GPAC Gas Sweetening Presentation

Gas
Sweetening
Michael Sheilan, P.Eng.
Senior Staff Engineer Webinar Part One
Amine Experts Inc.
Introduction
o GPAC is a non-profit organization formed to promote the interaction and exchange of
ideas and technology to those involved in the hydrocarbon processing industry.
o GPAC has many exciting things planned for 2021 including 12 technical webinars
o GPAC has operated in Alberta since 1959 because of the support of our membership and generous sponsors.
A big thank you to:
Gold Sponsors Silver Sponsors
2
Mike Sheilan
Mike was the co-founder of Amine Experts in 1999 and is currently Senior Principal
Engineer for Amine Experts and Dehydration Experts. For 40 years Mike has
provided expert advice, training and consulting services in the area of hydrate
control, gas dehydration, gas and liquid sweetening, hydrocarbon recovery and
sulphur plant operations.
Mike is an authority on gas processing and has been published in the Oil and Gas
Journal, Hydrocarbon Processing Magazine, LNG Industry Magazine, Petroleum
Technology Quarterly, Sulphur Magazine and Chemical Engineering Magazine and
has presented at various conferences, including the LRGCC, GPAC, GPA-Midstream,
NACE, SOGAT and AFPM. He is also a Senior advisor to the Laurance Reid Gas
Conditioning Conference in Norman, Oklahoma.
Mike Sheilan
He previously worked for Brenntag Chemicals (Travis Chemicals) as Technical Service
Engineer and then Technical Service Manager from 1981 to 1999, where he
provided technical support for the gas processing industry in North America.
Mike has a BSc. in Chemical Engineering from the University of Calgary. He is a

member of APEGA, NACE and GPAC.
• Headquartered in Calgary, Alberta
• over 3000 projects in over 60 countries
• 285 Amine and Sulphur projects in 2019
• senior staff has over 350 years combined experience
• employees have authored more than 70 papers
• provide technical support to every major oil and gas company in
the world
• provide technical support to all major process licensors
Operator
Designer Regulator
Builder Supplier
Primary Areas of Assistance
• gas, liquid sampling and
analysis
• training seminars
• on-site technical assistance
• engineering studies
Types of Sweetening Processes
• Absorption
• Physical, Chemical and Hybrid
• (Amines, Potassium Carbonate, Caustic, etc.)
• Adsorption
• Physical and Chemical
• (Molecular Sieves, Iron Sponge, Zinc Oxide, etc.)
• Changes in P & T
• Membranes, Fractionation/Distillation
CONTACTOR CHEMISTRY
● acid gases react with weak liquid bases to form thermally
regenerable salts
acid + base salt + heat
H2S
+ lean amine rich amine + heat
CO2
REGENERATOR CHEMISTRY
● adding energy (heat) to the salts reverses the reaction to form
the original bases and acids
acid + base salt + heat
H2S
+ lean amine rich amine + heat
CO2
Molecular Structures
of Amines
• AMMONIA
• building block for amines
e
e
• all amines react
instantaneously with H2S
• what changes between

amines is how reactive they
are with CO2
Primary Amines
MEA
• primarily in refineries; high capacity per
circulation volume (high molarity); max
concentration only about 20 wt%
• strong base, deep CO2 and H2S removal; good
COS & CS2 removal
• high energy consumer; high degradation
(CO2, O2, COS); reclaimable
DGA (same as MEA; plus)

• max concentration closer to 50 wt%; thus
high overall molarity/capacity
• high H2S removal capability at very high
temperatures; effective solvent when plant
has lean amine cooling problems
• high COS reactivity; reclaiming converts
degradation products back to DGA
Secondary Amines
DEA
• high use solvent; strong H2S and CO2
removal capability
• typical max strength around 35 - 37 wt%
• lower reboiler duty than primary amines;
less degradation; requires vacuum
distillation reclamation
DIPA (same as DEA; plus)
• maximum concentration ~ 45 - 55 wt%
• higher hydrocarbon solubility
• good CO2 slip characteristics in TGTU
applications
• reclaimable with atmospheric distillation
unit
Tertiary Amines
MDEA
• no direct reactivity with CO2
• two step reaction mechanism
(slow dissolution in water to form
acid followed by rapid reaction
with basic amine) allows for
slipping of CO2 into treated gas
• low regeneration energy
• high capacity; minimal CO2-related
degradation; lower inherent
corrosive tendencies
• works very well as base solvent for
formulated amines
• typical strength is 40-50 wt%.
Reaction Mechanisms
● H2S reactions (proton transfer)
- all amines
[R1R2NR3] + H2S [R1R2NR3]H+ + HS–
(hydrogen bisulfide, instantaneous)

Reaction Mechanisms
● CO2 reactions (primary and secondary amines) -

carbamate formation
2[R1R2NH] + CO2 [R1R2NH]H+ + [R1R2N-COO]–
(fast)
“carbamate reaction”
Reaction Mechanisms
● CO2 (primary and secondary)

acid-base reaction (slow)
CO2 + H2O H2CO3 (carbonic acid)
H2CO3 H+ + HCO3- (bicarbonate)
H+ + R1R2NH R1R2NH2+
________________________________________________________
CO2 + H2O + R1R2NH R1R2NH2+ + HCO3-

Reaction Mechanisms
CO2 reactions
● Tertiary Amines
CO2 + H2O H2CO3
(slow)
[R1R2NR3] + H2CO3 [R1R2NR3]H+ + HCO3–

(fast)
FORMULATED AMINES
(Ucarsol; Gas/Spec; JeffTreat; AdvAmine, etc.)
• most contain components that increase CO2 absorption properties
• some formulations show improved LP treated gas H2S specification;
very good solvents for Acid Gas Enrichment (AGE) and Tail Gas
Treating Units (TGTU)
• tailor-made outlet CO2 concentration
• more available “vendor-supplied” technical service
ACTIVATED AMINES
(aMDEA [BASF OASE]; AP800 series; etc.)
• MDEA-based solvents with an activator / energizer (piperazine)
that greatly enhances the CO2 removal capabilities of the solvent
• primarily used in CO2-only removal facilities (used extensively in
shale gas treatment facilities; LNG; fertilizer plants)
• high capacity; low corrosion; low degradation in the presence of
CO2
HINDERED AMINES
(Flexsorb; SCOT Ultra)
• solvent formulations containing a bulky side
group that reduces the CO2 shuttle rate and
reduces the carbamate formation for
exceptionally good CO2 slip
• best-in-class acid gas enrichment and tail gas
treating
• high loading capacity; low regeneration
energy; low circulation rates
• very expensive solvent – 4 to 5 times more
than MDEA
MIXED SOLVENTS
(Sulfinol D/M/X, etc.)
• combination chemical and physical solvent formulations (chemical /
physical / water)
• high capacity, reduced regeneration energy because part of solvent
simply regenerated by flash pressure reduction
• extended sulphur species removal possible (solvent of choice for
mercaptan removal )
• much higher hydrocarbon co-absorption than chemical solvents
• work better at high acid gas partial pressures
GENERAL DESIGN CRITERIA
TREATED GAS SPECIFICATION
Gas Plants (all amines)
• less than 2 mol% CO2; 4-16 ppmv H2S
Refineries (all amines)
• generally, less than 50 ppmv H2S; no CO2 spec
Tail Gas Treating Units (DIPA, MDEA, Flexsorb, SCOT Ultra)
• <10 ppmv up to around 250 ppmv H2S
Carbon Capture (MEA, MDEA)
• < 1 mole% CO2
LNG Production (activated MDEA equivalent)
• < 50 ppmv CO2 (-160°C; volume shrinks by a factor of about 600)
GENERAL DESIGN CRITERIA – Important Factors
• Partial Pressure of H2S and CO2
• higher partial pressure improves efficiency / capacity
●Lean Loading
• driven by regeneration conditions (higher energy or solvent choice)
●Rich Loading
• limited by corrosion, temperature bulge, partial pressure, equilibrium
GENERAL DESIGN CRITERIA – Column Design
• Number and Type of Trays / Height and Type of Packing
• normally around 20 trays (or equivalent height of packing)
• more trays if extended sulphur species removal required (weaker acid
sulphur species are not touched until almost all the H2S and CO2 have
already been removed)
• less trays for tail gas units (need to minimize contact stages for
improved CO2 slip); also design with multiple feed tray locations for
optimal slip
GENERAL DESIGN CRITERIA
• Energy Consumption Reduction
• lower circulation rates
• move to solvent that requires less reboiler duty
• additional hot flash
●Hydrocarbon Co-absorption
• reduced circulation rates; higher rich loadings; higher absorber
temperatures
• amine dependent (MEA<DEA<DGA<MDEA<DIPA)
OPERATING ISSUES
• Meeting Specification
• Heat Stable Amine Salts
• Degradation
• Corrosion
• Feed Preparation Next
• Foaming Webinar
• Filtration
MEETING SPECIFICATION
• quality of the treated gas (specification) is set by the quality of the
lean amine (lean loading and temperature)
• regenerate the solvent well (as required for application)
• keep lean amine temperatures as cool as possible but still warmer
than the feed gas temperature
• reduce foaming and fouling in the absorber
• have sufficient contact stages in the absorber
• maintain sufficient circulation rate to control absorber bulge
temperature
HEAT STABLE AMINE SALTS
• formed by the reaction of amines with acids stronger than H2S or
CO2;; build up in systems because they do not regenerate at normal
regeneration conditions
• tend to increase solution corrosivity (especially in the reboiler and
lower regenerator)
• can affect both acid gas absorption (reduces) and regeneration of the
amine (improves)
• controlled by ion exchange; vacuum distillation; electrodialysis or
‘bleed and feed’
DEGRADATION
• primarily caused by CO2, COS and oxygen
• thermal degradation also a possibility (watch reboiler temps and heat
flux)
• breaks down amine molecule into components that may not have the
same acid gas carrying capacity; are corrosive and also promote
foaming
• in TGTU service, with MDEA, can be catastrophic for CO2 slip, as
primary / secondary amines are formed by the breakdown of the
MDEA molecule.
• removed via vacuum distillation or atmospheric distillation if the
solvent allows for it
CORROSION!
CORROSION CONTROL
Recommendations:
• make sure the lean solution is well regenerated; do regeneration in the
column and not the reboiler
• don’t exceed recommended maximum strengths
• max total rich loading: 0.45 to 0.55 mol acid gas / mol amine (depending
on the type of amine; CO2 content)
• minimize heat stable amine salts (maximum 2-3 wt%)
• maximum amine pipe velocity: 2 m/s (6 ft/s); 1 m/s in exchanger tubes
• control temperatures in absorber and regenerator
• post-weld heat-treat all amine plant replacement work; proper metallurgy
FEED PREPARATION, FOAMING and FILTRATION
WEBINAR PART
TWO
WHY AMINE
SYSTEMS FAIL?
Philip le Grange, Ben Spooner & Mike Sheilan

Thank You GPAC
Any Questions!
[email protected]

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Gas

Gold Sponsors Silver Sponsors

Mike has a BSc. in Chemical Engineering from the University of Calgary. He is a

acid + base salt + heat

acid + base salt + heat

• what changes between

DGA (same as MEA; plus)

● H2S reactions (proton transfer)

[R1R2NR3] + H2S [R1R2NR3]H+ + HS–

(hydrogen bisulfide, instantaneous)

● CO2 reactions (primary and secondary amines) -

2[R1R2NH] + CO2 [R1R2NH]H+ + [R1R2N-COO]–

● CO2 (primary and secondary)

CO2 + H2O H2CO3 (carbonic acid)

H2CO3 H+ + HCO3- (bicarbonate)

CO2 + H2O + R1R2NH R1R2NH2+ + HCO3-

[R1R2NR3] + H2CO3 [R1R2NR3]H+ + HCO3–

Philip le Grange, Ben Spooner & Mike Sheilan

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