MEMBRANE TECHNOLOGY TREATING OILY WASTEWATER FOR REUSE

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1 MEMBRANE TECHNOLOGY TREATING OILY WASTEWATER FOR REUSE Jeff Peeters, P.Eng. ZENON Environmental Inc. SAWEA 2005 Workshop Al-Khobar Holiday Inn Hotel, Saudi Arabia November 29, 2005

2 Presentation outline Why are refineries considering wastewater reuse? Conventional refinery wastewater treatment Why use membranes? Membrane basics Membrane process configurations: Tertiary filtration Membrane bioreactor (MBR) Case studies: PEMEX Refinery, Mexico Marathon Ashland Petroleum Marine Repair Terminal, USA Conclusions

3 Why are refineries considering wastewater reuse? Regulatory increasingly stringent effluent quality requirements Supply diminishing freshwater resources Economic Opportunity to save on cost of process water and wastewater treatment (chemical consumption, activated carbon, sludge handling) Technology state-of-the-art membrane treatment meets wastewater reuse quality requirements

4 Conventional refinery wastewater treatment Influent Effluent to discharge API/DAF Aeration basin Secondary clarifier Sand filter and/or carbon adsorption Conventional flowsheet for refinery wastewater treatment for discharge

5 Why use membranes? Replace clarifiers for solid/liquid separation Ensure effluent is free of suspended solids Ensure complete removal of biologically degradable COD and TOC, including improved removal of refractory organics Reduce the footprint required for wastewater treatment Provide sufficient treatment for direct feed to RO for reuse in the refinery process Absolute barrier not subject to process upsets

6 Membrane basics

7 Membrane basics The filtration spectrum

8 Membrane basics Vacuum (1 to 10 psi) Treated effluent Solids Electron microscope view of membrane surface Reinforced structure Hollow fiber

9 Membrane basics

10 Membrane basics Membrane module Membrane cassette

11 Membrane basics

12 Membrane basics Backpulse tank Wastewater feed Immersed membranes Air injection Backpulse flow Membrane tank Treated effluent Waste

13 Membrane process configurations Tertiary filtration Membrane bioreactor (MBR)

14 Tertiary filtration vs. MBR Conventional Influent API/DAF Aeration basin Secondary clarifier Sand filter and/or carbon adsorption Effluent to discharge

15 Tertiary filtration vs. MBR Conventional Influent API/DAF Aeration basin Secondary clarifier Sand filter and/or carbon adsorption Effluent to discharge Tertiary Filtration Influent API/DAF Aeration basin Secondary clarifier Membrane filtration High quality effluent to reuse or RO feed

16 Tertiary filtration vs. MBR Conventional Influent API/DAF Aeration basin Secondary clarifier Sand filter and/or carbon adsorption Effluent to discharge Tertiary Filtration Influent API/DAF Aeration basin Secondary clarifier Membrane filtration High quality effluent to reuse or RO feed Membrane Bioreactor Influent API/DAF Aeration basin Membrane filtration High quality effluent to reuse or RO feed

17 Tertiary filtration vs. MBR Tertiary filtration Readily integrated into an existing wastewater treatment process Can be applied to only a portion of the wastewater flow Generates a reject stream that must be properly managed

18 Tertiary filtration vs. MBR Tertiary filtration Readily integrated into an existing wastewater treatment process Can be applied to only a portion of the wastewater flow Generates a reject stream that must be properly managed Membrane bioreactor (MBR) Optimized biological treatment process Reduced reactor volumes Improved removal of refractory organics (increased SRT) Integration of biological treatment and filtration Improved process resiliency

19 PEMEX Refinery, Mexico Case studies Marathon Ashland Petroleum Marine Repair Terminal, Kentucky

20 PEMEX Refinery, Mexico Tertiary treatment of combined refinery effluent as pretreatment for RO Located in Minatitlan, Mexico at one of Mexico s largest refineries (173,200 bpd) Wastewater treatment for reuse in the refinery overall water recycle efficiency is 70% RO permeate reused for cooling tower makeup and low-pressure boiler feed Treatment capacity of 6.8 MGD Commissioned in November 2001 Drivers process reliability, cost savings

21 PEMEX Refinery, Mexico

22 PEMEX Refinery, Mexico UF membrane process trains in treatment building

23 PEMEX Refinery, Mexico UF membrane process trains

24 PEMEX Refinery, Mexico UF membrane process equipment

25 PEMEX Refinery, Mexico UF system performance data Secondary Treated effluent, effluent to UF RO feed BOD (mg/l) 50 < 5 TSS (mg/l) 200 < 1 Turbidity (NTU) 25 < 0.1 SDI (-) N/A < 3.0

26 PEMEX Refinery, Mexico Reverse Osmosis system performance data UF effluent, RO RO permeate feed????????????????????????

27 PEMEX Refinery, Mexico 3-1/2 years of operating experience Consistent effluent quality for RO pre-treatment RO cleaning 2-3x per year Membrane recovery with cleaning following heavy free oil fouling event Membranes in FOG process upset condition Membranes recovered after cleaning

28 Marathon Ashland Petroleum Marine Repair Terminal, Kentucky MBR treatment of oily wastewater Located in Catlettsburg, Kentucky Treats wastewater from marine repair terminal (i.e.: oily wastewater from barge wash down) Treatment capacity of 50,000 gpd Severe variations in wastewater composition due to different crudes carried by barges Wastewater treated to reuse quality, however reuse infrastructure is not yet in-place Commissioned in July 2003

29 Marathon Ashland Petroleum Marine Repair Terminal, Kentucky Barge water Grit handler Equalization tank Oil coalescer ph adjustment Treated effluent to reuse or discharge Final effluent tank Arsenic filters UF membranes Bioreactor tank

30 Marathon Ashland Petroleum Marine Repair Terminal, Kentucky Membrane equipment building

31 Marathon Ashland Petroleum Marine Repair Terminal, Kentucky Pre-treatment processes Membrane equipment

32 Marathon Ashland Petroleum Marine Repair Terminal, Kentucky Raw wastewater Treated effluent BOD (mg/l) 775 < 5 COD (mg/l) 1,000 < 300 TSS (mg/l) 66 N/D TFOG (mg/l) 165 N/D BTEX (mg/l) 10 < 0.7

33 Marathon Ashland Petroleum Marine Repair Terminal, Kentucky 1-1/2 years of operating experience Membranes have not required cleaning to-date Membrane system able to handle severe variations in flow and wastewater composition > 95% removal of BTEX compounds Full compliance for discharge to POTW

34 Conclusions Demands exist for wastewater reuse in the petroleum industry Immersed hollow fiber membranes fit the need to treat refinery wastewater to the levels required for reuse Immersed hollow fiber membranes are the state-of-the-art in the treatment of oily wastewater for reuse Full-scale membrane facilities treating oily wastewater exist proving the technical feasibility of this technology

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