Refining Developments

G. HOFFMAN and D. LONGTIN,

Baker Hughes, Sugar Land, Texas

Manage the impacts of high-solids crude oil

more effectively
Solids in crude oils present refiners with many challenges.
Processing higher-solids-content crude oils increases the need
for the management of such solids even more. The Canadian
Association of Petroleum Producers forecast that oil production from the countrys oil sands will rise from 1.8 MMbpd
to 5.2 MMbpd by 2030.1 These high-viscosity crudes tend to
carry high solids loadings due to their extraction methods. The
shale crudes being produced in large quantities also have demonstrated high solids loadings. The problems associated with
high-solids crude oils will continue to pose major challenges.
Traditional treatment. The refining industry has been seek-

ing a means to increase solids removal via the desalter for

more than 40 years, but with minimal consistent success. Refineries that process high-solids-content crude oils effectively,
without experiencing operating and integrity issues, can increase the volume of opportunity crudes processed, and, consequently, raise profitability.
When present in the crude, these constituents can cause
many problems, including fouling of crude tanks, desalter unit
upsets, increased energy use, catalyst deactivation, and downgrading of product value. Poor desalter operation can also
strain wastewater treatment units (WWTUs) and lead to noncompliance issues. These attractively priced crude oils, however, remain desirable feedstocks. The alternative is to avoid
processing these challenging crudes and to miss significant
profits. A new method is needed to effectively remove solids,
and thus enable the processing of opportunity crudes.

NATURE AND IMPACT OF SOLIDS

Crude oil contains a wide range of naturally occurring solids and contaminants, and is co-produced with large volumes
of brine/water, which is largely removed at the production
site. However, a small proportion of the produced water remains in refinery crude receipts, carrying dissolved salts with
the crude. The first step in the refining process is the desalter;
it is a process designed to remove salts and water from the
crude oil. Crude oils also contain inorganic solids, e.g., silicon and aluminum oxides, iron sulfides/oxides, carbonates,
sulfates and basic sediment (BS). These solids are typically
coated with oil and are not easily separated from the oil by
the desalter. Instead, they accumulate in emulsion layers before being carried downstream with the crude oil, or released
(with entrained crude oil) into the effluent brine stream.

Solids are quantified by a filtration using (in most cases)

0.45- pore filter media. A more-recent concern arises with the
size of solids, with finer particulates (less than 0.45 ) becoming more prevalent. If not removed in a controlled and oil-free
fashion in the effluent brine, the solids and other contaminants
can cause various issues that cascade through the downstream
oil and WWTU:
Tank fouling, emulsions and sludge. Solids can stabilize
emulsions that accumulate as a layer of sludge in the bottom
of crude storage tanks. These layers reduce the effective working tank volume. If the sludge is disturbed and released into the
crude oil, it can negatively impact the desalter operation. Sludge
must also be handled and processed as hazardous waste during
tank cleaning, which adds to the refinery maintenance burden.
Fouling of downstream equipment. Equipment vulnerable to fouling includes heat exchangers, furnaces, towers, FCC
unit diplegs and expanders. There are many causes for fouling,
including organic fouling (asphaltene deposition and sodiumcatalyzed coke formation) and inorganic fouling (solids carrying
over with desalted crude). Inorganic constituents can be a major
contributor in the fouling process.
Desalter unit upsets. Slugs of high-water or high-solids crudes
from tankage, or the addition of slop oil (which is inherently high
in emulsion and solids) can upset the desalter and cause temporary loss of performance, translating into negative consequences
for downstream process units and WWT processes.
Wastewater noncompliance. Emulsions containing oily
solids can lead to oil undercarry in the desalter and, consequently, problems for the WWTU. Transition metals such as
iron (Fe), nickel and zinc can also harm WWTUs. These issues can make it difficult to maintain final effluent water quality
and achieve environmental compliance. Furthermore, the oil
and emulsions contained in these excursions are frequently returned to the crude charge unit as refinery slop oil.
Corrosion. Poor oil/water separation in the desalter leads
to higher levels of water (along with dissolved salts) in the desalted crude. The higher salt content can lead to higher corrosion incidences of the crude tower overhead system. Up to half
of refinery maintenance costs are spent on corrosion issues.
Increased energy use. Fouling can cause heat transfer loss
and increase energy use.
Catalyst poisoning. Iron and other transition metals can
deactivate downstream catalyst systems, thus reducing the catalysts effectiveness and service life.
Hydrocarbon Processing|NOVEMBER 201485

Refining Developments
Loss of product value. Because solids tend to concentrate
in bottom streams, they can introduce ash and metals into residual products, which downgrade the value of delayed coker
coke products.
Removing solids at the desalter is a highly desirable goal. It
provides substantial benefits for downstream processing units
and the WWTU. More importantly, effective solids management can enable refiners to maximize profit opportunities by
processing challenging crude oils.

CONVENTIONAL DESALTING AND

SOLIDS MANAGEMENT
The desalting process mixes water with crude oil and then
uses time, electrical fields and chemicals to separate the oil
and water. The goal is to produce desalted crude that contains
minimal salt and water, and oil-free effluent brine water. Missing in this scenario is what happens to the inorganic solids. The
oil-coated solids tend to accumulate at the oil/water interface
(often called the emulsion or rag layer) in the desalter.
Various primary demulsifying agents are applied to enhance oil/water separation, and adjunct chemicals (such as
wetting agents) may be applied to aid in de-oiling the solids.
The larger-size solids will fall to the bottom of the desalter
and are, ultimately, removed via periodic or continuous mud
washing. Smaller solids are neutral-buoyant, especially if the
residual oil remains on the surface; thus, they do not drop out
of the oil/water interface.
The desalter operation can be optimized to meet salt removal
targets. Increased mixing energy, higher wash-water rates, and
improved level control are variables that can optimize salt removal. However, experience shows that only marginal increases
in solids removal are achieved via these steps.
Demulsification. Primary demulsifier chemistries are routinely applied at the suction side of the desalter unit charge pump.
Demulsifiers can effectively break emulsions.2 The formulations
include chemistries designed to strip oil from the surface of solids. Injecting adjunct chemistries with the emulsion breaker is
often practiced using surfactants designed to water-wet the solids
(wetting agents). These conventional chemistries can help reduce the emulsion-stabilizing impact of oily solids. They do not
readily allow the solids to be released from the oil/water interface.
Treatments. In the 1980s, new pretreatment or precondition-

ing technologies were developed to address the challenges of

TABLE 1. Pretrial desalter prole
Sample

Filterable solids, PTB

Solids, %

Water, %

Oil, %

Raw

64

0.1

0.2

0.0

Desalted

44

0.05

0.5

0.0

3,715

73.3

21.7

Tryline #4

6,484

6.5

76.8

16.7

Tryline #3

26,744

28

48.7

23.3

Tryline #2

20,365

25

50.0

25.0

Tryline #1

4,907

6.6

86.7

6.7

11

100

0.0

Tryline #5

Effluent

86NOVEMBER 2014|HydrocarbonProcessing.com

desalting West Coast crudes.3 The principle is simple. Chemical

reactions rely on molecular interactions that can be relatively
slow when the treatment chemicals and emulsion-stabilizing
solids are present in ppm levels. Consequently, when chemical
agents are added to the desalter, insufficient time prevents the
agents from achieving their full potential. Adding the chemicals
early in the tankage can provide more time to react with the solids, thus making the process more effective.
Greater residence time enables the agents to associate effectively with, and water-wet, the solids; stabilize the asphaltenes;
and reduce the emulsion-stabilizing impact of solids. The
agents also break up micro-emulsions above and within the
sludge blankets found in crude storage tanks. Preconditioning
technology has been refined and applied as the most effective
solution for desalting heavy crudes and recovered oils, resulting
in improved solids removal.
However, efficient removal of solids remains a challenge, especially with the higher incidence of micro-fine solids (smaller than 0.45 ). Conventional technology, including advanced
pretreatment, can help manage the emulsion-stabilizing impact
of solids. As solids loadings rise, however, more tools are needed to remove these solids, using the desalter equipment.

A NEW APPROACH
Canadian oil sands are high-solids crude oils. They often
contain higher-than-average solids loadings due to the production methods. These oil-sand-derived crude oils are processed
in a significant number of North American refineries, and the
impact of solids from these crude oils is well documented.4, 5
In 2011, a research and development project was conducted to
generate an improved method to manage solids in the desalter.
The project focused on developing new emulsion characterization methods, pretreatment chemicals, and a desalter chemical
additive to help transport solids (including sub--diameter solids) from the emulsion layer into the brine.
Phase 1 of the project was a critical starting point because
the conventional testing methods were judged to fall short in
accurately assessing micro-fine solids stabilization mechanisms
and removal capabilities. The new test methods focused on
measuring solids in various phases (oil, water and emulsion)
and clearly distinguishing the efficacy of various chemistries to
promote solids release. In Phase 2, product development led
to several new product formulations. Phase 3 used chemical
screening to ensure that new solids-release chemistry would
not interfere with the primary function of the desalter (salts
and water removal from crude oil). In Phase 4, pilot testing was
designed and conducted to test the top product candidates and
chemical strategies, and to confirm potential options for field
tests. In Phase 5, an actual field test was undertaken to confirm
project learnings.
Through the project, an innovative solids release agent
(SRA) was developed to remove solids from the oil phase and
then to be removed in the brine water.a
Initial field application. In 2012, a trial was conducted on a

desalter processing 100% high-solids, heavy Canadian crudes.

The desalter routinely operated with excellent salt removal and
oil-free effluent brine water. However, the desalter vessel also
operated with a large emulsion layer between the oil and wa-

www.ConstructionBoxscore.com

Logon for a

FREE ONLINE
DEMO!

,
G
IN
IN
F
E
R
L
A
B
O
L
G
E
H
T
R
O
F
E
MARKET INTELLIGENC
S
IE
R
T
S
U
D
IN
G
N
/L
G
IN
S
S
E
C
O
R
P
S
A
G
D
N
A
L
A
IC
M
E
H
C
O
R
T
E
P
Hydrocarbon Processings Construction Boxscore Database,
the most reliable source to track active construction projects in the rening, petrochemical, gas processing,
LNG and solids industries throughout the world, now reaches further and is more powerful than ever before!

Welcome to the NEW

ase
Construction Boxscore Datab

Project details on thousands of active projects and global

construction contracts, including contact information for
key personnel
Advanced search that lters the listings by project type,
scope, region, investment and more
Daily updates for new and newly updated projects
The weekly Boxscore Update e-newsletter with new listings
and trends analysis

For more information, contact:

Lee Nichols, Director, Data Division, at Lee.Nichols@GulfPub.com
or +1 (713) 525-4626

Refining Developments
ter, and sometimes with an emulsion layer at the bottom tryline. This emulsion layer was very high in solids concentration
(> 2 wt%), which could negatively impact downstream units.
TABLE 1 summarizes the desalter profile before SRA injection.
The data indicate that the solids content in the effluent brine
was low, but the tryline solids loadings were very high. This is
a common result when processing high-solids crude oils. After

four hours of the new SRA, the impact was visually apparent;
solids settled in the tryline samples and solids-free oil rose in the
desalter.a FIG. 1 shows the appearance of the bottom tryline sample before chemical injection and after four hours of treatment.
Within three days of the new SRA treatment, the solids
profile in the desalter showed very clear downward migration
of solids.a FIG. 2 demonstrates the descent of the solids to the
lower trylines.6 During this same period, the total filterable solids volume in the trylines fell from 60,000 lb/1,000 bbl (PTB)
or 171,000 mg/l to 38,000 PTB (108,000 mg/l). The solids
content in the effluent brine also increased markedly from < 11
PTB, or 31 mg/l, to more than 1,400 PTB (4,000 mg/l), as illustrated in FIG. 3. As shown in FIG. 4, the effluent brine sample
exhibits significant accumulation of solids on the bottom and
no free oil in the sample.
The trial demonstrated that the new SRA technology readily released solids from the emulsion/interface and enabled the
solids to move into the brine, which remained oil-free.a The
original project objective of releasing solids to the brine without free oil was achieved.

FIG. 1. Tryline #1 sample and visual appearance before and after

treatment.
TR5
Pretrial
100% emulsion

TR4
TR3
TR2
TR1
Brine

Day 1

Day 2

Baseline

Day 3

SRA treatment

FIG. 2. Descent of solids in desalter trylines with and without SRA

treatment.a
FIG. 4. Brine sample containing more than 30% solids and no oil.
1,600
1,472
1,400

1,367

100

1,297

90

1,200
1,000

Filterable solids removal, %

Brine solids, PTB

80

800
600
400
245
0

6
Day 1
Baseline

70
60
50
40
30
20

200
11

Normal operations
Using SRA

Day 2

Day 3

Day 4

10
0
Pre-trial

Day 0

Day 1

Day 2

Day 3

SRA treatment

FIG. 3. Brine solids increase (PTB) with the new customized SRA.a

88NOVEMBER 2014|HydrocarbonProcessing.com

FIG. 5. Solids removal efficiency improved by more than 50% with

customized SRA.a

Refining Developments

Desalter trylines

Day 3

cation of the new technology was initiated in response to problems seen at a refinery fluid catalytic cracking unit (FCCU).
The FCCU feed includes crude unit tower bottoms, which
brings solids to the unit. These solids are high in Fe content.
The impact at the FCCU is two-fold:
Buildup of deposits on the regenerator expander blades
leads to vibrations and requires periodic cleanup.
High Fe content impacts catalyst activity.
The goal of the new SRA program was to reduce the vibration events and reduce Fe loading on the catalyst.a Improved Fe
control would reduce catalyst-makeup costs. The treatment resulted in a substantial increase in solids releasing into the brine,
where solids content increased from < 10 PTB (90 mg/l) to an
average of 380 PTB (>1,000 mg/l). Of equal importance, the
Fe content in the brine increased in conjunction with the solids
(FIG. 7), along with a comparable reduction in Fe loading on
the FCC catalyst (FIG. 8).
Program success was also indicated in the data by a mass
balance of the solids entering the desalter, with the solids leaving in the desalted crude and brine. In a typical desalter processing high-solids crude oil, it is not uncommon to see a 40%
to 60% reduction in solids from the raw crude to the desalted
crude oil. However, the solids measured in the effluent brine
often do not reflect the solids removed from the crude, which
indicates that the solids are accumulating inside the desalter (in
the rag layer and/or on the bottom of the desalter). In these
800

400
300

400

Iron, ppm

500
Baseline
solids = 4 PTB average
Fe < 1 ppm average

300

200

200

100

Brine solids, PTB

Brine Fe content, ppm

100
0

0
1

5
6
7
8
9
Time in operation, months

10

11

12

FIG. 7. Solids and iron content in the brine rose significantly with the
use of the new SRA technology.a
0.75

Day 4
0.65

0.35

0.25

Program maintenance
solids = 388 PTB average
Fe = 161 ppm average

Program optimization
700 solids = 106 PTB average
Fe = 69 ppm average
600

Fe on FCC catalyst, wt %

Day 0

Case 2: Iron reduction in FCC unit feed. An ongoing appli-

Solids, PTB

Case 1: 30% paraffinic-froth-treatment crude. A US Gulf

Coast refinery took possession of paraffinic-froth-treatment
(PFT) crude cargo when a nearby refinery, whose desalters were
treated with a different chemical treatment could only process
the heavy Canadian crude at less than 5% feed. Even at such low
levels, the sister refinery still experienced a large desalter emulsion band and significant oil undercarry, which upset its WWTU.
The new owner of the PFT crude parcel had previous success running low-percentage blends of this same crude after
the implementation of a crude management program.b, c However, the refinery wanted to maximize the blend percentage
of the PFT crude and determine the long-term potential to
fully exploit the lower-priced opportunity crude. To achieve
the ambitious goal, a new SRA technology was recommended
and developed specifically to handle the ultrafine solids in
PF-treated tar-sand crudes.a The active chemistries in the new
SRA remove oil from the fine solids, releasing them from the
emulsion layer to the brine, allowing them to be properly and
easily handled through the refinerys WWTU.
The maximum rate test was initiated with the PFT crude at
12% of crude charge and ramped up to 30% over the course of
several days, ultimately limited only by crude availability and
product yields. Throughout the run, brine quality remained
exceptional, and oil and grease levels were kept below established limits, thus preventing any detrimental impact on the
refinery WWTU.
The use of new SRA technology was successful in reducing
the size of the desalter emulsion layer and improving the solids
removal efficiency by more than 50%.a While normal filterable
solids removal at this refinery had averaged 50%60% during previous heavy crude operations, the use of new the SRA increased
removal to 80%85%, as shown in FIG. 5. Additionally, the downward migration of solids from the emulsion layer into the brine
was confirmed by filterable solids measurements of each of the
desalter trylines before and during the test run, as shown in FIG. 6.
As a result of the implementation of this new combined crude
management approach together with SRA, the refinery was able
to increase the blend percentage of the PFT crude to 30% without any detrimental impacts to the brine handling system or
wastewater treatment plant.a, c Given publicly available data on
crude margins at the time of this case study, the refiner captured
more than $350,000 in opportunity crude profits during the
four-day run and identified the potential for even greater longterm returns on this PFT crude oil by using SRA technology.a

5
10
15
20 0
5
10
15
20 0
5
10
15
20
Filterable solids content, %
Filterable solids content, %
Filterable solids content, %

FIG. 6. Downward migration of solids from the emulsion layer into the
brine with customized SRA.

0.55
0.45

Program
optimization

Baseline
1

5
6
7
8
Time in operation, months

Program maintenance
9

10

11

12

FIG. 8. With the use of the new SRA technology, e-cat Fe loading was
significantly reduced, helping to prolong catalyst life.a
Hydrocarbon Processing|NOVEMBER 201489

Refining Developments
cases, the measured brine solids often represent only a small
percent of the solids removed from the raw crude. If solids release is truly successful, a mass balance of the solids should be
reflected in the solids leaving with the brine water. During the
trial, the solids content in the brine was minimal during the
baseline period. After optimizing the SRA treatment, the solids
in the brine demonstrated excellent agreement with the solids
removed from the crude oil, as shown in FIG. 9.a
The new SRA program results were clear and sustainable.a
Increased solids and Fe released with the desalter effluent brine
water stopped the expander vibration events and improved

Solids material balance, %

Program optimization
Average closure = 17%

Options. The new SRA technology can greatly enhance the re-

lease and removal of solids from crude oils. It provides a striking improvement in solids removal and control, and reduces
the impact of solids and contaminants on refining processing
equipment. This new technology is another tool that can enable the refiner to process opportunity crudes and maximize
refinery profitability.a, b, c High-solids crudes, including those
prone to contain micro-fine-sized solids, are no longer off-limits. Solids management is a viable action.
ACKNOWLEDGMENT
This article is based on an earlier presentation at the 2014 AFPM Annual
Meeting in Orlando, Florida, March 2325, 2014.

Program maintenance
Average closure = 98%

Baseline
Average closure = 2%

Fe loadings on (and extended the life of) the FCCU catalyst.

These excellent results were achieved while maintaining outstanding desalter performance (salt removal and dehydration)
and oil-free brinewith no increase in wastewater chemical
oxygen demand (COD).

NOTES
A customized solids-release agent offered by Baker Hughes under the JETTISON
trademark.
b
A heavy oil demulsifier offered by Baker Hughes under the XERIC trademark.
c
The refiner used the Baker Hughes Crude Oil Management program and XERIC
heavy-oil demulsifiers.
a

0.25
1

5
6
7
8
Time in operation, months

10

11

12

FIG. 9. Solids material balance: Removal from crude vs. contained in

effluent brine.

LITERATURE CITED
Crude Oil Forecast, Markets & Transportation, June 2013, The Canadian
Association of Petroleum Producers (CAPP).
2
Chemical inventions that revolutionized the hydrocarbon processing industry,
Downstream Innovations, 1922 to Present, Hydrocarbon Processing, July 2012,
pg. D-140.
3
Kremer, L. and S. Bieber, Strategies for Desalting Heavy Western Canadian
Feedstocks, NPRA Annual Meeting, San Diego, California, March 911, 2008,
Paper AM-08-36.
4
Kremer, L. and S. Bieber, Rethink desalting strategies when handling heavy
feedstocks, Hydrocarbon Processing, September 2008, pp. 113120.
5
Cornelius, S., D. Jackson and D. Longtin, Baker Hughes Assault on Salt,
Hydrocarbon Engineering, 2012.
6
Desalter Solids Release Agent Test Results, Customer ReportReview with
Baker Hughes, Sept. 20, 2012.
7
A Strategy to Reduce Operating Costs and Increase Throughput, Internal reference, 1990, Baker Hughes.
1

GERALD HOFFMAN II is currently the senior separations

technologist for the Baker Hughes Separation Technology
Group. During his nearly 30 years of experience in the oil and
gas industry, he worked for Exxon for 15 years in roles including
manufacturing, management and sales in the refining sector;
prior to becoming the technical manager for BJ Services from
1996 until Baker Hughes purchased BJ in 2011. His expertise
includes the midstream sector, as well as desalting, corrosion and fouling
mitigation in the refining sector, and finished fuel treatment. Mr. Hoffman II holds
a BS degree from the University of Southwestern Louisiana and an MBA from
the University of Houston.
DOUG LONGTIN, technical manager for the Baker Hughes
Downstream Division, has more than 30 years of experience
in the hydrocarbon processing industry. For more than 10 years,
he has focused on and addressed refinery desalting issues to
improve customer operations, reliability and profits while
processing difficult opportunity crude oils. He has championed
Baker Hughes EXCALIBUR contaminant removal technology
and has recently worked in the development and implementation of Baker
Hughes JETTISON solids release agents technology, addressing emulsion
resolution and desalter solids management. Mr. Longtin holds a BS degree in
pulp and paper engineering from SUNY College of Environmental Science
and Forestry, Syracuse University.

90

Select 166 at www.HydrocarbonProcessing.com/RS