Advanced Mercury Removal

Technologies

© 2009 UOP LLC. All rights reserved. UOP 5241G-01

 Why Remove Mercury?
1. Equipment Protection

2. Improving product quality 4. HS&E

• Mercury found in refinery naphtha • TLV Limit = 0.025 mg/m3 air
• >50% of world’s ethylene plants • >> 1.0 mg/m3 has been
are naphtha fed measured
3. Catalyst protection
• Many precious metal catalysts are
susceptible to mercury poisoning
• 1:1 Hg amalgams with Pt, Pd are
stable at temperatures <150oC
UOP 5241G-02
Natural Occurrence of Mercury
Compounds in Hydrocarbon Streams
Natural Gas Condensate

Trace suspended Trace ionic Some organic

Some suspended

Elemental
Dominant

Types of Hg
Elemental Some ionic
Organic Trace organic
Ionic Trace suspended
Suspended
Crude Oil UOP 5241G-03
 Natural Gas Mercury Levels

Europe
1-500μg/Nm3

N. Africa
1-130μg/Nm33

Asia-Pacific
200-2,000μg/Nm3

Gulf
The Americas
1-100μg/Nm3 Off-Shore

Australia
50-200μg/Nm3

UOP 5241G-04
 Existing Mercury Removal Technologies

Sulphur Silver
Impregnated Impregnated Metal (Copper)
Activated Molecular Oxides and
Carbon Sieve Sulphides
Technology Non-regenerable Regenerable Non-regenerable
fixed bed fixed bed fixed bed
Reactor fill Larger Smaller Medium
volume
Contributory ΔP High Lowest Low
Capex High Lowest Low
Flow-sheet Dry gas In mol sieve Flexible
location dryer vessels
Disposal No use Hg-free Fully recyclable

Stability Sulphur Very stable Very stable

dissolution
UOP 5241G-05
UOP Hg Removal Product Range

Product Application
UOP HgSIV 1 Regenerative Hg removal
UOP HgSIV 3 Regenerative Hg removal
GB 346 Hg from H2S-containing liquid HC
GB 346S Hg from non H2S-containing HC
GB 562 Hg from H2S-containing gas
GB 562S Hg from non H2S-containing gas
GB 566 Dedicated co-removal of S and Hg

 UOP HgSIVTM products are  Liquids and gases treated

silver promoted zeolites
 GB products are copper based
 Multiple products for different
requirements
 Many contaminants removed
Regenerative molecular sieve products
Non-regenerative GB products
UOP 5241G-06
“Must Have” GB Product Features
Feature
Large pore volume
resistance to liquid carry-over
Specifically engineered pore
size distribution
High surface area substrate
Highly dispersed active phase
High crushing strength
High attrition resistance
Benefits
Superior Hg capacity. Better
Superior Hg capacity
Superior Hg capacity
Superior pick-up capacity
Low & stable pressure drop
with plug flow & no
channelling
No powder formation, no
downstream powder issues
UOP 5241G-07
Treatment Locations Within the Gas Plant

 Downstream of the dryers

 Inside the dryers
 On the regeneration gas from the dryers
 Upstream of the amine and dryer units

UOP 5241G-08
Downstream of the Dryers

Raw Natural Gas

Feed Gas Separator

UOP MOLSIVTM
Adsorbents

CO2 Removal Dryers

Activated carbon MRU

UOP 5241G-09
In the Dryers

Raw Natural Gas

Feed Gas Separator

UOP MOLSIVTM
Adsorbent

UOP HgSIVTM
Adsorbent
CO2 Removal Dryers

UOP 5241G-10
In the Dryers & on the Regeneration Gas

Raw Natural Gas

UOP GB MRU

Feed Gas Separator

UOP MOLSIV
Adsorbents

UOP HgSIV
Adsorbent
CO2 Removal Dryers

UOP 5241G-11
 Upstream of the Amine and Dryer Units

Raw Natural Gas

Feed Gas Separator

UOP GB MRU
UOP MOLSIV
Adsorbents

CO2 Removal Dryers

UOP 5241G-12
 GB Product Morphology & Chemistry

 Two distinct components

– Copper is present in
Alumina
a finely divided CuO
crystallite phase
– Alumina substrate
 Optimised pore size
distribution facilitating
undisturbed flow of CuS
liquid hydrocarbons
 High surface area,
internal porosity and
accessibility of the CuO
phase is key to transport
Hg through GB product

2CuS + Hg HgS + Cu2S

UOP 5241G-13
 GB Resistance to Liquid Carry-over
 More gas processors require the treatment of on and
off-shore raw gas streams close to their dew point
 Both liquid hydrocarbons and water can be an issue
with some MRU products
 Successful MRU products are developed to withstand
transient carry-over
Pore Size Distribution
of an Ideal MRU Product
0.6
0.5
Cumulative Pore
Volume, cc/g

0.4
0.3
0.2
0.1 Large macro pores are
preferable in handling
0 liquid carry-over
10 100 1000 10000 100000
Pore Width, A UOP 5241G-14
GB Pore Size Distribution Comparison

Pore Features of GB and Competitor Product

0.6
Cumulative Pore Volume,

UOP -GB-
0.5
Competitor

0.4
cc/g

0.3
0.2
0.1
0
10 100 1000 10000 100000
pore width, A
UOP GB Product has a balanced pore size distribution
with more macro pores
UOP 5241G-15
 Case Study 1: Gas Phase GB-562
 PTT GSP-5  Operating temp 18°C 38ppmV H2S
300 μg/NM3 Hg
 S-Up March 2008  4 year design life
 Flow-rate 265MMSCFD/vessel  Replaced carbon
 Operating pressure 48 Kg/cm2

GB 562 GB 562

<0.1ppmH2S (6months)
<0.01μg/NM3Hg
UOP 5241G-16
Case Study 1: Continued

PTT GSP-5 MRU GB-562

150
140
130
Mercury Concentration μg/NM 3

120
110
100
90
80
70
60
50
40
30
MRU Inlet
20
MRU Outlet
10
0
0 1 2 3 4 5 6 7 8 9 10 11 12
Months On Line

UOP 5241G-17
Case Study 2: Gas Phase GB 566

<0.1ppmVH2S <0.01μg/NM3 Hg
 Gas processor
 Ethane
 Operating temperature 35-40 °C
 Operating pressure 13Kg/cm2
 Flow 73,000 Kg/H GB 566

 Start-up December 2008

 12 months lifetime [H2S]
 >10 year lifetime [Hg]

5ppmV H2S 10μg/NM3 Hg

UOP 5241G-18
Case Study 3: Liquid Phase GB-346
<10ppbW Hg
<20ppbW H2S

 Oil refiner <10ppbW AsH3

 Successful operation since 2006

 70% propylene / 30% propane
 Flow-rate 14,000 Kg/H GB 238

 Operating temperature 35 °C
 Operating pressure 2045 KPaG
GB 346

3.5ppmW Hg
1.0ppmW H2S
1.0ppmW AsH3

UOP 5241G-19
Mercury Management:
From On Site Analysis to Hg Recovery
 Important to measure Hg to
0.01 μg/Nm3 at the plant site
 Each sample gathered and
analysed within hours
 Level of Hg quantified before
the analytical team departs
 Liquid analysis is available
 GB products are compatible
with Hg recovery processes
 Clients are placed in touch with
certified mercury recovery
outlets
 Hg is separated via retort oven
& vacuum distillation at 600°C
 Reclaimed Hg is used in
existing industries
 Copper waste goes to smelters
and is sold onto the open
market
UOP 5241G-20
UOP Mercury Removal Philosophy

 Gas processors need the choice of non-regenerable and

regenerable mercury removal options, as applicable
 Flexible flow-sheet location choices are paramount in
positioning an MRU
 Raw gas MRU technology should be able to resist
transient, episodic liquid carry-over
 Mercury measurement techniques need to provide
dependable, accurate and precise analytical data
 Secure and reliable mercury recovery is essential

UOP 5241G-21
UOP 5241G-22