PRODUCED WATER TREATMENT

Shale Gas in North America

Shale Gas Formations

Generally the shale formations in eastern US are dry. The produced water (Flow Back) is very salty TDS 100,000 to 200,000 ppm. In the western states the produced water is much lower in TDS 10,000 to 35,000 ppm. However, the shale is wet and a typical well will produce 100 to 200 bls/day for the life of the well.

CHARACTERISTICS OF PRODUCED WATER

Produced Water Management Requires a Customized Approach

Produced water characteristics and flows depend on:
Geographic location Geological formation Type of hydrocarbon being produced Lifetime of the reservoir Well operations (chemicals used) Produced water flow rates TSS and O&G concentration TDS concentration TOC concentration and its nature (PAH, Phenols, BTEX, etc) Metal concentrations Final treated water destination (discharge or reuse)

Main parameters needed to engineer a solution are:

VEOLIA PRODUCED WATER TREATMENT SOLUTIONS

Treatment Solutions depend on final use of the treated water

Reuse for reinjection purposes Reuse as Boiler Feed Water Discharge into surface water bodies Surface Irrigation Due to the high salinity of the Produced Water almost all treatment solutions require the use of either Evaporation or Reverse Osmosis.

Flow Back and Produced Water from Deposits in Eastern United States
Is generally substantially less than the amount of water used to frac the well. Very high TDS. Can be used to frac the next well to be drilled. Scaling compounds hardness and barium can be removed by lime softening. Can be treated for disposal by evaporation and crystallization.

Multiflo Lime Softener

Typical Evaporators

Brine Evaporator ZLD mode

NCG Vent Deaerator Chemicals Compression Device Brine Evaporator

Feed

Concentrated Brine

Feed Tank Recovered Water Feed Preheater

Level Tank Recirculation Pump

Seed Recycle

ZLD pilot testing (Marcellus)

Marcellus shale produced water
Brine crystallizer systems Capacities ranging from 50 to greater than 1,200 gpm 180,000 ppm TDS in produced water

Result: Salt able to be landfilled

Flow Back and Produced Water from Deposits in Western United States
Is generally substantially more than the amount of water used to frac the well. TDS: 10,000 35,000 ppm Can be treated by Reverse Osmosis (RO) and used as drilling mud, frac water or be discharged to the environment. Reject from RO can be treated for disposal by evaporation and crystallization.

Reverse Osmosis can:

Produce product water suitable for frac water, drilling mud or discharge to the environment. RO reject water (brine) can be evaporated in ponds, deep well injected or evaporated and crystallized in equipment designed for that propose. Approx 10 25% of the total influent flow.

Reverse Osmosis cannot:

Tolerate any Free Oil & Grease in the feed water: this would create fouling problems Tolerate high COD concentrations (8000mg/l max if pH>10, 350 mg/l max if 6<pH<9.5) in the reject: this would create fouling problems and organics breakthrough in the permeate Tolerate any hardness and alkalinity in the feed water if RO runs at high pH (>10): this would create scaling problems

Example of RO System

Produced Water Contains Organics

BTEX Aliphatic Hydrocarbons (Hexane Extractables - FOG) Poly Aromatic Hydrocarbons (PAH) Alcohols, ethers, ketones and phenols Low molecular weight organic acids High molecular weight organic acids

High Molecular Weight Organic Acids are the Problem:

Typically they are very weak acids and do not ionize well at neutral pH. The molecular weight range allows them to pass though a UF membrane, but not though an RO membrane. They are not very soluble in water as the concentrate up in the RO reject they precipitate on the membrane and foul the surface.

Methods to pretreat PW for RO feed

Remove the free oil and solubilize the organic acids by raising the pH of the RO Feed OPUS.
Requires all free oil to be removed. Requires all of the hardness to be removed. Requires most of the alkalinity be removed.

Remove the organics from the RO feed MPPE & NEOSEP MBR.
BTEX, PAH, and most biotoxic compounds can be removed with the MPPE process. The water is then treated with aerobic bacteria and ultra filtered .

OPUS TECHNOLOGY HIGH PH RO

OPUS Technology

OPUS - II - Next Generation Product

OPUS Technology - Applicability

When high water recovery rates are specified. When the quality of the treated effluent has to meet stringent limits (when OPUS is coupled with IX Ammonia removal and chemical oxidation of the permeate). When the COD present in the raw influent is mostly nonbiodegradable (BOD5/COD < 0.2). When the COD concentration in the reject is not too high (< 8000 mg/l: this means a COD in the raw influent of about 1000 2000 mg/l depending on the recovery rate). When the Hardness concentration in the raw influent is not too high (<250 mg/l). When TDS < 30,000 mg/l (above this value evaporation is recommended if a high quality permeate is needed). In ZLD applications combined with a reject crystallizer.

OPUS - Chemicals, Utilities consumption and Waste generation

Parameter Hydrated Lime Caustic Soda Ash Polymer Coagulant Acids Salt Sludge generated (85% chemical) H2O2 Power Value (mg / liter of raw influent) 250 200 1300 1.5 5 1000 4000 50% dry solids after dewatering: 3000 mg of wet sludge / liter of raw influent 15 513 kWh/kbl.

Reject to injection well or evaporation ~ 20% of raw influent flow pond or crystallizer

OPUS Technology - Benefits

High System Recovery Rates 70 - 90%+ depending on TDS Effective Fouling Control Bio-Fouling, Organic Fouling, Particulate Fouling Effective Scaling Control Silica, Calcium Salts, Metal Salts Ability to Handle Variations in Feed Water Quality TSS, Total Hardness, Silica, etc High Salt Rejection Silica > 99.9%, Boron > 99.4%, TOC > 99% No need for biological system Low risk of process upsets even in presence of shock loads or toxics Reliable Operation with Minimal Downtime

Chevron, San Ardo, CA

MPPE + MBR + RO ORGANIC REMOVAL BEFORE RO

MPPE & MBR System

MPPE process

MPPE effect on chemical composition

Compounds
Dispersed oil = Dispersed hydrocarbons = Dispersed Aliphatics = floating Dissolved hydrocarbons 100 - 800 Toxic: - Benzene - Toluene Aromatics - Ethyl benzene - Xylene 0.2 - 6 - PAHs and NPDs 0.1 - 0.2 - Alkyl Phenols Dissolved hydrocarbons Readily Biodegradable Polar: - Acids - Alcohols (Methanol)

ppm
40 - > 100

Composition

MPPE

DA

B T E X PAHs PAHs A Ph Polar

E X

100 1000

Polar Polar

MPPE demo unit

MPPE + MBR + RO Process - Applicability

When high water recovery rates are specified When the quality of the treated effluent has to meet stringent limits When the raw influent COD concentration is > 1500 mg/l and the BOD5/COD > 0.2 (COD is biodegradable) When TDS < 30,000 mg/l (above this value evaporation is recommended) When a lower COD reject stream needs to be generated In ZLD applications combined with a reject crystallizer When low molecular weight organics are present in high concentrations (benzene, methanol, etc)

MPPE+MBR+RO - Chemicals, Utilities consumption and Waste generation

Parameter Polymer Coagulant Phosphoric Acid Sludge generated (80% biological) Value (mg / liter of raw influent) 0 - 10 5 5 900 (consider 20% dry solids after dewatering: 4500 mg of wet sludge / liter of raw influent) 0.07 kg/bbl 770 kWh/kbbl ~ 20% of raw influent flow

Low Pressure Steam Power Reject to injection well or evaporation pond or crystallizer

MPPE + MBR + RO Process - Benefits

No need for hardness removal upfront MPPE can remove, BTEX, Bio-toxics and many Refractory Organics. MPPE can remove both dispersed and dissolved hydrocarbons. The extracted hydrocarbons are recovered as oil not sludge. Bacteria can cheaply oxidize most of the soluble organic compounds (COD) to carbon dioxide. RO membranes last longer. RO feed has lower membrane fouling tendencies. Lower risks of organics or ammonia leakage through the membranes. RO reject contains lower COD concentrations.

Zero Liquid Discharge System

Submerged Ultrafiltration

Biotreater

Reverse Osmosis Evaporation

MPPE Units at Pluto gas field

Burrup LNG park, Australia

22/08/2011

3 7

DBO approximate costs per barrel of Raw Produced Water Treated over 18 years
TECHNOLOGY Cost ($/bbl)

On site Evaporation (mobile units) On site RO based process (Deoling + OPUS or Deoling+ MPPE+MBR+RO) Off site Crystallization

3-4 2 -3 4-5