Gas Processing

Feed Gas Treatment, NGL

Recovery and Fractionation
Gas Utilization

• Definition of Liquid Products

• Block Flow Diagram
• Potential Products
Gas Utilization Definition of Liquid Products

96% Methane
3% Ethane

1% Propane
LPG NGL LNG
Butane
0.1%
Pentane +
LPG – Liquid Petroleum Gas
NGL – Natural Gas Liquids
LNG – Liquid Natural Gas
Gas Utilization Temperature Scale °C
1000 Gold Melts

100 Water Boils

0 Water Freezes
-20 Butane Condenses
-40 Propane Condenses
-110 Ethane Condenses
-162 Methane Condenses
-200 Air Condenses
-273 Absolute Zero
Gas Utilization Block Flow Diagram

SULPHUR REC
LNG PLANT LNG PRODUCT
CO2 INJECTION

ACID GAS
LPG PRODUCTS
PROCESSING

GAS/LIQUID PRE- ETHANE

NGL PLANT
PURIFICATION PRODUCT

NATURAL/
UPSTREAM TO GAS
ASSOCIATED
PROCESSING DISTRIBUTION
GAS

CONDENSATE
PRODUCTS
Gas Utilization Potential Products
BOTTLES
TRUCKS
SHIPS PLASTICS
FIBRES
LPG PRODUCTS RUBBER
PLASTICIZER
SOLVENTS
ETHYLENE DETERGENTS
ETHANE PROPYLENE
PRODUCT
POWER GEN
AMMONIA/
METHANOL
FERTILIZERS
TO GAS
PLASTICS/ FIBRES
DISTRIBUTION PAINT/ RUBBER
FUEL
PLASTICIZER
SOLVENTS

CONDENSATE
REFINERY
PRODUCTS

MOTOR FUELS GTL

Feed Gas Composition

• Typical Natural Gas Feed Analyses

• Typical Associated Feed Gas Analyses
• Trace Contaminants
• Sulphur Species
• Considerations
Feed Gas Composition Typical Natural Gas Feed Analyses – Mol %

San
Antonio
North Texas, Alberta, SE Lacq Typmen
Sea* USA Canada Mexico France USSR

N2 9.02 0.17 1.90 0.24

CO2 0.10 2.22 0.50 2.50 8.58 0.20
C1 81.80 90.10 91.46 72.87 67.89 98.60
C2 6.00 5.17 4.50 13.26 3.80 0.70
C3 2.50 1.65 1.10 5.49 0.80 0.50
C4 0.43 0.44 0.39 2.28 0.56
C5 0.06 0.12 0.11 0.65 0.23
C6+ 0.09 0.13 0.04 0.45 0.62
* Data for Arpet-Hewett Upper Bunter (0.12 mol% HE included with nitrogen)

Nitrogen content can be much higher as in Groningen Gas, which contains apprx.
14% Nitrogen, Gas in Kansas which contains 16-30% Nitrogen and gas sources in
Poland containing 40-75% Nitrogen.
Feed Gas Composition Typical Associated Gas Analyses – Mol %

Saudi
Iran Dubai Bahrain Arabia Syria Iraq Qatar
N2 0.55 8.33 0.50 7.20 1.12
H2S 0.16 0.79 0.05 2.20 3.40 7.08 2.93
CO2 2.10 5.50 4.64 9.70 3.50 3.50 7.02
C1 81.40 56.66 70.20 51.00 54.50 56.90 55.49
C2 11.90 16.63 6.64 18.50 11.70 21.20 13.29
C3 3.42 11.65 4.50 11.50 8.90 5.97 9.69
C4 0.82 5.41 2.69 4.40 6.10 3.74 5.63
C5 0.20 2.15 1.64 1.60 3.10 2.55
C6 0.75 0.86 0.40 0.90 1.61 1.06
C7+ 0.91 0.45 0.20 0.30 1.21
Others 0.40 0.01
Feed Gas Composition Trace Contaminants

• Sulphur Species
• Water
• Salt
• Waxes
• Aromatic Hydrocarbons – Benzene, Toluene, Xylene
• Mercury
• Arsenic
• Glycol
• Methanol
• Radioactive components – Polonium & Radon
• Helium
• Oxygen
Feed Gas Composition Trace Components – Sulphur Species

• Mercaptans
– Methyl Mercaptan (CH3SH)
– Ethyl Mercaptan (C2H5SH)
– Propyl Mercaptan (C3H7SH)
– Butyl Mercaptan (C4H9SH)

• Carbonyl Sulphide
– Usually found if Carbon dioxide and Hydrogen Sulphide Present
– CO2 + H2S = COS + H2O

• Carbon Disulphide – CS2

• Thiophenes – Cyclic Sulphur Compounds

Feed Gas Composition Considerations

• Accuracy of Feed Gas Analysis

• Variation of gas composition with time
• Variation in reservoir conditions
• Alternative sources of feed gas
• Blending feed gases
• Contaminants
• Carbon Dioxide Limitations
Gas Processing Objectives Removal of Components
• CO2 Impact on Heating Properties
• Freezing in LNG/NGL Plants
Corrosion
• Water Freezing in LNG/NGL Plants
• Aromatics Freezing in LNG Plants
• Mercury Aluminum Corrosion in
LNG/NGL Plants
• H2S Safety Issues including combustion
Corrosion - NACE
• COS Avoid hydrolysis in Propane
• Mercaptans Safety Issues from combustion
• Nitrogen Impact on Heating Properties &
LNG processing
• Oxygen Effect on Feed Processing
Gas Processing Objectives LNG Plant Feed Gas Processing

• Components with low solubility in LNG

– Water: < 0.1 ppmv
– Carbon Dioxide: < 50 ppmv
– Aromatics: Removed in LNG Process (Benzene < 1ppmv)
– Heavy hydrocarbons: Removed in Gas Plant /LNG Process (Scrub Column)

• LNG Product Specifications

– Hydrogen Sulphide: 3 to 4 ppmv
– Nitrogen: < 1 mol %
– Combustion properties: Heating value & Wobbe Index

• Potential Corrosion Problems

– Mercury: < 10 nanograms/Nm3
 Gas Processing Example NGL Removal with Feed and Product Treating

AMINE
TREATING OF
FUEL GAS
Acid Gas to Gas to
Sulphur LNG
Recovery Plant
ETHANE CO2
REMOVAL

Feed FEED ACID GAS NGL RECOVERY

PROPANE
Gas RECEPTION REMOVAL & SEPARATION
TREATING

DEHYDRATION BUTANE
& MERCURY TREATING
REMOVAL

CONDENSATE
TREATING
 Gas Processing Example NGL Removal with Feed and Product Treating

AMINE
TREATING OF
FUEL GAS
Acid Gas to Gas to
Sulphur LNG
Recovery Plant
ETHANE CO2
REMOVAL

Feed FEED ACID GAS NGL RECOVERY

PROPANE
Gas RECEPTION REMOVAL & SEPARATION
TREATING

DEHYDRATION BUTANE
& MERCURY TREATING
REMOVAL

CONDENSATE
TREATING
Feed Gas Treatment

• Carbon Dioxide & Sulphur (Acid Gas) Removal

• Gas Processing Consideration (Hydrates)

• Dehydration

• Mercury Removal
Acid Gas Removal

• Objectives
• Consideration of other components
• Processes
• Licensors
• Process Details
• Process Selection
• Acid Gas Treating
• CO2 Sequestration
Acid Gas Removal Objectives

• Reduce Carbon Dioxide and sulphur compounds

to acceptable levels to avoid freezing and to
ensure on-spec products
• Removal of CO2 to 50 ppmv for LNG Plant Feed
• Removal of H2S to less than Pipeline
Specifications (<4 ppmv) Safety & Corrosion
• Removal of Mercaptans and COS
• Total sulphur 20 - 40 ppmv
Acid Gas Removal Considerations

• Performance to a specification is the primary

concern

• Performance of the Acid Gas Removal Unit

(AGRU) can dramatically affect overall plant
economics

• Acid Gas Disposal – Sulphur Recovery Unit

(SRU) or Incineration
Acid Gas Removal Processes

• Process licensors
• Physical solvents
• Aqueous chemical solvents
• Mixed solvents
• Lean oil absorption - Ryan Holmes
• Solid bed
• Membranes
• Combined systems
Acid Gas Removal Process Licensors

• Amine data readily available for design purposes

• Proprietary Licensor technology enables more
efficient designs which will be guaranteed
• Competition between Licensors
• Licensor fees for provision of process data.
• Royalties must be paid by the Operator.
• Licensor contract is with the Operator
• Contractor – licensor process selection studies.
• Contractor liabilities are greater than those of
Licensor
Acid Gas Removal Physical Solvents

• Selexol DME of PE Glycol - UOP (Norton)*

• Rectisol I Methanol - Lurgi & Linde AG*
• Rectisol II Toluene/Methanol - Linde AG*
• Purisol NMP - Lurgi*
• Fluor Solvent Propylene Carbonate
• Estasolvan TBP - UHDE & IFP*
• Sepasolv MIE & OE Glycol - BASF*

* Licensors
Acid Gas Removal Physical Solvents - Characteristics

• High Acid Gas Partial Pressure

(Concentration)

• Selective H2S - CO2 Removal

• Removes COS and RSH

• Dehydrates Gas

• Absorbs Hydrocarbons
Acid Gas Removal Aqueous Chemical Solvents
• Amine Processes
– Primary: DGA (Huntsman)*
Amine Guard, MEA (UOP)*
– Secondary: DEA (SNEA)*, DIPA (Shell)*
– Tertiary: aMDEA (BASF)*
MDEA (SNEA)*
MDEA (UOP - UCARSOL)*
– Hindered: Flexsorb SE, MDEA (Exxon)*

• Hot Potassium Carbonate (Promoted)

- Benfield – UOP*
- Catacarb – Eickmeyer*
- Carsol – Kemira/Giammarco*

* Licensors
Acid Gas Removal Aqueous Chemical/Physical Solvents

• Sulfinol D DIPA, H2O, Sulfolane (Shell)*

• Sulfinol M MDEA, H2O, Sulfolane (Shell)*

Acid Gas Removal Typical Process Flow Scheme
Acid Gas

Reflux
Condenser
Treated Gas

Lean Amine

Lean Absorber /
Contactor
Low-Pressure Flash/
Regenerator/Stripper

Sour Gas
Flash Gas

Reboiler
High-
Rich Amine Pressure
Flash
Acid Gas Removal Comparison of Amines
MEA DEA DGA MDEA

Mol Wt. 61 105 105 120

Soln Strength,
wt% 15-20 25-35 40-60 50
Selective H2S
Absorption No No No Yes*

Limited Acid
Gas Pickup Due
to Corrosion Yes No Yes No
Solution
Degradation:
COS, CS2 Yes No Yes No
CO2 Yes Yes Yes No
Type Primary Secondary Primary Tertiary

Degradation: Primary>Secondary>Tertiary
* Reason for H2S Selectivity:
1. Tertiary amines do not form carbamate
2. Exxon uses hindered secondary amine to avoid carbamate
Acid Gas Removal Sulfinol – Process Characteristics

• Flow diagram similar to amine

• Absorbs significant amounts of HC due to sulfolane in sulfinol

solution

• Will absorb COS and RSH

• Hydrolyzes COS to CO2 + H2S

• Higher permissible acid gas pick-up

• With Sulfinol D the DIPA reacts with CO2 to form some

degradation product. DIPA also increases HC Absorption
Acid Gas Removal Promoted Hot Carbonate - Process Characteristics

• Used mainly for CO2 removal in Hydrogen and Ammonia

plants
• Licensed processes
– Benfield (UOP) – uses DEA additive
– Catacarb (Eickmeyer) – uses amine borates
– Carsol (Kemira/Giammarco)

• Operates at 120°C

• Lower heat requirement than amines

• Heat of reaction 50% of amines

• Solution Strength 23 to 30 wt% K2CO3
Acid Gas Removal Solid Bed Processes

• Molecular Sieve - CO2/H2S (Adsorption)

– UOP
– W.R.Grace
– CECA
– Zeochem
– Axens, Procatalyse

• Zinc Oxide – H2S (chemical reaction)

– Johnson Matthey (Synetix)
– United Catalyst
– BASF

• Iron Oxide - H2S (chemical reaction)

• Silica Gel – Mercaptan removal

Acid Gas Removal Membranes

• Spiral Wound & Hollow Fibers

• Gas molecules permeate across the thin skin of a

membrane wall driven by partial pressure difference.

• Permeation rate is specific to the gas - polymer pair. The

transport mechanism is a combination of solubility into,
and diffusion through the membrane.

• Separation capability is determined by the relative

permeation rates of individual gas components.
Acid Gas Removal Combined Systems

• Benfield High-Pure - UOP

– Potassium Carbonate / DEA

• Benfield 100 - UOP

– Potassium Carbonate / Molecular Sieve

• Membranes
– Bulk removal of carbon dioxide plus other system
for polishing.
Gas Processing Consideration (Hydrates)

• Introduction
• Hydrate Formers
• Structure
• Formation Conditions
• Hydrate Inhibition
• Engineering Considerations
Hydrates Introduction

• Chemical Compound - Clathrate

• Water molecules surround hydrate former molecule
• Forms a crystalline structure similar to ice
• Alternative Structures I, II, H
• Formation at high pressures and low temperatures
• Formation temperatures up to 30°C
• Present naturally on the sea floor
• In Gas Production must avoid hydrates
• Blockage of pipelines and equipment
• Hydrates also formed with liquid hydrocarbons
Hydrates Natural Gas Hydrate Formers

Depends on size of molecule. If size is greater

than 7.1A (n-Butane), hydrate is not formed

– Ethane 5.5A
– Propane 6.3A
– Iso-Butane 6.5A
– Carbon Dioxide 5.1A
– Hydrogen Sulphide 4.6A

1A = 1 x 10-8 cm
Hydrates Formation Conditions

• Tabulation of pure component data

• Calculation of Hydrate Formation Conditions

• Hydrate Formation does not require liquid water

Hydrates Formation Conditions

• Tabulation of Pure Component Data

METHANE ETHANE PROPANE
Pressure Temperature Pressure Temperature Pressure Temperature
bar Deg C bar Deg C bar Deg C

26 0 5.3 0 1.7 0
72.5 10 16.8 10 5.1 5
127.9 15 43.5 15
234 20 200 17.5
859 30
Hydrates Computer Software Predictions

• HYSYS
• PRO II
• ASPEN
• PROSIM
• CSMHYD
• EQUI-PHASE
Hydrates Inhibition

• Dehydration
• Molecular Sieves
• Triethylene Glycol
• Glycol Injection
• Monoethylene Glycol
• Diethylene Glycol
• Methanol Injection
Hydrates Engineering Considerations

• Process Engineering
– Identify hydrate potential
– Estimate formation temperature
– Apply suitable design margins

• Gas & Liquid Blow-down

– Valve types, double valves
– Wide sweep bends and use angled T sections

• Inhibitor Distribution
– Efficient contact with gas
– Tube-sheet coverage in Heat Exchangers

• Remedial action
– Heating & Pressure Reduction
– Methanol Injection
Hydrates Design Margins

CHILLED FEED GAS

FEED GAS
CHILLER
WET FEED 18ºC
GAS
SEPARATOR

REFRIGERANT

CONDENSED WATER
15ºC
(HT+5)
CALCULATED HYDRATE TEMPERATURE (HT) OF FEED: 10ºC
Dehydration

• Objective
• Processes
• Molecular Sieves
Dehydration Objective

• Removal of water to cryogenic specifications to

prevent build up of ice and/or hydrates which
would block equipment and piping operating at
low temperatures

• Requires water removal to 0.1 to 1.0 ppmv

Dehydration Processes

• Solid Bed DPºC (ppmv)

• Liquid Contactor DPºC (ppmv)
– Calcium Chloride
– Glycol (TEG) -9 (60)
– Silica Gel -60 (0.2)
– TEG with
– Alumina -70 (<0.1) gas stripping -50 (0.5)
– Activated Carbon – Drizo -90 (<0.1)
– Molecular Sieve -90 (<0.1) – Selexol

• Liquid Injection • Membranes -40 (2.5)

– Methanol -90 (<0.1)
– Glycol MEG -25 (14)
– Glycol DEG

DP = Water Dew Point

ppmv at 50 bar
Dehydration Molecular Sieves

• Most commonly used material for solid bed

dehydration
– synthetic crystalline zeolites
– size and shape of molecule determine adsorption
– Also used for liquid dehydration

• Design and operating considerations

– Coadsorption
– Contamination
– Regeneration Conditions
– Chemical Reactions
Dehydration Molecular Sieves

• Co-adsorption • Regeneration
– CO2
– Efficient use of heat
– H2S
– RSH – Operating Pressure
– Peak impurities
• Contamination – Disposal of effluent Gas
– Heavy Hydrocarbons – Bed lifting
– Glycol
– Methanol • Chemical Reactions
– Liquid Water – CO2+H2S = COS + H2O
– Acid Gas Solvent – 2 O2 + CH4 = 2 H2O + CO2
– Separation required
– Oxygen Limits:
• 10 ppmv max in feed
• 5 ppmv max in regen. gas
 Dehydration Molecular Sieves - Process Flow

Regeneration Gas
Compressor Regeneration
Gas Cooler

Drier
Precooler
Water
Regeneration Gas
Water Saturated
Knockout Drum
Natural Gas
from gas
sweetening unit

Driers Drier
(Ads) (Regen)
Water Hydrocarbon
Liquid Regeneration
Heater

Filter Dry Gas

Dehydration Molecular Sieves - Process Flow

• No of Beds: • Regeneration System

– 2, 3 or 4 – Open / closed cycle
– Cycle periods – Series Regeneration
– Need to purify
• Outlet specification regeneration gas
- <1 ppmv water
(0.1 ppmv • Guard Beds
achieved)
Dehydration 3 Bed Molecular Sieve Unit
Dehydration Typical MEG Injection System

Gas-Gas Gas Chiller

Exchanger Glycol-
Inlet Gas Hydrocarbon Hydrocarbon
Refrigerant Separator Vapour

Hydrocarbons Water
Vapour
Residue Gas Lean-Rich
Exchanger
Flash
Rich Glycol Tank Reboiler

Heating
Medium

Filter Surge
Tank

Lean Glycol
 Dehydration Typical TEG Contacting Unit
Water
Dry Gas
Vapour

Lean Glycol Still

Flash Gas

Reboiler

Flash
Tank
Surge Tank
Rich
Glycol

Wet Gas Inlet

Scrubber

Filter

Free Liquid Lean Glycol Pump

Dehydration Using Liquids

• Liquids
– Glycols, methanol and selexol

• Injection
– MEG / DEG / Methanol
– More difficult to get good contact and distribution
– High losses with methanol injection

• Contacting
– TEG / Selexol
– Good contacting
– Higher efficiency
Dehydration Molecular Sieves vs. Glycol

• Molecular sieve will reduce water content of gas to less than 0.1
ppmv. High energy for regeneration.
• MEG injection limited by freezing point of MEG/Water mix and high
viscosity at low temperature. Temperature limited to about -24ºC.
Umm Said NGL2 operating at -40ºC
• Maximum dewpoint depression with conventional glycol (TEG)
contacting is approximately 44°C. Limited by regeneration
temperature and pressure
• Improve with vacuum reboiler, stripping gas or “cold finger”.
• Drizo process claims dewpoint depression of 100°C with iso octane
injection and recycle also recovers BTX
• Drizo Unit for MOL (Hungary) claims 0.1-0.2 ppmv water in product
gas (108 MMSCFD)
Mercury Removal

• Objective
• Mercury Distribution
• Flow Scheme
• Catalyst Vendors
• Waste Disposal
Mercury Removal Objective

Traces of mercury have to be removed from natural

gas and its associated condensate to prevent:

• Corrosion in aluminum equipment

Removal of mercury in the gas phase is by:

• Adsorption on sulfur impregnated carbon or alumina

carrier
• Molecular Sieve
• Sulphided Metal (Puraspec)
Mercury Removal Typical Process Flow Scheme

From Dehydration Section

Mercury
Removal
Column

To Liquefaction Section
Outlet Gas Specification is generally 10
nanograms of Mercury per cubic meter of gas.
Mercury Removal Current Catalyst Vendors

Vapor Phase: Liquid Phase:

• ALCOA Mersorb • ALCOA Mersorb LH
• Barneby & Sutcliffe Type CBII • Calgon Type HGR-LH
• Calgon Type HGR • Stamicarbon Ion Exchange
• Lurgi Type Desorex HGD Process
• Norit Type RBGH
• Procatalyse CMG 273
• Union Carbide Type EB28
(UOP)
• Johnson Mathey (Synetix)
Mercury Removal Disposal of Mercury Contaminated Waste

Waste can include:

• Used Catalysts
• Contaminated Equipment
• Contaminated Soils

In the USA:
• Waste is classified as D009 and covered by 40
CFR 300 Superfund
• Best Demonstrated Available Technology (BDAT)
is Thermal Roasting and Vacuum Retort
NGL Recovery and Fractionation

• Phase Diagram + Chilling

• Typical Processes
Phase Diagram + Chilling
Ortloff’s Recycle Split Vapor (RSV) Process
Ortloff’s Gas Subcooled Process (GSP)
Ortloff’s Overhead Recycle (OHR) Process
Industry Standard Single-Stage (ISS) Process
Thank you…

Question?