.
xchangers where corrosion may
be most aggressive may require
alloy tubes (for instance, Inconel
25 for tube-side reactor e uent),
but the lower pressure shells (frac-
tionator feed) may still use carbon
steel with large corrosion allow-
ances. A N and 2205 have been
used with limited success where
corrosion was moderate. In crude
units, titanium has been successful
when chlorides are present.
• Avoid creating dead spots and
cold ones in susceptible exchang-
ers. Keep the exchangers insu-
lated well and review your ba e
arrangements. Wet NH4Cl deposits
on the shell are troublesome, since
they can result in shell corrosion.
Thermography of the shell can help
spot potential problem temperature
ones.
• Corrosion inhibitors may help
resist damage in the fractiona-
tion and e uent systems in cooler
ones. In naphtha reformer pre-
treater service, however, they may
send unwanted nitrogen to the
reformer.
• eview your fractionator or strip-
per relief system design for tube
failures in preheat exchangers. API
ecommended Practices 520 and
5215,6 contain published guidelines
for tube failure scenarios.
• stablish good chloriding agent
receiving practices. Never put any
chloriding agent to the sewer, flare,
or recovered/slop oil. If there is
extra agent after filling your chlo-
ride agent drum, send it back and
accept the restocking charge.
• Monitor, monitor, monitor.
Watch for chloride deposits and
damage when the unit is down for
turnaround. Track feed chlorides
by frequent sampling. Track chlo-
rides in your wash water. Watch for
losses in heat transfer in exchang-
ers where chlorides may deposit.
Chloride balance your reformers
and isomerisation units. Watch your
recovered/slop oil organic chloride
content. Watch your sour water
skims for organic chloride.
Conclusion
Chlorides can enter a hydroprocess-
ing unit via several routes. They
will adversely affect unit reliability.
The primary keys to controlling the
adverse effects centre around elim-
ination of the incoming chlorides,
intercepting the chlorides that do
enter, and controlling the effects of
the remaining chlorides.
By applying the principles dis-
cussed here, you can successfully
steer clear of the pitfalls posed by
chlorides in hydroprocessing units.
References
1 Lieberman N P, Four steps solve crude
overhead corrosion problems, Oil & Gas
Journal, 5 Jul 1993.
2 Lieberman N P, Process Design for Reliable
Operations, Gulf Publishing Company,
Houston, 1988.
3 Petreco Division, Petrolite Corporation,
Impurities in Petroleum, Houston, 1958.
4 Journal of Chemical Physics, Vol 12,
#71318, 1944.
5 American Petroleum Institute,
Recommended Practice 520, Sizing, Selection,
and Installation of Pressure-Relieving Devices
in Refineries, Part I – Sizing and Selection, Fifth
Edition, Jul 1990.
6 American Petroleum Institute,
Recommended Practice 521, Guide for
Pressure-Relieving and Depressuring Systems,
Fourth Edition, Mar 1997.
7 American Petroleum Institute,
Recommended Practice 932, Design,
Materials, Fabrication, Operation, and
Inspection Guidelines for Corrosion Control in
Hydroprocessing Reactor Effluent Air Cooler
(REAC) Systems, Second Edition, Jan 2014.
Steven Treese is a Hydroprocessing
Consultant with Becht Engineering in Gig
Harbor, Washington with 45 years’ industrial
experience. Email: streese@becht.com
PTQ Q3 2019 65
14/06/2019 09:59

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08/06/2018 19:22
 Fieldbus – is interest fading?
An end user perspective on why the oil and gas industry has a divided view of
fieldbus technology
MEGHDUT MANNA
Technical Advisor
I
n the late 1 0s, the advent of field-
bus technology created a buzz
equivalent to today’s Industrial
Internet of Things (IIoT). Fieldbus
technology quickly succeeded HART
– a hybrid protocol that marked the
transition to the digital era from the
long reign of the analogue 4-20 mA
signalling standard. Theoretically,
fieldbus has numerous advantages
over analogue or hybrid technolo-
gies. This technology was expected
to be a panacea of the ills suffered by
process control systems and millions
of devices that have been installed
across the globe. It has been at the
forefront of technology enhance-
ments in process automation and has
garnered the interest of automation
vendors. Though the technology has
matured substantially, the oil and
gas industry seems to be divided
over its adoption even today. An
attempt has been made to explore
the causes of this predicament and
suggest means for how issues may
be overcome.
Why fieldbus was deemed a
technology of the future
The first industrial computer sys-
tem was built in 1959 at Texaco’s
Port Arthur, Texas refinery.
Distributed control systems were
introduced in 1975 by Honeywell
and Yokogawa. Though digital
technology was in use in the con-
trol room, signalling by field instru-
ments was either analogue (4-20
mA) or used a hybrid (HART)
signal. With the introduction of
IEC-61158, local area networking
technologies were adopted for com-
munication with field devices. This
technology was introduced with the
following key prospects:
www.eptq.com
q3 manna.indd 1
• Decentralisation of control; ‘con-
trol in the field’
• Preventive maintenance, pro-
viding a high level of ‘diagnostic
coverage’
• Drastic reduction of field wir-
ing and the costs of cabling and
installation.
Fieldbus’s falling popularity
The introduction of fieldbus
brought encouraging optimism; it
was expected to disrupt the process
control industry. Everyone asso-
ciated with this industry dreamed
Large oil and gas
installations like
refineries were very
conservative in
accepting new digital
technology, as any
failure would lead to
high production losses
and unsafe conditions
of being part of the new move-
ment. Fieldbus was well regarded
in factory automation, assembly
line manufacturing, compact lay-
out floating production storage
and o oading, small gas gather-
ing stations, the pharmaceuticals
industry, power sector, and so on.
However, large oil and gas installa-
tions like refineries were very con-
servative in accepting new digital
technology, as any failure would
lead to high production losses and
unsafe conditions. Although many
refineries or upstream oil and gas
establishments were early imple-
menters, widespread acceptance
of this technology has yet to be
realised due to several underlying
challenges. While many grassroots
refineries did implement fieldbus
technology, at times they were not
inclined to adopt it for their future
expansion, add-on units or addi-
tional plant because of the compel-
ling issues presented in this article.
Although there is no globally pub-
lished data on the actual accept-
ance of fieldbus technology in the
oil and gas industry, according
to industry insiders the contribu-
tion of this sector is less than 10%
of overall fieldbus compliant field
device business across the globe.
The technology faced a number of
perceived challenges.
Licensors’ reservations
Process licensors providing basic
engineering design for refiner-
ies sometimes have strong res-
ervations about implementing
fieldbus technology. Some do
not specify the type of signal to
be used for field communication
and would prefer users or engi-
neering contractors to take the
decision. Others encourage its
use only for simple closed loops;
they are conservative and have
reservations about implementing
fast and complex loops like feed-
forward, split range and ratio con-
trol. The first layer of resistance,
then, comes from licensors, which
could be one of the key reasons for
non-proliferation of fieldbus tech-
nology in the sector.
PTQ Q3 2019 67
14/06/2019 10:11
 of the exchanger.
Control in field Scaling cost for It has
and been shown
maintain fieldbus thatsystems,
WHBs Elimination
Nathan (Nate) AofHatcher
segment is annoise and
Engineering
two-pass
Control inexchangers
field (CIF) introduces
was a prime a designed
it would with be a small
costlytubes
and and low
possibly rationalisation
Consultant of diagnostic
with OGT. He holds a infor- BS in
level
mover of complexity
of fieldbus in thetechnology.
cost anal- mass
unwise fluxes favour safetoheatconsider
proposition fluxes, mation engineering
chemical consumesfrom a lotthe of time.
University of
ysis that was
However, thisnot
keyexplored
feature has for been
this the lowestOften
fieldbus. tube the
wallindustry
temperatures,
strug- Kansas.
article.
greatly underutilised. Some instal- and
gles thewith lowest
legacy sulphidic
issues, as corro-tech- Email: Nathan.Hatcher@ogtrt.com
Importance of ‘diagnostics’ and
Another
lations usefactor not fully explored
a minuscule percent- sion
nologyrate.advances
ach of at these favourably
a much faster Clayton E Jones
‘prognostics’ joined 1Optimized Gas
functions
Treating, Inc as a Software Development
is theofpressure
age the totaldrop I/Oacross
for CIF theorfer-as aff ectsthan
pace the thelostindustry
profit opportunity
can adopt. In a large oil and gas establish-
Engineer in 2012. He holds a BS in chemical
rules,
closedalthough
loop I/O. theIt 1.5in
may tubebe notedsi e from
Perhaps downtime.
fieldbus isAdditionally,
one such exam- as ment such as a refinery, thousands
engineering from McNeese State University
appears
that the touse be ofthea best choice,
fieldbus not
instru- 5 of Part obstructive
ple. Common
Table 1 showed, issues small of instruments are spread across
and a MS in chemical engineering from the
only
mentfrom an economic
without standpoint
CIF functionality tubes
are: and high mass fluxes favour a wide geographical area. It is
University of New Mexico.
but also for hydrogen
downgrades its capability production
to that sulphur
• Water recovery
ingress into andthehydrogen
fieldbus impractical
Simon A Weilandto attend to each
is Technical indi-
Applications
and
of a sulphur recovery.
HART device. ThisTheis ferrules
not the make.
junction Considering
box causing all erroneous
these compet- sig- vidual instrument to fix
Engineer with Optimized Gas. He holds a BSa fault.
in
solethis si e for
reason tubethemay
growingcause high
unpop- ing
nalsfactors, a balance
and spurious mustfrom
alarms be struck
mul- Traditionally,
in chemical engineeringroutine scheduled
from the University of
enough
ularity of pressure
fieldbus; drop to outweigh
there are other oneelectronic
tiple that depends on the specifi
components. Ingressc maintenance has been de facto
Oklahoma.
the otherthat
issues benefi ts. creating hurdles
are plant’s
happenseconomic objectives
due to improper and its
closure of practice
Steven to address
M Fulk is Technical health,
Directormain-
with
rather than leading to the promised performance
the junction box requirements.
cover or unplugged tenance Gas
Optimized andTreating.
calibration
He holdsrelateda BS
benefits.
Conclusions opening of an ingress protection issues.
in However,
chemical engineeringthefromadventTexasofA&Mthe
The intelligent design of a cost (IP) rated junction
SulphurPro and ProTreatbox. are marks of HA T protocol
University and a PhD ininchemical
the mid-1 80s,
engineering
eff ective barriers
Cultural WHB is andquite
legacychalleng-
issues • Induced
Optimized noise due
Gas Treating, Inc. to improper leveraging
(2016) from themicroprocessor
University of Texas technol-
at Austin.
ing. There are that
A technology many, oftenaccepted
is well oppos- grounding, poor wiring practice ogy, paved the way for intelligent
Matt Bailey provides sales and marketing
ing factors support with Optimized Gas Treating, Inc.
in the US that
or go into not
Canada only face
might the and close proximity to rotating instruments. Diagnostic data gen-
He has over 10 years of industry experience
performance
inhibitions among and reliability of the
users in Africa, equipment such as motors, turbines
References erated by such instruments helps
in technical sales, creating safe engineered
exchanger,
the Middle butastthe or economics
the Far ast. as 1and
Karancompressors; improper
K, Mehrotra A K, Behie seg-
L A, Including to unearth the reasons for failures
radiative heat transfer and reaction quenching solutions for refineries, chemical plants and
well.
That Ifis aexactly
WHB is designed
the case with without
field- regation of electrical and fieldbus and enables condition based main-
engineering companies. He is a registered
in modeling a Claus plant waste heat boiler,
proper consideration
bus. efineries across of all
thethe fac-
world cables can be detrimental and may tenance.in So
Engineer instead
Training with ofthe the
Texasearlier
Board
Ind. Eng. Chem. Res., 33, 1994, 2651–2655.
tors, the design
are being operatedcouldbyfall flat infrom
people one 2cause
Martensdisruption of the
D H, Tube and tubesignal.
weld corrosion scheduled maintenance,
of Professional Engineers and holds an oper-
a BS
or more aspects.
different cultures. The In theSulphurPro
absence • A fieldbus system
and tube collapse, Brimstone-STS requires Sulphur
much ator
in couldengineering
chemical now schedule from Texas mainte-
A&M
simulator
of qualified correctly accounts
technicians and for main-all more commissioning
Symposium, Vail, CO, 2011. time than its nance by
University and anharnessing diagnostic
MBA from the University of
the important
tenance factors. to implement
engineers 3analogue/HART counterpart does.
http://igs.nigc.ir/STANDS/IPS/e-tp-760.PDF data without unnecessary exposure
Houston.

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68 www.eptq.com
PTQ Q3 2019 PTQ Q2 2019 85
www.eptq.com

Q2
q3 OGT.indd
manna.indd5 2 11/03/2019
14/06/2019 21:06
10:11
 to hazardous process conditions.
Hence, with instrument diagnos-
tics, one may unearth a dangerous,
undetected fault which otherwise
would have been ignored by a tech-
nician. The better the diagnostic
capability, the better the knowledge
of the process and the lower is the
uncertainty in measurement.
Instruments installed in a plant
measure variables like pressure,
flow, temperature, and so on. The
introduction of diagnostic capabil-
ities in field instruments not only
empower them to broadcast their
own health, but they also act as
prognostics for many other external
failures. They can predict problems
arising outside the instruments like
flow profile issues, corrosion, ero-
sion, contamination, issues with the
structural integrity of the primary
flow element, blocked impulse lines
and waxing. Diagnostics is what we
get from the sensors, whereas prog-
nostics convert that information
into meaningful condition based
maintenance metrics. Prognostics
are going to be the single most
attractive feature of IIoT and the
backbone of predictive analytics.
They give an indication of early
incipient fault as it progresses to
a more severe state but before an
actual failure event. However, this
is easier said than done.
With the passage of time, the
level of intelligence in fieldbus
devices has grown and today we
have a tsunami of diagnostic data
from field devices. This sounds
exhilarating but the reality is far
from utopian. The enormous num-
ber of diagnostic suites and their
management is becoming coun-
ter-productive. There is a tussle
between ‘perceived ease of use’
and ‘perceived usefulness’. There
are several probable reasons for the
unpopularity of advanced diagnos-
tic suites, as follows.
Diagnostics are well understood
by experts, but technicians/engi-
neers/operations groups may not
be able to utilise this data effectively
either due to lack of knowhow or
time constraints in analysing the
diagnostic data. Hence, the digi-
tal intelligence of fieldbus remains
largely unutilised in spite of its
powerful features.
www.eptq.com
q3 manna.indd 3
Current standards like ISO, AGA,
API and ISA do not mandate the
requirement of diagnostics in field
instruments, which has resulted
in lack of standardisation of diag-
nostic suites. So diagnostic suites
and their interfaces differ from one
instrument type to another and
from manufacturer to manufacturer.
Every OEM tries to project its diag-
nostic tool as unique and better than
those of its competitors.
A fieldbus device is essentially
a reservoir of data. One must be
aware of how to interpret and trans-
form the sea of information gener-
ated by the device into something
useful and of value to the end user.
Managing data from smart devices
is the key to the success of fieldbus
technology. Most organisations con-
sider this data as secondary infor-
mation and allocate few resources
and little time to analyse it. Many of
Diagnostics are
well understood
by experts, but
technicians/
engineers/operations
groups may not be
able to utilise this
data effectively
them lack a proper standard operat-
ing procedure (SOP) to handle field-
bus data. Lack of data management
and analysis creates more problems
than providing solutions.
While advanced diagnostics is
one of the key driving factors for
fieldbus technology, it is inter-
esting to note that presently both
fieldbus and HA T comply with
the NAMU standard N -107 rec-
ommendations. N -107 provides a
legitimate guideline for managing
and presenting data from intelli-
gent field devices using a standard
format. It is but natural to question
why use fieldbus in lieu of HA T
Enabling every possible diagnos-
tic capability of a fieldbus transmit-
ter implies inviting every possible
alarm in DCS under an instrument
asset management system (IAMS).
Technicians and operators are bur-
dened paying attention to every
possible alarm and in acting on one
that could impact plant operation.
Often the source of the alarm is a
matter of contention between the
DCS supplier and field instrument
supplier.
Diagnostic coverage is one of the
important requirements of a safety
instrumented system (SIS) based
on which safe failure fraction (SFF)
is determined. In practice, a SIS sys-
tem must be more reliable than a
basic process control system (BPCS).
SIS relies on HA T instruments and
a fieldbus system is yet to be imple-
mented for use in SIS. A school of
thought is of the opinion that if
HA T transmitters could be used
for SIS, they could be the de facto
standard for BPCS as well
Additionally, a large section of
field instruments including capital
intensive ones like analysers and
FMCW radar require high power
for their operation, which is not
supported by a fieldbus protocol.
A SIS loop has to be highly deter-
ministic and digital communication
is not allowed. Many of the major
package vendors for refineries are
not well versed in fieldbus technol-
ogy, which occludes the prolifer-
ation of fieldbus devices in major
sections of the plant.
Complexity in engineering
ngineering a fieldbus system is not
as straightforward as it is perceived
to be. Negotiating different parame-
ters like types of loops, loop length,
scan time, process response time
and so on requires more engaging
analysis than a 4-20 mA/HA T
signal, which uses uncomplicated
‘point to point’ connectivity. Getting
DD files in their latest revision and
interoperability test are formida-
ble tasks for a fieldbus system,
particularly for large grassroots
refinery projects. If these aspects are
not addressed correctly, it would be
a harrowing experience to sort out
the issues during commissioning.
Maximum number of instruments:
theory vs practice
Theoretically, 32 devices can be
connected in a fieldbus segment.
PTQ Q3 2019 69
14/06/2019 10:11
 However, for all practical pur-
poses no more than eight to 10
devices can populate a segment. It
all depends on the equipment lay-
out, loop execution time, macro-
cycle and other entity parameters.
In most cases, only two close loops
(with control valves) can be accom-
modated in a segment. In general,
for pressure and flow control loops
the maximum number of devices
is restricted to three with only one
control valve. For slower level and
temperature loops, nine devices
(eight transmitters and one control
valve) or fewer can be connected.
These limitations increase the num-
ber of costly fieldbus junction boxes
and trunks. One of the key driv-
ers of fieldbus was to reduce the
cabling cost. In reality, the cost of
installation of fieldbus could be
much higher due to additional elec-
tronics in the loop and the higher
cost of fieldbus cables compared to
standard instrumentation cables.
A fieldbus loop contains additional
items like field-barrier, surge pro-
tection devices, advanced diagnos-
tics modules, a fieldbus compatible
power supply, terminators and a
specially designed backplane.
According to Fieldbus Foundation
guideline AG181:
• For 250 ms macrocycle, a maxi-
mum of three devices can be config-
ured on a segment with at most one
control valve or hand valve.
• For 500 ms macrocycle, a maxi-
mum of six devices can be config-
ured on a segment that may include
at most two control valves.
• For 875 and 1000 ms macrocycles,
a maximum of 12 devices is allowed.
These guidelines place restrictions
on the number of devices that can
be connected in a segment, which is
much less than the theoretical limit
of 32 instruments.
Lower limit of macrocycle
Information is transmitted on a
fieldbus at fixed intervals called
macrocycles. A macrocycle is a sin-
gle iteration of a schedule within a
device. The macrocycle time of a
fieldbus segment is defined as the
sum of the scheduled execution
time of the function blocks and the
unscheduled spare time used for
all the devices within that segment.
70 PTQ Q3 2019
q3 manna.indd 4
Fieldbus does not support macrocy-
cles shorter than 250 ms and hence
cannot be used for fast control loops
that require a response time of 200
ms or less.
From the above, it is clear that
DCS vendors and engineering con-
sultants have to face various con-
straints and spend considerable
manhours designing the FF seg-
ments while such complexity never
arises in designing a 4-20 mA/
HART system.
Fieldbus safety instrumented
function (FF-SIF) – abrupt
dissolution
The FF-SIF concept was floated by
some end users and approved by
the Fieldbus Foundation in 2002. As
per the FF website, “Saudi Aramco,
a key global oil & gas producer, has
been at the forefront to spur devel-
opment of Fieldbus Foundation
safety products”. In 2005, TÜV
granted type approval for the
Fieldbus Foundation’s SIS protocol
specifications. Since the release of
various technical specifications by
Foundation Fieldbus in 2012, there
have been no further updates on the
status of FF-SIF. The concern is that
progress has been stalled and ven-
dors are not investing in creating
solutions. ssentially, FF-SIS looks
to be a closed chapter for now.
Management of interfaces in a
heterogeneous control system
A plant control system is usually
heterogeneous in nature, compris-
ing multi-O M platforms. With
digital technology, management
of ‘n’ number of devices from mul-
tiple manufacturers with diverse
interfaces, digital structures and
engineering tools is a daunting task
for users. very user looks for a
seamless and ‘easy to use’ system.
Understanding the nitty-gritty of
communication protocols and their
interfaces is generally beyond their
interest. Management of DD /
DD files and FDT/DTM tools is still
a big task for the user and a host
of system suppliers. Of late, there
has been an effort to harmonise all
interfaces into a common user inter-
face through a field device interface
(FDI) which promises to replace tra-
ditional DD /DD formats, so the
user has to put up with the pain of
backward compatibility.
Should fieldbus be discarded
or should it brace alternative
technology?
The general wisdom that advance-
ment in technology brings multiple
benefits to industry might not hold
true in all cases. The same applies
to fieldbus technology. very tech-
nology has its highs and lows. It is
incorrect to assume that fieldbus
has completely disrupted the exist-
ing 4-20 mA/HART technology.
Automation vendors have invested
fortunes in developing fieldbus
technology, so it is unlikely that it
will be discarded easily. Fieldbus
might be good choice for remote
installations such as integrated off-
shore platforms, FPSOs, compact
layout package equipment and
remote wellhead platforms where
there are serious space constraints
for cabling. Industries beyond the
oil and gas sector, such as pharma-
ceutical, non-hazardous plants, fac-
tory automation and assembly lines
can derive benefit from fieldbus
technology.
Considering the fact that refin-
eries are built on the integration of
heterogeneous platforms, we cannot
replace any technology abruptly.
With the introduction of various
new technologies in future, the
industry will have to put up with a
new ecosystem of coexistence.
In search of an Industrial
‘God Protocol’
The Blockchain technology on
which today’s bitcoin digital cur-
rency has been conceived is based
on the concept developed by Nick
Szabo in 1997. He coined the term
‘God Protocol’ and stated: “Imagine
the ideal protocol. It would have the
most trustworthy third party imag-
inable a deity who is on every-
body’s side. All the parties would
send their inputs to God. God
would reliably determine the results
and return the outputs. God being
the ultimate in confessional discre-
tion, no party would learn anything
more about the other parties’ inputs
than they could learn from their
own inputs and the outputs.”
Process control systems are hetero-
www.eptq.com
14/06/2019 10:11
 geneous systems with a multitude of
protocols such as HART, Foundation
Fieldbus, Profibus, Modbus, Control
Net, Ethernet/IP, and so on, all com-
peting with each other. The end user
is faced with the daunting task of
maintaining separate hardware and
software for each of these protocols.
While there is an attempt to harmo-
nise all inputs to a common third
party interface, FDI, why can indus-
trial leaders not promote a single
‘God Protocol’ that can get rid of all
interface issues? This sounds good,
but appears more suitable as the plot
for a fiction novel rather than being
impending reality.
What needs to be done to harness
the full potential of fieldbus
technology?
Taking into account the above nar-
rative, it is clear that even with
mature fieldbus technology and
advanced diagnostic capabilities,
the fieldbus system is unpopular
with real users. To make fieldbus
system diagnostics more relevant,
we need to direct our efforts to
achieve the following:
Level Measurement
■ Visual Level Indicators VLI
■ Tank Level Instruments TLI
■ Meets the design standards of the oil & gas,
petrochemical, hydrocarbon and LPG/LNG industries
■ Pressures from vacuum to 500 bar
■ Densities down to 0,27 g/cm³
■ No maintenance (fit and forget)
■ More than 50 years of experience
■ Certified according CE, EAC, Pattern Approval,
ABS, BV, DNV-GL, LR, RINA, RMRS ...
Oil & Gas Industry
Petrochemical Industry
Chemical & Pharmaceutical Industry
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q3 manna.indd 5
• Focus on data management and
allocation of resources
• Impart training to technicians
and operating staff
• Establish a diagnostic manage-
ment system or standard operating
procedure for the entire complex to
manage large volumes of data
• Assign a dedicated team – a ‘data
governance cell’ for managing data
effectively and to interface with
DCS suppliers to ‘keep it simple’.
Future of protocols
In the modern era of information
technology, one cannot just ignore
digital technology. Therefore,
industry leaders must collectively
strive to make fieldbus systems
user friendly and incorporate fea-
tures that offer convenience in
work and life. Millions of dollars
have been invested in the R&D of
fieldbus products and if the current
trend does not reverse or improve,
vendors will cease to invest further.
Unlike fieldbus, the Modbus pro-
tocol continues to be popular for
industrial communications, largely
for system to system communica-
tion as well as providing a field
instrument protocol. With the pen-
etration of IP technology, Ethernet/
IP over two wire will eventually
be the preferred choice for field
instrument communications pro-
vided industry bodies and vendors
join and take part in its deploy-
ment, otherwise 4-20 mA/HART
will continue to dominate in the
coming years.
Reference
1 Cousins T, Steven R, Setting the STANDARD
– Integrating Meter Diagnostics Into Flow
Metering Standards, NFOGM, 2019.
Meghdut Manna is the Technical Advisor to
a refining company with specialisation in
automation and digital technology. With 21
years’ experience serving the complete value-
chain of the oil and gas industry, upstream,
midstream and downstream sectors, he
manages digital refining solutions by deploying
modern integrated control and safety systems
coupled with the concepts of the Internet
of Things, safety instrumented systems
and manufacturing execution systems. He
holds a MBA in oil and gas and a BTech in
instrumentation and electronics. The views
expressed in this article are the personal views
of the author.
sit us
Please vi te:
si
at our web .ch
www.wek
a-ag
WEKA AG · Schürlistrasse 8
CH-8344 Bäretswil · Switzerland
Phone +41 43 833 43 43
Fax +41 43 833 43 49
info@weka-ag.ch · www.weka-ag.ch
PTQ Q3 2019 71
14/06/2019 10:11
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 Racing to meet IMO 2020 regulations
Looming new rules for low sulphur fuel oil leave refiners with the problem of
increased output of lower value material
VICTOR SCALCO and MAGGIE VIDAL
General Atomics Electromagnetic Systems
W
hen Kitack Lim won his
second, four-year term as
Secretary General of the
International Maritime Organization
(IMO) in November 2018, it solid-
ified the organisation’s aggressive
2020 deadline for a global <0.5%
sulphur limit on fuel oil used on
board ships.5 This reduced sulphur
requirement, commonly known as
IMO 2020, squeezes the oil and gas
industry, confounding the medium
and small si e refineries that strug-
gle to produce low sulphur fuel oil
(LSFO) and racking the nerves of
maritime freight shippers facing vol-
atile fuel pricing.
While the industry has come to
terms with the need for change in
order to support the health of the
oceans, keeping up with this type of
growth requires agility and flexibil-
ity, both on the part of the refineries
and the shippers.
So what is the problem?
At first blush, the IMO 2020 guide-
lines are in line with the type of
changes the oil and gas industry
has faced for years. IMO 2020 is cer-
tainly not the first time new regu-
lations have shaken the oil and gas
industry, a community used to year-
over-year changes in requirements
from the United Nations, IMO, and
other far-reaching organisations. In
1996, ISO 8217 MARPOL standards
enforced a 5% sulphur limit and
a maximum of catalyst fines at 80
ppm, and in 2012, MARPOL stand-
ards reduced those limits to 3.5%
sulphur and maximum catalyst fines
at <60 ppm.
The oil and gas industry has
proven resilient over the course of
these changes, innovating quickly
www.eptq.com
q3 ga.indd 1
Present 3.5% sulphur
HSFO LSFO
Future
0.5% sulphur M/M
HSFO
Figure 1 The changing criteria for LSFO
promote production of HFSO
to meet these global limits. The dif-
ference this time is the extent of the
change. While previous sulphur
limits were already significant,
IMO 2020 (MA PO Annex VI)
pushes the industry’s agility fur-
ther: an overall 3% reduction from
the current sulphur limit, versus a
2% reduction in previous regulation
shifts, as well as a reduction in max-
imum catalyst fines to 50 ppm from
<60 ppm.
Who is affected?
For some large refineries, SFO
that meets the IMO’s new limits is
already a reality because of exist-
ing Emission Control Areas (ECAs)
requirements with 0.1% sulphur
limits. For others, the limits are
within reach with minor invest-
ments/modifications. For small and
medium si e refineries that need to
modify their production methods
– and the shippers that are reliant
on the success of these refineries to
ensure adequate supply of compli-
ant fuel – the shift to the IMO 2020
limits is more complicated.
Because IMO 2020 effectively
changes the criteria for qualifying
as LSFO or high sulphur fuel oil
(HSFO) from 3.5% sulphur to 0.5%,
what is currently considered LSFO
may not qualify in the future, mak-
ing the current LSFO production
insu cient for market demand,
and saturating the market with
HSFO. The global supply of HSFO
is approximately 3.3 million b/d,
with a maximum 3.5 sulphur and
less than 100ppm catalyst fines (see
Figure 1).
In response to this paradigm shift
in definition of SFO/HSFO, refin-
eries will likely do one or more of
the following:
• Find ways (capital investments/
new technology/methods) to reduce
the amount of sulphur and particu-
lates in fuel oil in order to keep up
with the LSFO demand.
• Wait for shippers to bring in addi-
tional shipboard scrubbers for HSFO
(thereby putting the onus of sulphur
reduction on the shippers).
• Find other markets for HSFO.
• Reduce the overall fuel oil supply.
To succeed in the dramatic switch
to SFO, refiners will want to cut
their HSFO as much as possible to
offset the anticipated drop in value.
For refiners unable to upgrade in
time to meet the expected demand,
a shift in refinery low sulphur crude
processing will be the next step in
meeting production without reduc-
ing production from the crude dis-
tillation unit (CDU). This will alter
refineries’ bottom lines by causing
them to consider the extra cost of
upfront purchases of low sulphur
crude. Most market research sug-
gests that >70% of the industry will
make plans to reduce overall fuel oil
supply due to IMO 2020 regulation
tightening, or ultimately find other
markets for HSFO.
efiners will have little incen-
PTQ Q3 2019 73
15/06/2019 07:34
 tive to produce HSFO after the new
regulations are enforced. A small
demand will remain from shipping
companies installing scrubbers,
but tight regulations on backwash
scrubbers and even vessels contain-
ing HSFO can become a concern for
shipping companies relying solely
on exhaust scrubbers. The increase
in scrubber-equipped ships and the
increased demand for power gener-
ation will play a large role in balanc-
ing the call for HSFO in the market.
HFSO: catalyst for change?
One of the options available to refin-
eries is exploiting residue fuel from
the bottom of the CDU. To extract
more value from this stream, it is
processed using fluidised catalytic
cracking (FCC), hydrocracking, or
cokers to produce products that are
more valuable (though it is associ-
ated with a higher capital expense).
FCC processing, one of the most
versatile and profitable upgrading
opportunities in a refinery, requires
the removal of catalyst fines from
the slurry oil to produce a higher
quality fuel.
Slurry oil (SO), an FCC product,
is the lowest value liquid product
from an FCC unit or residual fluid
catalytic cracking unit ( FCC).
Worldwide, FCC SO production is
estimated to be about 750 000 b/d.
To increase the value of this stream,
refineries need to remove the cat-
alyst solids to low levels to make it
usable for fuel oil blending, carbon
black and needle coke feedstock,
and upgrading to lighter fuels.
Due to environmental regulations
that prevent dumping of SO, simply
getting rid of slurry is not an option.
Moreover, SO’s aromatic, dense,
high boiling, and viscous nature, as
well as the amount of FCC catalyst
particles found in the oil, can also
cause significant erosion to refinery
equipment. Moreover, asphaltenes,
a molecular substance found in
crude oils, increases the viscosity of
SO and frequently causes produc-
tion problems (fouling or coking)
when exposed to heat, particularly
if the SO contains other metals. So
how do refineries exploit this low
value product, sidestep penalties for
illegal dumping, and avoid damage
to their equipment
74 PTQ Q3 2019
q3 ga.indd 2
Catalyst removal methods
Catalyst fines are very small ( 25
micron) particles from the catalytic
cracking process. emoval of these
particles from fuel oil is compli-
cated and, in most cases, even the
use of settling tanks does not allow
the refiner to meet the specifications
required for marine fuel.
efiners with successful fines
separation have found the best
technologies available are the
di-electrostatic separator for clarified
SO and some mechanical removal
methods, though these methods are
generally burdened with high main-
tenance costs and frequent blockage
from asphaltenes or para ns.
Mechanical removal methods
(holding tanks, filtration, liquid
suspension)
Historically, refiners have primar-
ily processed SO using a combi-
nation of heated holding tanks
and extended residence times.
ess frequently used mechanical
approaches include filtration, hydro-
cyclones, and centrifugation.
Holding/sedimentation tanks
Holding tanks process SO through a
heating and settling process where,
after an extended settling period, the
tank’s heat facilitates the separation
of catalysts from the oil, resulting
in usable clarified slurry oil (CSO).
While this process is effective in sep-
arating the catalysts from the CSO,
there are drawbacks:
• Hazardous waste: catalysts sitting
at the bottom of the tank create a
ha ardous sludge that requires spe-
cial treatment for its disposal. An
estimated 1- 4 million is expected
per cleaning.
• Costly settling process: this pro-
cess can take up to several months.
Chemical settling aids are esti-
mated to be in the order of -20
per barrel treated4
• Variances in results: the tank
design, characteristics of the SO,
temperature of the tank, and use of
settling aids can all affect the result-
ing CSO’s quality/characteristics.
Membrane/mechanical filters
First used in 1 0, most mechanical
filtration uses tubular, porous-metal
elements to collect solids (cata-
lysts) on the inside of the elements
at around 600°F (315°C) without
affecting the rest of the oil. Other
filters use porous, sintered woven-
wire mesh metal filters (400- 50°F,
200-340°C) or a 2-5 micron woven
wire filter element (350°F, 175°C),
using CO as a backwash, and claim
85- 5 solids removal from the feed
slurry. Given the solid removal rate
for these types of filters, mechanical
filtration is a popular choice with
many refineries.
One of the main issues with
mechanical filtration is that, particu-
larly with FCC refineries, filtration
elements clog with asphaltenes and
waxes or erode, making the unit
inoperable.
Liquid suspension/slurry settlers
There are two types of liquid sus-
pension removal methods for SO:
hydrocyclones and centrifugation.
These methods are being phased out
of the oil and gas industry and are
generally viewed as ha ards.
Hydrocyclones are conically
shaped to create a vortex that pulls
catalyst particles out of the SO, fil-
tering larger particles through the
bottom of the unit and smaller par-
ticulars through the top.7 On the
other hand, centrifugation uses
a bowl-shaped device to spin the
SO, pulling the catalysts out of the
oil where they settle on the edges
of the bowl. While these methods
of liquid suspension are su cient
and low cost for some refineries,
they are not able to achieve the sol-
ids removal levels of the other
approaches ( 55 ).
Non-mechanical removal
approaches (electrostatic)
Unlike mechanical catalyst removal
approaches, electrostatic separa-
tion (see Figure 2) uses an electri-
cal charge to attract SO catalysts so
that they cling to glass beads during
a separation cycle. Because of the
strength of the electrostatic pull of
the charged beads, this type of filtra-
tion can remove up to 7 of cata-
lysts present in SO. Once the beads
have collected as much catalyst as
their surface can accommodate, the
back flush process (typically done
with raw feed, rather than pric-
ier CO or HCO, and without gas
www.eptq.com
15/06/2019 07:34
air liquide.indd 1 13/06/2019 10:04

Figure 2 Electrostatic separator
assistance) rinses the catalyst from
the beads. A final cycle, called the
purge cycle, then removes the back
flush and prepares the beads for
their next separation cycle.
In use for over 30 years, refiner-
ies champion electrostatic separa-
tors as unaffected by asphaltenes
or other tars, an issue that plagues
all mechanical removal methods.
Given the electrostatic separator’s
relatively small footprint (10m x
5m x 4m for a high capacity unit),
low maintenance cost, and resil-
ience against fouling, refineries will
increasingly favour electrostatic
separation.
Factors for consideration
Because the e cacy of catalyst
removal methods is highly contin-
gent on the composition of the SO
and the planned application for the
CSO, there is no single solution for
refineries looking to exploit this
FCC product. SO composition from
FCC and RFCC is a function of the
severity of the operation and is gen-
erally inversely proportional to such
factors as catalyst activity, tempera-
ture, catalyst to oil ratio, and so on,
and is directly proportional to the
nitrogen, sulphur, and asphaltene
(or alternatively vacuum bottoms)
content of the FCC feed.
Asphaltenes
Because refineries introduce
increasing levels of resid (and
therefore asphaltenes and het-
eroatoms) into the FCC, SO yields
76 PTQ Q3 2019
q3 ga.indd 3
will increase and the quality of the
SO will decrease.3 As a result, SO
asphaltenes levels are a growing
factor in deciding which technol-
ogy is best for removing particulate
solids.
SO quality
SO quality is a function of such var-
iables as the properties of the FCC
feed, severity of operation, type of
catalyst, operating conditions in the
FCC unit, and so on. The compo-
sition of the SO can determine the
e cacy of catalyst removal meth-
ods; oil testing can help refineries
and catalyst removal vendors assess
the best catalyst removal option for
SO quality.
Particle size distribution ranges
from a variety of SOs are shown
in Table 1. Note that for these SOs,
over 0 of the particles range in
si e from 0-25 microns in diameter.
Intended application (internal and
external to the refinery)
Most importantly, the intended
ultimate use for the SO determines
which processing method is best fit.
SO particle size distribution
Catalyst sizes
SO particle size distribution
Particle diameter (microns) % in range
0-5 30-60
5-15 30-55
15-25 2-12
25+ 1-5
Table 1
ach end use requires a different set
of specifications for the SO.
Market opportunities (external
to refinery)
1. Marine fuel (less than 50 ppm)
• Worldwide consumption of 3.
million b/d
• IMO 2020 egulations have
pushed the ppm requirement for
marine fuel from 50-150 to no more
than 50 ppm, in addition to a sul-
phur limit of 0.5 .
2. Needle coke feedstock (25-100
ppm)
• Worldwide consumption of
20 000 b/d (very limited market)
• Type of coke; used in AF steel.
3. Carbon black feedstock (50-500
ppm)
• Worldwide consumption of
130 000 b/d
• Used in automobile tyres, belts,
hoses, and pigments1
• The required density for carbon
black feedstock is high and special
attention must be given to operating
the FCC fractionator at high enough
temperature to obtain the desired
density1
• Some refiners do not have the
ability to get the required SO den-
sity for carbon black applications.
Internal refinery uses (50-150 ppm)
1. ecycle to extinction in FCC unit
• Increases coke make, which
increases regenerator temperatures
• Can adversely affect selectivity to
prime products
• Does not require low catalyst lev-
els, unless FCC injectors erode or
heat exchange equipment fouls.
2. efinery fuel
• Use of SO as fuel in the refinery
is practised routinely and is a good
option as long as applications have
been well thought out and equip-
ment to be used critically examined
for processing a solids containing
stream.
• Such equipment as piping,
burner tips, no les, and heat
exchangers need to be evaluated for
long term viability when charging
solids containing streams
• To minimise downstream pro-
cessing di culties, removal of the
contained catalyst to keep solids
diluted below recommended con-
centration levels.
www.eptq.com
15/06/2019 07:34
 the presence of a hydrocarbon liquid
Comparing liquefaction cycles for mid to large scale offshore FLNG projects8
3. Fuel oil blending stock the opportunity for answering the phasePetroleum
Guide, in the cycle.
Product & Gas Liquids: US
• Accounts for about 80% of marine industry’s call for fuel that The SMR
Caribbean and Latincycles
America, are Jan 2012. normally
production SMR meets IMO DMR 2020 Nitrogenrequirements
expander is 3appropriate
Silverman L D, options for
Winkler smallJ A,
S, Tiethof to
Train capacity, million t/y 1-2 >2 ≤0.8
• SO as efficiency
Thermal cutter stock for heavy fuel
Medium more lucrative.
High This may Lowmean the mid-scaleA, offshore
Witoshkin Matrix effects floating lique-
in catalytic
cracking, presented at the1986 NPRA Annual
oil Equipment
blendingcount Low oil and Medium
gas industry will see expan-
Medium faction systems due to their lower
Meeting, 23-25 Mar 1986, Los Angeles,
• Trace
Storage ofmetals deposited onMedium
liquid hydrocarbon FCC sions inMedium
these refineriesNone to include equipment count, resulting in a
California.
catalysts such as nickel, vanadium,
refrigerants the right catalyst and sulphur 4smaller
Minyardfootprint
W F, Woodson and Tlighter
S, Upgrade weight,
FCC
Reliability High High High
and sodium,
Capital or adhering to catalyst
investment Low removal equipment, High
Medium and other thereby lowering associated
Slurry Oil with Chemical Settling Aids, World capi-
particles and FCC catalysts them-
Offshore suitability High adjustmentsHigh to cut theirHigh HSFO pro- tal costs.
Refining, The 1999.
Nov/Dec DM cycles, offering
selves, which contain aluminum
Availability High duction High
as much as possible Medium to off- 5higher e ciency, are optimal solu-
www.platts.com/IM.Platts.Content/
and silicon
Motion impactsas major components Medium set theMedium
anticipated drop Lowin value.
tions for single, larger train
InsightAnalysis/IndustrySolution F NG
Papers/SR-
can combine with other elements to For those refineries bracing for applications. arger trains can offer
IMO-2020-Global-sulphur-cap-102016.pdf
form
Table high
2 melting point compounds facility upgrades to increase their 6economies
w w w. hy d rof
o cscale
a r b o n(thereby
p r o c e s s ireducing
ng.com/
that are corrosive to valve seats and SO to CSO conversion capabilities capital expenditure) and a reduced
conference-news/2019/03/afpm-19-imo-
exhaust
including valvesthe inproduction
diesel engines.
capacity, and meetbutIMO
options, it canrequirements,
be used for smallthe footprint, but less operational redun-
2020-and-beyond
7 Zhi-shan Bai, Hua-lin Wang, Shan-Tung Tu,
thermal e ciency, equipment count, electrostatic
scale F NG separator
productionmay be the
because of dancy and flexibility. In this case,
2009, Removal of catalyst particles from oil
Itrefrigerant
is all settled type,then reliability, specific best way to meet
its simplicity and easethe ofaggressive
sourcing the choices around equipment will
slurry by hydrocyclone, Separation Science
Despite
capital the impending
investment, IMO 2020
simplicity of catalyst ppm limits refrigerant
the non-flammable anticipatedfromin be also
and limited44:9,
Technology, with2067-2077,
longer deliv- DOI:
regulations,
operations, offshore not all suitability,
refineries avail-
will January 2020. Asgenerators.
onboard nitrogen with previous 10.1080/01496390902880149. potentially
ery periods, which could
make
abilitydramatic
and impact shiftsofinvessel
their motion
opera- growth in the face capacities
As production of increasingly
move affect economies of scale.
tions.
must Because
also be SO and CSO of
considered. vari-2
Table perilous
into the climate
mid-scale change
and andlargeevolv-
scale
Victor Scalco is Global Commercial Strategic
ous qualities
compares SMand types, and
, DM can be used
nitrogen ing environmental
ranges, needs, refiner-
there is a preference towards Outstanding liquefaction process
Business Development Manager-Gulftronic
for purposes
expander cycles, other
taking than
into marine
consid- ies
MRand shippers
cycles because willthey
find are
creative
more Selecting the appropriate liquefac-
Electrostatic Separators with General Atomics
fuel,
erationsmallthese refineries canmid
factors, for either rely
to large solutions
e cient to than staynitrogen
competitive and
expander tion process isSystems
Electromagnetic a key Group
focus (GAEMS),
for off-
on shippers
scale taking care of the IMO
F NG applications. address
cycles andglobalhavehealth
lowerneeds.
unit capital working on process design and developmentala
shore F NG projects. ecently,
requirements
As can been or funnel
from Tabletheir 2,
prod-the and operating costs at larger NG few processes
downstream have for
solutions beenhydrocarbon
proposed
ucts
nitrogen through
expander the cycle
other applica-
offers lower capacities. However, M cycles may
References for offshore
recovery, applications,
including developmentbutof none
new
tions
e ciencyfor SOthan that have
otherlesstechnology
rigorous 1beGuercio
affected byProducing,
V J, US sea motions due
exporting to
more have yet
filtration and been put systems.
separation into operation.
He holds a9
requirements. slurry oil, Oil & Gas Journal, 4 Oct 2010. MA degree from the University of San Diego,
For medium and large refineries, 2 Platts, Methodology and Specifications California.

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110 PTQ Q4 2018 www.eptq.com

www.eptq.com PTQ Q3 2019 77

q4 mokhatab.indd 4 15/09/2018 06:42

q3 ga.indd 4 15/06/2019 07:34

sionpec.indd 1 13/06/2019 10:30
 Process schemes to solve the
fuels/chemicals imbalance
Refiners who think only about production of transportation fuels need
to think differently

JOHN J MURPHY and CLYDE F PAYN

The Catalyst Group

T
here has been a long history
in the incremental develop- 10
ments (decades in fact) lead- 9
ing to what can be described as 8
Chemicals
5.6% CAGR
‘oil-to-chemicals (OtC)’ today. For a 7
long period of time, building larger
6
and larger world scale and more
complex refineries and steam crack- 5
ing plants was the economic solu- 4 Fuels
tion best suited to the fundamentals 2.1% CAGR
Growth, %

3
of medium to heavy crude oil con- 2
version, and in some countries this 1
will still be the case. However, we
0
have now entered an era where
e

ne

ne

ne
se

the socioeconomic and supply/

en

in

en

en
te

le

le
ie
ol
s

nz

yl
hy

xy
Bu
D
ro

as

op
demand trends are shifting, and the
Be

ra
Et
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traditional business models of seg-
regated refining vs chemicals pro-
duction no longer hold true. In the
future, we will see fewer naphtha
steam crackers, more petrochemical
fluid catalytic crackers (FCC) and
more swing olefin/benzene, tolu-
ene and xylene (BTX) units being
adopted. The molecular science and
process technology needed to do
this is here today.
With the ‘shale revolution’, which
started in the US and is spreading
worldwide, lighter feedstocks will
continue to be readily available, so
on-purpose molecular production
– for instance, methane to ethylene
(not yet commercial), ethane to eth-
ylene, propane to propylene, and
butane to butylenes – represents
a chemical course that is already
firmly entrenched. To remain or
be competitive over the next 5-10
years, both integrated and sole
chemical producers will need to
adopt these same models if they
intend international participation
through import/export of products.
The movement towards the
production of chemicals and pet-
Figure 1 Growth for oil derived fuels (diesel, gasoline) vs petrochemicals/chemicals
including olefins and BTX
rochemicals such as olefins and
aromatics directly from crude oil,
as opposed to via thermal crack-
ing of naphtha/ethane (for olefins)
and via traditional refining reform-
The traditional
business models
of segregated
refining vs chemicals
production no longer
hold true
ing (for aromatics), is being driven
by numerous factors. The most
important is the imbalance between
demand for oil derived liquid fuels
(diesel, gasoline) and the more
rapid growth in markets for petro-
chemicals such as olefins (ethylene,
propylene), aromatics (BTX), and
Pa
specialty intermediate streams like
C4s and higher olefins. The imbal-
ance (see Figure 1) has made the
idea of using crude as a direct feed-
stock more appealing for integrated
producers of fuels and chemicals as
well as direct chemical companies.
The technologies for these novel
and important chemical/petro-
chemical production processes are
being pursued by industry lead-
ers such as ExxonMobil and Saudi
Aramco/SABIC, but are also affect-
ing the competitiveness of peer
participants – all chemical produc-
ers, as well as EPCs, process licen-
sors, and technology developers.
Added to this, traditional routes
are potentially being made uncom-
petitive, such as naphtha cracking,
and there is strong, widespread
and urgent interest in approaches
to, and justification for, these
opportunities/threats.
Depending on the crude oil feed-
stock, the avoidance of refinery

www.eptq.com PTQ Q3 2019 79

catalyst group.indd 1 14/06/2019 10:23

 fuels production and using specialty
hydrocracking processes to naphtha
or via FCC to olefins or BT could
provide lower costs than participat-
ing in the current/historical refin-
ery value chain. As an example, CP
Chem’s Aromax can provide BT
from olefins, and the resid FCC
unit could be more inexpensively
tailored towards C2= and C3= ole-
fins production, rather than the
more costly and less selective steam
cracking of naphtha. Of particu-
lar interest to chemical producers
is how from the end product (such
as BT ) you back integrate into the
best configuration for costs based on
crude oil type, and are there attrac-
tive margins to consider for these
new configurations/combinations.
Oil-to-chemicals: advanced
approaches
There are noteworthy recent cata-
lyst and process advances relevant
to olefins and BT chemical prod-
ucts that avoid the upfront invest-
ment in catalytic distillation units
(CDU) and vacuum distillation
units (VDU) and other parts of the
refinery while maximising BT and
olefin yields (primarily C3 and
C4 ) beyond typical refinery eco-
nomics and normal/known process
configurations that have historically
been optimised for fuels production.
There are many different process
approaches/alternatives that can be
pursued together or individually to
improve an oil-to-chemicals strat-
egy. As demonstrated, xxonMobil’s
steam cracker modification(s) is
one of them; the approach by Saudi
Aramco/SABIC may be, too. Others,
such as petrochemical FCC (UOP-
PetroFCC or Axens-HSFCC with
metathesis), are also good exam-
ples. Also worth highlighting are
swing unit strategies such as KB /
SK-ACO, Gasolfin, Omega, and
Chiyoda. A directional step-out idea
involves the utilisation of radial
flow reactors.
The major conclusions and take-
aways include:
• There have been advances in pet-
rochemical FCC, as well as fixed
bed/swing reactor olefin processes,
plus BT reactor technologies. If
the objective is to maximise olefin
BT production, then taking a light,
80 PTQ Q3 2019
catalyst group.indd 2
tight oil ( TO) approach based on
these high para n compositions is
scientifically and margin justified.
• With certain feedstocks, for
instance with properties including
35 API, 50 ppm sulphur, and 30
ppm metals, you do not need to add
hydrogen (or should not add hydro-
gen) if the product goals are either
olefin or BT . Secondly, pyrolysis
approaches should be ruled out
because they are ine cient and
energy intensive. They produce too
much coke and too many refractory
products to be useful.
• In new process configuration
designs, engineers should be target-
ing combination schemes that yield
80 wt olefins BT with only 20
wt by-products (such as fuels,
PGs) and be aiming for an ISB
OSB capex in the 400- 00 million
range, without post-treatment steps.
• FCC olefins production has
There are many
different process
approaches/
alternatives that can
be pursued together
or individually to
improve an oil-to-
chemicals strategy
already gone through a steady
progression of higher olefin pro-
duction steps. This has led to the
commercialisation of petrochem-
ical/chemical FCC units such as
PetroFCC-UOP, HSFCC-Aramco,
2P-Total, Axens, TechnipFMC,
DCC-Sinopec, and so on. Most of
these will produce 35-50 wt ole-
fins, and perhaps using TOs as
high as 2 wt olefins and BT ,
with by-products gasoline about
38 wt maximum. Newer catalysts
might advance this position in the
future.
A series of cameos of newer tech-
nologies in various stages of com-
mercialisation reveals:
• The RFR proposed process con-
siders utilising radial flow reactors,
currently commercial in styrene
(ethylbenzene) processes. It pro-
vides a thermodynamic and kinetic,
as well as economic, rationale for
this new approach. New catalysis
would be required to optimise this
approach; advances in catalytic dis-
tillation provide intensification of a
proposed configuration.
• Other new olefin processes wor-
thy of note include ACO (which
could be viewed as an FCC modi-
fied process), Gasolfin, Omega, and
Chiyoda. These fixed bed swing
olefin BT technologies provide
a new approach and dimension to
reconfigurations; on-purpose aro-
matics routes, such as UOP’s Cyclar,
have made advances.
• New separation processes are
needed; as for TOs, adopting
some upfront feedstock separations
that avoid the VDUs, as well as the
incorporation of olefins/para ns, is
commercially close at hand.
Conclusion
efiners who only think about pro-
duction of transportation fuels must
think differently. Standalone chem-
icals producers really do have the
opportunity to break free from buy-
ing naphtha as the only feedstock
at lower cost. Integrated refinery/
chemicals producers (and the trend
for more will continue) do not need
to consider the conventional wis-
dom that a complex 400 000 b/d
refinery, coupled with a 2-3 mil-
lion t/y steam cracker with its high
capex being promoted by PCs, is
the best solution. F D studies need
to be more innovative in their think-
ing. This is not to say that complex
refineries or steam crackers have no
place; it means that if you already
have plant site investments in place,
there are better margin and lower
cost retrofits that need to be taken
into consideration, while simulta-
neously improving your chemicals
production and site margins.
John J Murphy is president of The Catalyst
Group Resources and Clyde F Payn is CEO of
The Catalyst Group, a boutique consultancy
serving via client directed projects (TCG
Consulting) and via various programmes and
studies (TCG Resources).
Email: TCGR@catalystgrp.com
www.eptq.com
14/06/2019 10:23
 Technical Bulletin – Two of Four
Precious
Metal
Mentality
Metals price volatility. Owning
versus leasing. Insurance and
liability. Environmental concerns.
The complexity of international
shipping. Lengthy payment terms. Complicated contracts.
As if the oil refining business didn’t have enough to
worry about … your company now has a full turn-
around of a unit containing precious metals catalyst
coming up and you have all of the above to contend
with as well.
Many responsible parties around the world believe that
the first decision to be made is whether it would be
best to send the catalyst to a precious metals refiner or
simply sell it outright by the kilo. When you get past all
of the ‘fake news’, REFINING is the only smart choice.
The problem usually begins when someone assumes
that they could sell the catalyst by the kilo to a broker
to “save money” or “save the trouble” of international
shipping, etc. This is a huge risk, as brokers are offering
50 to 60% of the PGM value at best. Refining, including
international shipping and all costs, still returns a net
average over 90% on petroleum catalysts true precious
metals value.
One metric ton of catalyst (2205 lbs.) is about $70K,
so that means that selling to a broker by the kilo is the
The Sabin Metal group of companies celebrated their 70th Anniversary
in 2015. Based in the United States and with sales/service offices around
the world, Sabin is the largest privately owned precious metals refining
organization in North America. Sabin provides customers with
logistical support, precious metal financial services, pre-reclaim
kilning and some of the most sophisticated facilities in the world for safely and responsibly processing, sampling
and refining precious metal-bearing catalysts.
TechBulletinAd
sabin.indd 1 2 of 4-PTQ.indd 1
equivalent of losing between $28K and $35K on every
metric ton you sell. In addition, many countries enforce
a “Grandfather Clause” regarding the liability of a
corporation indefinitely into the future. The bottom line:
if you sell your catalyst to a company who disposes of
it improperly, your company may still be responsible for
the pollution fines, the clean-up, the lawsuits, etc.
Advantages of Refining:
■ Net return after all costs typically over 90% of
precious metals value contained
■ Only requires lease or purchase of “make up” ounces
for replacement catalyst
■ With proper documentation and good standing,
metal advance available
■ Zero liability: fully insured from point of Sabin
possession; certificate of destruction at finish
Disadvantages of Direct Sale:
■ Net return after all costs typically less than 60% of
precious metals value contained
■ Assets sold at over 30% loss can trigger corruption
investigation
■ Replacement catalyst now require full new lease or
purchase of platinum
■ Unending liability: uninsured transport and final
treatment; no traceability of proper environmental
disposal
The Take-Away: Make sure your precious metals end
up with a responsible recycler, root out and eliminate
the unethical and the wasteful, and forge global
partnerships; allow for fair margins, invest in research
and development; discard perceived limitations and
challenge what is ‘normal’.
At Sabin, we believe that long-term wisdom and
meaningful innovation is best for business, and as a
result, it is what is best for the society of Mankind. If
you’d like to learn more about this topic, or any of the
other Sabin Metal Precious Metal bulletins, please visit
us at www.sabinmetal.com.
6/5/19 3:10
13/06/2019 PM
10:27
 NeXRing™ – the next big
thing in random packing
Join the many companies already using the innovative high-performance random packing
NeXRing™ developed by Sulzer experts. Using NeXRing™ will allow you to take advantage
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Europe, Africa, Russia Middle East and India North and South America Asia Pacific
Sulzer Chemtech Ltd. Sulzer Chemtech Middle East SPC Sulzer Chemtech USA, Inc. Sulzer Shanghai Engin. & Mach. Works Ltd.
Neuwiesenstrasse 15 3rd Floor Jawhara Plaza 1 Sulzer Way No.1688, Feizhou Road, Nanhui District
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Phone: 0041 52 262 50 28 Phone: 00973 1756 8400 Phone: 001 918 446 6672 Phone: 0086 21 3807 1000
chemtech@sulzer.com chemtech.bahrain@sulzer.com ttb.ctus@sulzer.com Sales-Shanghai-CTCN@sulzer.com

sulzer.indd 1 11/03/2019 16:04

 Sustainable technology for cleaning a
crude preheat exchanger network
Mitigating environmental impacts, saving time and reducing costs: cleaning a
heat exchanger network using a renewable cleaning agent

YOSHINORI KANNO JX Nippon Oil & Energy Corporation

GUIQING XU Softard Industries
IAN BAXTER Cat Tech International

H
igh energy costs and environ-
mental regulatory demands
mean that there is an ever
increasing focus on energy e -
ciency in the oil refining industry.
Crude oil distillation is an energy
intensive process consuming
around 20 of a refinery’s total
energy consumption. The oil is first
heated in a preheat exchanger net-
work by recovering the heat from
the product and reflux streams. It is
then further heated in a furnace
prior to entering the flash one of
the distillation column. In order to
reduce fuel consumption in the fur-
nace, the e ciency of the exchang-
ers in the preheat train is crucial.
Crude oil is complex in nature, con-
taining many impurities, and the
preheat exchangers are prone to
severe fouling, which in turn
reduces the thermal and hydraulic
performance of the network. The
immediate financial and environ-
mental penalties associated with
this are increased energy consump-
tion at the furnace, higher CO2 emis-
sions and eventually loss of capacity
throughput. The total estimated cost
of all heat exchanger fouling in the
UK is in the order of 2.5 billion and
15 billion in America.1
JX Nippon Oil & Energy group
(JX NOE) is a Japanese petroleum
company that operates six refineries
in Japan with a combined crude
processing capacity in the region of
1.3 million b/d. NO has a
strong commitment to the environ-
ment, constantly striving to reduce
environmental impacts and pro-
mote energy saving measures to
reduce global warming. This com-
mitment is demonstrated in an
environmental plan with key objec-
tives to cut CO2 emissions and take
steps to reduce waste, water use
and air pollution.2 In this regard,
the opportunity to evaluate the
Super Clean System (SCS) technol-
ogy seemed pertinent. SCS is an
online heat exchanger cleaning
method for atmospheric and vac-
uum crude distillation units (CDU/
VDU) that removes fouling in pre-
heat trains, transforming it into a
fully reusable product.
The CDU at NO ’s Sendai
refinery has a processing capacity of
145 000 b/d and historically
The total estimated
cost of all heat
exchanger fouling in
the UK is in the order
of $2.5 billion and
$15 billion in America
required a two week timeline to
clean the heat exchangers by a con-
ventional hydroblasting method.
This methodology involved the
coordination of many process steps,
created large amounts of wastewa-
ter and was time consuming.
NOE was looking for other, more
cost effective solutions to reduce the
cleaning turnaround time and
improve the reliability of its CDU
turnaround. In 2000, the company
elected to use SCS in a trial applica-
tion on its CDU and, following vali-
dation, continued to apply the
technology in subsequent years. In
2011, the refinery was shut down
following the devastating Great
ast apan earthquake and tsunami.
Almost one year later, commercial
production was restarted and JX
NOE once again applied SCS from
the 2012 turnaround of its repaired
crude distillation unit.
History of Super Clean System
Softard Industries primarily devel-
oped the SCS technology to simplify
and shorten the cleaning process for
CDU/VDU units. The patented
technology eliminates many of the
processes and problems associated
with cleaning by the hydroblasting
method. esearch and development
started in Japan in 1996, with the
first commercial application taking
place in Korea in 1 8. The cleaning
process involves the application of
an oil based compound to the heat
exchanger network whilst under oil
recirculation. The cleaning com-
pound is derived from a naturally
occurring, renewable source and
has the ability to penetrate fouling,
effectively removing deposits from
the internal surfaces of the tube and
shell exchangers. After cooling the
unit, the process crude oil is flushed
out and replaced with cleaning oil
such as light gas oil (LGO) or light
cycle oil ( CO). Once the unit is
flushed, it is put on oil recirculation,
followed by injection of the oil
based compound. The cleaning
solution is then circulated around
all the exchangers in the circulation
loop to remove fouling. This
method is somewhat different to
hydroblasting, which invariably
involves many more processes, each
with a time and cost implication
and additional ha ards that require
control. SCS application costs are
typically 30-50 those of hydro-

www.eptq.com PTQ Q3 2019 83

q1 cattech copy.indd 1 14/06/2019 10:49

 blasting, however this will depend
on unit type, number of exchangers
in loop, circulation loop volume and
specification of cleaning oil type.
Since the first commercial applica-
tion, the technology has undergone
further development and optimisa-
tion, resulting in a high perfor-
mance online cleaning technology.
It has now been used to clean thou-
sands of heat exchangers, with units
typically being cleaned in less than
two days. SCS has been widely
embraced throughout Japan, and
Cat Tech International, a specialist
catalyst handling and tower field
services company, licenses the tech-
nology for application in Europe,
Africas, Asia (excluding Japan),
Americas and Australia.
SCS benefits
For JX NOE, shortening the CDU
maintenance turnaround time was a
prime objective and key validation
point of the technology. However
the advantages of SCS extend
beyond this and can be categorised
as follows:
Time savings: unit shutdown
time reduced
The ability to clean all exchangers in
the network in less than 48 hours
results in significant shortening of
the turnaround schedule. As clean-
ing takes place online in a closed
loop without the need to open
exchangers, many of the processes
associated with conventional hydro-
blasting such as isolations, steam
purge, scaffold, bundle extraction,
bundle transportation to wash area
and hydroblasting are either elimi-
nated or minimised. This has a
direct impact on the time schedule
but also on the costs and labour
requirements associated with these
processes. The simplified SCS pro-
cedure results in a reduced cleaning
time line, reduced labour require-
ments, productivity improvements
and improved reliability of the
CDU turnaround.
Energy conservation:
environmental compliance
In certain cases where there is a
large number of exchangers in the
preheat network, it becomes very
di cult to effectively clean all
84 PTQ Q3 2019
q1 cattech copy.indd 2
exchangers by a hydroblasting
method due to turnaround time
constraints. Consequently, the
desired heat recovery of the preheat
network may not be realised as only
those exchangers most badly fouled
are prioritised for cleaning. In com-
parison, the simplicity and high
cleaning effect of SCS with its ability
to clean all exchangers in the loop in
less than 48 hours becomes appar-
ent. Application experiences in
these cases indicate improved heat
recovery of the preheat train, thus
reducing fuel consumption at the
furnace and lowering unit operating
costs. Further energy savings come
from the abolition of steam purge
normally used to remove hydrocar-
bons when opening exchangers.
As well as for a major turnaround,
the technology can also be used
during a run to quickly recover
The simplified SCS
procedure results in
a reduced cleaning
time line, reduced
labour requirements,
productivity
improvements and
improved reliability of
the CDU turnaround
heat transfer e ciency in order to
manage energy consumption and
unit capacity. The economics for
each unit will differ and will also
depend on market considerations.
Environmental impacts: waste,
water pollution, air and noise
pollution
Reducing the environmental
impacts of refining operations is a
major consideration for operators. It
extends beyond legal compliance
and social responsibility; it also
makes financial sense:
• No waste: the technology does
not produce any waste. Products of
cleaning are fully reusable, the used
cleaning solution being reprocessed
back into the crude feedstock. The
cleaning oil compound does not
contain any metals, carcinogens or
compounds that may be harmful to
plant metallurgy.
• Water pollution eliminated: large
amounts of contaminated wastewa-
ter are generated from conventional
cleaning methods. The contami-
nated water containing organic pol-
lutants has to be further processed
and is therefore an additional load
on the refinery wastewater treat-
ment plants. SCS is an oil based
cleaning compound and does not
rely on water, hence the costs asso-
ciated with water use and its subse-
quent treatment are eliminated.
• Air pollution: as cleaning takes
place online in a closed loop, with
no need to open heat exchangers, air
pollution is eliminated. There is no
requirement to apply steam purge
to remove light hydrocarbons as
these are absorbed into the cleaning
solution. If, after cleaning, opening
of selected heat exchangers is
required for inspection purposes
then only a small nitrogen purge is
necessary. In a clean state the pull-
ing of exchanger bundles becomes
much easier.
• Noise pollution: disturbing or
excessive noise often associated
with hydroblasting is eliminated.
• Sustainability: importantly, the
cleaning oil compound is derived
from a naturally occurring renewa-
ble source and so does not nega-
tively impact the environment.
• Safety - hazards and risk reduc-
tion: SCS eliminates many of the
processes and associated hazards of
hydroblasting methodology.
Hazards arising from processes
such as steam purge, isolations,
scaffold, bundle extraction, on-site
transportation and hydroblasting
are either minimised or eliminated.
The technology can therefore be
applied as an effective risk control
measure in contributing to a safer
system of work.
• Cost reduction: SCS offers many
opportunities for the refiner to save
money. The decreased downtime of
the unit can have an overwhelming
effect on the economics, the opera-
tor getting the time value of the
unit.
• Another significant saving from
the simplified procedure is the elim-
www.eptq.com
14/06/2019 10:49
 Liquid inventory = 500 m3 23-106F
23-105D

FIC 23-102B 23-104B 23-106D 21-107

147 23-114B 23-125B 23-106E

23-106C
32-104B 23-105C
23-114A
23-125A
To slop ZI
23-102A 23-104A 23-106A
101 23-101G 23-104D 23-102D 23-132D
23-106B
SC 32-104A
FS
23-101F 23-101D 23-105B 23-132C
23-101A 23-104C 23-102C 23-132B Existing
Temporary
31-101A-C
23-101E 23-101B 23-105A 23-132A

34-101B 21-101
23-103G 23-124B 23-126D

23-107B 23-103D 23-126B

34-101A
23-103A 23-124A 23-126C
PG 31-102A,B

LG
23-107A 23-103B 23-126A ZI
160
Mobile injection facility
31-109A-C

Figure 1 Closed circulation loop, CDU

ination of many of the process steps

and labour costs associated with a 80
hydroblasting cleaning method. L-value of fresh LCO: 94.3

Equipment costs for SCS are much

lower since existing facilities are 70
used – for instance, tower, tower
pump, furnace and pipework – and
L-value

only a temporary injection facility is 60

required. Further cost savings derive
from elimination of water use and
its treatment, lower fuel consump- 50
tion and abolition of steam purge. 12 hours

• Intangibles: non-quantifiable Inj. Cir.

advantages include improved work- 40

8 July 8 July 9 July 9 July 9 July 9 July 9 July 9 July
ing conditions and reduced load on 20:00 22:00 00:00 02:00 04:00 06:00 08:00 10:00
operators. Date and time of sampling

JX NOE’s operations
Sendai
The CDU turnaround at the Sendai
refinery historically used conven-
tional hydroblasting methods to
clean the heat exchanger network.
After draining the unit, hydrocarbon
vapours were removed by applying
a steam purge for up to three days.
This would be followed by blinding,
isolations, removing heads and
extracting the exchanger bundles.
Each bundle extracted would then be
transported to a suitable wash area
and cleaned by hydroblasting
method. The hydroblasting pro-
duced large amounts of contami-
nated wastewater that contributed to
a load on the e uent treatment facil-
Figure 2 L-value vs circulation time
ities. This methodology involved
many process steps, equipment and
labour requirements and was
time consuming.
SCS application procedure:
Sendai refinery’s CDU
The cleaning application employs
the injection of a proprietary oil
based compound to the crude pre-
heat exchanger network whilst
under oil recirculation. The closed
oil circulation loop (see Figure 1)
was identified and agreed with
NO , and included the flash drum,
furnace, distillation column, and 44
tube/shell heat exchangers. On
8 uly 2014 at 0 :00 h, cool down of
the CDU was started. At a tempera-
ture of about 120°C, CO was intro-
duced into the unit and, once
inventoried, oil recycle was estab-
lished around the closed loop. The
temperature was adjusted to 135°C
and, when target conditions were
met, the SCS oil cleaning compound
was injected over a one hour period.
The concentration of the compound
is low, typically between 1.5-5 of
the circulation loop inventory, and
is dependent on the application
type. The injection point was at the

www.eptq.com PTQ Q3 2019 85

q1 cattech copy.indd 3 14/06/2019 10:49


No. Item Time,
hrs 05 07 09 11 13 15 17 19 21 23 01 03 05 07 09 11 13
Unit cool down
1
Line up
LCO replace cir.
2
and heating
Set inj. unit leak test
3 HKS-101 inj.
Remove inj. unit
Cleaning (cir.) and
4 12
check L-value
Cool down and
5
LGO rinse
6 Drain out
Figure 3 SCS application timeline
low pressure, suction side of the
pre-flash pump using a temporary
injection facility. Alternatively, use
of the suction side of the tower
pump is an option.
Circulation was continued and
cleaning progress was monitored as
a direct correlation with the light-
ness, L-value of the cleaning solution
(see Figure 2). As fouling is removed,
the L-value decreases until it
remains at a constant value corre-
sponding with the removal of all
fouling. Following 12 hours of circu-
lation, the cleaning was deemed
complete, and cool down and pump
out of the solution started. The unit
was then flushed with GO followed
by a nitrogen purge prior to opening
up select heat exchangers for inspec-
tion purposes. The application time-
line and main process steps can be
seen in Figure 3.
Results
The CDU preheat exchanger net-
work was successfully cleaned
Figure 4 Atmospheric residue: shell side before and after
86 PTQ Q3 2019
q1 cattech copy.indd 4
First day Second day
6 mised and CO2 emissions were
1 cleaning process was used to
using SCS technology. All 44
exchangers in the closed loop were
cleaned in less than 48 hours, a key
validation point for JX NOE.
There was no requirement to open
heat exchangers for cleaning pur-
poses; however, following nitrogen
purge, a small number of selected
heat exchangers were opened for
inspection purposes. The cleaning
effect was high, with fouling being
effectively removed (see Figure 4, an
atmospheric residue shell side
exchanger). There was no wastewa-
ter to deal with or pollution load on
the e uent treatment facilities. The
simplicity of SCS eliminated many
of the processes and costs associated
with hydroblasting. In some circum-
stances, improved heat recovery of
the preheat train was evident,
resulting in lower fuel consumption
and unit operating costs.
Conclusion
SCS technology provided new pos-
sibilities for JX NOE to reduce both
maintenance and operating costs for
its CDU/VDU. Consistent with JX
NOE’s environmental objectives,
impacts such as water and air pollu-
tion were either eliminated or mini-
reduced. The simplified online
improve the reliability of CDU turn-
around whilst mitigating the finan-
cial, environmental and safety
impacts associated with conven-
tional hydroblasting. SCS is a cost
effective, environmentally sustaina-
ble technology that has superseded
traditional mechanical cleaning
techniques and is now ‘the method
of choice’ for JX NOE. It is currently
being rolled out to other refineries
in its operation.
The foregoing is not intended to
be an endorsement of SCS technol-
ogy by JX NOE. While JX NOE’s
experience was positive, each
refiner must exercise independent
judgment to decide whether the
technology is appropriate for use.
Acknowledgments
Special thanks to all the team at JX NOE for
their support and valuable assistance during
the SCS application.
References
1 Muller-Steinghagen H, Fouling in heat
exchangers surfaces, Chem. Ind., 1995, 5: 171-
175.
2 2014, JX Nippon Oil & Energy, 2014
CSR report, www.noe.jx-group.co.jp/english/
company/current_csr_report/pdf/report-
2014-en.pdf (Accessed: 20th Sept 2015).
Yoshinori Kanno is Assistant Manager of
the Technical Service Group, Sendai refinery,
Nippon Oil and Energy Corporation.
Guiqing Xu is a Process Engineer with Softard
Industries Co. Ltd and has over 30 years of
experience in petroleum refining, specialising
in hydrotreating catalyst and chemical
cleaning for the CDU/VDU. He obtained
his PhD in chemical and biological science
and technology from Tokyo University of
Agriculture and Technology.
Ian Baxter is Technical Lead for Cat Tech
International Ltd and has over 25 years of
experience in the refining and chemical
industries. Based in the UK, he provides
technical expertise across a number of
technologies related to the catalyst handling
industry and other industry led problems.
www.eptq.com
14/06/2019 10:49
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 Residuum hydrocracking: chemistry
and catalysis
Significant advances have been made in understanding the hydrocracking chemistry
of residuum oils and in the catalytic systems required for deep conversion of resid
JULIE CHABOT and WOODY SHIFLETT
Advanced Refining Technology and Chevron Lummus Global
T
he hydrocracking of residuum
oil fractions has been practised
for nearly six decades, evolving
from simpler, single catalyst ebul-
lated bed reactor systems capable of
some 65-70% vacuum bottoms con-
version to the latest slurry hydroc-
racking systems that effectively push
vacuum bottoms conversion well
beyond 90% and up to 97-98%. Deep
conversion of residuum enables the
production of ultra low sulphur
(ULS) fuels as well as feed prepara-
tion for petrochemicals production.
Throughout this development
history, a key challenge has been to
maintain robust and reliable opera-
bility by mitigating and ultimately
controlling what is generically called
sediment or sludge formation and
deposition. Sediment formation has
limited the performance of ebullated
bed reactor systems from achiev-
ing the potential conversion levels
possible with the LC-Fining reactor
platform. This is also highly depend-
ent on the feed characteristics, as
shown in Figure 1.
Key to fully utilising the full
reactor potential to maximising
conversion are the types of cata-
lyst utilised in conjunction with
appropriate operating conditions
and flow scheme. This article will
review the understandings in ana-
lytical petroleum chemistry and
catalysis that have enabled this
technology to arrive at this level of
success. Success in deep residuum
hydrocracking is only possible by
understanding the fundamental
hydrocarbon chemistry involved
and marrying it with the properly
designed catalysts and optimised
catalyst systems to meet high con-
version objectives.
www.eptq.com
q3 clg.indd 1
Typical acceptable level
Feed A high sediment forming
Feed B low sediment forming
Sediments, ppm
VR conversion
Figure 1 Sediments vs VR conversion
Understanding the chemistry
It is clear that fundamental concepts
of the hydrocracking chemistry of
residuum fractions have progressed
immensely since the 1960s when the
heavier components of residuum
fractions were characterised by car-
bon residue measurements relevant
to thermal visbreaking and coking
operations and fluid catalytic crack-
ers (FCC) and somewhat ill-defined
insolubles in one or more alkanes.
The term ‘asphaltenes’ was associ-
ated with alkane (typically heptane)
insolubles but poorly envisioned,
much less understood, on a molec-
ular level. They were highly aro-
matic in nature and deficient in
hydrogen, but little more was fun-
damentally known. Empirically,
it was established that sediment
formation, for the most part, arose
because the catalytic hydrogena-
tion associated with the residuum
hydrocracking was overly selective
in hydrogenating the hydrocarbon
fractions acting as the solvent for
the ill-defined asphaltene compo-
nents. At the same time, cracking
of the side chains and naphthenic
rings occurs in the asphaltene mol-
ecules, leaving the aromatic cores
mostly unaffected and incompatible
with the oil. These changes make
the oil product more para nic and
the unconverted asphaltene cores
more aromatic and condensed than
those in the feed. In consequence, a
disturbance in the asphaltene-resin
interactions occurs, leading to the
precipitation of asphaltene as sedi-
ments.1 Additionally, as temperature
increases, the rates of thermal crack-
ing reactions increase more rapidly
than the hydrogen addition coun-
terparts. Thus, hydrogen transfer
limitations occur, which can lead to
the growth of aromatic structures in
the asphaltenes, making them more
prone to precipitate once these com-
pounds leave the reactor zone.
Various filtration methods and
gradient of solvent experiments
led from saturates, aromatics, res-
ins and asphaltene (SARA) charac-
terisation to asphaltene solubility
PTQ Q3 2019 89
14/06/2019 10:55

80
Feed (disappearing)
70 Products (appearing)
60
50
40
30
20
10
DBE
0
0 20 40
Carbon number
Figure 2 Double bond equivalent vs carbon count
profiles. However, empirical char-
acterisation progress needed to be
matched by a coherent theoretical
understanding of the molecular
nature of residuum oil components.
Prior to the 1980s, theory on the
nature and structure of asphaltenes
and associated heavier ends focused
on them being polymeric in nature
and perhaps the result of geologi-
cal transformations or conversely
micellular entities consistent with a
colloidal view of petroleum.
However, in the 1 80s and
1 0s, the extensive effort first by
Boduszynski, et al and extended
by Ovalles, Moir et al at Chevron
Energy Technology Company2
established that the molecular com-
position of petroleum from light
ends through the heaviest residuum
components was a continuum in
molecular weight (the ‘Boduszynski
Continuum’) and developed more
and more advanced means of char-
acterising the molecular spectrum
that framed the species that lead to
sediment formation under residuum
hydrocracking conditions.
Enhanced asphaltene separation
techniques using liquid chromatog-
raphy apparatus and tailored sol-
vent gradient sequences, coupled
with in-line filtration developed in
the last few years by Rogel, Ovalles,
Moir and co-workers, now allow
asphaltene types to be separated
and characterised by their stabil-
ity and tendencies to precipitate as
sediment.
Today, advanced analytical tech-
niques such as ultra high resolution
90 PTQ Q3 2019
q3 clg.indd 2
60 80 100 120 140 160
Fourier transform ion cyclotron reso-
nance mass spectrometry enable the
mapping of the heavy oil molecular
continuum by carbon atom count
and aromaticity as indicated by dou-
ble bond equivalent (DBE). Indeed,
it is now possible to track reaction
dynamics molecularly by DBE and
carbon atom count (see Figure 2).3
Atomic force microscopy (AFM) ena-
bles us to ‘see’ various asphaltene
structures.4 Such advances better
enable the design and optimisation
of catalyst chemistry, porous struc-
ture and multi-catalyst reaction sys-
tems in residuum hydrocracking.
The role of catalysis
Most of the vacuum residuum con-
version in hydrocracking processes
is thermal in nature. The catalyst
or catalyst system provides a vari-
ety of concurrent benefits through
various catalytic reactions: removal
of sulphur (hydrodesulphurisation
or HDS) for U S fuels, nickel and
vanadium (hydrodemetallisation
or HDM) reactions to mitigate foul-
ing deactivation of downstream
catalyst systems, nitrogen removal
(hydrogenitrogenation or HDN)
and removal of micro carbon resi-
due (HDMC ) to mitigate inhibi-
tion in subsequent processes such as
vacuum gasoil (VGO) hydrocrack-
ing, and selective hydrogenation
for mitigation of sediment forma-
tion plus polynuclear aromatics
(PNA) reduction in lighter fractions.
Other reactions such as dealkyla-
tion of asphaltenes and other higher
molecular weight multi-ring aro-
matics must also be considered in
mitigating sediment formation.
Because catalysts are concurrently
added and removed from both ebul-
lated bed reactors (EBRs) and slurry
hydrocracking reactors in such pro-
cesses as LC-Fining and LC-Slurry,
they also serve the role of transport-
ing deposited nickel and vanadium
metals and heavy, carbonaceous
coke from the reaction zones.
The upshot of these catalytic
reactions is that significant effort
must be devoted to developing the
proper catalyst chemistry as well as
the distinct pore size distribution
to address operational needs and
targets, and similarly, the utilisa-
tion of multi-catalyst systems must
be understood in order to be opti-
mised. We will review the progress
in this area in both ebullated bed
(EB) catalysis (‘millimetre scale’)
and slurry hydrocracking catalysis
(‘micron scale’). We will also review
our findings for purported nano-
scale catalysts or co-catalysts in
residuum hydrocracking and their
subsequent implications for sedi-
ment mitigation. Processing con-
siderations have been reviewed in
some detail earlier.5
Catalyst development efforts on a
millimetre scale
To ensure that state-of-the-art cata-
lyst technologies are commercially
available for its ebullated bed and
slurry hydrocracking processes,
Chevron Lummus Global (CLG), a
joint venture between McDermott
and Chevron, established a coop-
erative agreement with Advanced
efining Technologies C (A T),
a joint venture between Grace and
Chevron.
ART is a leading supplier of resid-
uum hydroprocessing catalysts
worldwide. Resources, know-how
and ideas are shared between the
parties to assist in the development
of new catalyst technologies to meet
various commercial needs. State-
of-the-art research units located in
Richmond, California, are utilised
for ART catalyst screening studies
as well as CLG/ART joint catalyst
development and process optimisa-
tion studies.
The extensive database generated
from these units as well as CLG’s
www.eptq.com
14/06/2019 10:55
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itw.indd 1 11/06/2018 17:10

 MORE
THAN THE
COMBUSTION
AUTHORITY.
THE SMART
CHOICE.
Others may claim it.
We prove it.
With more installed equipment
than any other manufacturer
in our industry. The largest,
most advanced combustion
research and development
testing facility in the world.
And the largest, most
technically advanced
worldwide service
organization of its kind.

That’s smart. That’s JZHC.

For patent and trademark information,

see johnzinkhamworthy.com/legal
johnzinkhamworthy.com | +1 918 234 1800 ©2018 John Zink Company LLC.

j zink.indd 1 16/12/2018 14:46

 extensive commercial experience
ensure the best catalysts are selected
to achieve processing objectives.
This testing has led to the develop-
ment of several new and enhanced
catalyst technology platforms in the
last 10 years.
This was a natural evolution from
the initial formation of both joint
ventures. Indeed, shortly after the
formation of the ART and CLG
Vs in 2001, efforts commenced to
integrate each company’s catalyst
strengths. All parties contributed
significant residue upgrading tech-
nology, with Chevron’s 35 years
of process and catalyst expertise in
residue hydrotreating (including
ARDS, VRDS, OCR, and UFR tech-
nology), CLG’s 23 years of expe-
rience with the LC-Fining residue
hydrocracking process, and Grace’s
30 years of background with cata-
lysts for the EBR process.
The sharing of ideas from each
party provided leads with respect
to new catalyst designs specifically
to address sediment formation – a
problem common to both residue
hydrotreating and hydrocracking.
We have found that to achieve
the best performance it is critical to
provide the right balance between
meso- and macropores. The intrin-
sic reaction rate, which is inherently
related to the meso pores (the cata-
lyst surface area), controls the HDS,
the HDMCR, and the residuum con-
version characteristics of the cata-
lysts. The diffusivity, which is more
related to the macro pores (greater
than 25 nm), controls the demetalla-
tion and the sedimentation functions
of the catalyst.
The optimisation of the pore
volume and pore size distribu-
tion (PSD) is critical to the catalyst
development:
• Pores in the <20 nm range are
most useful for HDS and HDCCR
activity. Pores in the 25+ nm range
are effective in allowing diffusion of
the majority of the asphaltene mole-
cules into the catalyst.
• A select amount of pores >25
nm is essential to allow the largest
asphaltenes molecules to readily
enter the catalyst to achieve max-
imum HDM, while cracking the
molecules with minimum sediment
formation.
www.eptq.com
q3 clg.indd 3
Features of ART catalysts
EBR Catalyst platform application and examples
DCS Maximum metals removal; GR-61X
ECAD Metals removal with enhanced catalytic activity; GR-95X
HSLS Sediment control with good catalytic activity; GR-82X
HSLS Plus Sediment control with very good catalytic activity; GR-83X
LS Sediment control with enhanced catalytic activity; GR-LS10
HCRC Maximum catalytic activity; GR-73X
Table 1
The above characteristics are
established via the proper combi-
nation of chemical composition and
preparation techniques.
The active metals, both molybde-
num and the Group VIII promoters,
are also extremely important to get
proper catalyst performance. The
correct amounts of the two (or more)
elements dispersed throughout the
extrudate are necessary to ensure full
metals utilisation. This requires exact
control of the metals distribution and
dispersion. The optimum catalyst is
designed to deliver the maximum
residue conversion, with a high level
of asphaltene and CCR conversion in
order to minimise organic sediment
formation. In addition to the key role
the catalyst plays, the maximum con-
version level attainable is dependent
on the feedstock characterisation. In
particular, the colloidal instability
index (CII) and the characterisation
of the asphaltenes are important fac-
tors in benchmarking various feeds.
The CII is a measure of the ratio of
asphaltenes plus saturates to aro-
matics plus resins. A lower CII is
indicative of a feed which is easier to
process. In addition, the asphaltenes
can be characterised into those
which are easier or more di cult
to process based on a solvent based
analysis. The greater the percentage
of easier to process asphaltenes, the
higher the conversion level that can
be attained.
Features of ART’s DCS, ECAD,
HSLS, HSLS Plus, LS and HCRC cat-
alyst platforms are shown in Table 1.
LS technology platform
Developed and commercialised in
2002, the LS Technology Platform
continues to be in use in several
EB RHC units worldwide in both a
standalone and dual catalyst sys-
tem. It provides very good sediment
control, in particular for highly sedi-
ment forming feeds such as Urals.
HSLS technology platform
Developed and commercialised in
2007, this catalyst offers superior
sediment control in combination
with higher demetallation activity.
The unique pore structure of this
catalyst enables higher metals load-
ings (Ni + V), while still providing
superior sediment control activ-
ity. It has been successfully used
in several units, processing a wide
range of feedstocks, and offers a
cost e cient technology for residue
hydrocracking. The HSLS technol-
ogy incorporates a novel base, along
with an advanced and special pro-
cess technology for e cient metals
impregnation. The proprietary alu-
mina, with its unique pore size dis-
tribution, provides enhanced access
to the active metal sites.
Key performance features of this
technology platform include:
• Lower sediment formation
(decreased 7-20%), reducing the
cleaning frequency of downstream
equipment, higher on-stream fac-
tor and lower maintenance costs.
In some cases, this has allowed for
higher residue conversion and/or
flexibility to process more di cult
opportunity crudes.
• Higher micro carbon residue
(MCR) removal for better coker feed
quality.
• Improved HDS of the distillate
and unconverted residuum.
• Significant reduction (5-15 ) in
fresh catalyst addition rates with
higher metals removals, which also
means more value for metals recov-
ery on spent catalyst.
This catalyst is being success-
fully used in combination with LS
catalyst in a dual catalyst system
in Asian and European units, with
PTQ Q3 2019 93
14/06/2019 10:55

ART dual catalyst systems for EB RHC units
Stage 1
Technology platform DCS
Catalyst function Very high HDM/moderate HDS/
excellent sediment control
Stage 1
Technology platform ECAD
Catalyst function High HDM/good HDS & HDMCR/
excellent sediment control
Stage 1
Technology platform HSLS
Catalyst function Good HDM/High HDS & HDMCR/
excellent sediment control
Table 2
superior performance and sediment
control. In addition, it is also being
used in combination with our high
demetallation removal catalyst in a
US Gulf Coast unit.
HSLS Plus technology platform
Developed in 2009 and commercial-
ised in 2018, this catalyst technology
is an enhancement of the HSLS tech-
nology and geared for higher HDS
and HDMCR conversion in EB units
which are processing high sulphur
feeds and targeting lower bottoms
sulphur and MCR in the EB RHC
HT resid and converted products.
Key performance features of this
technology platform, in addition
to the HSLS Technology platform
described above, are:
• Higher HDS and HDMCR
conversion.
• Lower VTB bottoms sulphur and
MCR.
• No change in catalyst usage rates.
HCRC technology platform
This is A T’s next step-out tech-
nology platform, which was com-
mercialised in 2012. The HCRC
technology uses a new step-out
alumina and base that provides the
following key benefits, at constant
reaction severity, relative to the LS
platform:
• 4% higher residuum conversion
(preferentially to distillate).
• 4% higher HDS (lower sulphur in
the unconverted bottoms and con-
verted oil products).
• 6% higher MCR removal.
• 3% higher HDN (lower nitrogen
in distillate and VGO).
94 PTQ Q3 2019
q3 clg.indd 4
Stage 2/3 Status
HSLS
High HDS & HDMCR/ In use
excellent sediment control
Stage 2/3 Status
LS
Very high HDS & HDMCR/ Trial
very good sediment control
Stage 2/3 Status
LS
Very high HDS & HDMCR/ In use
very good sediment control
This technology provides the abil-
ity to achieve the same or higher
residue conversion at lower ther-
mal severity (lower temperature) at
higher cracking activity with compa-
rable sediment formation.
ECAD technology platform
Developed in 2016 and commercial-
ised in 2018, this catalyst platform
offers exceptional sediment control
in combination with significantly
higher metals capacity compared
to the HSLS platform. When com-
bined in a dual catalyst system with
the LS catalyst platform, very little
impact on HDS or HDMCR activity
is observed. The unique pore struc-
ture of the ECAD catalyst enables
higher metals loadings (Ni+V) while
providing superior sediment control
activity. This new platform is cur-
rently in trial in one unit, processing
a challenging feedstock, and offers a
cost e cient technology for residue
hydrocracking. The ECAD technol-
ogy incorporates a novel base, along
with an advanced and special pro-
cess technology for e cient metals
impregnation. The proprietary alu-
mina, with its unique pore size dis-
tribution, provides enhanced access
to the active metal sites.
Key performance features of this
technology platform include:
• Higher metals capacity than
HSLS, and higher activity than EBR
demet grades.
• In a dual system platform, ECAD/
LS provides improved residuum
conversion sediment trade-off rela-
tive to HSLS/LS.
• Significant reduction in fresh
catalyst addition rates with higher
metals removals, which also means
more value for metals recovery on
spent catalyst.
DCS catalyst platform
This catalyst platform offers excep-
tional HDM and metals capacity.
When combined in a dual catalyst
system with the HSLS catalyst plat-
form, robust catalytic performance
and sediment control could be
achieved while retaining very high
metals loadings (Ni+V) for a cost
e cient catalyst technology, even
for high metals feeds. The latest
addition to the DCS catalyst plat-
form, GR-611 introduced in 2017,
has been proven commercially in
dual catalyst mode operation (see
Table 2). This catalyst, with its
enhanced pore volume and pore
si e distribution, offers exceptional
access to active sites and superior
metals capacity, while retaining
physical strength and integrity.
Dual catalyst system
A T was the first catalyst supplier
to introduce and commercialise a
‘dual catalyst system’ in EB RHC
Units in 2009, and remains the only
catalyst supplier to offer such a cat-
alyst system option. This concept,
based on extensive commercial
experience, was developed with the
goal of maximising the performance
of front and tail reaction stages
while minimising catalyst addition
rates.
The first commercial application
of such a dual catalyst system, in
a US Gulf Coast unit, was found to
be very successful. Since then, addi-
tional specific catalyst platforms
have been developed to enhance
the specific performance of front
and tail reaction stages, and vari-
ous combinations of dual catalyst
systems have been tested by ART
and CLG in research units and are
in commercial use in numerous EB
RHC units, including LC-Fining
units in Asia and Europe, with
proven superior performance and
sediment control.
The use of a dual catalyst sys-
tem allows for unique catalyst
synergies and has been proven to
maximise residuum conversion,
HDS, HDMCR and HDM, while
www.eptq.com
14/06/2019 10:55
 retaining superior sediment control,
maximising catalyst metals capacity GR-LS10/GR-LS10 (2012)
and minimising catalyst addition HSL5/GR-LS10 (2012)
rate and cost. HSL5/GR-LS10 (2016)
The use of a state-of-the-art dual ECAD/GR-LS10 (2016)
catalyst system provides a signifi-
cant technology advantage, includ-

HTHP separator product

ing e cient catalyst utilisation and
operational flexibility in the oper-
ation and optimisation of the RHC

sediment, ppm
unit performance. While operat-
ing in a dual catalyst system mode,
these units have benefited from
lower sediment formation at equiv-
alent residuum conversion when
compared to single catalyst system
78 79 80 81 82 83 84 85 86 87 88
operation.
VR (579ºC+) conversion, vol%
As Figure 3 shows, the use of a
dual catalyst system, as opposed
to single catalyst system operation, Figure 3 Residue conversion – sediment trade-off
has been reliably proven both in
extensive research unit testing and this extensive testing, the addition provisions, handling and injection
commercial operation to reduce of the co-catalyst led to slightly requirements. Furthermore, such
sediment formation at a given resid- increased sediment, not lower sed- additives have been observed to
uum conversion. This improved iment, at a given residuum con- react and evolve quickly and con-
sediment-conversion trade-off leads version, since the co-catalyst solids tribute to problematic equipment
to reduced fouling and cleaning fre- were recovered in the unconverted and reactor fouling issues that could
quency of downstream equipment, product and contributed to addi- interfere and limit operation run
higher on-stream factor, lower main- tional inorganic sediments. cycle length.
tenance costs, and improved prod- In addition to contributing to Because of these key concerns,
uct stability. increased inorganic sediments in ART and CLG have favoured the
The dual catalyst system approach the unconverted oil without relia- more reliable and proven dual cata-
provides reliable sediment-conver- ble improvement in sediment-con- lyst system technology, as opposed
sion trade-off enhancement, while version trade-off or catalytic to the combination of a single cata-
also providing improved catalyst performance, the use of a co-catalyst lyst system plus co-catalyst additive
metals capacity, therefore direction- presents a number of key challenges. combination. The various combi-
ally reducing catalyst addition rate The use of such costly additives con- nations of dual catalyst systems,
and handling (see Figure 4). The tributes to significant additional cat- employing the above listed catalyst
dual catalyst system platform has alyst addition costs, and increased technology platforms, currently in
been proven, in extensive research operational complexity, requiring use or undergoing commercial tri-
unit testing, including larger scale additional catalyst supply logistical als, are summarised in Table 2.
research unit testing, to be more
reliable and economical than rely-
ing on the combination of a single
catalyst system and the addition
DCS
of a co-catalyst additive, such as
organomolybdenum compounds.
Indeed, such co-catalysts have been
described as ‘nano-catalysts’, but ECAD
the evidence does not support this
assertion, and this will be discussed
Metals capacity

further in our section on micron HSLS

scale catalysts. LS

As Figure 5 shows, the addition HCRC

of a costly co-catalyst has not been
shown to provide a sediment-resid-
uum conversion trade-off benefit
or any other performance benefits, Catalytic activity
including catalytic activity improve-
ments, when tested in CLG’s 1 bbl/
day research unit. In fact, during Figure 4 Metals capacity vs catalytic activity

www.eptq.com PTQ Q3 2019 95

q3 clg.indd 5 14/06/2019 10:55


Co-catalyst injection
Base (No co-catalyst)
HTHP separator product
Urals VR
sediment, ppm
MEVR
60 65 70 75 80 85
VR (579ºC+) conversion, wt%
Figure 5 Residue conversion sediment trade-off with complete co-catalyst recovery
Catalyst innovation on a micron In contrast to the LC-Slurry clean
scale system concept, the thermal slurry
The extension of residuum hydroc- processes that operate with higher
racking to the level of 90%+ vacuum temperatures require large amounts
bottoms conversion has required sig- of inactive or low activity solids
nificant changes in reaction transport and cannot produce a high quality
dynamics and catalysis approaches. heavy oil product, as Isoslurry does.
The LC-Fining reactor platform has The combination of a nickel-mo-
been demonstrated to have both the lybdenum slurry catalyst with the
flexibility and sustained robustness LC-Fining reactor system allows
to meet the needs of deep conver- even the most di cult V s, SDA
sion slurry hydrocracking of resid- tars, and other heavy residues to be
uum embodied in the LC-Slurry upgraded reliably and selectively.
process. The LC-Slurry process The catalytic chemistry, morphol-
utilises the Isoslurry catalyst. The ogy and porous structure of the
catalyst’s properties result in the e - Isoslurry catalyst is key to depend-
cient hydrogenation activity needed able high performance in residuum
to convert the heavy end to useful hydrocracking that reaches 97%
products and effectively mitigate vacuum bottoms conversion. As
sediment formation, thus ensuring Figure 6 shows, its micron scale par-
the reactor e uent is clean, which ticle size distribution ensures that
means that the fractionation section mass transfer limitations inherent to
equipment is not subject to fouling. high conversion are greatly reduced
CLG’s approach of using a nickel and, coupled with a high pore vol-
promoted molybdenum slurry cat- ume, maximises the access to highly
alyst with a defined structure has dispersed nickel-promoted MoS2
been found to be superior to other active catalytic sites. Furthermore,
approaches that have been tried the high pore volume (particularly
such as using organo-moly liquids pore diameters in excess of 10 nm),
as catalyst precursors, or conversely high internal surface area and high
employing low activity or no activ- particle geometric surface area
ity solids. allow for effective deposition of
I time at 770°F (410°C). Mass balance
EB catalyst pellets catalyst solids catalyst
Figure 6 Micron scale particle size distribution ensures that mass transfer limitations
inherent to high conversion are greatly reduced
96 PTQ Q3 2019
q3 clg.indd 6
nickel and vanadium sulphides plus
heavy carbonaceous foulants and
their subsequent transport out of
the reaction system.
The nature of Isoslurry synthe-
sis from low cost raw materials in
the LC-Slurry process ensures high
dispersion of the nickel promoted
MoS2 active sites and their effective
pre-sulphiding, activation and opti-
mal particle size distribution. Broad
flexibility exists in pre-production,
quality control and storage owing
to the long shelf life of Isoslurry cat-
alyst. Its particle size distribution is
optimised for subsequent separa-
tion and recovery for both economic
recycle catalyst operation and active
metal recovery.
In the past decade, significant pro-
gress has been made to improve the
performance of Isoslurry catalysts
by optimising their morphology.
The pore volume has been increased
by well over an order of magnitude,
and the macroporosity critical to
removal of metals and heavy carbo-
naceous deposits has been increased
by a factor of more than 15. In terms
of a commercial unit’s operating
economics, this has resulted in cata-
lyst addition rates being reduced at
a minimum by a factor of 25. This,
coupled with e cient catalyst recy-
cle technology, has been pivotal in
optimising process economics to a
minimum catalyst cost.
We return to a consideration of
the potential for true nano-catalysts
for residuum conversion. Along
the path to optimising Isoslurry
catalyst’s performance in terms of
both chemistry and morphology, a
number of organo- or, generically,
soluble molybdenum formulations
have been studied. In all cases, rapid
agglomeration of initially nano-sized
entities has occurred. Significantly,
active catalytic species of 250-400
nm have been clearly identified
after less than 15 minutes residence
closure has clearly shown that no
measurable quantity of potential
molybdenum nano-catalysts sur-
vive the rapid agglomeration phase.
While the performance of the result-
ant micron scale catalytic species is
by no means profoundly inferior
to Isoslurry catalyst with respect to
residuum conversion, they offer no
www.eptq.com
14/06/2019 10:55
 benefits in catalytic performance or
mitigation of sediment formation.
This supports the concept that a sta-
ble and fully formed Ni-Mo catalytic
entity is favoured over a rapidly
agglomerating singular Mo entity
for effectiveness in catalytic reac-
tions such as HDS, HDN and carbon
residue reduction in addition to the
more operationally critical ability
to mitigate sediment formation and
reliably transport contaminants out
of the reaction system without foul-
ing. This finding is not limited to a
specific comparison to Isoslurry cat-
alysts; we noted the comparable case
for ebullated bed Ni-Mo catalyst per-
formance earlier in our discussion
of the clear benefits of dual catalyst
performance compared to soluble
molybdenum co-catalyst coupled
with single catalyst performance.
Conclusion
Significant advances in the chem-
ical characterisation of residuum
petroleum materials coupled with
innovation in synthesising and
understanding catalysts and cat-
alyst systems has provided the
refiner with a portfolio of solutions
THE RVP PROFIT ANALYZER
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q3 clg.indd 7
for economic residuum hydrocrack-
ing. Catalysis and process research
and development efforts by C G
and ART, coupled with in-depth
analytical efforts at Chevron nergy
Technology Company have, in
large part, made this possible.
These efforts continue, not only to
produce the cleaner vehicle and
ship fuels of the future, but also to
address the needs for greater petro-
chemicals production.
References
1 Ovalles C, Rogel E, Morazan H, Moir M E,
Dickakian G, Method for determining the
effectiveness of asphaltene antifoulants at
high temperature: application to residue
hydroprocessing and comparison to the
thermal fouling test, Energy Fuels, 29, 4956-
4965, 2015.
2 Ovalles C, Moir M E, Editors, The Boduszynski
Continuum: Contributions to the Understanding
of the Molecular Composition of Petroleum, ACS
Symposium Series, Vol 1282, Chapters 1, 2, 4.
3 Rogel E, Witt M, Asphaltene characterization
during hydroprocessing by ultrahigh-
resolution fourier transform ion cyclotron
resonance mass spectrometry, Energy & Fuels,
31 (4), 3409–3416, 2017.
4 Schuler B, Fatayer S, Meyer G, Rogel E, Moir
M, Zhang Y, Harper M R, Pomerantz D, Bake K,
Pena D, Kushnerick J D, Mullins O C, Ovalles C,
v an den Berg F G A, Gross L, Heavy oil based
mixtures of different origins and treatments
studied by AFM, Energy & Fuels, 31 (7), 6856-
6861, 2017.
5 Mukherjee U, Gillis D, Advances in residue
hydrocracking, PTQ, Q1 2018.
ISOSLURRY, LC-SLURRY and LC-FINING are
trademarks of ART and CLG.
Julie Chabot is Residue R&D Technical
Manager with ART & CLG Applied Technology,
Richmond, California. She has 26 years
of experience in residue hydroprocessing
technology development and holds a MSc and
a PhD from the University of Western Ontario,
and a BSChE from Université Laval.
Email: chbt@chevron.com
Woody Shiflett is Manager, ART & CLG Applied
Technology, Richmond, California. He has 38
years’ experience in catalyst technologies
and enterprises and holds a PhD in chemical
engineering from the University of Wisconsin,
MBA from Texas A&M University, and BSChE
from the University of Akron.
Email: wosh@chevron.com
Additional contributors
The authors would also like to thank the
following individuals for their contributions
to this article: Balbir Lakhanpal, ART; Dan
Gillis, CLG; Bruce Reynolds, CLG; Cesar Ovalles,
Chevron.
01.03.2019 10:15:28
PTQ Q3 2019 97
14/06/2019 10:55
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nalco.indd 1 13/06/2019 10:25

 Best practice for refinery flowsheets
Refinery-wide flowsheets can demonstrate the true representation of changes in
key operating variables and their associated impact on refinery operation
JITENDRA CHELLANI KBC
ASMA AL SARIYAHI Orpic
D
ue to the integrated nature of
process units within a refin-
ery, change in key operating
variables has an impact on over-
all refinery operation and product
blending as well. efinery-wide
flowsheets demonstrate the true
representation of this effect as all
process units are linked together.
Non-linear kinetic or equilibrium
models in the flowsheet represent
the conversion units. Fractionation
models capture the e ciency of
separation between different cuts
or components.
KBC (A Yokogawa Company) has
developed and used refinery-wide
flowsheets for more than 30 years.
Developed in the 1 80s, Petrofine
was a FORTRAN based tool capa-
ble of refinery-wide flowsheeting.
In 2004, KBC launched Petro-SIM
with additional features to simu-
late refinery process units. These
standalone models are combined
to create a complex-wide flowsheet
which includes all process units
within the refinery.
Petro-SIM is KBC’s process simu-
lator used for rigorous modelling of
the entire refinery and petrochemi-
cal complex, from crude to finished
products. Since each unit, includ-
ing conversion units, is modelled
meticulously, the overall simula-
tion suitably reflects the non-line-
arity of petroleum refining which
enables sensitivity analysis over a
wide range of operating variables
and feedstocks.
The conversion units are based on
comprehensive kinetic models that
predict the unit yields and product
qualities. The kinetic models are
calibrated specifically to match the
available plant data for a particu-
www.eptq.com
q3 kbc2.indd 1
lar unit. This allows the simulation
to be representative of the specific
unit’s operation, independent of
the licensor.
Product separation is simulated
using fractionation technology that
represents current operation and
heat balances. Heat-and-material
balanced distillation models which
use a section-by-section approach
rather than simulating each tray are
calibrated to plant data.
KBC and the company’s clients
around the world have developed
numerous refinery-wide flow-
sheets. Petro-SIM based flowsheets
are being used for identification
and evaluation of margin improve-
ment opportunities which include
optimisation of stream routings,
blending strategies, molecular man-
agement, throughput maximisation,
feedstock selection, and improve-
ments in the unit operating con-
ditions. efinery-wide flowsheets
have also been used for configu-
ration studies for grassroots and
revamp configurations.
Flowsheet development
Standalone models for the process
units are the main building blocks
for the refinery-wide flowsheet.
Detailed kinetic and equilibrium
based Petro-SIM models are cal-
ibrated using test run data. Unit
configuration, operating parame-
ters from historian and laboratory
data are used to calibrate stan-
dalone models for the process units.
The data are reconciled to close
mass, sulphur, nitrogen, carbon,
and hydrogen balance. A calibrated
process model mimics the per-
formance of the process unit. The
models are valid over a wide range
of operation as they are based on
first principles and are non-linear
in nature.
To understand overall refinery
operation, a base month is selected.
Base month operation provides an
insight into marginal mechanisms
in the refinery. The data used for
standalone models are based on test
run operating conditions and these
test runs may have been conducted
at a different time period. Due to
this, it is essential to prepare a con-
sistent basis for operating condi-
tions of all process units.
The following guidelines are used
to select the base month for the
flowsheet:
• Crude blend for the month repre-
sents the typical crude blend used
by the refinery
• Crude throughput should be
close to the typical crude through-
put of the refinery
• Most of the process units in the
refinery should be operating at typ-
ical capacities and at normal oper-
ating conditions
• Most of the process units should
operate continuously in stable
conditions
• Changes in the inventory of inter-
mediate streams should not be sig-
nificant.
One of the major challenges is
with regard to inventory. Inventory
changes are not simulated in the
flowsheet as it represents steady
state operation of the refinery.
Inventory changes in feed and
product are used to estimate the net
feed processed and net products
produced in the refinery. Inventory
changes for intermediate streams
affect throughputs of the pro-
cess units and hence it is essential
PTQ Q3 2019 99
24/06/2019 09:07
 that the base month operation has
minimum inventory changes for
the intermediates.
Mass balance for different pro-
cess units may be inconsistent for
refineries which do not use data
reconciliation tools, for instance,
the throughput of a delayed cok-
ing unit measured by the feed
meter may not be the same as the
vacuum residue production meas-
ured in the vacuum distillation
unit. Validating consistencies for
a product which is routed to more
than one process unit and blending
is more challenging. Due to these
issues, data for the base month also
requires reconciliation.
To build a refinery-wide flow-
sheet, all standalone models are
combined. Crude blend for the
crude distillation units (CDU) and
throughputs are updated so that
the flowsheet feed represents base
month operation. Routing strate-
gies used by the refinery are rep-
licated in the flowsheet. During
the flowsheet development phase,
refinery strategies are used for rout-
ings rather than using optimum
routings. Sensitivity analysis to
validate optimum strategies is per-
formed after completing the base
case which represents as-is’ refin-
ery operation.
Understanding refinery stream
routing strategy can be a di cult
task if the refinery has multiple
trains or two to three process units
for a purpose, for instance more
than one diesel hydrotreating unit.
In this case, routings are fixed based
on the feedback from planning engi-
neers and base month data.
Petro-SIM’s blending unit oper-
ation allows flexibility of optimis-
ing refinery blends based on prices,
product demand, product spec-
ifications, and other constraints.
Marginal mechanisms used by the
refinery must be reflected in the
flowsheet product blenders. The
flowsheet must hit key specifica-
tions for each blend, such as octane
for gasoline, flash for diesel, viscos-
ity for fuel oil, and so on. The mar-
ginal streams used by the refinery
should be reflected in the flowsheet
as well.
The refiner also needs to identify
major changes which are planned
100 PTQ Q3 2019
q3 kbc2.indd 2
Round table discussion and
data collection
Unit data
Heat and mass
balance Overall yield data
refinery-wide
Historian
Lab analysis
Reconstruction of refinery
and unit data
Individual model calibration
Refinery-wide flowsheet
Unit throughput
Production of different grades
for base month
Crude basket
Product demand
Operating targets
Base case
Figure 1 Work process for refinery-wide
flowsheet development
in the near future including the
revamp of a process unit or a sig-
nificant shift in the crude basket.
The refinery-wide flowsheet may
be updated with these changes after
which it represents the base case
operation of the refinery.
The work process to develop the
refinery-wide flowsheet is shown in
Figure 1.
Flowsheet complexity
Before building a model, it is
crucial to recognise its purpose.
efinery-wide flowsheets are
used to understand the interaction
between different process units
and the impact on product blend-
ing. Including too many details
in the model increases the time to
build the refinery-wide flowsheet
and efforts required in analysing
the results.
Process engineers still need to
build rigorous standalone mod-
els for various analyses, including
heat integration, column hydrau-
lics, identifying constraints for
throughput maximisation, and so
on. It is recommended to simplify
the standalone model as much as
possible before using them in the
refinery-wide flowsheet. The refin-
ery-wide flowsheet usually includes
a kinetic and equilibrium based
reactor model followed by sec-
tion-by-section’ fractionation col-
umns. Simulating heat exchangers,
pumps, compressors, valves, and
other items is not recommended for
refinery-wide flowsheets.
Scenarios or problems which can
be evaluated using the refinery-wide
flowsheet are different from those
which require detailed standalone
models of the process units. The fol-
lowing should be evaluated using
the refinery-wide flowsheet:
• Optimum feed selection of the
process units
• Incentive of debottlenecking a
process unit
• Trade-off between unit through-
put and conversion
• Optimum product distribution
from a process unit
• Molecular management of naph-
tha components between different
process units and blends
• Estimation of the optimum unit
operating target.
The following should be eval-
uated using detailed standalone
models of the process units:
• Identification of constraints to
achieve optimum conversion or
operating target
• Required changes in the process
unit for achieving targeted through-
put vs conversion trade-off
• Investment required for unit
debottlenecking
• Detailed analysis of the equip-
ment in process units which
includes unit hydraulics, heat inte-
gration, and so on.
• Troubleshooting and root cause
analysis.
Models in the refinery-wide flow-
sheet should still be able to monitor
key operating constraints. Petro-SIM
reactor models allow monitoring
of major operating variables in
the process units such as main air
blower limitation in catalytic cracker
or gas/oil ratio in hydroprocess-
ing units. If the constraints are spe-
cific to any equipment such as fired
www.eptq.com
15/06/2019 07:37
 heater tube metal temperatures, this equipment
may be simulated in the refinery-wide flowsheet.
Petro-SIM Workflows provide a technique for
monitoring key constraints in a complex flow- WHAT CAN ENSURE MY
sheet. Workflows can be configured by the user
and key constraints in the refinery process units,
PLANT‘S LONG-TERM
blends and product logistics can be added in the
flowsheet. With Workflows available in the flow-
EFFICIENCY?
sheet, quality checks of the results can be per-
formed quickly. Hand-over of the flowsheet from
one process engineer to another can be done fast.
Workflows ensure that the results are always con-
sistent and constraints have not been overlooked.
For most cases, including extra equipment
increases the time required for building mod-
els and troubleshooting but has minimal impact
on the time for flowsheet convergence. The time
required for the convergence is a function of log-
ical ops, recycle and adjust ops. quipment or
process units within a recycle loop increase the

Refinery-wide flowsheets
are used to understand the
interaction between different
process units and the impact
on product blending
EXPERIENCE!
time necessary for convergence. Few of the recy- The know-how of more than 60 years empowers Böhmer
to build Ball Valves that help customers to realize their
cles include process units and product blending projects efficiently & successfully for the long term.
as well, such as light cycle oil used as cutter stock
and processed in a diesel hydrotreater, heavy
naphtha used as low flash blending component, 1/8 TO OIL, GAS, STEAM, CHEMICALS UP TO
56 INCH & SPECIAL APPLICATIONS 800 BAR
and feed for a naphtha hydrotreater (NHT).
The hydrogen network is one of the recycle
loops which may consume a significant amount
of time for flowsheet convergence. Kinetic based
models for hydroprocessing units in the flow-
sheet estimate the hydrogen demand. Kinetic
based models in the flowsheet estimate the hydro-
gen available from the producers. Using the sup-
ply-demand gap, the required throughput for the
hydrogen generation unit is estimated in the flow-
sheet. If the refinery uses low purity hydrogen in
the make-up for hydroprocessing units, the con-
vergence of the low purity recycle also increases
the time for flowsheet convergence.
Nesting is one of the techniques available in
Petro-SIM which can reduce flowsheet conver-
gence time. Using nesting, users can set the prefer-
ence for the process unit convergence. One of the
best options is to give preference to atmospheric
and vacuum residue processing units followed by
middle distillate processing units and then naph-
tha processing units. Vacuum residue process-
ing units produce naphtha due to cracking which
affects naphtha processing units whereas vice-
versa is occasionally possible.

www.boehmer.de

q3 kbc2.indd 3 15/06/2019 07:37


Base case
Cut point optmisation
Stream routings
Molecular management
Blending
Unit feed selection
Figure 2 Opportunity evaluation using refinery-wide flowsheet
Flowsheet utilisation
KBC and the company’s clients
have used Petro-SIM refinery
and complex-wide flowsheets for
numerous objectives. The refin-
ery-wide flowsheet is one of the
main tools used to evaluate oppor-
tunities under the company’s
margin enhancement programme
(Profit Improvement Program, PIP).
KBC uses the methodology shown
in Figure 2 to evaluate identified
opportunities.
The refinery-wide flowsheet
(the base case) is used to assess
the impact of a change in oper-
ating conditions, routings, blend
management, and so on. As it is
di cult to analyse results when
all independent variables are opti-
mised at the same time, only one
opportunity is assessed at a time
using the base case. This approach
is used to identify improvements
in operating strategies rather than
achieving optimum numbers from
a simulation. The flowsheet pro-
vides a quantitative analysis of
an opportunity, but it is essential
that the focus is on identifying
improved strategies rather than
targeting specific numbers. The
absolute value of the KPIs may
change in an operating refinery due
to various changes such as differ-
ent crude basket, varying product
demand, and catalyst change-over.
The improved strategy identified
using the flowsheet is usually valid
for all these changes but the values
of KPIs are different.
102 PTQ Q3 2019
q3 kbc2.indd 4
Opportunity cases
Opportunity case,
cents/barrel
Opportunity case
Opportunity case
Opportunity case
Opportunity case
Petro-SIM is capable of generat-
ing an automated xcel interface.
The xcel interface is linked with
Petro-SIM flowsheet and provides
mass and volume balance for the
overall flowsheet and for each
process unit as well. Properties
of streams within the flowsheet
and all operating variables of the
reactors and fractionation are also
available in the xcel interface. The
Flowsheets can
provide an in-depth
analysis of changes
in the product slate
with upgradation of
bottom of the barrel
and its impact on
existing units
xcel interface can be tailor-made
based on user preferences.
Mass or volume balance esti-
mated by the refinery-wide flow-
sheet along with the price set are
used to assess the economics of
each opportunity. Using this meth-
odology, techno-economic analysis
is performed for each opportunity.
KBC’s clients also use this approach
to identify and evaluate opportuni-
ties for improvements. One of the
user case studies is discussed later
in this article.
KBC has also used refinery-wide
flowsheets for configuration and
reconfiguration studies. Flowsheets
can provide an in-depth analy-
sis of changes in the product slate
with upgradation of bottom of the
barrel and its impact on existing
units. Non-linear equations used
for kinetic and equilibrium models
of the existing units are essential
for reconfiguration studies in which
considerable changes are expected
in feed for the existing process
units. The flowsheet linked with
the xcel interface along with capex
and opex estimation tools provide
inputs for financial analysis.
Users have applied the refin-
ery-wide flowsheet to evaluate dif-
ferent feedstocks available for the
refinery and petrochemicals com-
plex. Petro-SIM allows seamless
propagation of detailed naphtha
components available in the crude
assays. valuation of feed for an
aromatics complex requires rig-
orous simulation of the reformer,
trans-alkylation, isomerisation,
and component based fractionation
which includes extractive distil-
lation. A case study for feedstock
evaluation at an aromatics complex
is discussed later in this article.
efinery engineers usually per-
form quality give-away ( GA)
analysis on a monthly basis. GA
analysis focuses on the proper-
ties which are constrained in the
blends, such as ON and VP for
gasoline, or flash point and recov-
ery for diesel. One of the main
inputs for GA analysis is a loss
of margin per unit of give-away in
key constraint, for instance gasoline
ON of 2 compared with a spec of
1. The loss of margin can be eas-
ily estimated for some of the con-
straints, for instance gasoline ON
if naphtha is used as the low octane
blending component. stimation of
the loss of margin for some of the
properties requires rigorous sim-
ulation, say diesel recovery which
can be corrected by increasing the
cut point of heavy gasoil (HGO) in
the CDU which affects feed for the
diesel hydrotreater and fluid cata-
lytic cracker (FCC). KBC has used
the refinery-wide flowsheet to esti-
mate the impact of GA reduction
in numerous PIPs.
www.eptq.com
15/06/2019 07:37
 Photo ©Shutterstock
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afpm.indd 1 13/06/2019 10:04

CDU/VDU
Feeds
Figure 3 Orpic complex-wide flowsheet
Flowsheet maintenance
Maintenance of the flowsheet is as
important as developing it. Results
from the flowsheet may deviate
from actual operation if changes
are not made in the flowsheet on
a regular basis. efinery routings,
marginal mechanisms, blending
strategies, and so on do not change
on a frequent basis. Changes in the
infrastructure of process units, cat-
alyst replacement, and under-per-
formance of major equipment
affect the overall performance of
the refinery. Due to this, the main
changes are usually made in the
standalone models which need to
be updated in the flowsheet as well.
ecalibration of the standalone
models is required for replacement
of the catalyst. Catalyst deactiva-
tion in fixed bed reactors usually
does not require recalibration. If
users can provide the age of the
catalyst, then Petro-SIM can pre-
dict the status of the catalyst and
its impact on the yield distribu-
tion from the unit. If few items of
equipment are underperforming,
say damaged trays in a column, a
model may need to be recalibrated
for these changes.
KBC uses Petro-SIM’s collabora-
tion functionality to update kinet-
104 PTQ Q3 2019
q3 kbc2.indd 5
Conversion
Stream
units
routings
ics and fractionation models in
the flowsheet using updated stan-
dalone models. Collaboration can
be used o ine or through a com-
mon server which connects stan-
dalone models with the flowsheet.
Case study
Orpic is one of Oman’s largest
and most rapidly growing busi-
nesses. Orpic’s refineries in Suhar
and Muscat, as well as the aromat-
ics and polypropylene production
plants in Suhar, produce fuel, plas-
tics, and other petroleum products.
In a collaborative effort, KBC and
Orpic developed a complex-wide
flowsheet which includes the
Suhar and Muscat (MAF) refiner-
ies. The complex-wide flowsheet
also includes an aromatics plant.
The snapshot shown in Figure 3
provides an overview of the com-
plex-wide flowsheet.
The envelope of the flowsheet
starts at the feeds for the complex
and the finished products pro-
duced by Orpic are the final prod-
ucts from the flowsheet as well.
Crude to the CDUs is defined
using the crude assay, and few
of the import streams are defined
using the required properties and
detailed composition.
Product
blending
Products
Suhar
complex
Muscat
refinery
Stream routings in the flowsheet
represent the routing strategies used
by Orpic. All conversion units in the
refinery and aromatics complex are
simulated using Petro-SIM reactors
which are based on non-linear kinet-
ics and equilibrium. The process
units in the flowsheet include frac-
tionation models as well.
Petro-SIM blenders are used to
optimise product blending based
on prices of different products,
market demand, and specifications.
Petro-SIM workflows configured in
the flowsheet ensure that the major
constraints of the refinery and pro-
cess units are not violated.
The flowsheet provides a detailed
understanding of the interaction
between the different refineries and
the petrochemicals complex. As all
process units are interlinked, the
impact of change in the operating
condition of any process unit affects
all process units in the downstream,
recycles, and product blending
as well.
The Orpic flow sheet has been
utilised for many studies. One
of them was to utilise the excess
amount of condensate stream from
the MAF complex to the aromat-
ics (AP) complex to maximise the
Suhar isomerisation unit (ISOM).
www.eptq.com
15/06/2019 07:37
 In normal operation, OLNG con-
densate is imported feedstock used
as the main feed in MAF NHT
to maximise PENEX feed since it
comprises approximately 65% of
light naphtha components. In some
cases, and mainly when there is a
limitation in MAF NHT, the agreed
amount of this condensate is not
fully processed in the unit so the
excess amount of it is shipped to
Suhar and then sold out as light
naphtha stream or blended in the
Suhar gasoline pool.
It was found that processing of
this stream to the AP NHTs will
increase light naphtha feed to the
isomerisation unit, so it will be
recovered as gasoline with RON of
91. The current throughput of ISOM
unit ranges from 80% to 100% and it
can increase to 110%.
On the other hand, in some cases
the availability of AP imported
feed in the market contributes to
AP NHT utilisation which affects
ISOM feed. Processing OLNG con-
densate in the AP NHT in this case
could recover reduction of the
light naphtha stream and sustain
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isomerisation throughput in the
higher side.
Conclusion
efinery-wide flowsheets can
demonstrate the true representation
of changes in key operating vari-
ables and their associated impact
on overall refinery operation and
product blending. They are being
used for identification and eval-
uation of opportunities for mar-
gin improvement which include
optimisation of stream routings,
blending strategies, molecular man-
agement, throughput maximisation,
feedstock selection, and improve-
ments in unit operating conditions.
Detailed kinetic and equilibrium
based models for process units
are the main building blocks for a
refinery-wide flowsheet. These are
connected and calibrated using test
run data, and operating parameters
from historian and laboratory data.
Development of the flowsheets
is critical as including too many
details increases the build time as
well as the efforts required in ana-
lysing the results.
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Adding the price set data of the
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improvement programme or just
part of troubleshooting solutions.
To ensure top performance,
workflows and regular check-ups
are required. Changes in the infra-
structure of process units, catalyst
replacement, under-performance of
major equipment, and so on affect
the overall performance of the
refinery and therefore need to be
reflected in the refinery-wide flow-
sheet as well.
Jitendra Chellani is Senior Consultant with
KBC (A Yokogawa Company) in Abu Dhabi. He
has over 14 years of experience in refining,
process simulation and consulting and holds
a master’s degree in chemical engineering
from Institute of Chemical Technology,
Mumbai, India.
Asma Al Sariyahi is is senior Process Engineer
with Orpic in Sohare. She has over eight
years of experience in refining and process
simulation and holds a bachelor’s degree in
petroleum and natural gas engineering from
Sultan Qaboos University, Muscat, Oman.
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PTQ Q3 2019 105
24/06/2019 13:35
 Co-located with:

ASIA’S MOST INFLUENTIAL EVENT FOR

REFINING, PETROCHEMICALS & CHEMICALS
30 - 31 October 2019
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Organised by:

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ADS.indd 1 13/06/2019 10:03

 Preventative maintenance of
piping systems
The design of the piping system is a major part of the engineering of an operating
plant build

SHIRISH LAL
Piping Technology & Products

O
n average, piping constitutes
40-48% of the engineering
hours in a new refinery. The
challenge facing piping engineers
is rotating equipment locations and
process design are defined, and they
must make the piping system fit
within the designated space while
dealing with thermal stress, proper
flow, and allowable loads for all
equipment. With temperatures in
high energy lines often well over
1000°C, this can be very challeng-
ing. The following are some of the
goals of pipe stress engineering
and the placement of spring sup-
ports and expansion joints in the
piping system:
• Ensure stress at the interface to
moving equipment is below maxi-
mum allowable loads
• Minimise turbulent flow through
the piping system
• nsure the longevity of piping
system components.
Table 1 shows the strategies that
PT P commonly sees at different
operating plants. We have seen
many examples of each of these
strategies. Typically, the strat-
egy taken at an individual plant is
closely related to the overall operat-
ing philosophy of the organisation,
including finance. However, we
also speak to a number of organisa-
tions that have placed an emphasis
on preventative maintenance but
are not sure of the best practices for
the engineered pipe supports and
expansion joints.
A refinery case study at the end
of this article shows an example of a
programme executed in March 2019
on a turnaround. For preventative
maintenance, best practice is to not
just focus on the health of the pip-
ing system components, but on the
health of the overall piping system.
The following are some of the issues
PT P has found that cause system
level issues:
• Spring support failure impact:
the failure of a spring support will
impact other supports and cause
them to possibly fail as they attempt
to take on the additional load of the
failed spring.
• Damage to piping or rigid supports
changes elevation of spring sup-
ports: a variety of issues can cause
the piping to undergo strain, which
causes deformation. This will cause a
change of elevation or distance from
the pipe support to the pipe, and
impact the load setting and connec-
tions to other equipment.
• Improper travel stop management:
if travel stops are not removed, the
spring supports are essentially a
rigid support, and the load can be
redistributed among the spring
supports on the same line in a way
that is not consistent with the origi-
nal design.
• Improper initial installation: one of
the most common issues PT P finds
in its audits is that engineered sup-
ports are improperly installed dur-
ing initial installation.
By the time a plant reaches 10
plus years of age, our experience is

Pipe support and expansion joint maintenance strategy

Strategy Pros Cons

Fix when broken • Maximise short term cash flow
• Potentially moves financial impact from opex to capex
• Limits overspending on preventative maintenance
• Likely leads to allowable stress being beyond max for
some moving equipment
• Will lead to maintenance issues with moving equipment
• Can lead to premature failure of piping system
• Could lead to a plant shutdown

Periodically fix broken springs • Insures broken spring support are replaced prior to • Does not ensure the proper functioning of each spring
(component level focus) causing issues without adjusting spring supports which are out of position

Periodically return to original
design specification
(system level focus)
• Ensures the system is brought back to original design
minimising strain on moving equipment
• Minimises stress on the piping system
• Higher short term expense
• The business case can be challenging due to the
medium/long term nature of savings
• Potentially more opex vs capex
• Minimises risk of an unplanned outage

Table 1

www.eptq.com PTQ Q3 2019 107

q3 ptp.indd 1 15/06/2019 07:41

 Figure 1 Installed condition inspection of springs supporting a manifold of a heater (left, cold inspection; right, hot inspection)
that most plants have encountered
one or more of the above issues.
For this reason, it is essential to
take an approach of resetting the
line to the original design specifica-
tion. Best practices for performing a
reset to design specification are the
following:
• Hot and cold audit: required to
understand the range of movement.
• View of functioning of springs/
expansion joints across line: the view
of how a spring is functioning can be
highly dependent on whether there
are many failed supports on the line
versus just one.
• Plan for adjustments and replace-
ments: the overall plan for a turn-
around must be comprehensive in
terms of adjustments.
• Proper management of travel stops:
we have found tremendous confu-
sion on the proper timing for place-
ment of travel stops; if this is not
done correctly, in many cases it is
not possible to reset the line to the
original design specification.
Figure 2 Inspection following replacement of spring supports (left, cold; right, hot)
108 PTQ Q3 2019
q3 ptp.indd 2
• Repair rigid support issues: a com-
mon issue we have run across is a
damaged or removed pipe shoe or
saddle, resulting in the piping sitting
on the supporting pipe rack.
• Assess elevation changes: changes
in elevation due to changes or defor-
mation of piping can cause a spring
support to be out of position; this
issue should be addressed as an
issue with the line rather than the
spring support.
• Identify design changes: PT&P
sees many situations where there
have been alterations to the line,
such as new equipment without an
update of the stress analysis. The
best approach is to redo the stress
analysis; however, the budget or
time constraints may require a
quick and dirty approach such as
weighing the line.
• Adjust in real time as needed: given
all of the issues above, resetting a
piping line to design specification
takes real-time decision making dur-
ing an audit.
The challenge with this approach
to preventative maintenance is
that it takes a much deeper level of
expertise than a component level
inspection. Our experience is that
even the ability to operate a pipe
stress modelling software program
such as Caesar is far different than
a pragmatic understanding of the
proper functioning of all the ele-
ments of the piping line. Many per-
sonnel and firms supporting piping
system maintenance are challenged
with managing a broad range of
equipment at an operating plant,
and this can make it di cult to have
the depth in pipe stress that may be
required to properly execute a sys-
tem level audit and execute a plant
to return the piping system to the
original design specification.
The sole purpose of performing
audits is to maintain the piping sys-
tem and equipment to remain in
the proper condition. Therefore,
the system level (pipe stress audit)
that considers the physical condi-
www.eptq.com
15/06/2019 07:41
 tion of the system along with the
spring supports system should be
preferred. As mentioned earlier, the
component level audit is an impor-
tant part of the system level, which
if put together with other system
and/or deformation assessment can
give the overall picture of the system
and finally a better direction for the
proper maintenance.
Example of system level repair work
We performed an installed inspec-
tion on all the springs supporting a
manifold of a heater. The installed (or
cold) condition inspection showed
that most of the supports were oper-
ating properly. However, after per-
forming a second inspection in the
operating (or hot) condition, it was
concluded that most of the spring
supports did not show any signs of
movement (see Figure 1). This issue
was brought up with the customer,
and it was determined they were
having some issues with the heater
tubing affecting the e ciency.
Since this issue needed to be
addressed to prevent any failures in
the future, all the supports from the
manifold were assessed and it was
concluded that there was a need for
system level repair. Therefore, on a
2019 turnaround, all the spring sup-
ports of the manifold were replaced.
Figure 2 shows that the new sup-
ports are moving as designed and
system-wide repair was indeed
required. Altogether, 35 spring sup-
ports on manifolds were replaced
due to failure of previous spring
supports.
Turnaround plan and execution for a
major refinery
Pipe supports
10 units
>600 spring supports
12% adjusted
14% replaced
Expansion joint installation
supervision
36 expansion joints replaced
Work scope
PT&P provided two engineers for:
A. Pipe supports inspection during
the installed or cold condition
B. Supervision on adjustment of the
spring supports
www.eptq.com
q3 ptp.indd 3
C. Installation of spring supports for
the period of 30 days.
In addition to the above, we pro-
vided a supervisor (expansion joint
technical expert) to supervise the
installation of expansion joints.
Planning
We provided two engineers about a
year before the turnaround to per-
form the operating inspection of
the spring supports, while a cold
inspection was done in the previous
turnaround. All of these inspected
supports were documented in a
report and the conditions were cat-
egorised as good, replacement or
adjustment required.
Pre-turnaround
Based on the location provided in
the inspection report, and constant
communication between PT&P engi-
neers and turnaround co-coordina-
tors, the location where the scaffold
was to be built was pre-planned.
The materials were purchased a
few months before the turnaround.
All the required safety training, drug
tests, and background checks were
done prior to the turnaround date.
During turnaround
Out of 10 units, four were shut down
upon arrival at the site. Our engi-
neers performed a quick walk-down
on all the spring supports in the
units to see if there were any new
issues since the last inspection which
required immediate attention. This
gave enough time to order the mate-
rials and necessary hardware.
After the quick inspection, we
worked with a few client technicians
on two different units. The adjust-
ment and installation work on the
two units was done concurrently.
Once those units were completed,
our engineers were mobilised to
other units. There were a few new
discoveries, where the engineers
ordered materials for adjustment
and replacement. Within a couple
of days, we managed to supply the
parts and resolve the issues. It was
convenient to have engineers super-
vising the installation and repair,
as it allowed for design and/or
engineering changes to be made on
the spot.
In addition to the pre-planned
turnaround work, on several occa-
sions our engineers helped to resolve
issues such as bent struts, check
the condition of counterweights
(old style), and carry out some new
expansion work, which included the
addition of new pipe supports.
A rod was bent during the turna-
round because the contractor work-
ing did not reinstall the travel stop
while working with the line. The
support should have been locked
and disengaged from the system
for this specific work on the pipe
coming out of the reactor. The line
seemed to have higher movement
than anticipated during the turn-
around work. This was the sec-
ond time the rod was bent. PT&P
engineers, which were on-site for
other spring supports work, were
contacted immediately. Less than
an hour later, our field service tech-
nicians assessed the condition and
suggested an improved, robust
design. The materials were pur-
chased as per PT&P engineers’ rec-
ommendation. Within a couple of
days, the materials arrived and were
successfully installed. Everything
operated correctly during the fol-
low-up hot inspection.
For expansion joints (EJ)
Our supervisor was on site the entire
time, helping the contractor remove
and install the new EJs. Almost
all of the contractor workers were
inexperienced or had very limited
experience working with EJs. Our
supervisor provided training about
removing and installing the new
joints and pointed out the impor-
tance of being sensitive towards the
EJ fabric, since one small, improper
cut could damage the belt.
The supervisor assisted the con-
tractor with the proper marking of
the backing bar while removing the
old EJ. He inspected the condition
of the joint and guided contractors
to e ciently install the new joint,
then demonstrated the proper way
to splice the fabric materials to com-
plete the installation.
Shirish Lal is Vice President with Piping
Technology & Products, Houston, Texas.
PTQ Q3 2019 109
15/06/2019 07:41
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refining ad.indd 1 12/03/2019 14:25

 Technology in Action
Prescriptive maintenance software boosts
refinery performance
Saras is the owner of the most complex refinery in the
Mediterranean, with 300 000 barrels per day of refining
capacity. As part of a digitalisation programme, Saras is
evaluating ways to drive greater reliability in its capi-
tal and asset intensive refinery operations. The refiner
selected Aspen Mtell software based on a competitive
pilot project selection process which initially focused on
critical refinery equipment, such as large compressors
and pumps.
Aspen Mtell mines historical and real-time oper-
ational and maintenance data to discover the pre-
cise failure signatures that precede asset degradation
and breakdowns, predict future failures and prescribe
detailed actions to mitigate or solve problems.
Implementation
Aspen Mtell was able to execute this pilot project
within weeks, impressing Saras with its speed of
deployment, accurate early detection of asset failures,
avoidance of false alarms and ability to scale the solu-
tion system-wide. Saras plans to use its sister engineer-
ing company, industrial automation specialist Sartec, to
roll out Aspen Mtell refinery-wide. The initial project
focused on four pieces of equipment:
• Feed pump: pumps liquid charge from other plants
towards the exchange train
• Wash oil pump: recycles wash oil coming from the
separator toward the mixer
• Makeup H2 compressor: streams make-up H2 from the
hydrogen supply toward the main exchange train
• Recycle compressor: recycles H2 coming from the
exchange train.
The desired outcomes of the pilot project were:
• An accurate solution that detects precise patterns of
normal behaviour, failures and anomalies
• A solution that indicates early warning, with signifi-
cant lead time from point of detection to actual failure
• The ability to capture a failure signature and use it to
detect failures in unseen data on the same assets and/
or similar assets.
The data used for the Aspen Mtell agents consisted
of 52 million sensor values, including condition data
and process data. The team reviewed 1 3 quality issues
(such as bad values and missing values) and cross-
referenced the work order history of the four assets,
including 340 prior work orders. The maintenance his-
tory spanned 17 problem classification codes.
Measurable results
The project achieved all objectives, and the Aspen Mtell
agents were able to predict failures with significant
lead time:
www.eptq.com
tia copy 5.indd 1
• High valve temperature: 3 days
• Oil seal replacement: 45 days
• Pump seal replacement: 33 days
• Gas seal replacement: 24 days.
The agents accurately identified the specific failure
mode and did so without false positives. These capa-
bilities are expected to reduce unplanned shutdowns
by up to 10 days, increase revenue by 1-3 , reduce
refinery maintenance costs and cut operating expenses
by 1-5 .
Aspen Mtell executed the project within weeks,
thanks to its accurate early detection of asset failures,
speed of deployment, avoidance of false alarms and
ability to scale the solution system-wide. Alessandro
ucca Digital Platform Manager, Operations and
Assets with Saras, said, Improving reliability posi-
tively impacts a wide range of issues, from reducing
current maintenance costs to planning for abnormal
process conditions, avoiding emergency or unplanned
shutdowns and successfully managing unpredictable
feed and demands. Saras expects to achieve savings
from this initiative, which is part of an important digi-
tisation project.
Aspen Technology
For more information: alexs@whiteoaks.co.uk
Catalytic lube dewaxing defeats feed
contamination
A base stock manufacturer was experiencing poor lube
plant feed quality stemming from refinery equipment
problems. The hydrocracker producing the feed to the
lube plant had developed a leak in the high pressure feed
e uent heat exchanger. The unconverted oil (UCO) was
therefore contaminated with raw feed containing vac-
uum gasoil and coker gasoil, causing high nitrogen, sul-
phur, aromatics, and polynuclear aromatics in the UCO.
This situation could have diminished produc-
tion capacity and/or undermined the quality of the
base stocks. The manufacturer was concerned about
maintaining product quality and production rates,
which directly impact profitability, while avoiding a
costly shutdown.
xxonMobil engineers worked closely with the oper-
ator to assess options and identify the most effective
solution for maintaining production rates at the same
yields and quality. As an owner-operator, xxonMobil
has a lot of experience and understands how to address
similar operational issues.
An analysis of the situation indicated that
xxonMobil’s MSDW technology could easily with-
stand the increased contamination levels with simple
operational adjustments that would not affect produc-
tion rates nor yields.
PTQ Q3 2019 111
16/06/2019 13:13
 Hydrofinishing 50
UCO
feedstock (MAXSAT)
40

HDW ART increase, ºF

30

Base stock yield

20
Dewaxing High quality
(MSDW) base stock 10 Base stock yield
HDW ART increase
Figure 1 MSDW technology utilises two 0
0 1000 2000 3000 4000 5000
temperature stages
Normalised days on stream

MSDW technology indeed han- Figure 2 The refinery continued to operate the lube plant at full rate and unchanged yields
dled the refiner’s feed quality issue
because of its high tolerance to contamination even water washing of the crude is effective at removing
when the nitrogen feed content approached 50 wppm. these and that the oil can be e ciently separated prior
The technology uses proprietary catalysts to hydroi- to crude distillation.
somerise n-para ns and saturate aromatics for maxi- cient separation requires the use of accurate
mum yields of very high quality base stocks. and reliable interface control to manage its posi-
Over 20 years of operating experience and continu- tion and quality. An increasing number of refin-
ous D advances, the performance of the MSDW pro- ers have deployed the Tracerco Profiler for desalter
cess has progressed to offer high catalyst activity, yield, interface control.
and stability. The process is very simple and utilises This device provides an accurate measurement of the
two temperature stages (see Figure 1). The first stage density distribution within a desalter, offering continu-
contains the MSDW selective hydroisomerisation cata- ous high resolution imaging and control of each phase.
lyst, and the second contains the Maxsat hydrofinishing This allows the most e cient operating conditions to be
catalyst that removes polynuclear aromatics for thermal maintained as well as monitoring the effectiveness of
and oxidative stability, and colour. chemical additive and mud washing.
With repeatable, accurate, and reliable real-time pro-
Maintained production cess measurements, the Profiler provides operators
The refinery continued to operate the lube plant with with interface confidence. If the interface can be con-
nitrogen contamination much higher than 10 wppm for trolled, it is feasible to raise the interface level closer
over two years, at full rate and unchanged yields (see to the coalescing electrostatic grid system, which in
Figure 2). turn enhances separation of crude from water. By opti-
A shutdown to resolve the issues in the hydrocracker mising separation to improve feedstock flexibility,
was not necessary. upstream desalter mixing can be increased to maxim-
The company estimated the cost savings resulting ise wash water contact, thus removing more undesira-
from the ability to maintain rate, yields, and avoid a ble materials.
shutdown at approximately 75 million. Moreover, the Following a desalter improvement initiative, a
company’s reputation for reliable supply of high qual- uropean refiner said that the Profiler provided inter-
ity base stocks was maintained. esting information on the workings inside the desalter
that was otherwise unseen. It allowed the refiner to
ExxonMobil see rises in the solid layer along with the effect of mud
For more information: www.catalysts-licensing.com washing on this solid layer. The depth of the emulsion
layer and its position within the desalter have been seen
with significant changes on different feeds. It is used as
Desalter interface control optimises crude another tool along with lab analysis to make optimisa-
processing tion decisions around the desalter. One unusual thing
that the Profiler has shown is the emulsion layer of a
To improve margins, refiners continuously look to higher density than the water layer found to be asphal-
optimise feedstock blends. Variability can bring sig- tene stabilisation.
nificant operational challenges during the refining A North American refiner said that the accuracy and
process that must be overcome. One critical need is reliability of multiple real-time measurements gave the
the e cient removal of solids, salts, and water from company the confidence to run levels closer to the grid,
crude feedstock. yielding higher e ciencies and throughputs, includ-
This has become increasingly di cult when process- ing the ability to process lower cost opportunity crudes.
ing certain opportunity crudes that can have all of these The refiner gained the ability to effectively process
detrimental properties at high levels. It is essential that alternate feeds and increased throughput by 20 000 b/d.

112 PTQ Q3 2019 www.eptq.com

tia copy 5.indd 2 16/06/2019 13:13

 4 – 7 November 2019 | Hilton Warsaw, Poland
The single largest gathering of ref ining and petrochemical leadership within Europe

Topics and New Sessions to

Look out for in 2019:
Over 40 speakers already
conf irmed including:
An increased focus on downstream’s role in
the energy transition and the impact of the Dr. Mateusz Aleksander Bonca
circular economy CEO
Grupa LOTOS S.A.

• Sustainability Keynote: Redef ining Growth in the

21st Century
Eric Duchesne
• Future Ref inery Debate: A debate on how SVP Refining & Chemicals,
ref ineries can remain competitive during the Manufacturing & Projects
energy transition Total

• Stream Topic: Clean Fuels, Biofuels & Alternative Antonio Joyanes

Fuel Production
SVP, Refining
• Borealis Keynote: Moving away f rom CEPSA

Single-Use Plastics

Jean Sentenac
Embracing change: gaining a greater Chairman/CEO
understanding of upcoming regulations and Axens SA

disruptive technologies
Tracy Ellerington

• In-focus Workshop Day where we have extended Director - Europe and

Russia Operations
regulatory and digitalisation workshops looking Solomon Associates
at IMO, REDII, virtual reality and artif icial
intelligence. John Cooper
Director General
• Electric Vehicles Keynote and Q&A with Concawe
Audience: The Batteries Are Coming

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CONTACT
Sandil Sanmugam | Project Manager | World Ref ining Association
Sandil.Sanmugam@Wraconferences.com | + 44 207 384 7744

ertc.indd 1 13/06/2019 15:15

 By providing a high resolution measurement around
the emulsion layer, the tendency to overdose chemicals
is reduced. This enables refiners to reduce costs asso-
ciated with chemical dosing, and enhance safety and
associated environmental benefits.
Tracerco
For more information: SMenquiries@tracerco.com
Rust to robust for Spanish refinery
The e cient prevention and minimisation of corrosion
induced deterioration in distillation columns is a key
aspect helping refineries to remain productive and com-
petitive. One of the world’s major integrated energy
companies was experiencing corrosion issues on a num-
ber of units in its refinery complex in Spain. Sul er’s
automated weld overlay capabilities provided an eco-
nomical and e cient solution to debottleneck the differ-
ent columns and extend their service lives.
The refinery complex is one of the five largest in
Spain. The plant processes crude oil to obtain a broad
range of chemicals, such as methyl methacrylate
and polypropylene.
When the refinery noticed extensive corrosion
within the column shells of three main separation tow-
ers, it sought to investigate the issue and protect its
plant from costly shutdowns or lengthy periods of
suspended production.
The initial inspection revealed that the column shells
of the atmospheric distillation unit (ADU), the vacuum
distillation unit (VDU), and a third fractionator were
experiencing corrosion and erosion responsible for
cracks, pitting and material losses. In particular, the col-
umn showing higher levels of corrosion was the VDU.
The structure of the VDU consisted of one wash
bed and three pumparound circuits for the recovery
of heavy vacuum gasoil (HVGO), light vacuum gasoil
( VGO) and light light vacuum gasoil or very light vac-
uum gasoil ( VGO). The tower had an internal diame-
ter of .15m and its shell was made of carbon steel cou-
pled with a 3mm bonded plate to prevent corrosion.
Over time, the plate started to corrode and lost its abil-
ity to protect the underlying column shell. Based on the
visible damage present on the bonded plate, the surface
area of the damage was estimated at around 65 m2.
In order to repair and upgrade its columns, the refin-
ery turned to Sul er, whose Tower Field Service group
has been supporting the company in the past with rou-
tine maintenance activities and field services.
Reinforcing fractionating columns
Sulzer’s team performed an in-depth visual inspection.
To do so, the bonded plate was removed to expose the
carbon steel shell. This examination revealed that the
extent of column shell corrosion was almost double that
of the initial estimate, covering approximately 110 m2.
In these situations, refineries are often faced with the
choice between replacing the entire column or part of it,
which is costly and time consuming, or applying ther-
114 PTQ Q3 2019
tia copy 5.indd 3
Figure 1 Sulzer’s automated welding delivers corrosion protection
for distillation columns
mal spray coatings that can prevent column corrosion
only for a limited time.
Sul er offered a third, more time e cient, economi-
cal and long lasting option: weld overlay. By using this
in situ process, it is possible to cover large column sur-
faces with corrosion resistant alloys. The company has
developed fully automated weld overlay equipment to
support its operations.
This machine consists of a carriage travelling along
a laser levelled track system fixed to the column shell
wall. On the carriage, a robotic index arm moves the
welding torch and the oscillator in order to create weld
beads (see Figure 1). All the relevant process parame-
ters, such as carriage speed or bead thickness, are con-
trolled by a programmable logic controller (P C), with
which human operators can communicate by means
of human machine interfaces (HMI). One single P C
can monitor multiple welding machines following the
same instructions.
The automated process can quickly perform weld-
ing with high accuracy. As a result, refiners can benefit
from a consistent process as well as short downtime. In
this case, Sul er could complete the overlay of the 110
m2 VDU corroded surface in the time allocated to 65 m2.
In order to reduce the likelihood of future corro-
sion, the VDU column shell was overlaid with lay-
ers of austenitic stainless steel type 31 alloy, which is
widely used in welding processes to avoid carbide pre-
cipitation. In addition, the presence of molybdenum
and nickel makes the alloy suitable for applications in
harsh conditions.
Maintenance and revamp services
In addition to repairing the VDU column shell, Sul er
performed weld overlay on the corroded surfaces of the
other two towers, namely the ADU and the third frac-
tionator. Also, column internals, such as trays and pack-
ings, were replaced to further improve the performance
of the entire oil distillation system.
Sulzer performed the weld overlay process in two
weeks, while the entire revamp was concluded in 25
days, without any delays despite the discovery of
larger corroded areas within the VDU, increasing the
www.eptq.com
16/06/2019 13:13
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 required weld overlay to almost double the originally
estimated area.
Since the revamp, the refinery has operated smoothly
at full capacity and the solution from Sul er could also
support the shift towards different crudes without
affecting the columns’ corrosion resistance. The cus-
tomer was so pleased with the work that it offered to
provide positive reference to any potential customers
of Sul er.
Andrew Petticrew, Business Development Manager
at Sul er Tower Field Services, said, The ability of
Sul er’s experts to resolve unexpected issues, coupled
with our automated weld overlay capabilities, were
crucial to ensure the timely repair of the corroded col-
umn shells. In addition, the customer could benefit
from a one-stop shop for the revamp project, as we took
care of dismantling the existing column internals, as
well as the manufacture and installation of new ones.
Sulzer Chemtech
For more information: andrew.pettictrew@sulzer.com
Boosting refinery boiler efficiency
Based on work installing and upgrading refinery boil-
ers, there are certain lessons learned, from which other
refineries can benefit.
Design conservatively
efineries demand high reliability. Unscheduled down-
time must be avoided at all costs. Therefore, boil-
ers should favour a relatively conservative design.
One refinery, for example, needed a new boiler as part
of the processing of low sulphur crude oil. Its man-
agers understood that the specification of the lat-
est features could add operational risk. The refiner
wanted only field proven solutions and technologies
on the basis that a conservative design translates into
greater reliability.
That means no cutting corners on si ing to save on
price. In the case of this refinery, there was far more to
lose if the boiler was unable to cope with peak produc-
tion demands than can possibly be saved by attempting
to si e a boiler just right’.
The lesson learned is that it is generally advisable to
specify large furnaces, steam drums, and boilers that
may be somewhat oversi ed.
Larger steam drum
There is a trend in the industry to build smaller hot
rod’ boilers. They may offer a short term boost in per-
formance, but the lack of capacity tends to allow water
to carry over from the steam drum into the superheater.
This will eventually blow out the superheater.
A large steam drum installed at one refinery allowed
better separation to get water out of the steam before
it went into the superheater. If the feed water flow to
the boiler was lost, a bigger drum allowed more time
to correct the water issue before the steam level fell.
Instead of a minute before experiencing a low level trip,
116 PTQ Q3 2019
tia copy 5.indd 4
a larger drum offered refinery maintenance personnel
up to five minutes more. That proved to be more than
enough time to react and prevent the trip.
Superheater placement
Superheaters had previously posed a maintenance
problem for another refinery. To minimise issues
and boost reliability for an upgrade, it was recom-
mended that the superheater be buried back in the
convection section. This provided more protection
against the impact of hot exhaust gas and extended
lifespan. This design feature also reduced the amount
of refractory. As a result, operators did not need to
worry about replacing refractory seals or rebuilding
refractory walls.
Custom boilers
You can either try to fit the refinery to the boiler or fit
the boiler to the exact needs of the refinery. The for-
mer approach is often problematic. Yes, it is cheaper
as you can specify standard boilers. But where you run
into challenges is that the boiler may not fit in well with
ongoing processes.
It is the same with compressors. The needs of the pro-
cess are far more important than saving a few dollars
by opting for a standardised compressor. It makes long
term financial sense to specify a compressor or boiler
that exactly fits process requirements.
Minimise onsite work
Custom boilers are recommended over standardised
si es. But to cut down onsite work which adds cost, and
minimise onsite disruption during assembly/installa-
tion, several refineries have ordered a custom model
that was built, preassembled, and tested in the fac-
tory, then shipped in one or more pieces. Final instal-
lation and commissioning was then much faster, and
the boiler itself proved to be less expensive than a stick-
built version. This factor is especially important in an
operational refinery.
Pay attention to emissions
Most refineries operate under severe environmental
constraints. Older boilers are often a source of concern
for regulatory agencies. When upgrading or adding a
new boiler, the specification of larger furnaces is a good
way to curtail emissions and minimise problems with
flame impingement. SC s and Coen oNox burners can
also lower NOx production.
Design for the site
No two refinery sites are identical. quipment and
products produced can vary considerably. ecent
orders reflect a variety of requirements. One facility
needed a lot of steam, one wanted to make better use
of waste heat, and another had significant space con-
straints that limited its options. For each of these refin-
eries, boiler standardisation or a cookie-cutter approach
to specification could have caused problems.
Many refinery processes, for example, require a boiler
that follows steam load, firing up and down with the
www.eptq.com
17/06/2019 10:12
 demand. But certain units need a high turndown to
enable them to run reliably at low fire and ramp up
when needed.
The lesson learned is that the needs of the process and
the conditions of the site ultimately should determine
the boiler selected.
Rentech
For more information: hkumpula@rentech.com
Engineered composite repairs for refinery plant
Composite technologies have changed the way repairs
are carried out in petrochemical plants and refineries.
For decades, engineered composite repairs (ECRs) have
been used in a range of applications, proving their reli-
ability and durability in repairing pressurised lines.
Although ECRs can be designed for a breadth of oper-
ating conditions, it is important to recognise that their
e cacy is determined by the quality of the design. To
develop the design correctly, engineers need to have an
understanding of the regulations that govern the use
of composites, a thorough knowledge of the composite
materials that will be used, and an awareness of how
the leak-stop methodology affects the C design.
Applying the standards
Article 4.1 of ASME Post Construction Code 2 (ASME
PCC-2) provides complete guidance for all phases and
processes that use non-metallic composite repair mate-
rials to repair pressurised piping systems. This guid-
ance delineates the testing required based on the
intended use of the ECR system and the type of repair
for which it will be used. Leaking lines (Type B) are
most common in plant environments, and the variables
that must be considered when determining the correct
design for the composite solution are numerous.
One of the most important things to understand
is that a leaking’ repair design, as defined in ASM
PCC-2, refers to a line that has experienced a through-
wall defect that has been sealed by some means before
the ECR is applied, or for which the line is expected to
become through-wall during the repair life of the com-
posite system. The ECR is not designed to seal an active
leak, but it must be designed to withstand pressure
from a structural capacity and maintain an adhesive
bond that inhibits leak propagation.
Designing the ECR
The sealing method dictates the type of repair that
must be designed. If a plug is used to address the leak,
the repair is designed to contain axial propagation.
If a rubber patch and hose clamp are used, the defect
type changes from a circular defect to a circumferential
defect, which requires different design calculations.
Three equations which are based on defect geometry
and size are used to design the repair, each with a set
of limitations and criteria to consider: circular or near-
circular defects, circumferential slot defects, and axial
slot-type defects.
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tia copy 5.indd 5
The ECR also must take into consideration the
remaining pipe wall thickness. Guidelines dictate that a
remaining wall of 1mm (0.04in) or less be treated as a
Type B design even in the absence of an active leak. The
design case must take into account all operational and
environmental conditions.
Getting the design right is critically important, so
understanding the defect type, the extent of the dam-
age, the work environment, and the performance
requirements of the line being repaired are imperative.
Putting ECR solutions to work
The right repair leads to a reliable and durable solution.
A composite repair was applied as a solution to
severe internal corrosion and wall thinning in mul-
tiple sections of a 36in relief header that had led to
the development of three pin-hole leaks in a 6in long,
straight run. The line needed immediate attention,
and the next scheduled outage was 11 months away.
Failure of the relief header would have resulted in a
plant shutdown.
The header would have to remain in service during
the repair. Understanding the complications this situa-
tion presented, the owner consulted ClockSpring|NRI
to develop a solution. After evaluating the site con-
ditions, the extent of the damage, and the require-
ments for operations, the decision was made to use the
Thermo-Wrap inspectable composite repair system to
restore line integrity.
This ECR is a custom engineered system that employs
a glass fibre architecture and proprietary resin that
yield high strength characteristics with only a few lay-
ers per application. It is designed such that inspections
can be carried out effectively through the repair using
common radiographic inspection methods with high
visibility and contrast. This solution would allow the
relief header to function safely until it could be replaced
during the next scheduled shutdown.
Contractors installed stopgaps to arrest the leaks
and used a cold work surface preparation tool to cre-
ate the required anchor profile for the composite.
Trained technicians installed the Thermo-Wrap repair
on the active line, executing the project with minimal
manpower and without introducing heavy equipment
and tooling.
The composite installation was performed without
incident and without disrupting service to the units
attached to the relief header.
Delivering performance and reliability
Composites were developed specifically to contend
with corrosion and can repair a range of defects in
plants and refineries. xperience shows that with the
proper design, it is possible to safely repair in-service
lines to restore asset integrity and extend the service life
of critical refinery infrastructure. Advanced compos-
ite solutions reduce risks and deliver reliable, durable
repairs without compromising project economics.
ClockSpring|NRI
For more information: MGreen@CS-NRI.com
PTQ Q3 2019 117
16/06/2019 13:13
 • Optimise excess O2 and other process variables: oxy-
NOx control additives continue to gen is a key factor impacting reaction pathways of FCC
reduce emissions regenerator nitrogen. efiners should test full burn
units by varying excess flue gas oxygen to understand
its impact on NOx and optimise operations to other
ohnson Matthey’s ( M) NoNOx technology, in con- constraints like regenerator CO or afterburn. Other var-
junction with a non-platinum CO promoter like M’s iables known to impact regenerator NOx are antimony
COP-NP, can reduce NOx emissions below increasingly (Sb) and regenerator bed levels.
strict permit requirements without costly capital invest- • Minimise platinum based promoters: platinum combus-
ments. The following commercial examples from full- tion promoters effectively reduce afterburn and increase
burn FCC units demonstrate how refineries continue to HCN conversion. However, they also contribute to
utilise NoNOx and COP-NP products to control both increased regenerator NOx. Avoiding pre-blending plati-
NOx and CO emissions. num promoters is an important step in reducing NOx.
• Replace combustion promoter with non-platinum: lab-
Background oratory testing and many commercial trials of non-plat-
Nitrogen compounds in FCC regenerators are largely inum CO promoters, like COP-NP, have demonstrated
derived from basic nitrogen compounds in FCC feed significant reductions in NOx emissions relative to plat-
that adsorb on the acid sites of the catalyst. The nitro- inum promoters. Non-platinum alternatives enable con-
gen remains bound to the catalyst sites through the trol of regenerator afterburn and CO emissions, while
stripper and enters the regenerator where it is com- substantially reducing NOx.
busted with coke. In full burn FCC units, where coke is • NOx reduction additive: if NOx emissions are still
combusted in the presence of excess oxygen, the main above the required level, then a NOx reduction additive
nitrogen species formed in the regenerator are oxidised like M’s NOxGetter or NoNOx product lines will pro-
y, compounds like N2 and NOx. However, the chemical vide further reductions. We recommend a product trial
to assess the performance on each specific FCC unit.
There are opportunities for • Mechanical modifications: further improvements to
regenerator NOx performance are achieved through
refiners to optimise operating hardware technology enhancements to maximise the
homogeneity of the regenerator.
expenses with non-platinum CO
promoters and NOx reduction Impact of NOx reduction additive
The plots showing regenerator NOx as a function of
additives excess O2, presented in Figure 2, represent the results
of two commercial trials with M NOx reduction addi-
reactions to these oxidised compounds are not direct tives. Both trials were performed on full burn FCC units
and follow the pathways shown in Figure 1. in the US where the refineries had completed NOx
During coke combustion, much of the nitrogen is first reduction strategy steps through replacement of plati-
converted to HCN, which is thermally unstable at FCC num promoter with COP-NP non-platinum promoter.
regenerator operating conditions and will convert to In commercial xample 1, the refinery tested NoNOx
other nitrogen species. In full burn units, most of the additive at 1 wt and 2 wt concentrations in inven-
regenerator nitrogen (approximately 75 ) is converted tory. With 1 wt and 2 wt NoNOx in inventory, the
to inert nitrogen (N2). The remainder is converted to NOx emissions in the FCC regenerator flue gas reduced
NOx (NO, NO2, N2O) through further reactions with by 35 and 3 , respectively, at constant levels of
O2, NH3 through hydrolysis by steam, or remain HCN excess oxygen.
due to kinetic limitations, such as non-homogeneity or In xample 2, three products were tested separately
imperfect mixing, in the regenera- Additive , NOxGetter and NoNOx.
tor. educed nitrogen species (HCN, NoNOx is currently the most
2CO + 2NO 2CO + N2
NH3) are partially converted to NOx is very slow under FCC2conditions. advanced NOx reduction technology
due to oxygen-rich environments in NO, N2O, NO2
in the M product line. The results of
the regenerator and the relatively the trials showed Additive reduced
slow pathway from NOx to N2. O2 CH NOx by 30 , NOxGetter by 37 and
More detailed explanations of O2
NoNOx by 4 at constant levels of
regenerator nitrogen chemistry have Aromatic N HCN N2 excess oxygen.
(coke)
been published by M in conference H2O
O2 In both commercial examples, the
presentations and journal articles.1
refineries have a adopted a long term
Amines
O2 additive control strategy and con-
NH3 NOx
NOx reduction strategy (unstripped tinue to utilise NoNOx and COP-NP
M recommends the following products) products to control NOx and CO
series of steps for refiners pursuing below permitted levels. Other com-
reduced NOx emissions from their Figure 1 Regenerator nitrogen reaction mercial successes of NOx emissions
FCC units: pathways reductions with M NOx additives

118 PTQ Q3 2019 www.eptq.com

tia copy 5.indd 6 17/06/2019 11:53

 80 Waste to refinery hydrogen
Base
Corrected regenerator NOx, 70 1% JM NoNO
60
2% JM NoNO Italian refiner ni and plant construction engineer
50
Maire Tecnimont are developing a conversion tech-
nology based on high temperature gasification to pro-
40
duce hydrogen and methanol from solid urban waste
30
and non-recyclable plastic. The idea is to deliver hydro-
20 genation resources and energy with minimal environ-
10 mental impact.
ppm

0 The two companies are assessing the technical and

Regenerator excess O2, % financial impacts of the developing technology, which
is likely to be introduced at ni’s sites in Italy. So far,
140
Base ni is investigating and evaluating the waste to hydro-
gen technology at its bio-refinery in Porto Marghera,
Corrected regenerator NOx,

120 Additive X
JM NO Getter
100 JM NoNO Venice, urope’s first dedicated biorefinery, and has
80 carried out a feasibility study in collaboration with
Maire Tecnimont subsidiary NextChem.
60
The agreement will cite ni as co-developer of
40 NextChem’s technology, which has been described as
20 an example of the circular economy: it reuses hundreds
ppm

0
Regenerator excess O2, %
Figure 2 Commercial NOx reductions examples with JM additives
have been published in the public domain2 and the
company will continue to publish the results of future
technology enhancements demonstrated in laboratory
tests and commercial trials.
Conclusion
The commercial examples prove that NOx reduc-
tion additive technologies are effective and continue to
improve. The technology enhancements enable refin-
ers to further improve environmental performance
with increasingly strict regulations and avoid costly
capital investments. In addition, there are opportuni-
ties for refiners to optimise operating expenses with
non-platinum CO promoters and NOx reduction addi-
tives. For example, refiners may explore cost reductions
from ozone consumption in low temperature oxidation
processes.
There are opportunities to reduce NOx emissions by
up to 75% relative to base emissions with platinum CO
promoters and up to 50% relative to base emissions
with non-platinum CO promoters as demonstrated by
commercial case examples.
NONOX, NOXGETTER, and COP-NP are marks of the Johnson Matthey
group of companies.
Michael Talmadge, Ron Butterfield and Martin Evans
References
1 Xunhua M, de Graaf B, Radcliffe C, Diddams P, HCN and NOx control
strategies in the FCC, PTQ, Q2 2014.
2 Genç M, Gül A, Bayraktar Dalgıç E, Avcılar S, Ventham T, Taking steps to
reduce FCC NOx emissions, Hydrocarbon Engineering, Jul 2018.
of thousands of tonnes of non-recyclable waste to pro-
duce chemical products and fuel with the aim of con-
tributing to environmental sustainability at ni’s indus-
trial sites, forming part of an increasingly integrated
and e cient system designed to contain and reduce
atmospheric emissions of CO2.
According to ni, the technology will help to estab-
lish a circular economic process whereby fuel is pro-
duced from waste with low environmental impact.
Maire Tecnimont says that the partnership with ni is
an important step for its green acceleration project.
Maire Tecnimont
For more information: info@mairetecnimont.it
Ionic liquid alkylation unit starts up
The largest commercial adoption to date of Ionikylation
technology from Well Resources is up and running at a
brownfield unit in Sinopec’s 1 1 000 b/d iujiang City
refinery in iangxi Province, China. The unit is capa-
ble of producing 300 000 t/y of high quality alkylate
and Sinopec is on track to commission two additional
Ionikylation units of the same capacity at its Anqing
and Wuhan refineries later this year.
Construction of the unit at Sinopec’s iujiang refinery
started in February 2018 and completed in December
2018. Unit start-up preparation began in mid-March
201 . On 31 March 201 , the catalyst and feed were
introduced into the Ionikylation reactor. Sinopec
says that the first batch of alkylate was successfully
produced.
Ionikylation uses a composite ionic liquid as the cat-
alyst. Unlike traditional alkylation processes that use
hydrofluoric or sulphuric acid as the catalyst, the
Ionikylation catalyst is said to be safe to handle.

Johnson Matthey Well Resources

For more information: Michael.Talmadge@matthey.com For more information: info@wellresources.ca

www.eptq.com PTQ Q3 2019 119

tia copy 5.indd 7 17/06/2019 11:53

 Alphabetical list of advertisers

Advanced Refining Technologies 72 ITW Technologies 91

AFPM Operations & Process Technology John Zink Hamworthy Combustion 92
Summit 103 Johnson Matthey 13
Air Liquide Global Engineering & Johnson Screens 87
Construction Solutions 75 Magnetrol International 28
AMETEK Grabner Instruments 97 MAN Energy Solutions 52
Ariel Corporation 50 Metso Flow Control 22
Asian Downstream Summit 106 Nalco Champion 98
Axens OBC
Neste Engineering Solutions 68
Böhmer 101
Neuman & Esser 48
Borsig 42
OHL Gutermuth Industrial Valves 55
Bryan Research & Engineering 66
Process Consulting Services 16 & 18
Burckhardt Compression 40
Prognost Systems 25
Chevron Lummus Global 7
Refining India 2019 110
China Petrochemical Technology Company
Rentech Boiler Systems IBC
Limited 78
Sabin Metal Corporation 81
Crystaphase Products 2
Shell Catalysts & Technologies 4
Sulphur 2019 105
ERTC 2019 113 Sulzer Chemtech 82

ExxonMobil Catalysts and Technology TPS 2019 115

Licensing 9 Tracerco 56

Filtration Group 60 Tubacex 77

HCPect 27 W. R. Grace & Co 11
Hoerbiger 64 WEKA 71
Honeywell UOP IFC Zeeco 44
IPCO 32 ZymeFlow Decon Technology 88

Register to receive your regular copy of PTQ at www.eptq.com/register

120 PTQ Q3 2019 www.eptq.com

ad index copy 16.indd 1 17/06/2019 10:07

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