Advanced Mercury Removal Technologies

2009 UOP LLC. All rights reserved.

UOP 5241G-01

Why Remove Mercury?

1. Equipment Protection

2. Improving product quality

Mercury found in refinery naphtha >50% of worlds ethylene plants are naphtha fed

4. HS&E
TLV Limit = 0.025 mg/m3 air >> 1.0 mg/m3 has been 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 Organic Ionic Suspended

Some ionic Trace organic Trace suspended

Crude Oil

UOP 5241G-03

Natural Gas Mercury Levels

Europe
1-500g/Nm3

N. Africa
3 1-130g/Nm3

Asia-Pacific
200-2,000g/Nm3

The Americas
1-100g/Nm3

Gulf Off-Shore

Australia
50-200g/Nm3
UOP 5241G-04

Existing Mercury Removal Technologies

Sulphur Impregnated Activated Carbon Non-regenerable fixed bed Larger High High Dry gas No use Sulphur dissolution Silver Impregnated Molecular Sieve Regenerable fixed bed Smaller Lowest Lowest In mol sieve dryer vessels Hg-free Very stable Metal (Copper) Oxides and Sulphides Non-regenerable fixed bed Medium Low Low Flexible Fully recyclable Very stable
UOP 5241G-05

Technology Reactor fill volume Contributory P Capex Flow-sheet location Disposal Stability

UOP Hg Removal Product Range

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

UOP HgSIVTM products are Liquids and gases treated silver promoted zeolites Many contaminants removed GB products are copper based Regenerative molecular sieve products Multiple products for different requirements Non-regenerative GB products
UOP 5241G-06

Must Have GB Product Features

Feature
Large pore volume Specifically engineered pore size distribution High surface area substrate Highly dispersed active phase High crushing strength High attrition resistance

Benefits
Superior Hg capacity. Better resistance to liquid carry-over 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 a finely divided CuO crystallite phase Alumina substrate Optimised pore size distribution facilitating undisturbed flow of liquid hydrocarbons High surface area, internal porosity and accessibility of the CuO phase is key to transport Hg through GB product

Alumina

CuS

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
Cumulative Pore Volume, cc/g

0.5 0.4 0.3 0.2 0.1 0 10 100 1000 10000 100000

UOP 5241G-14

Large macro pores are preferable in handling liquid carry-over

Pore Width, A

GB Pore Size Distribution Comparison

Pore Features of GB and Competitor Product

0.6
Cumulative Pore Volume, cc/g

0.5 0.4 0.3 0.2 0.1 0

10 100 1000 pore width, A

UOP -GBCompetitor

10000

100000

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 18C S-Up March 2008 4 year design life Flow-rate 265MMSCFD/vessel Replaced carbon Operating pressure 48 Kg/cm2
38ppmV H2S 300 g/NM3 Hg

GB 562

GB 562

<0.1ppmH2S (6months) <0.01g/NM3Hg

UOP 5241G-16

Case Study 1: Continued

PTT GSP-5 MRU GB-562
150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 0 1 2 3 4 5 6 7 8 9 Months On Line
UOP 5241G-17

Mercury Concentration g/NM 3

MRU Inlet MRU Outlet

10 11 12

Case Study 2: Gas Phase GB 566

Gas processor Ethane Operating temperature 35-40 C Operating pressure 13Kg/cm2 Flow 73,000 Kg/H Start-up December 2008 12 months lifetime [H2S] >10 year lifetime [Hg]
<0.1ppmVH2S <0.01g/NM3 Hg

GB 566

5ppmV H2S 10g/NM3 Hg

UOP 5241G-18

Case Study 3: Liquid Phase GB-346

<10ppbW Hg <20ppbW H2S

Oil refiner Successful operation since 2006 70% propylene / 30% propane Flow-rate 14,000 Kg/H Operating temperature 35 C Operating pressure 2045 KPaG

<10ppbW AsH3

GB 238

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 g/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 600C 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