Amine units improvements at the Aruba Refinery

Rubila Lampe-Chiquito MSC ChemEng & Cedric Charles MSC ChemEng.

Valero Aruba Refinery

SUMMARY
High amine losses, high H2S in the fuel gas, and poor unit reliability were the norm for the amine
regeneration units at the Aruba refinery. In 2003, the three amine units were revamped to increase
capacity, to improve unit operation and reliability, and to minimize the losses. The three high
pressure amine absorber systems at the hydrotreaters were also revamped. These changes
(revamps) resulted in significant reduction in amine losses; the amine purchases went from
1,791,060 (2002) Lbs/yr to 178,120 Lbs/yr (2005) after the revamp. No amine was purchased in
2006 and 2007, this resulted in significant amine solution savings of $406,000/Year.
Subsequent to the revamps and unit restarts, frequent rich amine cartridge filter replacements and
high Heat Stable Salts (HSS) were observed. An AMIPUR (HSS removal skid) was installed to
remove the HSS, and rich amine acid gas loadings were targeted to 0.35 mol H2S/mol MDEA
maximum. The AMIPUR operation and the new operating targets for the amine system resulted
in significant filter costs savings of 65% on the rich amine filters and 34% on the lean amine
filters. A savings of $119,000 per month amounting to annual savings of about $1.5 Million were
achieved by continuing to operate the units on lower rich amine acid loadings and lower HSS
contents.
The amine losses also reduced further due to less filters being changed out. Besides the
economical benefits, fewer filter change-outs resulted in safety and environmental benefit because
of the reduced potential for H2S exposure and release.

265

BACKGROUND
The Aruba refinery amine system uses a 45 wt% MDEA solution for removing H2S from various
gas streams and an LPG stream.
The Amine regeneration units, M1AR, M2AR and M3AR, have a designed capacity of 1450 BPH
(barrels per hour) or 1015 GPM each. These units regenerate the amine solution, removing
hydrogen sulfide gas (H2S) from a solution of water and amine (MDEA), and provide lean amine
solution for H2S absorbers. The high pressure H2S absorbers are at the hydrotreaters: D2AR (Gas
oil Hydrotreater unit) and D3AR (Gas oil Hydrotreater unit). The medium pressure absorbers are
at the D1AR (Diesel Hydrotreater unit), N1AR (Purge gas unit) and the LPG absorber. The low
pressure absorbers are the two DC1AR and DC2AR Coker units absorbers and the two FS1AR
and FS2AR fuel gas absorbers.
The following tables (Table 1.0, 2.0) show the design and operating conditions of the regenerators
and absorbers at the Aruba refinery:
Table 1.0: Aruba refinery amine units design data
Amine units
Circulation
Regen. Tower
(regenerators) Flow (BPH)
Pressure (Psig)
M1AR
1450
13
M2AR
1450
13
M3AR
1450
13

Amine
units

M1AR

M2AR

M3AR

Table 2.0: Aruba refinery absorbers data for max crude sulfur case.
Absorber
Lean
Rich amine
Rich amine,
Absorber
Amine
H2S loading,
mol H2S per
Pressure
Flow, BPH
lbs/hr
mol MDEA
(Psig)
D1AR
D2AR

FS1AR
FS2AR
N1AR
LPG

DC1AR
DC2AR
D3AR

611
719
1330

11,199
16,151
27,350

606
476
128
46
1,256

8,588
6,748
2,885
708
18,928

373
429
617
1,419

6,481
7,465
13,847
27,793

266

420
730
0.46
75
75
400
320
0.39
80
80
730
0.43

DESCRIPTION OF THE ARUBA REFINERY AMINE UNIT.

Figure 1 provides a schematic of the typical amine regeneration unit at Aruba.
The rich amine solution enters the hydrocarbon flash drums in each amine unit. The flash drums
operate at approximately 10 psig, where entrained hydrocarbons are removed. The light
hydrocarbon is flashed off as a gas and goes to the fuel gas unit. Liquid hydrocarbon that is too
heavy to flash will rise to the top of the amine solution and be drawn off to the closed drain
header. The rich amine is pumped to the rich amine filters, then through the tube side of the feed
bottom exchangers and on to the amine regeneration tower. In the feed bottoms exchanger, hot
lean amine solution from the reboiler is used to pre-heat the rich amine solution before it enters
the regeneration tower.
The rich amine solution enters the regenerator tower near the top at tray 15 (trays are numbered
from bottom to top). The three trays above the feed allow reflux water to contact the vapors rising
up the tower and wash down amine vapor and droplets. The rich amine solution flows down the
tower. As it travels over the valve trays on its way down, it comes in contact with hot vapor
traveling up through the trays. The hot vapor heats the rich amine solution, and in the process
breaks the MDEA-H2S bond, stripping the H2S from the amine solution.
The overhead vapor from the regenerator tower is cooled in the overhead condenser which is an
air-cooled fin fan exchanger. This condenser cools the overhead vapors to 115-120 oF. The
pressure on the regenerator tower is controlled by the release of acid gas from the reflux drum to
the sulfur plants. The reflux is returned to the regenerator by the reflux pumps.
The amine solution becomes leaner and hotter as it travels down the tower. The temperature is
around 255 oF in the bottom of the tower. The solution leaves the bottom of the regenerator and
enters the shell side of the regenerator reboiler. In the reboiler, the MDEA solution is heated by
60 psig steam flowing through the tubes. The reboiler vaporizes some of the water from the
MDEA solution and the vapor is returned to the regenerator below the first tray to continue the
stripping process.
The hot lean amine solution from the shell side of the reboiler enters the shell side of the
feed/bottoms exchangers and is cooled by the rich amine stream flowing through the tube side.
The partially cooled lean amine then enters the product coolers, where it is cooled by seawater
flowing through the tubes. The lean amine temperature is maintained in the range of 110-125 oF.
The lean amine solution exits the coolers and goes to the lean amine storage tank. The lean amine
tank is the surge for the amine system. The lean amine pumps take suction from the tank and
pump lean amine to the absorbers.
The lean amine filter pump also takes suction from the tank and pumps amine to the lean amine
pre-filter, the carbon treaters and the post-filters. Regular changing of the filter elements is
necessary to keep the system clean and keep the filters online. The lean amine filtration system
filters 10-20% of the total amine circulation.

267

Figure 1.0: Aruba refinery M3AR Amine unit

268

PROBLEM DIFINITION
The Aruba refinery observed high amine losses, high H2S in the fuel gas, and poor unit
reliability at the amine regeneration units. High corrosion rates resulted in leaking of the
lean/rich exchangers and also the lean amine coolers; for example, the leaking lean amine
cooler resulted in seawater contamination of the amine at M3AR unit. After exchanger
tube repairs, the unit equipment were washed with clean water and the unit was
replenished with fresh amine. Contamination and foaming caused great losses of the
solution and off spec treated gas.
AMINE UNIT REVAMP
In an effort to correct the many problems at the amine units, and at the same time
accommodate higher projected sulfur loads (at higher sulfur crude rates) while
minimizing cost, it was agreed to revamp the existing amine units. The units were
originally designed for MEA but were revamped for MDEA. The revamp directive
included higher amine circulation rates and higher MDEA concentration of 45 wt. %.
As part of the revamp, the capacity of each amine regeneration unit was increased to
1450 BPH (1015 GPM), from 1000 BPH (700 GPM) at M1AR and M2AR units, and
1250 BPH (875 GPM) at M3AR unit. The revamp included larger feed flash drum to
increase the residence time and prevent hydrocarbon carryover to the amine regenerator.
REGENERATION SYSTEM REVAMP
Revamp of each of the three amine units included replacement of existing rich amine
hydrocarbon flash drum with a larger drum to provide 25 minutes of residence time for
the rich amine entering the drum, new rich amine feed pumps, new rich amine cartridge
filters, a closed drain system for all amine drains in the amine unit, and new lean amine
coolers. The trays in the amine regeneration towers were replaced with high capacity
trays. Larger lean and rich amine piping were added, along with larger off gas piping
inside and outside unit battery limit. One additional low pressure amine pump was added
at M3AR, while one additional high pressure amine pump was added as a common spare
for M1AR/M2AR.
REVAMP OF ABSORBERS TOWERS.
In addition, the absorber towers at the three hydrotreaters (one Diesel HDS, and two Gas
Oil HDS) were replaced. The old absorber towers had a water wash section at the top,
then the amine section, then another water wash section, and a pseudo-three phase knock
out section at the tower bottom where the gas enters to be treated. As part of the absorber
revamp, a new high pressure gas fin fan cooler, new three phase separator drum upstream
of the new absorber, and a knock out drum downstream of the absorber were added.
Wash water is now added upstream of the new gas fin fan cooler; the sour water is
separated in the new three phase separator. The quantity of wash water has also been
increased to improve ammonium bisulfide salt removal.
LOWER FOAMING INCIDENCES EXPERIENCED.
The contamination and foaming of the amine was the result of hydrocarbon and
particulates. The larger rich amine flash drum with the higher amine residence time has

269

resulted in the ability to effectively separate heavy hydrocarbon from the rich amine.
This reduces the residual heavy hydrocarbon content in the rich amine. The net effect is
the significant reduction of amine foaming in the absorbers/regenerators.
The change-out of the activated carbon filter on a more regular (6 month) basis was also
done to clean the amine solution; prior carbon change-outs were once every 1-2 years.
The lean amine cartridge filters (50 micron size) were replaced with the smaller 10
micron cartridges to help in the removal of particulates.
AMINE SOLVENT LOSSES
As part of the revamp, a closed drain system was also installed to recover amine drains
and minimize the amine losses.
The industry average MDEA consumption is at 10 Lbs/MMSCF. 1 Aruba Refinery
amine consumption exceeded this industry average, but since the revamp, the MDEA
losses were reduced significantly as shown in Figure 2.0. The MDEA purchases for 2002
were 1,791, 060 Lbs; this was reduced to 178,120 Lbs in 2005 as shown in Table 3.0. In
2006 and 2007, no MDEA was purchased because the stored high HSS amine was
reintroduced to the amine unit and treated by the HSS removal unit (AMIPUR skid).
With the reduction in amine losses after the revamps, an increase in filter change-outs
and iron content in amine were soon observed.
Total MDEA Consumption
140

100
80
60
40
20

Date (month)

Figure 2.0: MDEA consumption

270

Fe
b05

ec
-0
4
D

ct
-0
4
O

Au
g04

Ju
n04

Fe
b04
Ap
r04

ec
-0
3
D

ct
-0
3
O

Au
g03

Ju
n03

Fe
b03
Ap
r03

ec
-0
2
D

ct
-0
2

MDEA Consumption
(Lbs/MMscf)

120

Table 3.0: MDEA purchased in LBS/Year

Year
Lbs
2002
1,791,060
2003
410,416
2004
374,008
2005
178,120
2006
0

LOW H2S IN THE TREATED FUELGAS

The fuel gas absorber is a liquid amine-gas absorber. The fuel gas absorbers at FS1AR
and FS2AR remove H2S from the low pressure off gas. These gases come from the low
pressure separator and the strippers at the hydrotreaters, and other low pressure gases
from the crude unit area and the saturate gas plant. These absorbers are trayed towers.
The lean amine loading was typically between 0.07 to 0.13 mole H2S per mole of MDEA.
Prior to the revamp, high H2S (800 ppmv 2000 ppmv) episodes were frequently
observed in the refinery fuel gas. This was attributed primarily to foaming at the
absorbers and amine regeneration towers, low amine strength, and high lean amine H2S
loading and temperature. Since the revamps of the amine units and the hydrotreater
absorber systems, the H2S in the fuel gas is at steady (<100 ppmv).
UNIT RELIABILITY IMPROVED
Hydrocarbon carryover, foaming in the towers, poor amine stripping, and the various unit
upsets resulted in poor unit reliability and efficiency. Severe internal blistering of the
high pressure absorber towers was observed. For example, the D3AR absorber tower had
to be replaced within two years due to blistering. Various inspections and metallurgical
testing of the three hydrotreater absorber towers revealed severe Hydrogen Induced
Cracking (HIC). At various intervals, leaks at the absorber tower shell and nozzles
resulted in unit shutdowns with periodic replacement of vessel sections. The aggressive
corrosion at the absorbers was evidence of the high HSS in the amine solution. The new
absorbers were all designed and built with HIC resistant carbon steel and stress relieved.
Failures in the rich amine piping due to corrosion, and the eventual leaks resulted in
amine losses, and sometimes unit shutdowns. Various amine piping sections that were
not originally stress relieved have been replaced with stress relieved piping.
These modifications and changes in the unit operation shave significantly improved the
reliability of the amine treating systems.
FREQUENT FILTER CHANGE OUT
The new 100% flow rich amine filter system is a cartridge type filter designed to filter
iron sulfide, scale and other impurities out of the amine system. Each amine unit has two
of these rich amine filter vessels; one is typically on line and the other on standby. The
removal of impurities/particulates helps to reduce the foaming tendency of the amine as
well as reduce erosion of the carbon steel piping in the amine system. The rich amine
filter vessel/housing holds 28 cartridge filters each.

271

During the start up of the amine units, 100 micron filter cartridges were initially used in
the rich amine filters. Over a five week period after startup, the cartridge size was
reduced stepwise from 100 micron, 75 micron, 40 micron, 25 micron, and eventually to
10 micron which required filter cartridge change-out twice in each 8 hour operating shift.
The decision was made to return to 25 micron size cartridges, which required change-out
once every day.
At two of the amine units treating the hydrotreaters and the Coker units, the filter change
out frequency was high: on average once a day. The total rich amine cartridge filter
replacement for the three amine units was approximately 1700 cartridge filters per month.
These frequent replacements were indicative of high levels of iron (FeS) in the amine
solution due to corrosion. The economic effect of these change-outs included: high filter
cost and amine losses. The safety impact due to the potential H2S exposure (during filter
change outs) and the environmental impact due to disposal of spent filter cartridges were
of concern.
HEAT STABLE SALTS (HSS)
After the revamp, the Heat Stable Salts (HSS) buildup rate was 1.3 wt.% per month. This
increase in HSS buildup rate since the 2003 revamp can be attributed to better amine
operation and lower amine losses.
The primary HSS's are formate and thiocyanate anions, which are degradation byproducts
from the delayed coker units. The upper limit recommended for formate is 500 ppmw, but
numbers as high as 19,600 ppmw have been measured at the amine unit. These heat
stable salts are formed with MDEA in the presence of CO or HCN. The amine stream
treating the Coker gas showed a high amount of HSS between 3.0 and 8.5 wt.%.
Although DuPart, Bacon and Edwards mentioned in their 1993 paper that HSS should
not exceed 10% of total amine circulation, we believe that this number should be much
lower for the Aruba refinery based on our observations. 2 Rooney, Bacon, and DuPart
have stated in a later 1997 article: Total HSAS level should not exceed 0.5% of the total
solution.
Table 4.0: HSS in MDEA Solution

Acetate (ppmw)
Formate (ppmw)
Thiocyanate (ppmw)
HSS (total) (wt%)

Aruba
Refinery data
2070
19,690
7000
3.0 8.5

Upper limit 4
recommended
1000
500
10,000
0.5

The iron in solution had increased from 11 to 40 ppmw since the revamp, and was an
indication of increased corrosion in the amine system. The dark color of the amine and
frequent filter replacements also confirmed the corrosion mechanism, due to high HSS.

272

The data below (accumulated from the Aruba refinery) shows that the required amount of
filter cartridges triples from 200 to 600+ cartridges when the HSS is above 4 wt.%.

900

Amount filters replaced

800
700
600
500
400
300
200
100
0
0

4
HSS (wt%)

10

Figure 4.0: HSS vs. Rich filter replacement at Aruba Refinery

The improved water wash project at the Coker units was commissioned to help remove
cyanides and other acid salt precursors from the Coker gas stream upstream of the amine
absorbers; however no significant improvement has been observed.
RICH AMINE ACID GAS LOADING
By closely analyzing the plant operating data, a correlation was observed between the
rich amine acid gas loading and the amount of iron in the amine. At a rich amine acid gas
loading of 0.30 mol H2S/mol MDEA, significantly less rich filters have to be replaced
compared to a rich amine gas loading of 0.42 as illustrated in Figure 5.0 below.
The amine units were designed to operate at a maximum rich amine gas loading of 0.50.
However after the assessment, a new target of 0.35 mol H2S/mol MDEA was established
to minimize corrosion. As has been published in various articles, high acid loading
increases the corrosion tendency of the amine. 3
Due to lower refinery crude rates (220-240 KBD) and resultant lower H2S production, the
amine circulation rate was able to be increased in order to lower the rich amine gas
loading to < 0.35 mol H2S/mol MDEA. The lean amine strength was also increased to
45 wt.% MDEA. Consequently less iron in amine solution was measured and filter
change out frequency dropped as shown in Figure 6.0.

273

1000

Amount of Rich filters

800

600

400

200

0
0.20

0.25

0.30

0.35

0.40

0.45

0.50

Rich Acid Loading

Figure 5.0: Rich loading vs. Rich filter change-outs

M3 Iron and HSS Levels

100

9
Total HSS, wt%
Iron

90

80
7

70

60
5
50
4
40
3
30

2
20

0
14-Jan-04

10

23-Apr-04

01-Aug-04

09-Nov-04

17-Feb-05

28-May-05

0
05-Sep-05

Figure 6.0: HSS vs. total iron in amine solution ppmw

274

Soluble Iron Level, ppmw

Total HSS, wt%MDEA

HSS REMOVAL SKID

In June 2005, an AMIPUR skid for Heat Stable Salt removal was installed and
commissioned. The project took 11 months to purchase, design, and construct.
This AMIPUR skid includes a resin bed, cartridge filters for lean amine and water,
caustic reservoir, and a PLC panel for automatic control. The skid is designed to remove
dissolved heat stable acid salts from a 21.8 GPM flow of M3AR lean amine. The key to
the AMIPUR process is the ion exchange resin used to absorb the heat stable acid salts
dissolved in the circulating amine solution. The AMIPUR also uses a six step process
and low strength caustic to regenerate the resin bed. The operating cycle period can be
changed to Low, Medium, and High depending on the content of heat stable salts in the
lean amine feed.
Before the commissioning of the AMIPUR skid, the M3AR amine unit was frequently
replenished with fresh MDEA to maintain a low HSS in the amine solution. The
contaminated high HSS amine was removed from the amine unit and stored in ISO
containers; this amine continues to be slowly reintroduced to the M3AR unit for HSS
reduction by the AMIPUR skid. At the M3AR amine unit, the HSS was reduced to
below 4 wt.% by the AMIPUR unit; this resulted in less filter change-outs.
No MDEA has been purchased since the AMIPUR start-up in 2005. Without the
AMIPUR, amine change-out at M3AR would have to be done every 3 months at an
annual cost of over $250,000 in amine cost only.
In less than 6 months after start up of the AMIPUR, high Sodium (10,000 ppmw) was
observed in the amine samples. This indicated that caustic was bleeding into the system.
The high sodium and high HSS began to adversely affect the H2S stripping in the
regeneration towers and also affected H2S absorption. To correct this sodium increase, a
longer waste step was added to the AMIPUR skid to ensure that the resin would be
properly washed and regenerated. The sodium in the amine has since dropped and is
approximately 2100 -2300 ppmw; H2S stripping in the regeneration towers and H2S
absorption at the absorbers are effective and steady.
CONCLUSION
The problems of high amine losses, high H2S in the fuel gas, and poor unit reliability at
the amine units of the Aruba refinery are now in the past. The revamps, the AMIPUR
skid, and the various parameter changes have resulted in significant savings and
improved amine unit reliability for the Aruba refinery.

275

BIBLIOGRAPHY:

1) Stewart, E.J. and Lanning R.A. Reduce amine plant solvent losses,
Hydrocarbon Processing, 1994.
2) DuPart, M.S, Bacon, T.R, and Edwards, D.J Understanding Corrosion in
Alkanolaine gas treating plants, Part 2 Hydrocarbon processing, 1993.
3) Rooney, P.C., Bacon, T.R, and DuPart, M.S Effect of heat stable salts on MDEA
solution Corrosivity, Part 1, Hydrocarbon Processing, March 1996.
4) Rooney, P.C., Bacon, T.R., and DuPart, M.S., Effect of heat stable salts on
MDEA solution Corrosivity, Part 2, Hydrocarbon Processing, April 2007.

276