BLENDED AMINES

Houston Refining LP
By: Charalambos Patsatzis

Overview
In August of 2002 LCR underwent a solvent
upgrade from conventional DEA (25-28 wt%) to a
formulated UcarsolTM LE-713
DEA and UcarsolTM LE-713 supplied by the same
company

Solvent upgrade took approximately 4 months to

complete
No unit shutdowns
No equipment upgrades
Except for reliability improvements that were identified

Outline

Reason for Change

DEA Regeneration Overview
Unit Limitations
Contactor Limitations
Tighter specifications on product stream

Available Options
Capital expenditure
Solvent upgrade

Solvent Upgrade
What Changed Since 2002?

Reason for Change

FCCU and Coker off gas streams had to be rerouted
to an alternate processing unit.
Existing processing location was scheduled for an
extensive outage
This meant increased amine circulation to meet product
specifications

Product specifications were reduced from 160 to 30

ppmw for H2S
CO2 specification remained at the same target

If specifications were not met refinery would have

to route the streams to the flare system
Extensive environmental implications

DEA Regeneration Overview

Plant Amine Regenerators

DEA
System

Typical
System
Capacity
Needs

431

1250 B/H

Regenerator
Regenerators
Capacity
431-A

900 B/H

431-B

600 B/H

Available
Excess
Capacity
250 B/H

Original unit 1954 First amine regenerator

Built in 1968 - upgrade to 431B regenerator

DEA Regeneration Overview

Plant Amine Regenerators

DEA
System

Typical
System
Capacity
Needs

431

1250 B/H

436

1750 B/H

Regenerators

Regenerator
Capacity

Available
Excess
Capacity

431-A
431-B

900 B/H
600 B/H

250 B/H

436-A
436-B

1000 B/H
1000 B/H

250 B/H

Built in 1974 - Part of sulfur/refinery expansion

DEA Regeneration Overview

Plant Amine Regenerators
DEA
System

Typical
System
Capacity
Needs

Regenerators

Regenerator
Capacity

431

1250 B/H

431-A

900 B/H

431-B

600 B/H

1750 B/H

436-A

1000 B/H

2500 B/H

436-B
441

1000 B/H
3000 B/H

250 B/H
500 B/H

6500 B/H

1000 B/H

436
441

5500 B/H

Available
Excess
Capacity
250 B/H

Built in 1995 - Part of major sulfur/refinery

expansion

DEA Regeneration Overview Contd

There are 17 Amine Absorbers in the Refinery
Gas Phase Contactors:
Liquid Phase Contactors:
Unit
Process Stream
Unit
Process Stream
230 GP
Fuel Gas
Idle
ARU C3/C5
631-A&B
LPG
LPG
Recycle H2
632
FCCU
Liquid PPs
Recycle H2
633
736
Liquid PPs
Recycle H2
634
737
Liquid PPs
Recycle H2
635
Recycle H2
636
Recycle H2
FCCU
Dry Gas
736
Dry Gas
737
Dry Gas
Mag
Recycle H2
BTU
Recycle H2

DEA Regeneration Overview Contd

Amine Loading
Lean amine loading 0.01-0.02 mol H2S/mol solvent
Rich amine loading 0.4-0.6 mol H2S/mol solvent

Amine Velocities
Lean/Rich velocities between 4-7 ft/sec
No PWHT on older amine system piping
1 out of 3 systems

Corrosion Rates
Corrosion coupons indicate 8-16 mils/yr on rich amine
system piping

Amine Regenerator Flow Diagram

431-A&B DEA REGENERATORS

431-A

431-B

436-A&B DEA REGENERATORS

441 DEA REGENERATOR

Unit Limitations
Amine Regenerators

Lean amine cooling In excess of 140oF

Rate limitations Already at 125% of design capacity
Reboiler duty Steam supply limitation
Throw-away limitation For ammonia control
Metallurgy limitations No PWHT

Amine Piping
Line velocities (specially around control loops)

Single Storage Tank Feeds all Three Systems

Rich Amine Flash Drums
With higher rates amine retention times are reduced

Contactor Limitations
Absorbers

Lean amine cooling

Rich amine loading
Instrumentation limitations
CO2 loading
Metallurgy limitations No PWHT

Amine Piping (IBL)

Line velocities (rich amine return outlet)
Hydraulic constraints

Contactor Limitations Contd

High CO2 in the
contactor feed

Brimstone Analysis
Untreated 732 Before LE-713
Component
Molar%
H2
N2
CH4
CO
CO2
C2H4
C2H6
H2S
C3H8
i-C4
n-C4
i-C5
n-C5
C6+
Total

14.394
7.44
36.002
1.293
1.669
17.984
15.118
0.581
2.927
1.049
0.925
0.382
0.174
0.062
100

Contactor Limitations Contd

CO2 within acceptable
range

Brimstone Analysis
Treated 732 Before LE-713
Component
Molar%
H2
N2
CH4
CO
CO2
C2H4
C2H6
H2S
C3H8
i-C4
n-C4
i-C5
n-C5
C6+
Total

14.104
7.593
36.969
1.279
0.369
18.465
15.471
Non Detected
2.784
1.099
1.076
0.474
0.215
0.102
100

Contactor Limitations Contd

Brimstone Analysis

No CO2 concern on this

contactor

Untreated 737 Before LE-713

Component
Molar%
H2
N2
CH4
CO
CO2
C2H4
C2H6
H2S
C3H8
i-C4
n-C4
i-C5
n-C5
C6+
Total

6.293
0.095
51.506
0.534
0.231
2.277
20.437
11.072
7.433
0.058
0.041
0.006
0.019
Non Detected
100.0

Available Options
Capital Upgrade
Upgrade existing
regenerator(s)
Invest on new
regenerator

Solvent Upgrade
Upgrade single
amine system
Upgrade entire
amine system (three
amine systems)

Available Options Contd

Capital Upgrade
Time constraints
ROI below 50%
OBL piping
upgrades would be
required

Solvent Upgrade
Relatively quick
transition
ROI at 75%
No equipment
upgrades would be
necessary

10

Solvent Upgrade
Engineering analysis was performed on entire
amine system
Simulations were constructed with new solvent
properties for amine system including contactors

Economics were evaluated

Energy savings
Reliability
Solvent losses
Solvent selection
Solvent percent strength

Choice was to upgrade solvent on the entire amine

system

Solvent Upgrade Contd

TM

Initial charge was performed using Ucarsol to

TM
get system volume up to desired Ucarsol LE-713
formulation
Due to the large system volume capacity ~600,000
gallon
Solvent strength was to be stepped in three different
phases
30%
35% (target)
40% (if needed)

Solvent loaded directly into the individual systems

Monitor closely solvent losses
Monitor solvent performance for absorbers in different
service

11

Solvent Upgrade Contd

TM

Target Ucarsol LE-713 formulation was

achieved approximately 4 months from the time
that system was initially charged
Primary driver for the extended time was cost
Fresh amine tank was then converted to UcarsolTM LE713 tank

System leveled at 35 wt% on solvent strength

Fresh amine tank was then converted to UcarsolTM
LE-713 tank
Brimstone Engineering Services conducted plant
wide performance testing
Testing performed before initial charge
Testing performed 1 year after system was at steady
state

Solvent Upgrade Contd

Systems in place for monitoring
Purchased state of the art GC for in house sampling
Training to mitigate system losses
Technical department
Operations department

Supplier Involvement

Instrumentation upgrades on key amine absorbers

Updated control configuration

Temperature control
Upgraded analyzers
Real time rich loading equations

More intense corrosion monitoring system

Going away from corrosion probes and focusing more on TML
readings
Ion exchange system for anion and HSAS control

12

Solvent Upgrade Contd

Current Situation
Amine concentration at 40 wt%
Primarily from circulation reduction

Energy savings 27.5 MMBtu/hr

Amine losses Down by17%
Primarily due to increased awareness and training
Better instrumentation on amine absorbers

Solvent Upgrade Contd

Current Situation
Amine Loading
Lean amine loading 0.01-0.015 mol H2S/mol
solvent
Rich amine loading 0.4-0.45 mol H2S/mol
solvent

Amine Velocities
Lean/Rich velocities <4 ft/sec

Corrosion Rates
Corrosion coupons indicate 5-8 mils/yr on rich
amine system piping

13

Summary
Solvent upgrade was successfully completed
Refinery has increased solvent concentration for
energy savings (currently at 40%)
COS and trace sulfur species removal was within
target after solvent upgrade
No equipment upgrades
No unit shutdowns were required

What Changed Since 2002?

FCCU Dry Gas Contactor CO2
specifications changed
New contract signed in conjunction with a
compression station
New CO2 specification at 500 ppmv

Operation of FCCU has changed over the

last two years causing more CO2 slip to the
absorber

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What Changed Since 2002?

Pilot plant data (tests performed at DOWs pilot
plant facilities) confirmed that a solvent upgrade
was required to meet product specification
Solvent upgrade would be specific to this system
only
Upgrade is planned for 2nd week of October

Equipment that would allow system optimization

had to be installed

What Changed Since 2002?

Equipment that would allow system
optimization had to be installed
Installation complete

Training on new system

Technical department
Operations department

Supplier Involvement

Product exports to 3rd party facility to begin

in November

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