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Paper No.

08556

Desalter Acidification Additives and Their Potential Impacts on Crude Units

Sam Lordo
Nalco Company
7705 Highway 90A
Sugar Land, TX
salordo@nalco.com

John M. Garcia
Nalco Company
7705 Highway 90A
Sugar Land, TX

Sandra Garcia-Swofford
Nalco Company
7705 Highway 90A
Sugar Land, TX

Abstract

The increased challenges refiners face with frequent crude changes, processing of new
opportunity crudes, and limited mechanical systems have resulted in difficult operations that require
alternative treatment methods. In terms of chemical treatment, one potential option to alleviate difficult
desalter operations is the use of acidification aids. This paper will cover the key drivers for desalter
acidification, the benefits from this approach and the downstream effects (e.g., corrosion, fouling) from
the application of this type of technology. Also discussed will be the different type of chemistries,
reactions, the fate of acids in the desalting operation, and their potential impacts on downstream
operations. Field experience and observations from acidification programs will be presented and
discussed.

Keywords: Desalter, Desalter Acidification, crude unit corrosion, fouling, organic acids

Copyright
©2008 by NACE International. Requests for permission to publish this manuscript in any form, in part or in whole must be in writing to NACE
International, Copyright Division, 1440 South creek Drive, Houston, Texas 777084. The material presented and the views expressed in this paper are
solely those of the author(s) and are not necessarily endorsed by the Association. Printed in the U.S.A.

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Introduction

Processing lower quality crude oils such as those containing high levels of solids, asphaltenes,
oil soluble metals and inorganic metal contaminants provides for higher profit margins as long as the
refiner can meet finished product specifications, while minimizing the impact on the crude unit’s
overhead system, downstream units, and the wastewater treatment plant.

An important aspect of any acidification program is to determine if there will be any processing
difficulties during crude unit operations focusing on the desalting aspect of the crude feedstock.
Injection of an organic acid or transitioning from one acid to another acid must be transparent. This
means no desalter operational issues should be encountered when using an acid injection program.
Ultimately, good or improved desalting performance should always be the expectation of any
acidification program.

An effective acidification program can minimize crude unit upsets and lost production.
Operational challenges such as high conductivity, crude oil-water emulsions, oil undercarry, corrosivity,
fouling tendencies, as well as catalyst poisoning do present themselves if not effectively managed
when processing difficult crude oils as blend components in a refinery’s feedstock.

Desalter acidification has been shown to be an effective means of resolving difficult emulsions
in desalters while enhancing the effectiveness of the applied desalting demulsifiers.1,2 Some of the
reasons that refiners may turn to using acidification additives are:

• Enhancing desalter oil water separation (reduce oil under carry and water carryover)
• Extracting amine/amine salt contamination from crude oil3
• Contaminant removal (e.g., oil soluble metals; acid soluble particulates, calcium carbonate
(CaCO3), iron sulfide (FeXSy))

Acidification additives typically are either mineral acids (e.g., sulfuric acid) or simple organic
acids (e.g., acetic acid, glycolic acid, citric acid). There are both positive and negative impacts
associated with most of the acids used as adjunct chemistries to acidify desalter wash water. The acid
program selected should meet the following criteria:

• Cost effectiveness
• Ease of control
• Low volatility
• Does not impact wastewater
• Does not impact downstream processing units
• Does not generate solids

Effects of pH on Desalter Operations

Emulsions can be stabilized by surface-active polar asphaltene and resin fractions within the
crude oil. Rigid interfacial films form at the oil water interface and interfere with the coalescence of
brine droplets. These films can be composed of asphaltenes and resins contain organic acids and
bases as well as fine solids, waxes, scales and corrosion by-products, which become oil-wet as the
asphaltenes and resins adsorb onto these solids found at the interfacial film. As a result, these solids
further stabilize the emulsion through steric effects preventing brine droplets from coalescing. If the
rigid films are destabilized with demulsifier, emulsion resolution will occur.

Acidification with any acid applied as a desalting aid along with the demulsifier package
changes the rigid interfacial film formed at the oil-water interface allowing brine droplets to coalesce

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within a tight pH range. The acid also changes the chemistry of the brine, which plays a vital role in
emulsion stabilization and is different for each crude oil-brine system due to chemical composition.

Adjustments of pH can significantly affect the film forming, oil wetting, and emulsion stabilizing
properties of the asphaltenes and resins present in crude oil. Additionally by altering brine composition
emulsion stability is affected due to the interaction of the ions present in the brine-asphaltene system1.
Thus, changes in pH affect emulsion stability. The stability of the emulsion depends not only on the
polar asphaltene and resin content, but also on the physical properties of the crude oil (e.g., API
gravity, viscosity), temperatures, and, of course, crude oil and brine composition. Acidification of the
desalter’s inlet wash water to an appropriate pH, which is specific for a given crude oil-brine system,
improves emulsion resolution, thus reducing water and solids carryover.

Correct acidification of the inlet wash water is critical to altering the rigid interfacial film allowing
brine droplets to coalesce. Acidification to the proper pH will also dissolve acid soluble solids (CaCO3,
FeXSy) without oil wetting the solids. Dissolving acid-soluble solids allows for emulsified oil and water
droplets to coalesce and separate, thus preventing oil under carry. Acid insoluble solids will drop out
into the effluent brine without being carried into the oil phase.

Consequently, only dirty water (not oily) is observed for a given crude oil-brine system. As A
result of over acidification, the desalter’s effluent brine becomes crystal clear with the oil-wet solids
reporting to the oil phase and emulsified brine droplets containing a variety of contaminates (e.g., free
acids, acid salts) found in the emulsified brine droplets within the crude.

At one West Coast location, the use of sulfuric acid to improve brine quality, led to amine sulfate
salt contamination in the jet or in the naphtha draws coming out of a crude unit. Moreover, the
overhead line also experienced severe corrosion (perforation)3.

For example, at one refinery, high solids crude slates were being processed. Filterable solids
ranged from 400 – 1,000 ppm leading to high oil undercarry of 5 – 10%. Previous attempts using an
acidification program were unable to satisfactorily reduce the oil undercarry to <5%. The refiner then
changed the primary demulsifier, which reduced the oil content to 2 – 5%. The acidification acid was
transitioned to another acid along with the demulsifier package, which further reduced the oil
undercarry to <100 ppm. Ultimately, the benefit to the refinery was increased throughput of over 3,200
barrels/day (500 m3/day) without experiencing any significant oil undercarry. Figure 1 shows the impact
of a controlled desalter acidification program on oil undercarry. The improvement was rapid and
sustainable.

Using Acidification for Amine/Amine Salt Removal

More recently, acidification of a desalter’s inlet washwater was used to enhance removal of free
amines during desalter operations. Free amine and, more likely, their associated salts can be found as
contaminates in crude oils from upstream operations and/or recycled to the desalter from internal
streams such as, sour stripper bottoms, amine units, or crude tower overhead corrosion control
programs.4,5 Depending on the type and concentration of these contaminants, negative impacts on
downstream operations may occur, such as corrosion and amine salt fouling.

Table 1 shows the relationship between pH and the partitioning of two amines between oil and
water phases. Through the desalting process, refiners have attempted to reduce amine contamination
from crude oils through pH adjustments of their desalter’s inlet wash water. Injection of strong acids
(e.g., sulfuric acid) and simple carboxylic acids (e.g., acetic acid, citric acid, glycolic acid) are used to
convert the contaminating amine to the corresponding amine salt.

Removal of the amine salt from the system occurs as the salt partitions into the desalter’s
effluent brine.

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Amine Extraction From Crude Oil in the Crude Unit

Table 2 is an overview of anecdotal field observations in the refining industry’s attempt to


remove contaminant amines and metals from crude oil during the desalting process at four separate
refineries, located in various regions of the world. Amine salt removal was generally inefficient leading
to a number of concerns for the refiners implementing this reduction strategy using simple carboxylic
acids and mineral acids. The acids were used to make pH adjustments to acidic conditions in hopes of
removing contaminating amines and removing their associated salt6.

Use of glycolic acid is not considered a viable option since glycolic acid not only leads to acid
carryover in the distillation column, but also thermally self-polymerizes at 122oF (50oC) leading to
dimeric or oligomeric materials7. These materials can result in deposition within the desalter, crude
preheat train, or in the crude column’s overhead system.

Reactions of Amines with Acids

By virtue of adjusting the pH of the desalter wash water to acidic conditions in hopes of
removing contaminating amines, one would expect that the solubility of the protonated amine would
increase in the brine water. The solubility of protonated amines in water does increase due to
hydrogen bonding. The extent to which an amine is protonated dictates its solubility in water in the
order NH4+ > RNH3+ R2NH2+ > R3NH+ with the tertiary amine least soluble since this protonated amine
can only form a single hydrogen bond8.

The question then remains, why are refiners who are using an amine reduction strategy (based
on simple carboxylic and sulfuric acids for pH adjustments to acidic conditions) do not observe the full
benefits without the unwanted side effects?

The answer lies simply in the fact that under acidic conditions, all protonated amines undergo
reversible salt formation9. Below are the general reactions of carboxylic and sulfuric acids with a
primary amine such as MEA:

H H
O
R N: + R' C OH R N+ HR'COO (1)

H H

Reaction of amine with a carboxylic acid.

H H

R N: + H2SO4 R N+ HHSO4 (2)

H H
Reaction of an amine with sulfuric acid.

Both sulfuric acid and simple carboxylic acids readily convert the primary amines to the
corresponding amine salt under acidic conditions. However, the protonated amine is in ionic form and

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the salts can revert back to the free amine as the pH of the desalter wash water becomes sufficiently
alkaline or the amine salt encounters a strong base such as the hydroxide ion (OH-). This reaction is
reversible.

Partition Coefficients for Organic Acids

The partitioning of simple carboxylic acids such as acetic, citric, and glycolic as well as other
carboxylic acids between the oil and water phase is a function of their partition coefficients, K, at a
given pH, where K is defined as:

K= Concentration of acid in oil _ (3)


Concentration of acid in water

The work of Reinsel et al. studied the effects of pH, temperature and acid concentration on the partition
coefficients of acetic, propionic and butyric acids in two dissimilar crude oil-water systems10.

In their study, understanding the extent to which these simple carboxylic acids partition between
the oil and water phases provided insight into the “souring” of oil reservoirs undergoing secondary
recovery, since sulfate reducing bacteria residing in the water phase utilize these organic acids as a
metabolite resulting in the observed change their environment.

For these simple carboxylic acids, the study found that of the three parameters (pH,
temperature and acid concentration), pH imparted the greatest influence on the partitioning of the acids
into water phase. Reinsel concluded that at a 5 – 7 pH range, the majority of the organic acids (85+%)
dissolved into the aqueous phase. However, if the pH falls below 5 pH units, a significant concentration
of carboxylic acid will partition into the oil phase. Therefore, care must be taken not to over acidify the
desalter’s wash water, otherwise these simple carboxylic acids will partition into the oil phase and
carryover to the atmospheric tower of the crude unit leading to corrosion of the overhead system.

Crude Unit Amine Reduction Strategy

The implementation of an amine reduction strategy using simple organic acids or a strong acid
(e.g., sulfuric acid) to salt out an amine, the salts of which are in equilibrium in the water phase under
acidic conditions (Equations 1 and 2), it stands to reason that lowering the pH to < 5 in an attempt to
extract the contaminating amines from the bulk crude oil will serve to drive more acid into the oil phase.
Exacerbating this situation is the emulsification tendencies when over acidifying the desalter’s inlet
wash water as previously discussed.

Under acidic conditions, emulsified brine droplets in the desalted crude will also have soluble
free acid or the acid salt of the amine.

This is a plausible explanation for the anecdotal observations shown in Table 2.

Acidification used to Extract Metals

Similar to amine removal, acidification aids are being employed to enhance removal of oil
soluble metals during standard desalter operations. Organically bound metals in crude oils present a
unique challenge to the refiner since normal desalting operations do not remove these oil soluble
contaminants as opposed to inorganic contaminants such as iron sulfide, inorganic chloride salts,
calcium sulfates and carbonates.

One such organically bound metal is calcium. Presumably this “oil soluble” calcium is present in
the form of calcium naphthenates. Calcium naphthenates are known surfactants, which can lead to

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emulsion stabilization and oil undercarry negatively affecting wastewater treatment systems. Calcium
naphthenates and their thermal degradation products are also responsible for deposition in heaters and
heat exchangers. Calcium can also be responsible for poisoning of catalysts in downstream operations
and fluidized catalytic cracking processes. It can also be involved in reducing the quality of anode
grade coke.

Simple organic acids such as acetic acid should be utilized rather than employing strong acids
as acidification aids during the desalting process. Organic acids employed as metal removal agents
from crude feedstocks react with the contaminating metal to form a salt, which reports to the desalter’s
effluent brine. The acid must have a stronger affinity for the metal (e.g., calcium) than for the oil soluble
species.

Carboxylic acids will react with inorganic salts such as CaCO3 and calcium chloride (CaCl2),
while chelating oil soluble calcium presumably in the form of calcium naphthenate as discussed above.
Appropriately selected acidification aids produce acid salts that naturally partition into the wash water.
This minimizes acid carryover into the crude unit distillation tower practically eliminating corrosion of the
overhead system.

Removal of organically bound and inorganic calcium to specified target levels is feasible as long
as the stoichiometric demand is met. This demand can be met by taking into account the total calcium
content of the crude oil and the characteristics of the wash water (e.g., brine pH, NH3, tramp amines,
renegade acids).

For example, the reaction of a carboxylic acid with calcium naphthenate will yield the calcium
salt of the carboxylic acid and the corresponding naphthenic acid. The simplified reaction using acetic
acid producing naphthenic acid is represented in reaction 4.

2CH3COOH + Ca-Naphthenate → (CH3COO)2Ca + 2Nap-COOH (4)

The resulting naphthenic acid will remain soluble in the oil phase, while the calcium acetate
solubilizes into the effluent brine and exits the desalter.

Conversely, when acids react with inorganic calcium in the form of carbonates, which are often
found in crude oil, the corresponding salt is formed along with carbon dioxide and water (Equation 5).

2CH3COOH + CaCO3 → (CH3COO)2Ca + H2O + CO2(gas) (5)

The solubility of the calcium salts is dependent on the type of acid used. The use of acids to
remove undesirable metals from crude oil such as calcium can be done effectively, however, prudent
acid selection is required. Care must be taken to ensure that the resulting salt formed during acid
addition is sufficiently soluble in the effluent brine allowing removal from the desalter. Metal salts can
reach their solubility limits resulting in calcium salt precipitation in the desalter vessel and downstream
equipment.

For example, at 100oC, the solubility of calcium acetate shown in reactions 4 and 5 is 29.7 g/100
ml. On the other hand, calcium citrate has a water solubility of 0.96 g/100 ml at 100oC, while the
solubility of calcium glycolate is 4.6 g/100 ml at 100oC.

At one European refinery, injection of acetic acid for metals removal led to overhead acid
carryover increasing crude tower overhead corrosion, resulting in increased neutralizer demand.
Moreover, acetic acid and its salts were not easily removed from a desalter‘s effluent brine and passed
through the primary wastewater treatment system before passing on through to the secondary
(biological) treatment system.

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In one instance, citric acid injection led to solids and scale formation in a desalter due to high
metals contamination in the refiner’s crude slate. Calcium citrate salt concentrations were high enough
to promote salt precipitation in the desalter’s effluent brine. Figures 2 and 3 depicit the calcium citrate
found in the desalter. Moreover, precipitated calcium citrate also severely fouled the wash water/brine
effluent exchangers resulting in a unit shutdown.

Potential Downstream Impact of Acidification Programs

As discussed above, the partitioning of acids to the oil phase, and the acid/acid salt
concentration in the brine droplets contained within the desalted crude lead to acids being carried
downstream of the desalter. Once downstream of the desalter, these materials can have several
notable impacts on a crude unit.

Table 2 shows some of these impacts. The most common impact from injecting organic acids is
on the corrosion potential of the crude tower overhead. Organic acids, such as acetic and glycolic, are
known to distill and/or decompose into the overhead system of the crude tower. This increase is noted
by an increase in corrosion and neutralizer demand.

Table 3 shows the results of a volatility study of various calcium-organic salts. The distillation study
parameters were:

• 60 ppmw calcium naphthenate in kerosene extracted with 2X stoichiometric amount of acid


• Distilling the kerosene
• Distilled condensate collected was water washed using distilled water at a 10:1 ratio
• Quantitative analysis of calcium in overhead extract using ion chromatography (see Figure 4)

This study clearly demonstrated that organic acids used to extract the calcium from the organic phase
can leave the desalter and distill in the crude tower. Some of the acids can thermally decompose at
crude unit temperatures forming other acidic species, such as acetic and formic acids.

Figure 5 shows the effect of using acetic acid in the desalter. Control of the pH in the crude
tower overhead was erratic resulting in severe corrosion. Because of the severity of the corrosion, the
refiner upgraded the overhead line metallurgy.

Use of sulfuric acid is difficult to control, resulting in increased corrosion in crude tower
overhead systems due to the formation of SOx acids. Sulfuric acid can also cause rapid corrosion in
the proximity of the acid injection point of the wash water line. Most acidification programs using
sulfuric acid are discontinued due to aggressive corrosion.

In addition, injection of acids into the desalter wash water line to control brine effluent pH to 5.5-
6.0 can result in a desalter washwater inlet pH of < 4. Laboratory testing on various metallurgies (e.g.,
carbon steel) showed that desalter wash water at pH 4 could lead to corrosion rates of 100-200 mpy
(2.5-5.0 mm/yr). Metallurgical upgrades or reliable corrosion inhibitor additives need to be used to
protect the wash water system and mix valves. Otherwise, this can result in severe corrosion in the
desalter and desalter wash water line.

As previously discussed, metal salt solubility will inevitably become an issue if an inappropriate
organic acid is applied as a metals removal additive. Metal salt deposition can result in the fouling of
preheat exchangers downstream of the desalter as well as in brine effluent coolers, not to mention the
fouling of desalter vessels shown in Figures 2 and 3.

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Acidification can also impact the wastewater treatment unit (WWT). Issues can arise due to an
increase in Chemical Oxygen Demand (COD) loading if the WWT is COD limited. All organic acids
contribute to COD loading (see Figure 6). In addition, with some acidification agents, solids loading can
increase. In many cases this is not an issue as the desalter brine effluent is mixed with other waste
streams diluting the solids contribution. Since desalter brine effluent can range from 10-80% of the
WWT loading, design of the acidification program must take this into account.

Conclusions

Desalter acidification can be used successfully to improve desalter performance, amine removal,
including metals removal. Many acidification technologies exist, but as discussed in this paper they are
not all the same. A careful review of the system and establishing a comprehensive chemical
management program implementing good controls prior to feeding acidic additives should be
conducted to prevent unwanted downstream impacts such as corrosion and fouling.

Acknowledgements

The authors would like to thank Robert Reynolds and Mike Braden of Nalco Company for their
assistance with this paper.

Table 1
Effect of pH on Amine Partitioning
Brine % Amine % Amine in
Amine in Brine pH in Brine Oil Phase
Monomethyl Amine 6 99.4 0.6
Monomethyl Amine 7 96.7 3.3
Monomethyl Amine 8 83.5 16.5

Monethanol amine 6 98.9 1.1


Monethanol amine 7 92.3 7.7
Monethanol amine 8 81.3 18.7

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Table 2
Acid Selection Impact on Amine Removal

Acid Cost Performance Concerns


Generally Overhead carryover, COD
Acetic 3
Inefficient loading to WWTP

Generally Scaling, solids formation,


Citric 2
Inefficient COD loading to WWTP
Design & control issues,
Generally low pH < 2, acid
Sulfuric 1
Inefficient carryover, sulfates in
sidecuts
Overhead carryover &
Generally
Glycolic 4 deposition, COD loading
Inefficient
to WWTP
Note: Relative cost key 1=lowest; 4=highest

Table 3
Volatility Study of Several Organic Acids
Acid Brine Pot Temp Column Temp Recovered
o o o o
pH F/ C F/ C Condensate
ppmw Acid
Acetic 5.0 478/248 471/243.9 11.8
Glycolic 3.5 478/248 471.6/244.2 >10*
Proprietary 3.0 486/252 479.7/248.7 0.04
*Large peaks eluted just prior to glycolic acid. Peaks are assumed to be
decomposition products of glycolic acid (see Figure 4)

Oil Reduction with


Acidification
8
BEGIN ACID INJECTION
7

6
% Oil in Effluent

3
Low
2 Level

0
4/13 5/3 5/23 6/12 7/2 7/22 8/11 8/31 9/20

Favorable crude slates

Figure 1 : Oil Reduction with Desalter Acidification

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Figure 2: Calcium Citrate on Desalter Grids

Figure 3: Calcium Citrate on Desalter Inlet Distributor

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Figure 4: Kerosene Extract Distillation - Gylcolic Acid

10 Overhead pH

8
pH

4
Oct Dec Feb

Figure 5: Overhead pH Control with Acetic Acid Injection into the Desalter

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COD of Acetic, Malic & Glycolic Acids, and Calcium Acetate Concentrations
12,000
11350
11,000 Proprietary Acid
Acetic Acid
10,000 Glycolic Acid
9100 9330
9,000 Calcium Acetate
9120
Linear (Acetic Acid)
8,000 Linear (Proprietary Acid) 8080
COD, ppm

Linear (Glycolic Acid) 7120


7,000 Linear (Calcium Acetate)
6690
6950
6350
6,000 5670
5650
5250
5,000
4300
4,000 3910
3100 3250
3,000
2550
2100
2,000
1560
1,000 900

-
0.00% 0.25% 0.50% 0.75% 1.00% 1.25%
wt% Acid in Water

Figure 6: COD of various Organic Acids

References

1. Strassner, “Effect of pH on Interfacial Films and Stability of Crude Poil-Water Emulsions”,


SPE 1968, paper no. 1939.
2. Schutt and Horvath, “Crude Column Overhead Corrosion Problems Caused by Oxidized
Sulfur Species”, NACE Corrosion 1987, paper no. 198
3. Kokal, “Crude-Oil Emulsions: A State-Of-The-Art Review”, SPE 2002, paper no. SPE 77497.
4. Duggan and Rechtien, “Identifying the Impact of Amine Contamination On Crude Units”,
NACE Corrosion 2006, paper no. 06581.
5. Garcia and Lordo, “Chemistry And Impacts Of Commonly Used Amine-Based H2S
Scavengers On Crude Unit Towers And Overheads”, NACE Corrosion 2007, paper no.
07571.
6. John Wiley & Sons, Encyclopaedia of Chemical Technology 4th Edition, Vol. 6, Pg. 354-360
7. DuPont Glycolic Acid, Technical Information,
http://www2.dupont.com/Glycolic_Acid/en_US/tech_info/techinfo.html, “K15525 Glycolic
Attributes”
8. Andrew L. Ternay, Jr., Contemporary Organic Chemistry, Second Edition, W. B. Saunders
Company, Philadelphia, p 873 – 918.
9. Michigan State University, Search: Amine “Virtual Textbook of Organic Chemistry”, Amines-
Reaction of Amines with Nitrous Acid, Document 5, www.chemistry.msu.edu
10. Mark A. Reinsel, John J. Borkowski, and John T. Sears, “Partition Coefficients for Acetic,
Propionic, and Butyric Acids in a Crude Oil/Water System”, J. Chem. Eng. Data 1994, 39,
513-516.

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