Minor constituents

Nitrogen Rejection (Chapter 13)

Trace-Component Recovery or Removal (Chapter 14)
Based on presentation by Prof. Art Kidnay
Plant Block Schematic

Adapted from Figure 7.1,

Fundamentals of Natural Gas Processing, 2nd ed.
Kidnay, Parrish, & McCartney

Updated: January 4, 2019

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Copyright © 2019 John Jechura ([email protected])
Topics
Nitrogen Rejection (NRU)
▪ Nitrogen Rejection for Gas Upgrading
▪ Nitrogen Rejection for EOR
Trace-Component Recovery or Removal
▪ H2, O2, NORM, As
▪ Helium
▪ Mercury
• Amalgam Formation
• Removal Processes
▪ BTEX

Updated: January 4, 2019

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Nitrogen Rejection (NRU)

Updated: January 4, 2019

Copyright © 2017 John Jechura ([email protected])
Nitrogen Removal / Rejection
Nitrogen rejection required to:
▪ Lower N2 level to meet pipeline
specifications
▪ Recover N2 for use in enhanced
oil recovery (EOR)
▪ Obtain raw N2 / He stream for He
recovery

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Subquality gas and EOR
16% of the non-associated reserves (2000) were subquality in
nitrogen and consequently require blending or processing to meet
the 3 mol % total inerts specification for pipelines

In 1998 EOR methods contributed about 12% of the total US oil

production.
about 55% from thermal methods,
28% from carbon dioxide flooding,
12% from natural gas flooding,
4.5% was from nitrogen flooding.

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Removing N2 from natural gas
Process Flow range Complexity Heavy Stage of
MMscfd hydrocarbon development
(MSm3/d) recovery
Distillation > 15 Complex In product Mature
gas
Pressure 2 – 15 Simple: batch In regeneration Early
Swing operation gas Commercial
Adsorption
(PSA)
Membrane 0.5 – 2.5 Simple: In product Early
continuous gas Commercial
operation

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Conventional Cryo Process

Adapted from Figure 12.15,

Fundamentals of Natural Gas Processing, 2nd ed.
Kidnay, Parrish, & McCartney

Updated: January 4, 2019

Copyright © 2019 John Jechura ([email protected]) 8
Conventional Cryo Process

Updated: January 4, 2019

Copyright © 2019 John Jechura ([email protected]) 9
Distillation
nitrogen

normal boiling point, oF

VERY COLD
nitrogen + methane feed N2 -320

CH4 -259

methane

Updated: January 4, 2019

Copyright © 2019 John Jechura ([email protected]) 10
Two-column cryogenic distillation

Adapted from Figure 13.1,

Fundamentals of Natural Gas Processing, 2nd ed.
Kidnay, Parrish, & McCartney

Updated: January 4, 2019

Copyright © 2019 John Jechura ([email protected]) 11
Adsorption – Modes of Regeneration
Temperature Swing Adsorption (TSA) Pressure Swing Adsorption (PSA)
▪ Increase temperature for ▪ Decrease pressure for regeneration
regeneration ▪ Good for enriching streams
▪ Good for trace impurities with high ▪ Components have low heat of
heat of adsorption adsorption
▪ Rapid cycles (seconds to few
minutes)

Updated: January 4, 2019

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Adsorption

Updated: January 4, 2019

Copyright © 2019 John Jechura ([email protected]) 13
Adsorption

Updated: January 4, 2019

Copyright © 2019 John Jechura ([email protected]) 14
Adsorption

Updated: January 4, 2019

Copyright © 2019 John Jechura ([email protected]) 15
Adsorption

Updated: January 4, 2019

16
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Membranes
Composite membrane structure used to separate nitrogen from
natural gas
▪ Membrane is a silicone rubber/polyetherimide (PEI) composite

Updated: January 4, 2019

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Membranes
Membrane unit to treat gas containing 8 - 16% N2 to bring it to
Btu gas specifications and 5 to 10% N2 in the treated stream.

Adapted from Figure 13.2,

Fundamentals of Natural Gas Processing, 2nd ed.
Kidnay, Parrish, & McCartney

Updated: January 4, 2019

18
Copyright © 2019 John Jechura ([email protected])
Trace-Component Recovery or
Removal

Updated: January 4, 2019

Copyright © 2017 John Jechura ([email protected])
Possible trace components
Hydrogen Helium
▪ Rare unless refinery cracked gas ▪ Valuable!
is fed to plant
Mercury
Oxygen
▪ Mechanical damage to brazed
▪ Not naturally occurring. Major aluminum exchangers
source – leaks in sub-
atmospheric gathering systems BTEX (benzene, toluene,
Radon (NORM) ethylbenzene, and xylene)
▪ Solids collect on pipe walls & ▪ Aromatic emissions from TEG &
inlet filters amine vents

Arsenic
▪ Toxic nonvolatile solid

Updated: January 4, 2019

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Oxygen
Oxygen issues
▪ Enhances pipeline corrosion
▪ Forms heat stable salts (HSS) with amines
▪ Forms corrosive acidic compounds with glycols
▪ Forms water with heavy hydrocarbons during reactivation of adsorbent
beds
Oxygen removal techniques
▪ Non-regenerative scavengers
▪ Catalytic reaction to form water and CO2 (H2O removed in dehydration
process)
• Sulfur compounds poison oxidation catalysts

Updated: January 4, 2019

Copyright © 2019 John Jechura ([email protected]) 21
Radon (NORM)
Naturally Occurring Radioactive Material
Natural gas contains Radon (Ra222) at low concentrations
▪ gas is rarely health problem
▪ half-life of about 3.8 days
Radon gas → radioactive solids
Ra222 → Po218 → Pb214 → Bi214 → Po214 → Pb210 → Bi210 → Po210 → Pb206
3.8 d 3.0 m 27 m 20 m 164 ms 22.3 yr 5.0 d 138 d

Solids collect on pipe walls & inlet filters

Scale generates large quantities of low-level radioactive waste
which must be discarded in disposal wells.

Updated: January 4, 2019

Copyright © 2019 John Jechura ([email protected])
Arsenic
Toxic nonvolatile solid
Predominately trimethylarsine (As(CH3)3)
Typically collects as fine grey dust

Removed from gas using nonregenerative adsorption

Facilities reduce concentrations in sweet raw gas from 1,000 to
less than 1g/m3

Updated: January 4, 2019

Copyright © 2019 John Jechura ([email protected]) 23
Helium
Valuable!
Pressure or Welding
Purge 13% Breathing
Natural gas most viable source 18% Mixtures
2%
“Helium-rich” gas > 0.3 vol%
helium Controlled
Other Atmospheres
▪ Rarely > 5 vol% 13% 18%

United States (2003) produced Leak Detection

84% of world production of 4%

Grade-A helium (99.995% purity) Cryogenics

▪ Remainder from Algeria, Poland 32%

& Russia. Adapted from Figure 14.4, 2008 H3 Uses in the U.S.,
Fundamentals of Natural Gas Processing, 2nd ed.
Kidnay, Parrish, & McCartney
New large helium plants:
▪ Qatar (2005)
▪ Darwin, Australia (2007)

Updated: January 4, 2019

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Feed compositions to Ladder Creek (mol %)
He-Rich Gas He-Lean Gas
Nitrogen 61.92 31.58
Helium 3.54 1.81
Carbon Dioxide 0.98 0.91
Methane 26.65 52.84
Ethane 2.60 6.40
C3+ 4.30 6.46

N2/He ratio 17.49 17.45

Updated: January 4, 2019

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Helium recovery plant (Ladder Creek)

Adapted from Figure 14.5,

Fundamentals of Natural Gas Processing, 2nd ed.
Kidnay, Parrish, & McCartney

Updated: January 4, 2019

Copyright © 2019 John Jechura ([email protected]) 26
Mercury
Two major problems of mercury in natural gas
▪ amalgam formation with aluminum
▪ environmental pollution - compounds readily absorbed by most biological
systems
May be present as
▪ elemental mercury
• Majority will condense in cryogenic section
▪ organometallic compounds, CH3HgCH3
(dimethylmercury),CH3HgC2H5(methylethylmercury), C2H5HgC2H5
(diethylmercury)
• Will concentrate in hydrocarbon liquids
▪ inorganic compounds such as HgCl2

Updated: January 4, 2019

Copyright © 2019 John Jechura ([email protected]) 27
Typical mercury levels
Location Elemental Mercury Concentration
in micrograms/Nm3 (ppbv)
South America 69 – 119 (8 to 13)
Far East 58 – 93 (6 to 10)
North Africa 0.3 – 130 (0.03 to 15)
Gronigen (Germany) 180 (20)
Middle East 1 – 9 (0.1 to 1)
Eastern US Pipeline 0.019 - 0.44 (0.002 to 0.05)
Midwest US Pipeline 0.001 - 0.10 (0.0001 to 0.01)
North America 0.005 - 0.040
(0.0005 to 0.004)

Updated: January 4, 2019

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Copyright © 2019 John Jechura ([email protected])
Mercury removal processes
Nonregenerative chemisorption
▪ Removes elemental mercury to < 0.01g/Nm3
▪ Typical bed capacities > 10%
▪ Most use sulfur impregnated on high surface area support
Regenerative chemisorption (1 process)
▪ Silver on mole sieve chemisorbs elemental mercury and dehydrates at the
same time
▪ Can be added to existing dehydration unit
▪ Generates mercury waste stream

Updated: January 4, 2019

Copyright © 2019 John Jechura ([email protected]) 29
Mercury Recovery
No Treatment of Regeneration Gas

Updated: January 4, 2019

Copyright © 2019 John Jechura ([email protected]) 30
Mercury Recovery
Treatment of Regeneration Gas

Updated: January 4, 2019

Copyright © 2019 John Jechura ([email protected]) 31
BTEX:
Benzene, Toluene, Ethylbenzene, Xylenes
Possible problems:
▪ Freeze out and plugging in cryogenic units
▪ Excessive aromatic hydrocarbon emissions
• Venting from TEG regenerator largest source
• Venting from amine regenerators lesser source
• Recovery systems eliminate problem

Updated: January 4, 2019

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Copyright © 2019 John Jechura ([email protected])
BTEX Absorption in glycol dehydrators
TEG absorbs aromatic (BTEX) hydrocarbons
▪ Absorption enhanced at low temperatures, high TEG concentrations, and
higher circulation rates
▪ Most of the absorbed BTEX vented with steam at top of regeneration
column
BTEX Emission Control Methods
▪ Adjusting glycol unit operating conditions to minimize the quantity of BTEX
absorbed
▪ Burning glycol still offgases prior to venting
▪ Condensing glycol offgases and recovering BTEX as a liquid product
▪ Adsorbing BTEX on a carbon adsorbent

Updated: January 4, 2019

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Copyright © 2019 John Jechura ([email protected])
Summary

Updated: January 4, 2019

Copyright © 2017 John Jechura ([email protected])
Summary
Nitrogen removal to improve calorific value of gas and/or use for
EOR gas injection
▪ Large scale removal by cryogenic distillation
Trace component removal
▪ Mercury removal upstream of brazed aluminum exchangers in cryogenic
sections
▪ Control of BTEX in gas emissions – air quality concerns
▪ Helium recovery by cryogenic distillation
• Even small concentrations could make the helium more valuable than
the remaining natural gas & NGLs

Updated: January 4, 2019

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Copyright © 2019 John Jechura ([email protected])
Supplemental Slides

Updated: January 4, 2019

Copyright © 2017 John Jechura ([email protected])
Commercial unit sold to Towne Exploration
for treating gas containing 8-16% nitrogen.

Updated: January 4, 2019

37
Copyright © 2019 John Jechura ([email protected])
Comparison Design & Actual Performance
First of Towne Exploration’s Commercial Nitrogen-Separation Membrane Units
at Rio Vista, California (August 25, 2007).

Updated: January 4, 2019

38
Copyright © 2019 John Jechura ([email protected])