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.

USA Port Arthur. Washington. Ohio. USA Jakarta.T. INDIA Sharjah. Florida. USA California. P. USA Garyville. Illinois. Texas. USA NETHERLANDS Gujarat. California. USA Bakersfield. USA Ferndale. dilute caustic soda is used to regenerate the resin column. with different HSS removal capacity. Texas. Texas. UNITED ARAB EMIRATES Zhejiang. This cycle is automatically repeated every 10-15 minutes. Texas. INDONESIA Texas. Texas. CHILE Houston. PXP/DCOR SINCOR Valero Aruba Refining Location Pasadena. Motiva Enterprises LLS Shell Opus Conco Phillips Sunoco Mid-America Torch Energy Marketing Duke Energy Marathon Ashland Petroleum Tampa Electric/Polk Power Plant Marathon Ashland Petroleum Petrox S. .Table 1. The unit draws concentrated caustic from tanks or drums and dilutes it to the proper strength automatically. USA Tyler. 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. USA Hallettsville. USA Snyder. ITALY California.A. USA Robinson. CHINA Texas City. A typical AmiPur® unit is presented at Figure 1. Loading step: R’OH + RN3+HHCOOR’HCOO + RN3 + H2O During caustic regeneration step. USA San Nazzaro de Burgondi. AmiPur® user’s list Customer Crown Central Petroleum Corp. Texas. Lean amine solution is pumped through a cartridge filter and into the resin column. USA Toledo. Susila – Krakatau Steel Enbridge Pipelines LP San Nazzaro Gasification Plant – Snamprogetti Vintage Petroleum Inc. There are basically two steps in the AmiPur® operating cycle: amine loading and caustic regeneration. USA VENEZUELA ARUBA Eco-Tec offers seven different models of AmiPur®. USA Mulberry. USA Talcahuano. Lyondell-CITGO Refining Company La Gloria Nerefco – Europort Reliance Petroleum – Jamnager Complex Amoco (BP) Sharjah Oil Company Sinopec Zhenhai Praxair Inc. Louisiana. Texas.

Regeneration step: R’HCOO + NaOH R’OH + HCOONa Note: R’OH – resin surface. RN3 – tertiary amine. . AmiPur® uses the least amount of resin. Skid mounted AmiPur® unit With the same HSS removal capacity. • • • • • AmiPur® uses the least amount of NaOH for regeneration. HCOOH . AmiPur® has the following advantages over other amine purification systems using ion exchange technology. AmiPur® generates the least amount of waste.HSS Figure 1. AmiPur® has the least amine loss. AmiPur® has the smallest skid size.

after a unit shut down for maintenance and a replacement of the amine regenerator tower. The HSS in solution were at approximately 2. By March 1999. The tail gas unit’s amine system is very similar to the main amine system. increasing velocities and pressure drop to the point of increasing the overall amine losses. since about 80% of the amine unit inventory is kept in this tower. amine losses. an AmiPur® unit was installed in 1998 to effectively remove HSS from MDEA solution. and this pressure drop is used to monitor tower pluggage and foaming. AmiPur® Operation at CCPC At Crown Central Petroleum’s Pasadena. A significant decrease in corrosion rate was observed. amine filters.%. The liquid-liquid amine contactor is a trayed tower with 15 trays. The sour gas enters the bottom of the column above the tower’s rich amine liquid level. and sulfur plant upsets. and within 30 days the HSS went down to less than 2 wt. Texas refinery. one amine regenerator a flash drum. USA The amine unit in CCPC contains a gas liquid contactor or fuel gas absorber. potentially poor H2S treat. The tower is designed to remove about 1000 ppm H2S from 21. environmental non-compliance. and several associated pumps. Tower internals became fouled.4 wt% (as MDEA) when the AmiPur® unit was started up. tower instability. 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 unit’s regenerator reboiler. with no flash drum and only a single amine absorber. it was decided to decrease the HSS . contacting the sour fuel gas and removing the H2S. heat exchangers. The ultimate goal of the refinery is to keep corrosion rate as close to zero as possible. 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. Case Study I: Crown Central Petroleum Corporation (CCPC). a slip stream amine reclaimer. To achieve this goal.3. a liquidliquid C3/C4 amine treater.%. the HSS level was down to 1.000 BPD C3/C4 mix.4 wt.5 wt. The tower’s pressure drop is measured over inlet gas line to outlet gas line.75 wt. The HSS level in the solution increased back to 2.% was then introduced back into the process. 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 unit was started up in October 1998. Material that had been accumulated from the amine unit prior to installation with HSS level of 3. The lean amine feeds the top bed of packing through a distributor and flows down the column. As HSS build.%. This tower also serves as an amine surge tank.

97 4. As shown in Figure 3.49 0.62 0.69 0. .598 0.62 2.5 wt.5 wt.27 0.6153 0.8352 0.49 1.5565 0. see Figure 5.41 0.42 0.7151 0. Due to the decrease in HSS level.28 0.46 5.14 1.49 1.56 0.000 pounds since year 2000.4 3.6 0. filter change frequency decreased from more than 10 times per month to average once per month.25 0. and less foaming.59 1.26 0. As shown in Figure 4.3962 0.62 1.5755 0.000 pounds in 1998 to about 50.71 0.22 19 97 /0 19 5/1 98 6 / 19 04/ 98 27 /1 19 1/2 99 3 /0 19 4/2 99 6 / 20 08/ 00 23 /0 20 1/0 00 3 /0 20 5/1 00 5 /0 20 9/2 01 5 / 20 03/ 1 01 9 /0 20 7/3 02 0 /0 20 2/2 02 6 / 20 07/ 02 29 /1 20 2/0 03 2 /0 20 7/2 04 8 /0 1/ 23 DATE Figure 2. so the unit was upgraded with extra capacity.76 2. 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).2 2.34 0.77 1.88 1.53 0.% to 0. Due to more stable operation. Figure 2 is the curve of the heat stable salt decline.86 1.28 0.73 0.95 2. from 1. less filter change.38 4.%. now average less than 10 mpy.15 0.16 2.42 0. which had been as high as 160 mpy before. corrosion probe readings.34 0.42 0.6368 0.2978 0.5 0.6309 0. the readings have always been close to zero. since year 2001.41 0.701 0. HSS By INEOS 6 5 4 % HSS 3 2 1 0 5.13 1.concentration further.42 0.77 0.28 0. HSS level at the main amine unit at CCPC Pasadena refinery.82 0.998 0.311.71 0. annual amine purchase has been decreased from 200.

6 1.8 1 11 11 Figure 4.1 1 2. N ov A pr A pr .MONTHLY MPY 120 108 103 100 102 100 84 80 87 81 75 85 60 48 51 50 50 53 40 33 40 37 28 27 MONTHLY MPY 20 20 17 17 17 15 13 13 12 10 6 7 65 4 4 5 5 3 4 4 2 111 1 1 2 00 00000 00000 00000 0000 00000 00000 000 A ve A ve A ve A ve A ve A ve A ve F eb 04 0 A ve A ve A ve A ve S ep t9 9 99 A ve 98 00 01 97 02 97 00 02 03 Ju ly F eb Ju ly Ju ly M ay D ec N ov Figure 3.1 0. Corrosion probe readings at CCPC Pasadena refinery. Filter changes per month at CCPC Pasadena refinery. Filter Changes Per Month # Changes per Month 15 10 5 0 Ave 97 Ave 98 Ave 99 Ave 00 Ave 01 Ave 02 Ave 03 Ave 04 2.

Annual amine purchase at CCPC Pasadena refinery Total Hours H2S Out Of Compliance 2500 2037 2000 1938 1500 1166 1000 525 420 55 0 1993 1994 1995 1996 1997 1998 1999 2000 2001 2002 2003 2004 504 500 21 0 30 10 0 Figure 6. Total Hours H2S out of Compliance at CCPC Pasadena refinery P u rch a se s 1 9 9 4 1 9 9 6 1 9 9 8 2 0 0 0 2 0 0 2 .Amine Purchases 500000 450000 400000 350000 300000 250000 200000 150000 100000 50000 0 1 9 9 2 P o u n d sM D E A P u rch a se s P u rch a se s P u rch a se s P u rch a se s P u rch a se s Figure 5.

In July 2002.0 wt.wt% 6. frequent filter clogging. amine losses due to foaming and equipment fouling (see Figure 7.29 6. China Problems in #2 catalytic cracking/amine scrubbing unit #2 catalytic cracking unit in Zhenhai refinery.000 Tonne/year. This FCC unit is connected to an amine scrubbing unit using MDEA.22 6.% Table 2.2 7. treating capacity of LPG was increased to 600. as shown Figure 10.82 6.4.% (as MDEA). The low mode will keep the HSS concentration in amine solution below 1 wt. lowest at 0. There are two operation modes: hig HSS mode and low HSS mode.000 Tonne/year of dry gas and 450. The high mode is used to bring HSS level down to 1 wt. #2 FCC amine scrubbing unit Heat Stable Salt analysis results in 2001 Date HSS.000 Tonne/year of LPG. By September 6. an Eco-Tec AmiPur® unit (AM15) was selected to keep the system HSS level below 1 wt.27 wt.90 7.2 The system was installed on August 11.26 6. Case Study II: SINOPEC Zhenhai refinery.% as fast as possible. AmiPur® operation at Zhenhai refinery Based on the HSS analysis results shown in Table 2.28 6. the whole unit was shut down for repair.000 .%. 2001.76 6. On December 5. which treats 160. has cracking capacity of 3. The system was switched to low HSS mode and the HSS level in solution has been kept below 1 wt.000. leaking in gas piping was found.27 6.00 Tonne/year. In 2001.% to 1. Major problems with the amine scrubbing unit are: (1) high concentration of suspended solids. both inlet and outlet piping and lean/rich heat exchanger started leaking. China. There was 60 Tonne of 24% dirty amine drained from the unit. the system had been running for 2300 cycles at high HSS mode and the HSS level was brought down from 3.8 wt. Corrosion was also observed at all connections. In September 2002. higher temperature piping and lean/rich heat exchanger (see Figure 8).42 6. 9). 2003.25 6.700.75 6. (2) severe corrosion problems found in reboiler. 2003 and started up on August 22.% (as MDEA). .81 6.%.

Reboiler piping Figure 9.Lean/rich heat exchanger piping Figure 8.Figure 7. Erosion inside lean/rich heat .

%. shown in Table 3. HSS level change in amine solution at Zhenhai refinery. When HSS level was 6 wt.5 wt. both foam height and break time in #2 FCC amine unit are obviously better than other amine units. When the HSS level is lowered.% (as MDEA). foam height was 20 cm and break time was 20 seconds. 5% 1. Because of the low HSS level. system corrosion rate has been decreased dramatically. In Zhenhai refinery. the corrosion rate at the top of regenerator is as low as 2 mpy. 5% 0. 5% 2. China Due to the continuous removal of HSS by AmiPur®. . a 25% of amine saving was realized one month after the start up of AmiPur®. especially break time. more amine is available for sour gas treating. 0% 1. When HSS level was brought down to 0. 5% 3. shown in Figure 12. 0% 2. 0% 3.HSS l evel 4. 0% 8/ 7 HSS in AmiPur® i l t HSS in AmiPur® tl t 8/ 17 8/ 27 9/ 6 9/ 16 9/ 26 10/ 6 10/ 16 10/ 26 11/ 5 11/ 15 Figure 10. 0% 0. Average Corrosion rate at the top of the regenerator before AmiPur® was 90 mpy as shown in Figure 11.

Corrosion rate before AmiPur®® operation at Zhenhai refinery. China . Figure12. Corrosion rate after AmiPur®® operation at Zhenhai refinery.Figure 11.

63 0.8 3.5 5.5 5 5 6 5 6 5 5 4. elimination or reduced use of antifoamers.0 4. and the performance absorber and regenerator becomes less stable.5 0. The amine unit performance begins to deteriorate as the HSS level increases.0 3. China Time HSS #2 FCC Foam height Break time HSS #1 FCC Foam hetight Break time HSS Delayed coking Foam height Break time 10.foam height(cm).95 4.0 5.0 4.0 6.0 3. elimination of the cost associated with previously used methods of HSS removal.88 4.87 5.5 3. and break time(s)in different amine units at Zhenhai refinery.5 5.76 4.Table 3. Summary Amine degradation causes the formation of heat stable salts (HSS) that can lead to corrosion. elimination of periodic chemical cleaning of the absorber tower.5 4. One of the most important results of an AmiPur® installation is the STABLE and RELIABLE operation of the amine plant.59 0. Comparison of HSS level(wt%).65 4.1 7 10.62 0. improved gas treating capacity of the unit due to increased amount of amine available for gas treating.58 3.0 4.69 4.45 3.2 0 11. The continuous removal of HSS has immediate and easily quantifiable results: reduction of filtration costs.62 4. neutralizers and corrosion inhibitors. which in turn has a dramatic environmental impact.0 12 10 12 13 11 12 3. . All AmiPur® installations have demonstrated the benefits of continuous removal of HSS for both oil refineries and natural gas plants.0 5.5 3.65 0.59 0.67 3.1 6 10.1 8 10.1 5 10.5 3.0 18 21 23 18 19 20 5.1 9 10.5 3.75 3.5 4.60 0.62 3.