Emulsion breaker and metal removal
technology increased FCC residuum processing
Frequent and unexpected changes in crude blending properties result in operational
and performance challenges from the desalter to the catalytic cracker
KRIS KOHL, PAUL WHITE, ANIBAL VALLE and JIM TRIGG
GE Power & Water
A
s the global economy
slowly recovers, refiner-
ies can expect to see a
positive shift in the demand for
finished petroleum products in
mature markets and growing,
developing regions. Refining
facilities around the globe will
continue to look for ways to
increase production and profit
margins, while reducing or
eliminating unscheduled shut-
downs and the subsequent
untimely cost of cleaning and
replacing equipment.
The utilisation of opportunity
crudes in the refinery process-
ing diet is a key driver of
refinery profitability, given that
crude oil accounts for more
than 85% of a refiner’s cost
structure. Opportunity crudes
are those that trade at a
discount compared to similar
crudes in the marketplace. The
availability of such opportunity
crudes such as oil sands, light
tight oils (LTOs) and high
naphthenic acid containing
crudes, continues to be an
excellent profit improvement
opportunity for those refineries
able to process these
feedstocks.
The production techniques
www.digitalrefining.com/article/1001118
necessary to economically
extract oil sands and tight oil
add to a refinery’s processing
challenges. For example, these
crudes typically contain greater
levels of solids than conven-
tionally produced crudes, with
the distribution of those solids
shifted toward smaller particle
size, increasing the difficulty of
solids management. Tight oils
can also contain significant
levels of production chemicals,
including hydrogen sulphide
(H2S) scavengers containing
amines. Critical characteristics
can vary greatly from batch to
batch, even within shipments
labelled as coming from the
same crude oil supply. This
high degree of variation adds
significant complexity to the
processing strategy and puts a
premium on the ability to
rapidly respond to unexpected,
frequent changes in crude
blending properties.
While processing these
opportunity crudes creates
clear cost advantages for the
refiner, many of the distin-
guishing characteristics that
drive the discounts are at the
root of a variety of processing
issues, particularly desalter
operation and performance.
When processing opportunity
crudes, refiners often operate
the desalter more as an extrac-
tion vessel, removing many
more contaminants than just
salt; for instance, metals, solids
and tramp amines can be
dealt with in the desalter.
While the individual desalter
challenges may not be
particularly new, their conver-
gence is.
For these converging chal-
lenges, the optimal solution
emerges from the ability to
leverage an understanding of
the interplay between chemis-
tries and their application, with
the operational experience and
expertise to optimise refinery
systems for maximum perfor-
mance. Included are practices
such as split feed, whereby the
primary emulsion breaker is
injected into both the oil and
the water. Crude stabilisers,
wetting agents, reverse emul-
sion breakers, amine/metals
removal aids, and pH modifi-
ers comprise the balance of the
chemistry tools suite in the
solution mix. Their common
points of application are shown
in the key of Figure 1.
Processing Shale Feedstocks 2015 1
 Crude storage A Crude stabilisers
and feed B De-emulsifiers
preparation
C Solids wetting agents
A D Metal and amine removal aids
B
E Metals removal
B F Liquid/solid separation aids
C
Secondary G Bio-augmentation aids
D
H MACarrier
Scenario 1
B I Phosphate removal
G I
C Pond/lagoon
system

Wash Scenario 2
water Desalters Crude unit G Clarification
Activated sludge
Brine Primary (Biological Tertiary
C
effluent Reclamation treatment) E
D B
(via slop system) Non-oily F I F
Influent wastewaters Underflow Filtration
Oil E F Discharge
source 2 recycle (multimedia)
Non-hazardous
Influent sludge
APIs DFUs
source 3 ... and/or
Oily sludge EQ membrane-based
Influent
upgrades
source 4
Hazardous F Dewatering Landfill
Oily waste- sludge Oily float
waters
Recycling
Scenario 3
G H I Membrane
F Dewatering Incineration Intra-plant
bio-reactor Export
use
Wastewater operations

Figure 1 Flow diagram: view of crude unit and wastewater operations

Metal contamination remove metal contaminants in effects, including low boiling

Contaminants in crude oil the past, including filter point compounds that will
feedstocks can be an impedi- adsorption, precipitation, and increase fractionator overhead
ment to processing discounted treatment with inorganic acids issues by partitioning to the
crude oil supplies in a reliable, among many others.4 Work overhead system, compounds
safe and profitable fashion. over the past 20 years has that degrade at crude preheat
Specifically, metals contamina- shown a highly effective temperatures to low boiling
tion poses a threat to a wide method to improve metal point compounds previously
array of refinery operations removal in the desalting mentioned, autopolymerisation
including crude unit fouling, process is to effect a transfer of in the crude preheat that result
catalyst contamination, and the metals from the hydrocar- in fouling, and scaling tenden-
finished product quality. bon phase to the water phase cies in the brine system. Due to
Almost all crude oils contain utilising water-soluble these known issues, the MR
detectable metal levels, and hydroxyacids. An additional technology has evolved from
their solubility and concentra- benefit to this method is the commodity acids, through the
tions can vary widely.1 While removal of amine and ammo- addition of scale inhibitors to
some forms of metal contami- nia compounds from the crude prevent scale adherence, to the
nation can be effectively oil, which will reduce crude most recent proprietary blends
removed via the normal desalt- tower fouling and overhead that include solution modifiers
ing process, other types do not system salt-induced corrosion. to prevent scale formation. The
readily transfer to the water Care must be exercised when recent product evolution
phase and therefore require selecting a metal removal (MR) successfully removes metals
additional means to remove aid treatment programme. and amine compounds without
them.2,3 A number of Many hydroxyacid compounds introducing harmful side
approaches have been used to will introduce unwanted side effects, resulting in a robust

2 Processing Shale Feedstocks 2015 www.digitalrefining.com/article/1001118

and commercially viable tech-
nology that can allow increased
volumes of discounted, high
metal crude oils to be
processed.
Iron removal capabilities
GE initiated work in the 1980s
to remove iron from various oil
streams to reduce the impact
on finished products.
Additionally, it is widely
known that metal contamina-
tion of catalysts used in
production of hydrocarbon
fuels results in undesirable
conditions that increase hydro-
gen and coke production and
ultimately limit fuels produc-
tion. For example, a number of
indices have been developed
for fluid catalytic cracking
(FCC) catalysts to relate metal
contamination on the equilib-
rium catalyst to hydrogen and
coke production, including:
Jersey Nickel Equivalent Index = 1000 *
(Ni + 0.2V +0.1 Fe), and
Shell Contamination Index = 1000 *
(14Ni + 14Cu + 4V + Fe)5
As can be seen, iron plays
a marked role in metal
contamination of FCC catalyst,
albeit lower than nickel and
vanadium.
Emulsion breaking
The proprietary Embreak
emulsion breaking products
are usually oil-soluble chemi-
cals designed to improve crude
oil dehydration, salt removal,
and effluent brine quality in
electrical desalters and other
similar process equipment.
Embreak products help reduce
emulsion build-up at the oil/
water interface and increase
solids removal from the crude
www.digitalrefining.com/article/1001118
into the brine effluent. They
provide consistently superior
desalter operation during peri-
ods when high BS&W crudes
and slops are processed, and
aid in maximising crude rates
by controlling emulsion
build-up at the desalter inter-
face. Benefits which often
result can be summarised as
follows:
• Lower overhead corrosion
rates, allowing for extended
run lengths
• Lower neutraliser and emul-
sion breaker usage, creating
lower treatment cost
• Lower water in desalted
crude, reducing the fuel
required at the crude furnace,
saving energy cost and reduc-
ing furnace emissions
• Lower amps on transformers,
reducing electrical cost
• Reduced slop oil production,
lower reprocessing costs and
potential increase in unit
charge rate.
Case study: challenge
A US Gulf Coast refinery
adopted an aggressive strategy
of blending tight oils, including
Eagle Ford (EF), to significantly
increase its profit margin and
supply flexibility. This blend
contained significantly higher
levels of solids and metals.
Unfortunately, it also presented
two obstacles that added to the
cost of operations. First, the
desalter suffered from periodic
oil undercarry in the desalter
brine; second, high metals
loading, specifically calcium
and iron, limited the refinery’s
ability to process vacuum
tower bottoms (VTB) in the
FCC unit. The non-GE chemi-
cal supplier was unable to
improve performance.
The refiner needed a solution
that would allow them to
maintain optimal desalter
performance while taking
advantage of the margin
improvement gained from
increasing the rate of vacuum
tower bottoms (VTB) processed
in the FCC unit. GE’s team of
on-site engineers and product
application specialists were
invited to initiate a 90-day trial
to improve desalter operations.
The crude blend was contami-
nated with levels of solids and
surfactants that prevented the
desalter from achieving good
emulsion resolution and solids
removal. Together with tech-
nologists at GE’s hydrocarbon
process lab, the team deter-
mined that the desalter rag
layer had grown considerably
as the WTI and EF blend was
processed. That large rag layer
trapped high levels of solids,
and the solids were the source
of many metals such as iron
compounds. In addition, the
crude blend contained organic
metals including calcium
naphthenates.
Finally, the team concluded
that the oil undercarry in the
desalter brine resulted from
oil-coated solids. Using GE’s
proprietary desalter simulator,
the team was able to demon-
strate that the solids and
metals could be removed much
more efficiently with a combi-
nation of Embreak emulsion
breaker and Predator metals
removal chemistry in conjunc-
tion with strategic operational
changes to help improve
removal performance. This
combined programme would
permit the refinery to effec-
tively process these crude
blends. Using this desalter
analysis, the new strategy and
its application at the desalter
Processing Shale Feedstocks 2015 3
 rag layer. Most importantly,
700
Average = 56 metals and solids removal
600 increased dramatically. Metals
Oil and grease, ppm removal efficiency gains were
500 evident, as illustrated in Table
400 1, Figures 4 and 5. Figure 6 also
shows that filterable solids
300 removal averaged over 80%
with the GE solution.
200

100 Benefits
Based on the high level of
0 improvement demonstrated,
0 10 20 30 40 50 60 70
Elapsed time, days the refinery opted to continue
with GE rather than pursue
Figure 2 Oil and grease on GE programme alternate suppliers and technol-
ogy. Since that time, the
Embreak and Predator
700
programme has continued to
Average = 160 deliver value and stable unit
600 operations. This technology
Oil and grease, ppm

combination is a potent solu-

500
tion for desalting tight oil
400 crude blends dependably, with
reduced oily undercarry, tight
300
rag layer control, excellent
200 solids removal and outstanding
metals reduction.
100 Prior to adopting Embreak
and Predator, the refiner was
0
0 15 30 45 60 75 90 105 only able to process up to 9%
Elapsed time, days of the FCC unit feed as VTB.
After implementing GE’s
Figure 3 Oil and grease on competitor’s programme programme, the VTB rate into
the FCC unit has increased by
Metals removal efficiency nearly 49% at a constant cata-
lyst quality. This has produced
Competitor Raw crude, ppm (avg) Desalted crude, ppm (avg) Removal rate, % an annualised marginal
Na Fe Ca Na Fe Ca Na Fe Ca upgrade of over $12MM/yr.
GE 35.6 21.6 8.9 7.3 5.2 2.5 80.0 75.9 71.9
Incumbent 30.1 11.8 12.3 14.2 13.9 9.7 52.8 0.0 21.1 This refiner continues to capi-
talise on opportunity crude
Table 1 blends, and does so with
confidence.
was recommended. Applying Case study: solution
the Predator metals remover in As illustrated in Figures 2 and Conclusions
concert with a traditional 3, the Embreak and Predator GE’s suite of emulsion breakers
Embreak demulsifier at the technologies significantly and metal removal (MR) chem-
desalter ensures these solutions impacted desalter performance istries has been successfully
address two of the more by reducing oil undercarry. applied in a growing number
important emulsion antago- High amp excursions and level of applications. While exact
nists; namely, solids and swings were also reduced by a goals differ, all are geared
surfactants. significant compression of the toward removing contaminants

4 Processing Shale Feedstocks 2015 www.digitalrefining.com/article/1001118

from the crude oil supply that
140
will have harmful effects
downstream of the desalter, 120

Iron in crude out, ppm

including fouling, heat transfer
loss, impact on catalytic 100

processes and finished fuel 80

GE solution
implemented
quality issues. The example
cited shows solids removal of 60
80%, iron removal of 75% and
40
calcium removal in excess of
70% from the crude stream. 20
Every application of Embreak
and Predator is unique and 0
0 50 100 150 200 250 300 350 400 449
offers its own set of challenges Elapsed time, days
that can influence ultimate
performance. As the volume of Figure 4 Crude out iron (Fe)
experience grows, the informa-
tion obtained deepens the 80
understanding of how to
Calcium in crude out, ppm

successfully apply these prod- 70

ucts to an ever broader set of 60

operating conditions and feed- GE solution
50
stocks. Operating parameters implemented
such as dehydration efficiency, 40
pH control, operating tempera- 30
ture, desalter type, slop oil,
20
mix valve ΔP, wash water
quality and other potential 10
process limitations all must be 0
considered when selecting and 0 50 100 150 200 250 300 350 400 449
evaluating a treatment Elapsed time, days
programme.
Figure 5 Crude out calcium (Ca)
Embreak and Predator are trademarks
of General Electric Company; may be
registered in one or more countries.
100
References
90
1 Speight J G, The Desulfurization of
Heavy Oils and Residua: Technology and 80
Economics, CRC Press, 1999, 105-106. 70
Efficiency, %

2 Pillon L, Interfacial Properties of 60

Petroleum Products, CRC Press, 2007,
50
25-28.
3 Standal S H, Blokhus A M, Haavik J, 40
Skauge A, Barth T, Partition coefficients 30
and interfacial activity for polar 20
components in oil/water model systems,
10
J Colloid Interface Sci, 212, 1999, 33-41.
4 Howe W W, Williams A R, Classes of 0
0 20 40 60 80 100 120 140 160 180 203
Metallic Complexes in Petroleum, J.
Elapsed time, days
Chem. Eng. Data, Vol. 5, 1960, 106-110.
5 Sadeghbeigi R, Fluid Catalytic Cracking
Handbook: Design, Operation, and Figure 6 Filterable solids removable efficiency on GE programme KPI ≥70%

www.digitalrefining.com/article/1001118 Processing Shale Feedstocks 2015 5

 Troubleshooting of FCC Facilities, Gulf
Publishing, 2nd Ed, 2000, 63-66.
Kristopher “Kris” Kohl is Sales Director
at GE Water & Process Technologies.
Email: kristopher.kohl@ge.com
Paul White is Area Manager at GE
Water & Process Technologies. Email:
PaulEdward.White@ge.com
6 Processing Shale Feedstocks 2015
Anibal Valle is Account Manager at
Water and Process Technology at GE
Water & Process Technologies. Email:
Anibal.Valle@ge.com
Jim Trigg is Senior Process Applications
Specialist at GE Water & Process
Technologies. Email: jim.trigg@ge.com
LINKS
More articles from the following
categories:
Corrosion / Fouling Control
Shale/Tight Oil & Gas
www.digitalrefining.com/article/1001118