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 fed 3. Catalyst protection Many precious metal catalysts are susceptible to mercury poisoning 1:1 Hg amalgams with Pt, Pd are stable at temperatures <150 o C 4. HS&E TLV Limit = 0.025 mg/m 3 air >> 1.0 mg/m 3 has been measured 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 1-500μg/Nm 3 The Americas 1-100μg/Nm 3 N. Africa 1-130μg/Nm 3 Gulf Off-Shore Asia-Pacific 200-2,000μg/Nm 3 Australia 50-200μg/Nm 3 UOP 5241G-04
Existing Mercury Removal Technologies Sulphur Impregnated Activated Carbon Silver Impregnated Molecular Sieve Metal (Copper) Oxides and Sulphides Technology Non-regenerable fixed bed Regenerable fixed bed Non-regenerable fixed bed Reactor fill volume Larger Smaller Medium Contributory ΔP High Lowest Low Capex High Lowest Low Flow-sheet location Dry gas In mol sieve dryer vessels Flexible Disposal No use Hg-free Fully recyclable Stability Sulphur dissolution Very stable Very stable UOP 5241G-05
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 H 2 S-containing liquid HC Hg from non H 2 S-containing HC Hg from H 2 S-containing gas Hg from non H 2 S-containing gas Dedicated co-removal of S and Hg UOP HgSIV TM products are silver promoted zeolites GB products are copper based Multiple products for different requirements Liquids and gases treated Many contaminants removed Regenerative molecular sieve products 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 MOLSIV TM Adsorbents CO 2 Removal Dryers Activated carbon MRU UOP 5241G-09
In the Dryers Raw Natural Gas Feed Gas Separator UOP MOLSIV TM Adsorbent CO 2 Removal Dryers UOP HgSIV TM Adsorbent 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 CO 2 Removal Dryers UOP 5241G-11
Upstream of the Amine and Dryer Units Raw Natural Gas Feed Gas Separator UOP GB MRU UOP MOLSIV Adsorbents CO 2 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 2CuS + Hg Alumina HgS + Cu 2 S CuS 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 Cumulative Pore Volume, cc/g 0.6 0.5 0.4 0.3 0.2 0.1 0 Pore Size Distribution of an Ideal MRU Product 10 100 1000 10000 100000 Pore Width, A Large macro pores are preferable in handling liquid carry-over UOP 5241G-14
GB Pore Size Distribution Comparison Cumulative Pore Volume, cc/g 0.6 0.5 0.4 0.3 0.2 0.1 0 Pore Features of GB and Competitor Product UOP -GB- Competitor 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 S-Up March 2008 Flow-rate 265MMSCFD/vessel Operating pressure 48 Kg/cm 2 Operating temp 18 C 4 year design life Replaced carbon 38ppmV H 2 S 300 μg/nm 3 Hg GB 562 GB 562 <0.1ppmH 2 S (6months) <0.01μg/NM 3 Hg UOP 5241G-16
Case Study 1: Continued Mercury Concentration μg/nm 3 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 PTT GSP-5 MRU GB-562 0 1 2 3 4 5 6 7 8 9 10 11 12 Months On Line MRU Inlet MRU Outlet UOP 5241G-17
Case Study 2: Gas Phase GB 566 Gas processor Ethane Operating temperature 35-40 C Operating pressure 13Kg/cm 2 Flow 73,000 Kg/H Start-up December 2008 12 months lifetime [H 2 S] >10 year lifetime [Hg] <0.1ppmVH 2 S <0.01μg/NM 3 Hg GB 566 5ppmV H 2 S 10μg/NM 3 Hg UOP 5241G-18
Case Study 3: Liquid Phase GB-346 <10ppbW Hg Oil refiner Successful operation since 2006 70% propylene / 30% propane Flow-rate 14,000 Kg/H Operating temperature 35 C Operating pressure 2045 KPaG <20ppbW H 2 S <10ppbW AsH 3 GB 238 GB 346 3.5ppmW Hg 1.0ppmW H 2 S 1.0ppmW AsH 3 UOP 5241G-19
Mercury Management: From On Site Analysis to Hg Recovery Important to measure Hg to 0.01 μg/nm 3 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
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