Advanced Mercury Removal Technologies

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 world’s ethylene plants

are naphtha fed3. Catalyst protection• Many precious metal catalysts are

susceptible to mercury poisoning• 1:1 Hg amalgams with Pt, Pd are

stable at temperatures <150oC

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

measured

UOP 5241G-02

Natural Occurrence of Mercury Compounds in Hydrocarbon Streams

Natural Gas Condensate

Crude Oil

Elemental Dominant

Some organic

Trace organic

Trace ionic

Some ionic

Trace suspended

Trace suspended

Some suspended

Types of HgElementalOrganic

IonicSuspended

UOP 5241G-03

Natural Gas Mercury Levels

N. Africa1-130μg/Nm3N. Africa1-130μg/Nm3

Gulf

Asia-Pacific200-2,000μg/Nm3

Off-ShoreThe Americas1-100μg/Nm3

Australia50-200μg/Nm3

Europe1-500μg/Nm3

UOP 5241G-04

Existing Mercury Removal Technologies

Sulphur Impregnated

Activated Carbon

Technology Non-regenerablefixed bed

Reactor fill volume

Larger

Contributory ΔP HighCapex HighFlow-sheet location

Dry gas

Disposal No use

Stability Sulphur dissolution

Silver Impregnated

Molecular Sieve

Regenerablefixed bedSmaller

LowestLowest

In mol sieve dryer vessels

Hg-free

Very stable

Metal (Copper) Oxides and Sulphides

Non-regenerablefixed bedMedium

LowLow

Flexible

Fully recyclable

Very stable

UOP 5241G-05

UOP Hg Removal Product Range

UOP HgSIVTM products are silver promoted zeolitesGB products are copper basedMultiple products for different

requirements

Liquids and gases treatedMany contaminants removed

Regenerative Hg removalUOP HgSIV 3

Hg from H2S-containing liquid HCGB 346Hg from non H2S-containing HCGB 346SHg from H2S-containing gasGB 562Hg from non H2S-containing gasGB 562SDedicated co-removal of S and HgGB 566

Regenerative Hg removalUOP HgSIV 1ApplicationProduct

Regenerative molecular sieve productsNon-regenerative GB products

UOP 5241G-06

“Must Have” GB Product Features

Feature BenefitsLarge pore volume Superior Hg capacity. Better

resistance to liquid carry-overSpecifically engineered pore size distribution

Superior Hg capacity

High surface area substrate Superior Hg capacityHighly dispersed active phase Superior pick-up capacityHigh crushing strength Low & stable pressure drop

with plug flow & no channelling

High attrition resistance 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

Raw Natural Gas

CO2 Removal Dryers

Feed Gas SeparatorUOP MOLSIVTM

Adsorbents

Activated carbon MRU

Downstream of the Dryers

UOP 5241G-09

Raw Natural Gas

CO2 Removal Dryers

Feed Gas Separator UOP MOLSIVTM

Adsorbent

UOP HgSIVTM

Adsorbent

In the Dryers

UOP 5241G-10

Raw Natural Gas

CO2 Removal Dryers

UOP HgSIVAdsorbent

UOP MOLSIVAdsorbents

UOP GB MRU

In the Dryers & on the Regeneration Gas

Feed Gas Separator

UOP 5241G-11

Raw Natural Gas

CO2 Removal Dryers

Feed Gas Separator

UOP MOLSIVAdsorbents

UOP GB MRU

Upstream of the Amine and Dryer Units

UOP 5241G-12

CuS

Alumina

Two distinct components– Copper is present in

a finely divided CuOcrystallite phase

– Alumina substrate Optimised pore size

distribution facilitating undisturbed flow of liquid hydrocarbons High surface area,

internal porosity and accessibility of the CuOphase is key to transport Hg through GB product

GB Product Morphology & Chemistry

2CuS + Hg HgS + Cu2SUOP 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-overPore Size Distribution

of an Ideal MRU Product

00.10.20.30.40.50.6

10 100 1000 10000 100000 Pore Width, A

Cum

ulat

ive

Pore

Vo

lum

e, c

c/g

Large macro pores are preferable in handling

liquid carry-over

UOP 5241G-14

GB Pore Size Distribution Comparison

Pore Features of GB and Competitor Product

0

0.1

0.2

0.3

0.4

0.5

0.6

10 100 1000 10000 100000

pore width, A

Cum

ulat

ive

Pore

Vol

ume,

cc/g

UOP -GB-Competitor

UOP GB Product has a balanced pore size distribution with more macro pores

UOP 5241G-15

38ppmV H2S300 μg/NM3 Hg

<0.1ppmH2S (6months)<0.01μg/NM3Hg

GB 562GB 562

Case Study 1: Gas Phase GB-562 PTT GSP-5 S-Up March 2008 Flow-rate 265MMSCFD/vessel Operating pressure 48 Kg/cm2

Operating temp 18°C 4 year design life Replaced carbon

UOP 5241G-16

Case Study 1: Continued

PTT GSP-5 MRU GB-562

0102030405060708090

100110120130140150

0 1 2 3 4 5 6 7 8 9 10 11 12

Months On Line

Mer

cury

Con

cent

ratio

n μg

/NM

3

MRU InletMRU Outlet

UOP 5241G-17

<0.1ppmVH2S <0.01μg/NM3 Hg

5ppmV H2S 10μg/NM3 Hg

GB 566

Case Study 2: Gas Phase GB 566

Gas processorEthaneOperating temperature 35-40 °COperating pressure 13Kg/cm2

Flow 73,000 Kg/HStart-up December 200812 months lifetime [H2S]>10 year lifetime [Hg]

UOP 5241G-18

<10ppbW Hg

<20ppbW H2S

<10ppbW AsH3

3.5ppmW Hg

1.0ppmW H2S

1.0ppmW AsH3

GB 346

GB 238

Case Study 3: Liquid Phase GB-346

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

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-overMercury measurement techniques need to provide

dependable, accurate and precise analytical data Secure and reliable mercury recovery is essential

UOP 5241G-21

UOP 5241G-22