Gas Quality

From Reservoir to Market

Natural Gas Lecture, NTNU, 17.10.2011
Kjersti O. Christensen and Stathis Skouras
Principal Researchers, Statoil R&D Centre Trondheim

Outline
Introduction to gas quality

Gas quality parameters related to

Water
Carbon dioxide

Part one,
Kjersti

Hydrogen sulphide
Mercury
Hydrocarbon dew point
Combustion properties

Part two,
Stathis

Why gas quality specifications?

Ensure unproblematic transport of gas
Ensure unproblematic processing of gas
Prevent corrosion and erosion of equipment
Prevent condensation of liquid
Prevent ice and gas hydrates
Ensure interoperability / interchangeability

Transport network Norwegian continental shelf

Production sites
Transportation pipelines
Multiphase
Rich gas
Sales gas
Gas processing
Marked terminals

Source: Gassco.no

Subsea and wells

Gas chain elements

Platform processes
Preparing for transport

Onshore processes
Preparing for sale
Extracting high value components

Receiving terminals

Metering and distribution

Gas quality specs along the value chain (1/3)

Rich gas transport specs

Specification
210
112
60
-10
105
40
-18
2
2
2
2.5
20
8

Preparing for transport

Rich gas flow

Designation and unit

Max operating pressure (bar g)
Min operating pressure (bar g)
Max operating temperature (C)
Min operating temperature (C)
Max cricondenbar pressure (bar g)
Max cricondentherm temperature (C)
Max water dew point (C at 69 bar g)
Maximum carbon dioxide (mole%)
Max hydrogen sulphide and COS (ppmv)
Max O2 (ppm vol)
Max daily average methanol content (ppmv)
Max peak methanol content (ppm vol)
Max daily average glycol content
(litres/MSm3)

Platform processes

Onshore processes

Gas quality specs along the value chain (2/3)

LNG production specs
Component

Specification

Reason

Water

<0.1 ppmv

Precipitates and
freezes on cold
surfaces

CO2

50 100 ppmv

Precipitates and
freezes on cold
surfaces

Heavy HC

1 -10 ppmv

Precipitates and
freezes on cold
surfaces

Mercury

<0.01 micro
gram/Nm3

Solid formation,
accumulation

H 2S

4 ppmv

Product specification

Onshore processes

Preparing for sale

Extracting high value components

Gas quality specs along the value chain (3/3)

Onshore processes

Dry gas flow

Sales (dry) gas specs

Receiving terminals

Water removal
Water occurs naturally in the gas from the reservoir
Water must be removed from the gas to avoid:
Free water in gas pipelines (corrosion)
Ice formation (plugging of equipment and pipes)
Hydrate formation (plugging of equipment and pipes)
Water removal processes:
Condensation (cooling and separation)
Absorption by glycol processes
Adsorption on solids

Water removal
Platform processes

Onshore processes

Transport
specification:

Process
specification:

-18C at 79 barg

0.1 to 1 ppmv

Process needed:

Process needed:

Glycol absorption
process

Adsprotion on
solids

Water removal - Glycol absorption

Water
vapour

Counter-current mixing of tri ethylene

glycol (TEG) and natural gas
Meets pipeline gas specifications (-18C
at 69 barg)

Dry
natural
gas

Lean TEG

Regenerator

Filters
Contactor

Wet
natural
gas

Pump

LT HX

HT HX

Surge drum

Cooler
Rich TEG

Glycol/condensate
separator

Filter

Upstream precautions:

Downstream effects:

Remove condensate

Liquid glycol in the dry gas (carryover)

Condensate could accumulate in

the bottom section of the
contactor
Remove particles

Gaseous glycol in the dry gas

(solubility)

The glycol absorption process

Water
vapour

Dry natural
gas

P=1bar
T=200C

Flash drum
P=70 bar

Regenerator
Filters

T=30C

Lean TEG

Contactor

Surge drum

Wet natural
gas

Pump
HT HX

LT HX
Cooler
Rich TEG

Glycol/condensate
separator
Filter

Water removal - Adsorption on solids

Can be regenerated
Obtains low water content
(<0.1ppmv)
NGL and LNG plants

Upstream precautions:

Downstream effects:

No free water

Dust particles

No condensate
Minimise glycol

Water adsorption process

Wet gas

Silica gel
Molecular sieve

Regeneration gas

Dry gas

Regeneration of water adsorbents

Pressure reduction

Temperature increase

Combination

Acid gas
Most natural gas contains acid gas
CO2
H2S and other sulfur compounds (COS, CS2, and RSHs)
Why remove acid gas:
Corrosion induced by acid gas (+ free water)
Freezing of acid gas in process equipment
Sales specifications
Toxicity and reactivity (H2S)
Typical specification for sweetened gas:
CO2 in pipeline gas: < 2-2.5 mol%
CO2 in gas for LNG-production: < 50 ppmv CO2
H2S: a few ppmv

Acid gas removal by amine absorption

H2S removal on metal oxide

Acid gas content < 1%
Chemical reaction
MeO + H2S -> MeS + H2O
< 0.1ppm(vol) H2S in product gas
Non-regenerative
Upstream precautions:

Downstream effects:

No liquids (free water / condensate)

Water

Minimise glycols

Dust particles

Minimise amines
Minimise particles

Mercury
Mercury is liquid at standard conditions for temperature
and pressure (20C, 1 atm)
Mercury occurs naturally in the gas
Mercury concentration vary from one gas field to another,
and also through one fields lifetime [1].
High mercury concentrations (several hundreds g/Nm)
have been reported for gas from North Germany, Algeria
and Indonesia [2].

Source: Wikipedia.com

1) M. A. El Ela, I. Mahgoub, M. Nabawi and M. A. Aziem, Egyptian gas plant employs absorbents for Hg removal, Oil and Gas Journal, 104, December (2006)
2) S. M. Wilhelm, The effect of elemental mercury on engineering materials used in ammonia plants, Process Safety Progress, 10, 189-193 (1991)

Location
Algeria (wellhead)
Algeria (pipeline entrance)
Algeria (Skikda plant inlet)
Groningen (wellhead)
Groningen (to pipeline)
North Germany (wellhead)
North Germany (wellhead)
South America
Far East (Pakistan)
Far East
Far East
Africa (Angola)
Middle East (Iran)
Eastern U.S. Pipeline
Midwestern U.S. Pipeline
North America
Sumatra, Indonesia

Mercury concentration (g/Nm)

50 80
0.1 89
0.001 0.65
180
12
15 450
<0.1 0.3
69 119
3 20
58 193
0.02 0.16
0.3 130
19
0.019 0.44
0.001 0.10
0.005 0.040
200 300
Source: Wikipedia

Mercury removal
Mercury compounds are highly toxic
Mercury must be removed from the gas to avoid corrosion
of aluminium equipment
Mercury corrosion mechanism:
Formation of an aluminium-mercury amalgam
Selective corrosion (oxidation) of aluminium in the
amalgam in the presence of water [3]
Mercury removal process:
Adsorption on solids

3) J. B. Bessone, The activation of aluminium by mercury ions in non-aggressive media, Corrosion Science, 48, 4243-4256 (2006).

Mercury removal by adsorption on solids

Mercury is adsorbed on metal sulphide
Chemical reaction
MeO + H2S -> MeS + H2O
MeS + Hg -> MeHgS
<10 ng/Sm3 in product gas (NGL/LNG spec)
Can not be regenerated
Upstream precautions:

Downstream effects:

H2S needed

HgS

No liquids (free water / condensate)

Water

Minimise glycols

Dust particles

Minimise amines
Minimise particles

Part two - Topics

Phase envelopes of natural gas
Examples of phase envelopes
Effect of composition in phase envelopes
Importance of phase envelopes
Gas quality specifications along the Value Chain HC dew point
Manipulation of phase envelopes along the Value Chain HC dew point control
Experimental measurements and modelling of phase envelopes

Combustion properties
Heating values
Wobbe index
Combustion characteristics

Phase envelopes - pure components

Relationship known as
saturation pressure (Psat) curve

16

Propane

14

Psat
12
Pressure, bar

As long as both phases

(liquid+vapour) are present,
pressure and temperature
cannot be changed
independently.

Liquid

10
8

Vapour

6
4
2
0
-40

-20

20
o

Temperature, C

40

60

Phase envelopes-binary systems (50/50 wt% C2/C3)

60

C
50

Pressure [bara]

40

Liquid
30

V+L

20

Bubble
point line

10

Vapor

Dew point
line

E
0
-140

-120

-100

-80

-60

-40
-20
Temperature [C]

20

40

60

80

Natural gas phase envelope-multicomponent

system
Dense phase

Cricondenbar

Liquid

Critical point

Cricondenbar

Cricondentherm

Cricondentherm

Vapor + liquid
Gas

The phase envelope is ONLY

a function of COMPOSITION

Effect of composition on phase envelopes

Effect of heavy ends (C7+)

Source: A. M. Elsharkawy / Fluid Phase Equilibria 193 (2002) 147-165

Importance of phase envelopes

Gas transport in pipelines
b

Pipeline 1: a-b path

a
2
b

Transport in dense phase

No liquid formation

Pipeline 2: a-b path

-

Liquid formation / two-phase

flow

Manipulate phase envelope by

removing heavy ends (C7+)

Subsea and wells

Gas quality specs along the

Value Chain HC dew point
HYDROCARBON DEW POINT
specifications are related to
phase envelopes

Platform processes
Preparing for transport

Onshore processes
Preparing for sale
Extracting high value components

Receiving terminals

Metering and distribution

Classification: Internal

Gas quality specs along the Value Chain

HC dew point (cont.)
Offshore Processing - sgard transport
Designation and unit
Max operating pressure (bar g)
Min operating pressure (bar g)
Max operating temperature (C)
Min operating temperature (C)
Max cricondenbar pressure (bar g)
Max cricondentherm temperature (C)
Max water dew point (C at 69 bar g)
Maximum carbon dioxide (mole%)
Max hydrogen sulphide and COS (ppmv)
Max O2 (ppm vol)
Max daily average methanol content (ppmv)
Max peak methanol content (ppm vol)
Max daily average glycol content
(litres/MSm3)

Specification
210
112
60
-10
105
40
-18
2
2
2
2.5
20
8
sgard Transport: 70 MSm3/d, 830 km

Gas quality specs along the Value Chain

HC dew point (cont.)
Onshore Processing Krst Plant

Krst: Europes largest gas plant, 88 MSm3/d

Manipulation of phase envelopes along the Value ChainHC dew point control
Offshore
processing

Source: A.O. Fredheim, E. Solbraa, Compendium Industrial Processes, TEP4185 NTNU

Onshore
processing

Measurements and modelling of phase envelopes

Two techniques for determination of HC dew
points

Manual standard
Chandler device

Automatic Ametek
model 241CE II

Direct: Manual or automatic devices

(field instruments, chilled mirror
principle, gas condensation by cooling)
- Manual Chandler device
- Condumax II (Michell instruments)
- Ametek model 241 CE II (Ametek)
- Cong-Prima 10 (Vympel)

Indirect: Dew point calculation based on

gas composition analysis (GC) and a
thermodynamic model (EoS)

GC-analysis + EoS

Pressure [bara]

Dew point measurements at R&D Centre Trondheim

120
110
100
90
80
70
60
50
40
30
20
10
0

Individual dew points

-10

-5

5
10
Temperature [C]

15

20

25

36

Modelling of phase envelopes

Phase envelope predictions:
GC-analysis + EoS

Important issues

Gas chromatographic (GC) analysis

How detailed analysis: C6+, C7+, etc.?

Characterisation of C7+ fraction

Which physical properties for C7+?

SRK:

Thermodynamic models
Which EoS: SRK, PR, etc?

PR:

Modelling of phase envelopes effect of GC

analysis
Effect of GC-analysis

How detailed should the gas

120

analysis be?

110

Enough with GC-analysis up to

100
90

Extended gas analysis above C6+

80

is not routine

But has a significant effect on

phase envelopes

Pressure [bar]

C6+, C7+ fraction?

70

GC-analysis up to C5 (C6+ fraction)

60
50

GC-analysis up to C6 (C7+ fraction)

40
GC-analysis up to C9

30
20
10
0
-35

-25

-15

-5

Temperature [C]

15

25

35

Modelling of phase envelopes effect of C7+

characterisation
Effect of C7+ characterisation
C7+ as pseudo-components

Is it enough to characterise C7+

components as n-alkanes?

Is it important to distinguish

How should we assign physical

properties (mol. weight, density) and
model parameters (Tc, Pc, ) to the
pseudo-components?

110

Tc, Pc and from generalised correlations*

90
Pressure [bara]

pseudo-components (C7*, C8*, etc)?

Mol.weight and density by detailed GC-analysis

100

between paraffinic (P), napthenic (N)

and aromatic (A) components?

Shall we characterise them as

120

80
C7+ components as n-alkanes

70
60

PNA characterisation

50
40

C7+ components as pseudocomponents

30
20
10
0
-15

-10

-5

10

15

Temperature [C]

Tc, Pc from Riazi-Daubert (1987) and from Kesler-Lee (1976)

20

25

30

35

Modelling of phase envelopes effect of EoS

Effect of EoS

Subsea and wells

Gas quality specs along the

Value Chain
combustion properties
Platform processes

Preparing for transport

Onshore processes
Preparing for sale
Extracting high value components

Receiving terminals

Metering and distribution

Classification: Internal

Combustion properties
Energy content

Energy load

Gross Calorific Value (GCV)

Wobbe Index (WI)

or

WI =

Net Heating Value (NHV)

Combustion characteristics

Soot index (SI):

Incomplete combustion factor (ICF):

Flame behaviour

GCV

rel

Energy content - Heating values

Gross Calorific Value (GCV): Heat
produced on combustion of gas with
stoichiometric amount of air
- Water formed by combustion cooled to the
reference temperature and condensed

Net Heating Value (NHV): Same as

GCV but with formed water in vapour
state (normal way)

Heating values are important contractual terms

Used for billing purposes gas volumes
translated to energy content

Heating values are a function of

COMPOSITION

ISO 6976 gives guidelines for calculation of

calorific values based on composition

Krst plant: GCV spec. for sales gas

Energy load: Wobbe Index (WI)

Wobbe Index (WI): Is a measure of
burner compatibility

WI =
where:

rel

GCV

rel

= gas
air

The main indicator of interchangeability

Interchangeablity: The ability of a distributed

natural gas to be substituted by another gas
without the need for adjustment of equipment.

WI is a function of COMPOSITION

ISO 6976 gives guidelines for calculation of WI

based on composition

Krst plant: WI spec. for sales gas

Wobbe Index - Gas group application areas

Group L: 39.1 < WI < 44.8 MJ/m3
Group H: 45.7 < WI < 54.7 MJ/m3
Group E: 40.9 < WI < 54.7 MJ/m3

Blue: Group H
Green: Group L
Red: Group L + H
Orange: Group L + H + E

Gas burner

European Gas Quality Parameters (EASEE-gas)

Harmonisation work

WI - Gross (Superior) Wobbe Index

d - relative density
S - Total Sulphur
H2S + COS - Hydrogen sulphide +
Carbonyl sulphide
RSH - Mercaptans
O2 - Oxygen
CO2 - Carbon dioxide
H2O DP - Water dew point
HC DP - Hydrocarbon dew point

Combustion characteristics

Normal flame behaviour

Soot index (SI)

Indication of the risk of soot formation

Incomplete combustion factor (ICF)

Indication of the risk of CO formation during the
combustion process
Yellow-tipping

Flame behaviour
Yellow tipping: Incomplete combustion where
excess hydrocarbons could, but does not
always, result in unacceptable levels of carbon
monoxide. May result in soot deposition and a
continuing deterioration of combustion

Thank you
Gas Quality From Reservoir to Marked
Presenters name: Kjersti O. Christensen and Stathis Skouras
Presenters title: Principal Researchers, Research Centre Trondheim, Norway
kchr@statoil.com, tel: +47 99 48 76 84 / efss@statoil.com, tel: +47 97 69 59 62
www.statoil.com

Typical offshore process

Sour gas
treatment

HC dew
point control

(CO2, H2S)

Inlet
separation
(3-phase flash)

Water dew
point control

Gas treatment
Recompression

Condensate
stabilisation

Typical onshore process (Krst plant)

Rich gas
pipeline

Gas pretreatmet
(conditioning)

NGL extraction (HC

dew point control) NGL fractionation

Sales gas
Sales gas
compression
pipeline