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Gas Treating Unit Training

• Click to editMellitah,
Master text styles
Istanbul
• Second level
July 28-29, 2015
• Third level
• Fourth level
• Fifth level
Click to edit Master title style
Introduction and Chemistry
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Section 1
• Second level
• Third level
• Fourth level
• Fifth level
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Gas Treating Seminar

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• Click to edit Master text styles

• Second level
• Third level
Components
• Fourth level
•
of Gas Upgrading
Fifth level

Focus on Amine Treating

Acidic Gas Components
Hydrogen Sulfide (H2S)
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• Toxic at low concentrations
title style
• Contaminant to many catalysts
• Corrosive to carbon steel
• Click to edit Master text styles
• Environmental hazard
• Second level
Sources• ofThird
H2Slevel
• Found with hydrocarbon
• Fourth level in formations S
• Fifth level
• Formed in refineries when large
hydrocarbon molecules are reduced H H
• Side reaction in trace amounts were sulfur
present in feed

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Why Do We Remove H2S
Safety - H2S is a poisonous gas
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• 0.13 ppm: Minimal odor
• 1-5 ppm: Moderate odor of rotten eggs
• 10 ppm: Beginning eye irritation
• • Click to edit
25 ppm: Master
Strong, text styles
unpleasant odor
• •100Second level
ppm: Coughing, eye irritation, loose sense of smell in 2-5 minutes
• Third
• 200-300 ppm:level
Eye inflammation, respiratory tract irritation in 60 minutes
• Fourth
• 500-700 ppm: levelof consciousness and death in 30-60 minutes
Loss
• Fifth level
• 700-1000 ppm: Rapid unconsciousness, pausing of respiration and death
• 1000-2000 ppm: Unconsciousness at once, death in a few minutes. Death
may occur even if individual is removed to fresh air at once.

Environmental - Government Regulations

When H2S is burned ==> SO2 leaves the plant

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Acidic Gas Components
Carbon Dioxide (CO2)
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• Reduces heating value
title style
• Takes up space pipelines
• Forms a solid in LNG plants
• Click to edit Master text styles
• Reacts with H2S for form COS
• Second level
O C O
• By-product in synthesis gas & ethylene
• Third level
crackers
• Fourth level
Sources of CO2 • Fifth level

• Found with hydrocarbon in formation

• Formed during processing via reaction with
carbonate formations
• Generated in many syn gas applications

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Why Do We Remove CO2
CO 2 in to
Click inlet gasMaster
edit title style
– Removal is required upgrade the heating value of the gas
– CO2 causes the gas to go off-spec on Btu value
• –Click
Plants mayMaster
to edit requiretext
certain
stylespercentage of CO2 for downstream
• processing
Second level
– For• Cryogenic
Third level Process - CO2 will freeze in unit and cause issues
in expander
• Fourth level
• Fifth level

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Other Contaminants
Other Contaminants Include:
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O C S S C S
• Click to edit Master text styles
• Second level Carbon DiSulfide (CS2)
Carbonyl
• Sulfide (COS)
Third level
• Fourth level
H S
• Fifth level C H
H H
Mercaptan

N N O
O
Nitrogen Mercury
Oxygen

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Technologies for Acid Gas Removal
•Non regenerable technologies
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• Scrubbing with caustic, potassium permanganate or triazine
• adsorption onto iron oxide
• Regenerable technologies
• Click to edit Master text styles
• Scrubbing carbonate salt solutions, amino acid solutions, transition
• Second level
metal redox solutions of iron or vanadium chelants, amine solutions
• Third level
including ethanolamines
• Fourth level
• Where gasses contain
• Fifth level significant amounts of H 2S & CO2 regenerable
technologies are usually the most economical

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 DOW CONFIDENTIAL - Do not share
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Gas Treating Seminar

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• Second level
• Third level
• Fourth level
•
Amine Chemistry
Fifth level
 Contaminants are Acids
Acid gas contaminants act as Weak Acids
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pKa

• S Click to edit Master text styles 6.97

H • H Second level
• Third level
• Fourth level
• Fifth level

O C O 6.53

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General Chemistry
Reactivity
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• Acids react with Bases to form Salts and Heat
• Reactions between Strong Acids and Strong Bases are not easily
reversed
• • Click to editbetween
Reactions Master Weak
text styles
Acids and Bases are thermally reversible
• •Certain
Second level are suitable weak bases and react reversibly with Weak
Amines
Acids• Third level
• Fourth level
• Fifth level

Base + Acid Salt + HEAT

BOH + AH (BOH2+ + A- ) + E

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General Chemistry
Amines are a base
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• Amines react reversibly with weak acids
• H2S
• COto2 edit Master text styles
• Click
• Many amines
• Second that have been tested for the Gas Treating Application
level
• Third level
• Fourth level
• Fifth level
Amine Base + Acid Amine Salt + Anion + HEAT

R2NH + H2S R2NH2+ + HS- + E

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General Chemistry
Primary & Secondary amines have a labial H available to react
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• Click to edit Master text styles

• Second level
2 – Amines + Carbon
• Third level
Protonated + Amine
Dioxide
• Fourth level Amine Carbamate
• Fifth level

Tertiary amines do not have the H

• CO2 must hydrolyze to react with Tertiary amines

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General Chemistry – CO2
SLOW
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CO2 Hydrolysis is Rate Limiting
•• CO
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2 must hydrolzye to carbamate before it can react as a base
• CO• 2 hydrolysis
Second level is slow and therefore rate limits CO2 removal
• Tertiary• amines
Third level
(MDEA; TEA) do not have the labial H needed to form an
• Fourthand
amine carbamate leveltherefore only react with carbonic acid
• Fifth level

Carbonic Acid

MDEA

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 Commodity Gas Treating Amines

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Primary Amines Simple Formula Structure
Name
• Click to edit Master
Monoethanolamine MEA H2NCH2CH2OH
text styles
• Second level DGA
Diglycolamine H2NCH2CH2OCH2CH2OH
• Third level
Secondary Amines
• Fourth level
Diethanolamine • Fifth DEA
level HN[CH2CH2OH]2

Diisopropanolamine DIPA [CH3CH(OH)CH2]2NH

Tertiary Amines
Methyldiethanolamine MDEA CH3N[CH2CH2OH]2

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 DOW CONFIDENTIAL - Do not share
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Gas Treating Seminar

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• Second level
• Third level
Amine Solvent Selection
• Fourth level
• Fifth level
Factors for Gas Treatment
Treatment Scheme and Solvent Determination Influenced by:
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Treating Conditions
• Pressure
• • Click
Temperature
to edit Master text styles
• Amount of H2S or CO2 in feed gas
• Second level
• Presence oflevel
• Third other gas contaminants (mercaptan, nitrogen, etc)
Treated gas •H2Fourth
S orlevel
CO2 outlet specifications
• Fifth level
Volume of gas to be treated

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Treating Technology Selection Guide

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• Click to edit Master text styles

• Second level
• Third level
• Fourth level
• Fifth level

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General Amine Process Flowsheet

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• Second level
• Third level
• Fourth level
• Fifth level

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Evolution of Gas Treating Solvents

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• Click to edit Master text styles

• Second level
• Third level
• Fourth level
• Fifth level

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Solvent Selection – Dow’s Offerings
Commodity Amines Specialty Offerings
Click to edit Master
Ethanolamines
titlespecialty
UCARSOL styleformulations for CO ™
2
• MEA and H2S removal
• DEA
• Additional Gas Treating Products
• Click
TEA to edit Master text styles
• Iron Chelates for use in commercial H2S
• Second level
Isopropanolamines Abatement Technologies (Sulferox®)
• MIPA• Third level • Selexol® Solvents and Technology for gas
• DIPA • Fourth level treating
• TIPA
• Fifth level • UCARKLEAN™ Unit Cleaning Products
• HSAS Management technology
Alkyl Alkanolamines • UCARSEP™
• NMEA • DHM Neutralizer
• MDEA • Antifoam (GT-8715, GT-10)
• DMEA
• DEEA

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UCARSOL™ Gas Treating Solvents
Designed for all Gas Processing Situations
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>20 Unique Solvents
Tertiary Amine-Based
• • Higher
Click Selectivity
to edit Master than MDEA
text styles
•• Proprietary
Second level Additives
• Inhibited or Enhanced CO2 Kinetics
• Third level
Efficient CO2• Removal
Fourth level
• Fifth level
Able to treat to < 5 ppm H2S
Both Gas/Liquid and Liquid/Liquid Hydrocarbon Treating

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UCARSOL™ Gas Treating Solvents
Significant Treating Experience
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>1000 Worldwide Applications
• Natural Gas
• Refinery
• Click to edit
• NH3, H2, Master text
Ethylene, Fe styles
Ore Reduction
•• Second level
Gasification
• Third level
Specialized Applications
• Fourth level
• CO2 Slip • Fifth level
• Promoted H2S Removal
• Liquid Hydrocarbon Treating
• COS/RSH Removal
Technical Service Assistance Included with Solvent Purchase

Dow continues to advance solvent technology via ongoing

Research and Development

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UCARSOL™ Gas Treating Solvents

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UCARSOL HS 101
UCARSOL HS 102 High Selectivity (Preferentially Absorbs H2S
UCARSOL HS 103 While Slipping CO2)
• Click to edit
UCARSOL Master text styles
HS 104
UCARSOL
• Second HSlevel
115
• Third level
• Fourth level
UCARSOL LE 713
• Fifth level Total Acid Gas Removal for Refinery System
UCARSOL LE 714

UCARSOL LE 701 Hybrid Physical/Chemical Solvents for COS

UCARSOL LE 702 and Mercaptan Removal

UCARSOL NH 608 ……. CO2 removal for the Ammonia Synthesis

Facilities

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UCARSOL™ Gas Treating Solvents

Click to
UCARSOLAP edit
802 Master title style
UCARSOL AP 804 Controlled CO2 Removal Low Energy Reg
UCARSOL AP 806
• Click to edit Master text styles
UCARSOL APlevel
810 Cryogenic CO2 Specifications
• Second
UCARSOL AP 814 (Ammonia/Hydrogen/ HyCo)
• Third level
• Fourth level
UCARSOL Shale• …….
Fifth level
Formulated for the Shale Gas
UCARSOL LL ……. Designed for NGL Liquid Treatment after Cryo unit

SELEXOL Physical Solvent

UCARSOL GT-8715 and GT-10 Antifoam for Gas Treating

UCARSOL DHM for HSAS Neutralization
UCARKLEAN® AC and DS Solutions for Cleaning Gas Treating Systems

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Value for Existing and/or New Plants
Dow’s UCARSOL Solvents can help:
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Meet Specification - UCARSOLTM Solvents can be used to meet even the
toughest specifications, whether tough to process contaminants like COS
• and
ClickMercaptan are present
to edit Master text styles
• Second level
Reduce Corrosion - UCARSOLTM Solvents can be used to optimize the
• Third level
acid/base chemistry in gas processes to minimize corrosion
• Fourth level
Increase Capacity• –Fifth
Dow level can increase unit capacity with UCARSOL specialty

amines

Reduce Energy Consumption – Circulation rate and reboiler duty can be

minimized by using UCARSOL Solvents
Reduce Capital Expenditure – In design, CAPEX can be reduced using
UCARSOL Solvents

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Dow’s Gas Treating Capabilities
Selecting UCARSOL Provides Access to Dow’s Other Capabilities
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Simulation technology
• Proprietary simulator based on vapor/liquid equilibria developed internally
• • Click
Advanced integration techniques in a rate-based thermo package ideal for
to edit Master text styles
amine systems
• Second level
• Extensive plant data to calibrate and optimize simulation recommendations
• Third level
• Fourth level
• Fifth level

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 Dow’s Simulation Technology
Click to edit
Simulation/Optimization
Master title style Commercial
Ongoing Experience in
Dow developed Rate-Based Research and over 1000
Simulator Development customer/end
• Click to edit Master text styles users

• Second
Most accurate component
level
modules available
• Third level State-of-the-Art
• Fourth level Simulation
• VLE and Physical Properties
• Fifth level
measured Support
• Thermodynamics internally
developed
• Predictions in customer Investment in
Lab data Pilot Plant
facilities complements
• Kinectics
• Continuous upgrade budget • Vapor Liquid and validates lab
Equilibrium studies
• Transport Properties

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Dow’s Gas Treating Capabilities
Selecting UCARSOL Provides Access to Dow’s Other Capabilities
Click to edit Master title style
Simulation technology
• Proprietary simulator based on vapor/liquid equilibria developed internally
• Advanced integration techniques in a rate-based thermo package ideal for
• Click
aminetosystems
edit Master text styles
• Extensive
• Secondplant
leveldata to calibrate and optimize simulation recommendations
• Third
Operations level
Support
• Fourth level
• Analytical Expertise – Dow provides extensive analytical support and rapid
• Fifth level
customer response times
• Technical Service – Knowledgeable and highly skilled service support

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Operations Support
Ongoing Support to Ensure Top System Performance
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State-of-the-art analytical procedures
• Gas treating analytical laboratories
• Routine samples ensure ongoing amine system
• Click to edit Master text styles
Routine analyses
• Second levelinclude:
• Amine concentration
• Third level
• Acid gas• loadings
Fourth level
• Heat-stable salt concentration
• Fifth level
• Foaming tendency
• Metals analyses

Specialized analysis for troubleshooting available

Start-up field assistance and routine service visits part of UCARSOL

Programs

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Dow’s Gas Treating Capabilities
Selecting UCARSOL Provides Access to Dow’s Other Capabilities
Click to edit Master title style
Simulation technology
• Proprietary simulator based on vapor/liquid equilibria developed internally
• Advanced integration techniques in a rate-based thermo package ideal for
• Click
aminetosystems
edit Master text styles
• Extensive
• Secondplant
leveldata to calibrate and optimize simulation recommendations
• Third
Operations level
Support
• Fourth level
• Analytical Expertise – Dow provides extensive analytical support and rapid
• Fifth level
customer response times
• Technical Service – Knowledgeable and highly skilled service support
Management Services
• Core Technical Group – Global technology expertise with local presence
• Licensed Technology – Dow can bring strong engineering partnerships to
projects to provide licensed technology
• World Class Logistics – Dow’s world wide reach can supply product to keep
your project on-time

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 Management Support Ongoing
Facility Design Plant Start-up Operations
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Non-Licensed Technology

UCARSOL Technology
UCARSOL Make-up
Evaluation & Selection

Process Material & UCARSOL Manufacture UCARSOL Laboratory

• ClickEnergy
to edit Master
Balance text&styles
Delivery (Initial Fill) Analysis

• Second level Plant Optimization &

Reference Customers UCARKLEAN
• Third
Provided uponlevel
request Troubleshooting
• Fourth level
Engineering
Equipment Evaluation
• Fifth level On-Site Start-up
Consultation &
(conversion preparation) Assistance
Computer Simulations

EPC by reputable Amine Management

company Services
Licensed

UOP Technology & Engineering

AmineGuard FS™ & Selexol
Plus start-up and on-going technical service

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Click to edit Master title style
Plant Design and Application
• Click to edit Master text styles
Section 2
• Second level
• Third level
• Fourth level
• Fifth level
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Gas Treating Seminar

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• Click to edit Master text styles

• Second level
• Third level
Typical• Amine
Fourth level
•
Plant And Major Equipment
Fifth level
Typical Amine Plant Equipment
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• Click to edit Master text styles

• Second level
• Third level
• Fourth level
• Fifth level

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Major Equipment Summary
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Standard Amine System Includes:

Gas/Liquid Separators Lean/Rich Heat Exchanger (LRHX)

• • In
Click to of
& out edit Master text styles
Absorber • Heat Exchanger recovers energy
• Second level
Absorber/Contactor Stripper/Regenerator
• Third level
• Acid Gas reacted with amine
• Fourth level
• Steam Stripping of Acid Gas
• LL or Gas-Liq Counter
• Fifth levelCurrent Flash Column
Contactor • Appropriate for systems with high
Flash Vessel partial pressure specifications
• Recover dissolved volatile gas Pumps
• Two or three phase separator Filters
• Flash gas scrubber Pipe

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Separators
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• Click
Used to edit Master
in multiple locations textinstyles
• Second level
process
• Third level
• Slug Catcher
• Fourth level
• Absorber overheads
• Fifth level

Different internal types exist

• Conventional
• Settling tank with demister
• High Effiency Coalescers
• Used for mist separation

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 High Efficiency Separators
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• Click to edit Master text styles

• Second level
• Third level
Used to both filter and coalesce
• Fourth level
• Feed gas scrubbing
• Fifth level

• Treated gas scrubbing

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Absorber
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Internals
• Clickdetermined
Staging to edit Masterby: text styles
• Acid
• gas in/out
Second level
• Solvent/gas
• Thirdratio
level
• Gas conditions
• Fourth level
• Fifth level
• Depth set by solvent type

Trays
All types are used:
• Sieve, valve, bubble cap,
Sulzer, KochGlitsch, Shell, ….
• Avoid high capacity trays
(gas/solvent disengagement)

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Absorber
Click to edit Master title style

• Click to edit Master text styles

• Second level
Random• Packing
Third level
• Typical 50 to 70 mm
• Fourth levelpacking
size • Fifth level

• Stainless steel required

• 6000 mm maximum depth per
section
• Less depth for large ID towers

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Absorber
Click to edit Master title style

• Click to edit
Structured Master text styles
Packing
• Second
• Stainless level
Steel
• Similar•HETP
Third level
• Smaller ID •vs.Fourth level
random
• Fifth level
packing commonly used

Contact
• Absorber allows intimate
contact between streams
• Promotes mass transfer
• Acid gas rich stream
• Acid gas lean stream (amine)

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 Rich Amine Flash Drum
Click to edit Master title style

• Click toVessel
Separation Purpose
edit Master text styles
• Remove dissolved
• Second level gases by
pressure• let-down
Third level
• Recover valuable
• Fourthflash
level gas
• Design with as low
• Fifth level
pressure as
possible to maximize hydrocarbon
flash gas
• Drum can also remove liquid
Hydrocarbon via 3-phase design
• Skimming design
• Liquid hydrocarbon separator
from aqueous phase

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Regenerator
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Internals
• Click to edit Master text styles
• Trays
• Second level • Random Packing
• Third level
• Structured Packing
• Fourth level
• Fifth level
Acid gas (Base of reacted acids) are removed from
solvent
• Reverse reaction of absorber
• Energy consumption in reboiler

Reboiler Types vary

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 Heat Exchangers
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Multiple Exchangers in System
• Click to edit Master text styles
Lean/ Rich Amine Exchangers
• Second level
• Plate & frame
• Third or shell & tube
level
• Fourth level Plate and Frame
Regenerator reboiler
• Fifth level
• Vertical or Horizontal Shell and Tube
Condensate Cooler
• Water or Air Cooled
• Plate & frame or shell & tube
Lean Amine Cooler
• Water or Air Cooled
• Plate & frame or shell & tube Shell and Tube

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Anti-Foam System
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•Foaming
Click to Prevention
edit Master text styles
• Second level
• Simple system with a drum and a pump that tied to critical injection
• Third level
point
• Fourth level
• Injection pressure is high due to need to inject into absorber column
• Fifth level

• Critical to have as back-up system in both absorber and regenerator

• For best use, the system should be a fast response system

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Activated Carbon Filter
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Contaminant Removal
• Click to edit Master text styles
Activated carbon filter
• Second level
• Removes heavy
• Third level hydrocarbons
• Hydrocarbons
• Fourth
cause
level foaming
• Fifth level
• Will also absorb antifoam
Mechanical filter
• Installed upstream and downstream of the activated carbon filter
• Often installed in lean amine slip stream
• 5 to 10% of lean amine stream
Normal life of carbon is 4 to 6 months but can last as long as 1 year

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 DOW CONFIDENTIAL - Do not share
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Gas Treating Seminar

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• Click to edit Master text styles

• Second level
• Third level
• Fourth level
Simulation and Minimizing Project Risk
• Fifth level
Simulation
Simulation Process
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Dow offers simulation support for clients for both new projects and
debottlenecking studies
• Simulation can be involved  please plan proper lead time for Dow
• Click to edit Master text styles
• New project simulation time can be minimized as conventional tray
• Second level
column can be utilized for feasibility/costing work
• Third level
• Fourth level
Tray vs Packing• Fifth level
Cost dominates selection criteria
• Both are frequently utilized and design can be done with each
• Trays are the simplest to design in simulation
• Highest size random packing will provide larger diameter tower
allowing debottlenecking

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Design Considerations
Tray vs Packing
Click to edit Master title style
Tray columns
• Applicable for high pressure columns
• Pressure drop must not be an important consideration
• • Standard
Click to editdesign
Masterattains gas purity spec with 20 trays
text styles
• Trays are the
• Second standard for H2S removal
level
• Third level
Packed Columns
• Fourth level
• Common when• aFifth high
level degree of CO removal is required
2
• Reduces height of tower over lower efficiency tray
• Utilized when pressure drop/foam formation are likely considerations
• Packing will plug if gas contains O2 contaminated H2S

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Design Considerations
Temperature and Composition Profile – high acid gas loading
Click to edit Master title style

• Click to edit Master text styles

• Second level
• Third level
• Fourth level
• Fifth level

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Design Considerations
Temperature and Composition Profile – low acid gas loading
Click to edit Master title style

• Click to edit Master text styles

• Second level
• Third level
• Fourth level
• Fifth level

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Simulation – New Plants
Simulation requirements:
Click to edit Master title style
Feed gas conditions
• Pressure
•• Temperature
Click to edit Master text styles
• Flowrate
• Second level
• Detailed
• Third level
composition
• Fourth level
• Treated gas spec (in term of CO2, H2S and other requirements)
• Fifth level

Dow will determine the simplified process flow diagram if not otherwise
specified by customer

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Simulation – Existing Plants
Simulation requirements:
Click to edit Master title style
Plant Configuration
• Feedgas Conditions
•• Pressure
Click to edit Master text styles
• Temperature
• Second level
• Flowrate
• Third level
• Fourth level
• Detailed composition
• Fifth level
• Lean amine flowrate and temperature
• Current type of amine used and amine strength
• Lean/rich exchanger data
• Current reboiler duty

Note: all of above is required for accurate simulation result.

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Engineering Support by Dow
Grass Roots Projects
Click to edit Master title style
Dow Can Support Owner and/or Engineering for FS and FEED

Services
• Click toOffered:
edit Master text styles
 Simple Process
• Second level Flow Diagram (PFD)
 Simple
• Third level Balance and Utility Consumption
Material
• Fourth level
 Expected Energy Conservation Benefit over Commodity Amine
• Fifth level
Processes
 Published Literatures
 Estimated Tower Sizing and Heat Exchanger Duty Requirements
 Global UCARSOL™ References as needed
 Material Selection Consultation

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Engineering Support by Dow
Upon Purchase Commitment for Initial Fill, Dow Will Supply
Click to edit Master title style
Process Design & Proposal
• Simulation Flow and PFD
• • Click
Material Balance with Stream Data Sheet
to edit Master text styles
• Material Selection Guide
• Second level
• Other • Design Information
Third level
• Standard• Operating
Fourth levelManual
• Fifth level
• Case Studies
• Review of P&ID (Piping & Instrumentation Diagram)
• Performance Guarantee (Under a Separate Agreement)
• Training for Operators and Lab Technicians
• Start Up Assistance by Qualified Engineer at Site
• Optimization of Operating Conditions
• Solvent Analysis and Diagnosis

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Dow/UOP Relationship
If a Process License is Desired
Click to edit Master title style
If you require a Process License – Please Call UOP LLC
(A former J/V of Dow and Honeywell)

• Click to edit Master text styles

If a process
• Second level is not needed – Please Call Dow
license
• Third level
• Fourth level
If you are uncertain whether a license is needed – Please call Dow for
• Fifth level
consultation

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 DOW CONFIDENTIAL - Do not share
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Gas Treating Seminar

Click to edit Master title style

• Click to edit Master text styles

• Second level
• Third level
Corrosion
• Fourth level
•
and Recommended
Fifth level

Materials of Construction
Types of Corrosion
In general, corrosion can occur in
Click to edit Master title style
many different ways within a gas
processing system:

•1. Click to edit

General Master text styles
Corrosion
2. • SecondCorrosion
Localized level
• Third
• Erosion level
induced
• Fourth level
• Under deposit corrosion
• Fifth level
• Inclusions

Example of under deposit

corrosion in reboiler tube

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Causes of Corrosion
Mechanisms differ whether: Corroded 316 stainless steel
Click to edit Master title style
1. Chemical Attack
• CO2/H2S attack of the metal
• • Amine
Click degradation
to edit products
Master text styles
•• HCN/NH3
Second corrosion
level
(refinery/gasifier)
• Third level
• Fourth level 200x Magnification
2. Erosion • Fifth level
• Amine solution corrosion is the
corrosion of the carbon steel with
the presence of aqueous amine

1000x Magnification

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Wet Acid Corrosion
Wet CO2 Corrosion
Click to edit Master title style
• CO will dissolve in the water to form carbonic acid, H CO .
2 2 3
• It will form ferrous carbonate, which is only slightly soluble and does not
form a very protective film
• Click to edit Master text styles
• Second level
Fe + H2CO 3  level
• Third
FeCO3 + H2
• Fourth level
• Fifth level

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Wet Acid Corrosion
Wet H2S Corrosion
Click to edit Master title style
Fe + H2S  FeS + H2

• It will form a weakly adherent and somewhat protective FeS film. FeS is more
• protective
Click to edit
thanMaster
FeCO3. text styles
• Second
• However, level
contaminants which disrupt this FeS film are not present and
• Third
mechanical level minimize the erosion-corrosion, and wet acid corrosion of
design
• Fourth
exposed carbon levelsurfaces will be eliminated.
steel
• Fifth level

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Other Types of Chemical Corrosion
Sources of corrosive contaminants
Click to edit Master title style Example of Formic
• In source gas Acid Induced Corrosion
• HCN in offgas from Coal/Oil
• Acids
• Click to edit Master text styles
• Formates, acetates, glycolates, etc
• Second level
• Third level
• Formed in• Amine System
Fourth level
• Oxygen induced
• Fifth level
amine degradation
• Carbon Monoxide is oxidized to form formic
acid

Corrosion
Groove

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Erosion
Mechanically induced corrosion is common in amine systems
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High velocities anywhere in process equipment has potential to cause
corrosion due to high sheer rates
• Click to edit Master text styles
• Second level
• Third level
• Fourth level
• Fifth level

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Corrosion Prevention
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Three Control Strategies
• Click to edit Master text styles
Control via design considerations
• Second level
• Third level • Materials of construction
• Fourth•level
Engineered solutions
• Fifth level

Control via amine unit operations

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 Design Considerations
Stainless steel
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recommended in
areas of potential
corrosion
• Click to edit Master text styles
• Second level
• Third level
• Fourth level
• Fifth level

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Materials of Construction
Dow Suggested Materials
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Material of construction can generally be of carbon steel, except that
SUS316 or SUS304 is recommended to the following sections.
• Bottom 1/3 of absorber shell: SS clad
• Click to edit Master text styles
• Absorber Trays: SS
• Second level
• Upper 1/3 of regenerator shell: SS clad
• Third level
• Bottom• 1/3 of level
Fourth regenerator shell: SS clad
• Regenerator• Fifth
Trays:
level SS
• Regenerator Overhead section: SS
• Heat Exchanger Tubes
• Lean/Rich HE highest temperature sets: SS
• Acid Gas Condenser: SS
• Reboiler: SS
• Plates of P&F Heat Exchanger: SS

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Materials of Construction
Material of construction can generally be of carbon steel, except that
Click to edit Master title style
SUS316 or SUS304 is recommended to the following sections.

Piping
• Click to edit Master text styles
• From Lean/Rich HE to Regenerator: SS
• Second level
• Reboiler
• Third Vapor
level Return: SS
• Acid Gas:
• Fourth level SS
• Fifth level
• Reflux returns line: SS
• Flashed Vapor: SS
• Downstream of the Control Valve to the
Flash Drum (potential 2 phases): SS

Pump Casing and Impellers SS

Control Valve Body and Trim SS

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Design Considerations
Regenerator
Click to edit Master title style
• When the amine solution completely wets all the exposed carbon
steel surface, it greatly raises the pH of the condensate and reduces
its corrosiveness
• Click to edit Master text styles
• Acid gas > 95% CO2, amine spray in the regenerator overhead will
• Second level
be recommended to minimize carbon steel corrosion.
• Third level
• Sufficient• amine should be injected so that the reflux contains 0.5
Fourth level
wt% amine. • Fifth level
• An amine spray should be considered for regenerator for CO 2
removal only.

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Design Considerations
Absorber:
Click to edit Master title style
• High CO2 content of the acid gas can be prevented by introducing
gas through a distributor immersed in the amine absorber sump
liquid.
• Click to edit Master text styles
• If the distributor is installed above the solution level, wet CO 2 can
• Second level
rapidly attack the shell of the absorber and its internal elements.
• Third level
• If tray is used, the
• Fourth undersize of the bottom tray should be stainless
level
steel • Fifth level

• Another factor is to minimize high velocity acid gas vapor

impingement on carbon steel surfaces.

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Amine Unit Operations
Amine solution corrosion can be caused by a number of factors
Click to edit Master title style
including the followings:
• High operating temp
•• High
Click rich/ lean
to edit amine
Master loading
text styles
• The ratio oflevel
• Second CO2 to H2S in the acid gas
• Amine • solution
Third levelcontaminants including amine degradation products
and heat •stable
Fourth amine
level salts (HSAS)
• Fifth level
• Amine solution concentration
• Primary and secondary amine types used in too high a
concentration

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Amine Unit Operations
Impact of Loading and Temperature on Corrosion Potential
Click to edit Master title style
• High rich amine loading can lead to excessive corrosion
• In a typical absorber, most of the heat of reaction is released in the
bottom of the column.
• •Click to is
If there edit
tooMaster text in
little amine styles
relation to the amount of acid gas, the
•temperatures
Second level bulge move to the top of the column.
• With•the Third
richlevel
amine loading, it minimize the chance of severe corrosion
• Fourth level
due to the temporary of the overloading of the rich amine solution and
• Fifth level
minimize lean amine pumping and rich amine stripping cost.
Effect of H2S/CO2 Ratio on CS corrosion
• The solution of most amine is not corrosive if the ratio of H 2S/CO2 > 1/19
or 0.05.
• This is because when sufficient H2S is present, a protective FeS deposit
layer is formed.
• CS corrosion will be minimal as long as the H2S partial pressure > 5.1
kPa or 0.74 psia

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Amine Unit Operation
Effects of Amine Type on Amine Solution Corrosion
Click to edit Master title style
• Primary > Secondary > Tertiary Amine in terms of corrosion
• However, all amines are equally non-corrosive when there is no acid gas
presents.
•• Click
MDEAto edit Master
differs from thetext
otherstyles
amines is that it does not form amine CO2
• Second level
degradation products.
• Third level
• Fourth level
General Solution• toFifthCorrosion
level

• In general, in an amine unit, the solution to corrosion is to use the correct of

material of construction.
• Minimize all the corrosive materials such as HSAS, amine degradation
products, correct strength of amines.

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Gas Treating Seminar

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• Click to edit Master text styles

• Second level
• Third level
• Fourth level
The Importance of Analysis
• Fifth level
Why is Sample Analysis Necessary?
Amine Systems can fluctuate dramatically:
Click to edit Master title
• Feed gas changes can impact the system
style
• Solvent composition can change
• Intrusion/formation of contaminants can impact system performance
• Click to edit Master text styles
• Second level
Impact of non-ideal chemistry
• Third level
• Reduction in
• system performance
Fourth level
• Corrosion (acid •base system!)
Fifth level

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Case Study – Analytical Error
Impacting Energy Consumption
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Simulated case - Analytical error of 5% in amine concentration
Action: Operation corrects lean amine flow rate to compensate
• 11% decrease in lean amine flow rate
• Click to edit Master text styles
• Increases reflux condenser duty by 24%
• Second level
• Forces the reboiler to work harder – 10% increase in duty
• Third level
• Fourth level
Impact: at $10/MM btu impact is $390,000 in added energy expense
• Fifth level

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Dow’s Gas Treating Lab Testing
Acts as a QC Lab for plant
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Provides advance warning of potential problems
• Monitor contaminants levels
• Evaluate solvent degradation
• Click to edit Master text styles
• Monitor for excessive plant corrosion or corrosive conditions
• Second level
• Manage• changes
Third levelin formulation
• Fourth level
• Fifth level
Provides data to facilitate Plant troubleshooting

Required due to variability of chemistry in the process

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Analytical Services
Solvent monitoring is the most basic requirement of any good Amine
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Management Program

• Click to edit Master text styles

• Second level
• Third level
• Fourth level
• Fifth level

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Recommended Site Testing
Local testing for quick response is needed for good system
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management

Dow recommends
• Click the following
to edit Master text styleslocal solvent analysis:
• Wt% Amine by Titration – Daily
• Second level
• Acid Gas levelby Titration –Daily on lean amine stream
Loading
• Third
• Foaming Tendency – daily at multiple process locations
• Fourth level
• Optional - HSAS• Content
Fifth level
by Titration - weekly

Dow can provide methods and training for the above tests upon request

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Dow’s Analysis Program
Dow’s program complements the local analysis program
Click to edit Master title style
• Free quarterly sample analysis for Ucarsol customers
•• Quarterly process
Click to edit Master checks are essential to monitor metals
text styles
concentration,
• Second levelimpurity accumulation and to provide calibration check
for local lab level
• Third
• Dow will maintain
• Fourth level
a database for each process unit which is used to
• Fifth level
track system performance over time
• Data is trended to evaluate long term unit trends

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Sustained Unit Performance
Troubleshooting
Click to edit Master title style
• Trended data is utilized to assist Dow in troubleshooting unit
problems
•• Dow
Clickhas developed
to edit Master state-of-the-art
text styles analytical procedures and
technology used to troubleshoot Dow’s chemical plants
• Second level
• Dow’s•Oil & Gas
Third level business can access these lab capabilities to
troubleshoot non-routine
• Fourth level issues that arise in a customer’s process
• Fifth level
• Other specialized analyses, such as corrosion monitoring, can also
be performed.

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•Add plant specific data here
Click to edit Master title style

• Click to edit Master text styles

• Second level
• Third level
• Fourth level
• Fifth level

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 DOW CONFIDENTIAL - Do not share
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Gas Treating Seminar

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• Click to edit Master text styles

• Second level
• Third level
• Fourth level
•
Plant Fouling Issues
Fifth level
What Causes Amine Unit Fouling?
Solids/Droplets in inlet Gas:
Click to edit Master title style
Upstream Particulates
• Sand
• Pipeline scale and corrosion products
• Click to edit Master text styles
• Salts (from production water carry over)
• Second level
Mists • Third level
Carbon bed •fines
Fourth level
• Fifth level
Iron Oxide from improper start up and shut down

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What Causes Amine Unit Fouling?
Contaminants in the inlet Gas
Click to edit Master title style
Liquids/Mists in inlet Gas
• Hydrocarbon liquids
• Production chemicals (Foamers, etc)
• Click to edit Master text styles
• Corrosion inhibitors
• Second level
Oxidants• inThird
inlet Gas:
level
• Oxygen• Fourth level
• Fifth level
• Sulfur dioxide
• Strong acid gas

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What Causes Amine Unit Fouling?
Formation of Particulates from Iron
Click to edit Master title style
Scale come off from equipment wall:
• FeS, FeCO3, Fe(OH)2 etc.
Reaction
• Click toproducts fromtext
edit Master Fe2styles
O3 formed during shut down:
•• FeS, FeCO
Second 3, Fe(OH)2 etc.
level
Reaction• products
Third level in Absorber from corroded metals:
• Fe++ +• HFourth
2S  FeS↓ + 2H
level +
• Fifth level
Scale causes Erosion-Corrosion supplying Fe++
The Fe++ reacts with H2S and increase solid volume causing the vicious
cycle

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Impact of Fouling in the Amine Unit
Fouling issues can have a negative impact on unit performance including:
Click to edit Master title style
• Not Meeting treated gas specifications
• Operated under Capacity
•• High
Clicksolvent
to edit losses
Master(foaming)
text styles
• Corrosion
• Second tolevel
equipment internals
• Under
• Third
deposit
level corrosion
• Fourth level
• Poor exchanger & heater efficiencies
• Fifth level
• Erosion to equipment internals by solids in circulating solvent
• Higher energy consumption
• High filtration costs (increased filter change- out)

Overall sub par performance will result!

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Fouling Prevention
Inlet gas filtration
Click to solids
• Remove editandMaster
particulates title style
• Remove Hydrocarbons, mists & other liquids continuously
• This step reduces impact of well head chemicals which can impact the
• Click to edit
amine Master text styles
system
• Second
Solvent level
filtration
• Third level
• Contaminant removal via activated carbon bed
• Fourth level
• Removes surfactants
• Fifth level & hydrocarbons
Avoid overheating solvent
Oxygen exclusion in system
• Oxygen ingress into amine system causes multiple issues
• Upstream equipment including vacuum hydrocarbon recovery systems
should be monitored
Routine solvent analysis
• Monitor for contaminant buildup, HSAS, degradation products

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Eliminating Fouling via Design
Fouling
Click tocanedit
be managed
Masterthru design
title choices
style
Sufficient Mechanical filtration is essential.
• If insufficient - a temporary filter may be required if particulate level is
• tootohigh
Click editfor slip stream
Master filter control
text styles
Limit• flow velocity
Second level< 1.8 m/sec for CS
• Third
Control Acid Gas Re-Flash in piping because it may cause erosion-
level
corrosion.• Fourth level
• Fifth level
• increase amine strength
• increase amine circulation rate
• limit the rich amine temperature
• replace to stainless steel

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 DOW CONFIDENTIAL - Do not share
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Gas Treating Seminar

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Amine System Troubleshooting
• Click to edit Master text styles
Section 3
• Second level
• Third level
• Fourth level
• Fifth level
 Issue: Meeting Gas Specification
Possible Causes Signs and Symptoms Things to Check Actions/possible solutions
Click to edit Master title style
1) Inadequate • High lean loading • Analyze lean solvent
stripping • Low regenerator OHD • Regenerator conditions • Increase reboiler heat
temp • OHD temp & pres • Stabilize pressure control
• Click to edit Master text styles • Regenerator tower dP • Clean fouled stripper
• Tower pressure trend • Clean fouled LRHX
• Second level • Rich feed temp
• Third level
• Fourth level
2) Absorber • High dP
• Fifth level • Gas/lean temp delta • Add antifoam
foaming • Treated gas sep dumping • Solvent particulates • Increase gas/lean temp
–solvent carry over • Feed gas coalescer dP delta (6oC) or more
• Absorber liquid level • High flash gas flow • Filter solution
unstable • Replace filter elements

3) Regenerator • High dP • Flash tank pressure • Add antifoam

foaming • Regen bottom liquid level • Flash tank level (HC) • Skim HC from flash tank &
unstable • HC in flash tank reflux accumulator
• Reflux accumulator high • HC in reflux accumulator • Reduce regenerator
level pressure
• Increase reflux temp

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 Issue: Meeting Gas Specification
Possible Causes
Click toSigns
editand Symptoms Things to Check
Master title style Actions/possible solutions

4) Solvent • Excessive skimming • Lean & gas temp • Reduce lean temp
condition • Excessive rich flashing • Solvent strength • Add amine to system
• Dark solvent color • Solvent HSAS level • Neutralize HSAS
• Click to edit Master
• High filter dP text styles• Particulate filters • Check system for cooling
• Second level • Feed gas separators water leak
• Change filter elements
• Third level
• Fourth level
5) Feed gas • Fifth level
• High temp • Fouled coolers/HX • Adjust amine flow rate
conditions • Solvent carry over, • Feed gas rate • Adjust amine concentration
treated gas KO dumping • Feed gas analysis • Increase lean temp
• Increased acid gas vs. • Decrease gas rate
design

6) Mechanical • High dP relative to • Gas flow trends • Clean fouled tower

damage historical rates • Tower inspection • Repair tower internals
• Towers • High lean loading • Tower scan. • Repair LRHX leak
• Heat exchanger • Solvent particulates

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 Issue: High Solvent Losses
Click
Possible Causes
to edit Master
Signs and Symptoms
title style
Things to Check Actions/possible solutions

1) Entrainment • Treated gas separator • Foaming, tower dP • Antifoam; filtration

• Click
• Liquid in to edit Master text
dumping frequently styles
• Design max gas flow • Limit gas flow
• gas
overhead • Lowlevel
Second vessel solvent • Liquids in flash gas • Install/replace demister
levels • Demister performance
• Third level
• Fourth level
2) Entrainment • HC in downstream • Emulsion formation • Antifoam; filtration
• Fifth level
• Amine in coalescer • Column hydraulics • Limit HC flow
LPG/NGL • Low vessel solvent • Design max HC flow • Reduce amine concentration
levels • Solvent concentration • HC water wash

3) System • Abs/Regenerator dP • Trend of flash tank LCV • Limit HC feed rate

instability and • Hot rich temp variation to • Contactor design capacity • Make feed rates constant
upsets regenerator • Controller response • Filtration/particulate removal
• Flash tank hydrocarbon • Tune controller (PI)
accumulation
• System pressure swings

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 Issue: High Solvent Losses
Possible Causes Signs and Symptoms Things to Check Actions/possible solutions
Click to edit Master title style
4) Treated gas • Liquids accumulating • Instrument signal • Manual valve operation
Knock out • Excessive dumping • Drain valve operation • Validate free flow in drain
• Click
drum to •edit
High Master
liquid leveltext styles• Location of drain valve and line/reconfigure line
line • Relocate control valve
• Second level • Drain line size
• Third level
5) Solvent Leaks • • Fourth
Cooling levelhigh pH
water • Heat exchanger leaking • Repair leaks; repair seals
• • level
Loosing Fifth level • Pump seals • Replace leaking valve
• Loosing strength • LI taps • Inspect all open line
• Solvent puddles • Block valves leaking

6) Solvent • Solvent discoloration • O2 in feed • Analysis, source of O2

degradation • Heat exchanger fouling • Solvent flow through • Solvent temp in/out &
• Sludge & char reboiler hydraulic evaluation
• Poor treating • Reboiler temperature • Reduce temperature
• Reboiler pressure (131OC max)
• Inspect reboiler

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 Issue: Amine Contamination
Possible Causes Signs and Symptoms Things to Check Actions/possible solutions
Click to edit Master title style
1) Particulates • Amine color • Line velocity • Evaluate line velocity
• HX performance • Make-up water purity • Quality make up water
• Tower fouling/dP • Amine contaminant/ • Storage vessel vapor space
• Click to edit Master text stylesstorage corrosion
• Feed gas scrubbers • Gas filter/coalescer elements
• Second level • Carbon in solvent • Carbon bed supports
• Third level
• Fourth level
2) Hydrocarbons • Tower dP • Absorber HC layer • Feed gas coalescer
• Fifth level
• High flash gas rate • Flash tank HC layer maintenance
• Unstable regenerator • Reflux accumulator • Lean solvent temp increase
operation Hydrocarbon layer • Skim hydrocarbons
• Carbon bed activity • Increase regenerator reflux
temp

3) Foulants • Absorber/Regenerator • Amine chemistry • Adjust solvent chemistry

dP • Sludge formation • Make up water quality
• Frequent filter changes • Make up water quality • Cooling water leak
• Poor HX performance • Antifoam type • Feed gas contamination
• Change from Si antifoam

Gas Treating Seminar 95

 Issue: Amine Contamination
Click toSigns
Possible Causes
edit Master title
and Symptoms
style
Things to Check Actions/possible solutions

4) Oxygen • Reduced capacity • Feed gas source/quality • Wellhead operation

• Off spec. gas • Vent lines/positive pres • Blower infiltration
• Click to edit
• HeatMaster text
stable salts styles• Pad gas contamination • Improve pad gas
• Amine chemistry • Solvent maintenance
• Second level
• Third level
5) Heat stable • Reduced capacity • Feed gas quality • Up-stream operations
salts • •OffFourth
spec. level
gas • Up-stream unit • Control systems/ops
•
• Corrosion level
Fifth performance • Solvent maintenance
• Solvent chemistry • Coalescer elements
• Feed gas coalescer

6) System • Oxygen symptoms • Line passivation • Inerting following

maintenance, • Foaming • Filter element maintenance
filter changes, • Corrosion • Type of carbon • Cleaning new parts
operation • Quality carbon
stability • Carbon prep procedure

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 Issue: Corrosion
Possible Causes Signs and Symptoms Things to Check Actions/possible solutions

Click to
1) Erosion editdirtyMaster
• Chronically amine title
• Lean style
and rich amine line • Erosion survey, reduce
• Frequent filter changes velocity amine flow rate
• Elbows & Tees fail before • Rich amine loading • Increase amine conc.
pipe • Feed gas scrubbers • Feed gas conditioning
• Click to edit Master text styles• Carbon in solvent • Carbon bed supports
• Suspended solids
• Second level
• Third level
2) Heat Stable • Off
• Fourth
spec treated
level gas • HSAS > 2% as amine • Feed gas coalescer
Salts • High solvent
• Fifthparticulate
level • Gas source/comp. maintenance
load • Sulfur plant operation • Solvent maintenance
• SO2 break through to TGU • Make up water quality • Condition feed gas
• FCC or gas liquids

3) Acid Gas • Pipe leaks after CV • Amine color/particulates • Increase amine flow
Flashing • Pump cavitation • Sludge formation – filter • Increase amine strength
• Frequent filter changes change freq. • Increase flash tank press.
• Poor HX performance • Lean loading • Increase reboiler steam
• LRHX rich out temp • Upgrade materials (metal)

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 Issue: Corrosion
Click toSigns
Possible Causes
edit Master title
and Symptoms
style
Things to Check Actions/possible solutions

4) Stress cracking • Cracks formed in pipe • Areas adjacent to welds • Weld stress relieve
• Dye tests showing crack • Thinning areas of metal • Increase solvent flow or
• Click to edit Master text styles• Rich loadings concentration
• Make up water quality • Improve water quality
• Second level
5) Poorly stripped• Third
• Highlevel
filter change • Lean solvent loading • Increase reboiler heat
solvent •frequency
Fourth level • Lean/Rich Heat exchanger • Upgrade metals
• Lean/Rich
• Fifth Heat
level temperature trends • Evaluate Lean/Rich Heat
exchanger performance • Reboiler line thickness exchanger operation/
• Off spec treated gas pressure

6) Degradation • Generalized corrosion in • CO2/amine reaction • Reclaim solvent

products hot and cold areas products • Purge & replace solvent
(primary & • Amine chemistry
secondary
amine)

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