Marcellus Shale Marcellus Shale Wastewaters Wastewaters

Management by Management by Resource Recovery Resource Recovery

Shale Gas Innovation ContestShale Gas Innovation Contest Ben Franklin Technology Partners Ben Franklin Technology Partners

April 13, 2012April 13, 2012Timothy Keister, CWT , Chief ChemistTimothy Keister, CWT , Chief Chemist

ProChemTech International, Inc.ProChemTech International, Inc.

51 ProChemTech Drive51 ProChemTech Drive

Brockway PA Brockway PA

Marcellus Shale Wastewaters Marcellus Shale Wastewaters

Each well produces Each well produces 200,000 to 1+ million 200,000 to 1+ million gallons of flowback gallons of flowback wastewater during wastewater during hydrofracture hydrofracture

Production wastewater Production wastewater is expected to average is expected to average 200 to 4000 gpd per 200 to 4000 gpd per wellwell

Shale wastewaters Shale wastewaters contain high levels of contain high levels of many constituents many constituents

The Marcellus Shale is the largest natural gas

development in North America

Marcellus Deposit Outlined in Blue

Typical Wastewater Typical Wastewater ChemistryChemistry

barium (toxic heavy metal) 6,500 mg/lcalcium 18,000 mg/lchloride 116,900 mg/liron 60 mg/lmagnesium 1,300 mg/lsodium 48,000 mg/lstrontium 4,000 mg/ldissolved solids 195,000 mg/ltotal hardness as CaCO3 54,500 mg/lsuspended solids 1,200 mg/l

Resource Recovery is the Resource Recovery is the Environmentally Sound Environmentally Sound

Means to Manage Means to Manage Marcellus Shale Marcellus Shale WastewatersWastewaters

ProChemTech International, Inc. has ProChemTech International, Inc. has

developed a sequential precipitation developed a sequential precipitation fractional crystallization technology fractional crystallization technology

that converts Marcellus shale that converts Marcellus shale wastewaters into salable commoditieswastewaters into salable commodities

Step 1 - ClarificationStep 1 - ClarificationAs flowback and As flowback and

production wastewaters production wastewaters are delivered to the are delivered to the

treatment facility, they are treatment facility, they are treated by passage treated by passage

through a free oil and through a free oil and solids separator, inclined solids separator, inclined

plate clarifier, as plate clarifier, as delivered. Clarified delivered. Clarified wastewater is then wastewater is then

pumped to an aerated pumped to an aerated chemical equalization chemical equalization

tank.tank.

Tank capacity is set to Tank capacity is set to equal daily system equal daily system

throughput. throughput.

Step 2 - First Precipitation Step 2 - First Precipitation

Clarified wastewater is pumped to a series of mix tanks where the following chemicals are added:

• sulfuric acid

• potassium permanganate

• sodium hydroxide

• anionic polymer

Step 3 - Barite RemovalStep 3 - Barite Removal Under the specific conditions of pH and Under the specific conditions of pH and

ORP obtained in the step 2 chemicalORP obtained in the step 2 chemical

additions, barium is completely additions, barium is completely precipitatedprecipitated

as a commercial purity barium sulfate.as a commercial purity barium sulfate.

Iron, manganese, and radioactives Iron, manganese, and radioactives presentpresent

are also removed and incorporated into are also removed and incorporated into thethe

barite. barite.

Radioactivity level of the barium sulfateRadioactivity level of the barium sulfate

is equal to commercial barite samplesis equal to commercial barite samples

• Precipitated barite is removed from the Precipitated barite is removed from the wastewater stream using an inclined wastewater stream using an inclined plate clarifier as a liquid sludge.plate clarifier as a liquid sludge.

• Liquid sludge is dewatered using a plate Liquid sludge is dewatered using a plate and frame filter press, washed, and frame filter press, washed, discharged, and air dried prior to sale discharged, and air dried prior to sale as commodity barite.as commodity barite.

• Barite use in the United States in 2004 Barite use in the United States in 2004 was about 2.65 million tons, 79% was about 2.65 million tons, 79% imported imported

Note: Our first barium sulfate system was Note: Our first barium sulfate system was designed and built in 1990 for MuRata designed and built in 1990 for MuRata ElectronicsElectronics

Step 4 - Strontium Recovery

Optionally, strontium can be recovered from the barium stripped wastewater by addition of sulfuric acid, sodium hydroxide, and anionic polymer under defined conditions to precipitate strontium sulfate. The strontium sulfate is then removed by an inclined plate clarifier, dewatered, and dried as the barium sulfate.

Step 5 - Factional Step 5 - Factional CrystallizationCrystallization

Distilled Water ProductionDistilled Water Production• Barium and strontium stripped wastewater is pumped to an evaporator-crystallizer• Steam from the evaporator-crystallizer is condensed using a heat exchanger to preheat the wastewater entering the unit - producing distilled water

• In the evaporator-crystallizer, the wastewater concentrates by water loss due to evaporation

• Of the three major salts present in the stripped wastewater, sodium chloride is the least soluble followed by magnesium and calcium chloride

• Sodium chloride fractionally crystallizes from the the concentrating wastewater and is removed by sidestream filtration

• At concentrated calcium chloride levels of above approximately 34%, the sodium chloride level has been reduced to less than 2.5%, resulting in a salable commodity calcium chloride solution

Step 6 Sodium Chloride Purification • Sodium chloride crystals removed

by sidestream filtration are washed with distilled water and dried• Fractional crystallization produces a very high quality sodium chloride product which is suitable for a large number of commercial uses• Sodium chloride use in the United State is many millions of tons per year

Step 7 Calcium Chloride Step 7 Calcium Chloride Product Process and Product Process and

Quality Control Quality Control • Commercial calcium chloride solution has to contain 28 to 40% calcium chloride by weight with less than 2.5% sodium chloride present. • The sidestream removed from the evaporator-crystallizer will be monitored by specific gravity, after sodium chloride crystal removal, and when within specification diverted to a calcium chloride solution holding tank• Energy recovery will be accomplished via preheat of the spent sodium chloride wash water as it is returned to the evaporator-crystallizer• Calcium chloride is 46 th volume chemical produced in United States

Current StatusCurrent Status

• Process has been laboratory bench tested on four actual production wastewaters and the products analyzed • A pilot scale unit is needed to confirm the laboratory testing and to provide data for process scale up to commercial sized units, PADEP pilot plant permit in final stage of approval• Major pilot plant question concerns specific design of evaporator - crystallization unit, which is the single most costly equipment item • Investors require pilot plant operation to prove viability of process and to generate product samples for buyer evaluation • Two process patents filed to date• Additional R&D is planned to examine bromine and lithium recovery

Late News Flash

The Program Committee of the International Water Conference has accepted the paper by

Timothy Keister titled “Sequential Precipitation - Fractional Crystallization

Treatment of Marcellus Shale Flowback and Production Wastewaters” for presentation at

the 73 rd Annual International Water Conference, San Antonio, TX, November, 2012

Thank You - Questions

PCT Sequential Precipitation Fractional Crystallization Process - Right to Left

raw water - barite - stripped brine - sodium chloride crystalcalcium chloride solution - distilled water