Amine Purification System (AmiPur) Continuous Heat Stable Salts Removal

from Amine Solutions

Jenny Shao, Group Leader Oil & Gas, Eco-Tec Inc. Canada

1. Introduction

Amine scrubbing solutions are used to remove hydrogen sulfide (H2S) and carbon
dioxide (CO2) from gas streams and LPG in many oil refineries and natural gas
conditioning plants. Due to its high selectivity to H2S, Methyldiethanolamine (MDEA) is
most commonly used to remove H2S in the presence of CO2 from gas streams and LPG.

Amine plant operational problems, such as excessive foaming, corrosion, and capacity
reduction, are often attributed to the accumulation of amine heat stable salts. These heat
stable salts lead to costly maintenance problems such as corrosion, frequent filter
replacement, foaming in the absorber column, absorber tower plugging, heat exchanger
fouling and a reduction in the amount of amine available for gas treating.

Continuous amine purification is being increasingly recognized as the most effective

solution for HSS related problems. The benefits of continuous HSS removal go beyond
limiting the level of impurities in the amine loop. A continuous on-line purification
system helps to ensure a stable and uniform gas conditioning operation where
contaminant level in the amine solution is prevented from building up, thus minimizing
the rate of corrosion. It also ensures that amine unit operation is reliable and provides the
designed gas treating efficiency.

Developed by Eco-Tec Inc. Canada in 1998, AmiPur (Amine Purification System) uses
anion exchange technology to continuously remove heat stable salts. Therefore, it ensures
reliable operation of amine plant.

2. AmiPur Heat Stable Salt Removal System

Eco-Tec AmiPur employes its Reciprocating Flow (RecofloTM) ion exchange

technology, which has been extensively used since 1973 in many chemical recovery and
water treatment systems. The AmiPur, a unique and cost effective on line amine
purification system has the following features:

Fine particle size resins;

Countercurrent regeneration;
Short column heights (12 inch, 30 cm);
Low resin loading;
Fast flows and short cycles;

These on-line Eco-Tec Amine Purification (AmiPur) systems are now successfully
operating in 25 petroleum refineries and natural gas plants in 10 countries worldwide,
Table 1.
Table 1. AmiPur users list
Customer Location
Crown Central Petroleum Corp. Pasadena, Texas, USA
Motiva Enterprises LLS Port Arthur, Texas, USA
Shell Opus Bakersfield, California, USA
Conco Phillips Ferndale, Washington, USA
Sunoco Mid-America Toledo, Ohio, USA
Torch Energy Marketing Snyder, Texas, USA
Duke Energy Hallettsville, Texas, USA
Marathon Ashland Petroleum Garyville, Louisiana, USA
Tampa Electric/Polk Power Plant Mulberry, Florida, USA
Marathon Ashland Petroleum Robinson, Illinois, USA
Petrox S.A. Talcahuano, CHILE
Lyondell-CITGO Refining Company Houston, Texas, USA
La Gloria Tyler, Texas, USA
Nerefco Europort NETHERLANDS
Reliance Petroleum Jamnager Complex Gujarat, INDIA
Amoco (BP) Sharjah Oil Company Sharjah, UNITED ARAB EMIRATES
Sinopec Zhenhai Zhejiang, CHINA
Praxair Inc. Texas City, Texas, USA
P.T. Susila Krakatau Steel Jakarta, INDONESIA
Enbridge Pipelines LP Texas, USA
San Nazzaro Gasification Plant Snamprogetti San Nazzaro de Burgondi, ITALY
Vintage Petroleum Inc. California, USA
PXP/DCOR California, USA
SINCOR VENEZUELA
Valero Aruba Refining ARUBA

Eco-Tec offers seven different models of AmiPur, with different HSS removal capacity.
A typical AmiPur unit is presented at Figure 1.

There are basically two steps in the AmiPur operating cycle: amine loading and caustic
regeneration. This cycle is automatically repeated every 10-15 minutes.

Lean amine solution is pumped through a cartridge filter and into the resin column. The
ion exchange resin removes the heat stable salts and the purified amine solution is
directed to the flash tank or returned into the amine batch.

Loading step: ROH + RN3+HHCOO- RHCOO + RN3 + H2O

During caustic regeneration step, dilute caustic soda is used to regenerate the resin
column. The unit draws concentrated caustic from tanks or drums and dilutes it to the
proper strength automatically.
Regeneration step: RHCOO + NaOH ROH + HCOONa

Note: ROH resin surface, RN3 tertiary amine, HCOOH - HSS

Figure 1. Skid mounted AmiPur unit

With the same HSS removal capacity, AmiPur has the following advantages over other
amine purification systems using ion exchange technology,

AmiPur uses the least amount of NaOH for regeneration;

AmiPur generates the least amount of waste;
AmiPur uses the least amount of resin;
AmiPur has the least amine loss;
AmiPur has the smallest skid size.
3. Case Study I: Crown Central Petroleum Corporation (CCPC), USA

The amine unit in CCPC contains a gas liquid contactor or fuel gas absorber, a liquid-
liquid C3/C4 amine treater, one amine regenerator a flash drum, heat exchangers, amine
filters, a slip stream amine reclaimer, and several associated pumps.

The main fuel gas absorber is a packed column with 2 beds of random packing and
demister type separation at the top gas outlet. The lean amine feeds the top bed of
packing through a distributor and flows down the column, contacting the sour fuel gas
and removing the H2S. The sour gas enters the bottom of the column above the towers
rich amine liquid level. The towers pressure drop is measured over inlet gas line to outlet
gas line, and this pressure drop is used to monitor tower pluggage and foaming.

The liquid-liquid amine contactor is a trayed tower with 15 trays. This tower also serves
as an amine surge tank, since about 80% of the amine unit inventory is kept in this tower.
The tower is designed to remove about 1000 ppm H2S from 21,000 BPD C3/C4 mix.

The tail gas units amine system is very similar to the main amine system, with no flash
drum and only a single amine absorber.

As HSS build, the amine filters plugged more frequently. Iron in the solution started to
climb. Heat exchanger surfaces became fouled forcing the operator to increase the energy
input to the units regenerator reboiler. Tower internals became fouled, increasing
velocities and pressure drop to the point of increasing the overall amine losses. The
amine solution itself started to foam more easily due to the increase of impurities in the
solution, and an rapid changes in absorber feed rates caused amine carryover, amine
losses, tower instability, potentially poor H2S treat, environmental non-compliance, and
sulfur plant upsets.

AmiPur Operation at CCPC

At Crown Central Petroleums Pasadena, Texas refinery, an AmiPur unit was installed
in 1998 to effectively remove HSS from MDEA solution. The unit was started up in
October 1998.

The HSS in solution were at approximately 2.4 wt% (as MDEA) when the AmiPur unit
was started up, and within 30 days the HSS went down to less than 2 wt.%. Material that
had been accumulated from the amine unit prior to installation with HSS level of 3.5
wt.% was then introduced back into the process. The HSS level in the solution increased
back to 2.4 wt.%.

By March 1999, after a unit shut down for maintenance and a replacement of the amine
regenerator tower, the HSS level was down to 1.75 wt.%. A significant decrease in
corrosion rate was observed. The ultimate goal of the refinery is to keep corrosion rate as
close to zero as possible. To achieve this goal, it was decided to decrease the HSS
concentration further, from 1.5 wt.% to 0.5 wt.%, so the unit was upgraded with extra
capacity. Figure 2 is the curve of the heat stable salt decline.

Due to the decrease in HSS level, corrosion probe readings, which had been as high as
160 mpy before, now average less than 10 mpy. As shown in Figure 3, since year 2001,
the readings have always been close to zero.

As shown in Figure 4, filter change frequency decreased from more than 10 times per
month to average once per month.

Due to more stable operation, less filter change, and less foaming, annual amine purchase
has been decreased from 200,000 pounds in 1998 to about 50,000 pounds since year 2000,
see Figure 5.

Figure 6 shows that the total hours H2S out of compliance each year decreased from
hundreds of hours each year (even more than one thousand hours sometimes) to less than
50 hours ( sometimes zero 0 hour).

HSS By INEOS

6
5.46
5.38
5 4.97
4.4
4
3.76
% HSS

3 2.95
2.62
2 2.16 2.13 2.14
1.86 1.88 1.77
1.62 1.59
1.49
1.491.311.2 1.15
1 0.82 0.998 0.8352
0.71 0.690.77
0.73
0.6 0.7010.71
0.62
0.598 0.63090.7151
0.6153
0.6368
0.49
0.42
0.42
0.410.42 0.56
0.5
0.42 0.53 0.41
0.3962 0.5755
0.5565
0.27
0.28 0.34 0.340.28
0.25 0.28
0.26
0.22 0.2978
0
6

98 27

00 23

02 29

8
23
19 5/1

19 1/2

19 4/2

20 1/0

20 5/1

20 9/2

1
20 7/3

20 2/2

20 2/0

20 7/2
19 04/

20 08/

20 03/

20 07/

1/
/0

/1

/0

/0

/0

/0

/0

/0

/1

/0

/0
/

/
97

98

99

99

00

00

01

01

02

02

03

04
19

DATE

Figure 2. HSS level at the main amine unit at CCPC Pasadena refinery.
 MONTHLY MPY

120

108
102 103
100
100

87
84 85
81
80 75

60
53
51
5050
48

40
40 37 MONTHLY MPY
33
28 27

20
20 17 17 17
15
13
13 12
10
65 6 7
4 5 5 3 4 4 2 111 4
1 1 2 00 00000 00000 00000 0000 00000 00000 000
0
ve
ve

ve
ve

ve

ve

ve

ve

ve
ve

ve

ve
A
A

A
A

A
A

A
9
99

04
97

98

00

01

02

03
97

00

02
t9
eb

eb
ec

ly

ov

ly

ov

ly
ay

pr

pr
ep
Ju

Ju

Ju
A

A
M

N
F

F
S

Figure 3. Corrosion probe readings at CCPC Pasadena refinery.

Filter Changes Per Month

# Changes per Month

15 11 11
10
5 2.6 2.1
1.1 1 0.8 1
0
Ave Ave Ave Ave Ave Ave Ave Ave
97 98 99 00 01 02 03 04

Figure 4. Filter changes per month at CCPC Pasadena refinery.

 Amine Purchases

500000
450000
Pounds MDEA

400000
350000
300000
250000
200000
150000
100000
50000
0
Purchases

Purchases

Purchases

Purchases

Purchases

Purchases
1992

1994

1996

1998

2000

2002
Figure 5. Annual amine purchase at CCPC Pasadena refinery

Total Hours H2S Out Of Compliance

2500

2037
1938
2000

1500
1166

1000

504 525
500 420

55 21 30 10
0 0
0
1993 1994 1995 1996 1997 1998 1999 2000 2001 2002 2003 2004

Figure 6. Total Hours H2S out of Compliance at CCPC Pasadena refinery

4. Case Study II: SINOPEC Zhenhai refinery, China

Problems in #2 catalytic cracking/amine scrubbing unit

#2 catalytic cracking unit in Zhenhai refinery, China, has cracking capacity of 3,000,000
Tonne/year. This FCC unit is connected to an amine scrubbing unit using MDEA, which
treats 160,000 Tonne/year of dry gas and 450,000 Tonne/year of LPG. In 2001, treating
capacity of LPG was increased to 600,000 - 700,00 Tonne/year. Major problems with the
amine scrubbing unit are: (1) high concentration of suspended solids, frequent filter
clogging, amine losses due to foaming and equipment fouling (see Figure 7, 9). (2) severe
corrosion problems found in reboiler, higher temperature piping and lean/rich heat
exchanger (see Figure 8). Corrosion was also observed at all connections. On December
5, 2001, leaking in gas piping was found. In July 2002, both inlet and outlet piping and
lean/rich heat exchanger started leaking. In September 2002, the whole unit was shut
down for repair. There was 60 Tonne of 24% dirty amine drained from the unit.

AmiPur operation at Zhenhai refinery

Based on the HSS analysis results shown in Table 2, an Eco-Tec AmiPur unit (AM15)
was selected to keep the system HSS level below 1 wt.% (as MDEA). There are two
operation modes: hig HSS mode and low HSS mode. The high mode is used to bring
HSS level down to 1 wt.% as fast as possible. The low mode will keep the HSS
concentration in amine solution below 1 wt.%

Table 2. #2 FCC amine scrubbing unit Heat Stable Salt analysis results in 2001
Date 6.22 6.25 6.26 6.27 6.28 6.29 7.2
HSS,wt% 6.42 6.75 6.76 6.81 6.82 6.90 7.2

The system was installed on August 11, 2003 and started up on August 22, 2003. By
September 6, the system had been running for 2300 cycles at high HSS mode and the
HSS level was brought down from 3.8 wt.% to 1.0 wt.%. The system was switched to
low HSS mode and the HSS level in solution has been kept below 1 wt.% (as MDEA),
lowest at 0.27 wt.%, as shown Figure 10.
Figure 7.Lean/rich heat exchanger piping

Figure 8. Reboiler piping

Figure 9. Erosion inside lean/rich heat
 HSS l evel

4. 0%

3. 5%

3. 0% HSS in AmiPur
i l t
2. 5%

2. 0%

1. 5%

1. 0%

0. 5% HSS in AmiPur
tl t
0. 0%
8/ 7 8/ 17 8/ 27 9/ 6 9/ 16 9/ 26 10/ 6 10/ 16 10/ 26 11/ 5 11/ 15

Figure 10. HSS level change in amine solution at Zhenhai refinery, China

Due to the continuous removal of HSS by AmiPur, system corrosion rate has been
decreased dramatically. Average Corrosion rate at the top of the regenerator before
AmiPur was 90 mpy as shown in Figure 11. When HSS level was brought down to 0.5
wt.%, the corrosion rate at the top of regenerator is as low as 2 mpy, shown in Figure 12.

When HSS level was 6 wt.% (as MDEA), foam height was 20 cm and break time was 20
seconds. Because of the low HSS level, both foam height and break time in #2 FCC
amine unit are obviously better than other amine units, especially break time, shown in
Table 3.

When the HSS level is lowered, more amine is available for sour gas treating. In Zhenhai
refinery, a 25% of amine saving was realized one month after the start up of AmiPur.
Figure 11, Corrosion rate before AmiPur operation at Zhenhai refinery,

Figure12, Corrosion rate after AmiPur operation at Zhenhai refinery, China

Table 3. Comparison of HSS level(wt%),foam height(cm), and break timesin
different amine units at Zhenhai refinery, China

Time #2 FCC #1 FCC Delayed coking

HSS Foam height Break HSS Foam Break time HSS Foam height Break time
time hetight
10.1 0.63 3.5 5 4.62 4.0 12 3.58 5.0 18
5
10.1 0.65 3.0 5 4.65 4.5 10 3.62 5.5 21
6
10.1 0.62 3.5 6 4.69 4.0 12 3.67 5.0 23
7
10.1 0.60 3.5 5 4.76 4.5 13 3.75 6.0 18
8
10.1 0.59 3.0 6 4.88 4.0 11 3.8 5.5 19
9
10.2 0.59 3.5 5 4.95 4.0 12 3.87 5.0 20
0
11.5 0.45 3.5 5

5. Summary

Amine degradation causes the formation of heat stable salts (HSS) that can lead to
corrosion. The amine unit performance begins to deteriorate as the HSS level increases,
and the performance absorber and regenerator becomes less stable.

One of the most important results of an AmiPur installation is the STABLE and
RELIABLE operation of the amine plant, which in turn has a dramatic environmental
impact. The continuous removal of HSS has immediate and easily quantifiable results:
reduction of filtration costs; elimination of periodic chemical cleaning of the absorber
tower; improved gas treating capacity of the unit due to increased amount of amine
available for gas treating; elimination or reduced use of antifoamers, neutralizers and
corrosion inhibitors; elimination of the cost associated with previously used methods of
HSS removal. All AmiPur installations have demonstrated the benefits of continuous
removal of HSS for both oil refineries and natural gas plants.