## ASSESSMENT OF COILCHEM’S WATER TREATMENT TECHNOLOGY

D. Steven Tipton, PE ALL Consulting, LLC August 2 6 , 2015

CoilChem, LLC is conducting a pilot test of their water treating technology for Brigham Resources, LLC at their Salty Brigham 10 1SW location in Pecos County, Texas. David Essman, a corporate sales representative for CoilChem invited me to see the test. Gavin James, a civil engineer for ALL Consulting and I visited the site on Augus t 1 9 , 2015. At the time, CoilChem was normally processing approximately 20,000 barrels of produced water per day to be used by Brigham for their hydraulic fracturing operations. For our visit the treatment rate had been reduced to approximately 10,000 BW PD so we
could view the inside of their weir tank while it was operating

. As can be seen in Figure 1, water samples that were collected at our request, show the water has been cleaned from dirty black
to clear. According to Danny Wesley, CoilChem’s presi dent, the processed water meets Brigham’s requirements for use in their slick water hydraulic fracturing; however, when asked, CoilChem could not provide us the water treatment specifications that Brigham is requiring them to meet.

In Brigham’s field produced water is either pumped through a pipeline gathering system or trucked to a 100,000 barrel settling pit where it gravity flows into a pretreatment pit. The pit shows evidence of considerable oil and iron sulfide floating on the surface (see Figure 2 ). Based on conversations with Danny Wesley, Brigham skims the pit from time to time to collect the oil . Water then moves into the second or pretreatment pit

. Based on CoilChem’s extremely small amount of oil recovery from the produced water the majority of oil is caught in the settling and pretreatment pits. Most of the large suspended solids are probably being caught in the same pits.

The water is pumped f rom the pretreatment pit to CoilChem’s processing equipment where it is cleaned using an accelerated oxidation process. The flow rate of the water is measured via a
turbine meter, a pH probe senses the pH of the water while metering pumps inject either ac id or
caustic soda to bring the pH of the water to 8 or above. Once this occurs a small volume of hydrogen peroxide is introduced into the water and the oxidati on red uction potential (ORP) is measured. Adjustments to the chemicals are made until the redo x potential reaches a value of at least a positive ORP with the pH at or above 8. At a pH above 8 the hydrogen peroxide begins Fig. 1 Comparison of produce water
before and after treatment

Figure 2 , Settling pi tto convert the soluble Fe 2 + to its insoluble form (Fe 3 + ) thus allowing the iron to be more readily

removed by coagulation and pr ecipitation in the weir tank.

The peroxide treatment also aids in destroying bacteria and removing dissolved solids such as organic pollutants, BOD, COD and reducing toxicity levels. This oxidative process additionally disrupts the water by releasing an o xygen molecule during the iron conversion process and producing a varying amount of hydroxyl free radicals. This not only destroys and converts many of the dissolved solids but it causes a reduction in the density of the water thereby helping the
small dr oplets of oil that are contained within the water to separate away from the main body of
the water.

The water is passed through a square tubing bundle (reactor) making directional changes within the bundle to further aid in the oil and solid particles disassociation from the water and eliminating the need for retention tanks commonly used in conventional water treatment. The square tubing is use d for the reactor and pressure conduit because the square shape generates a cavitation effect helping to destroy bacteria
and further disassociate the solids from the

water. The reactor is designed to operate at 50 psig to keep the hydrogen peroxide in sol ution thereby reducing the dosage requirements and enabling the oxidizer longer contact time with
elements within the water As the water is pumped through the reactor
at full rate

, the peroxide get distributed throughout the fluid. Th e operating pressure prevents hydrogen sulfide ( H 2 S ) from vaporizing out of the water thereby enabling the oxidizer to contact and destroy the H 2 S before it can reach a
gaseous state

. Once the reaction phase is completed

, the water flows into the weir
tank where the converted iron generates a pin flock that allows the solids to agglomerate and separate. This tank provides directional changes within the weirs that allow the solids to gravitationally separate. The solids sink to the bottom of the weir tank and are purged every hour. Thirty to forty yards of solids are being removed from the produced water per week.

After the fluid passes through the weirs the fluid moves through a coalescing media that is made in such a way that
th e droplets of the oil that have been pushed out of phase by the hydrogen peroxide can coalesce or group together and float to the top where they can be skimmed as clean usable oil. During the time of our
visit to the site the coalescing media was not be in g used since the oil was being separated from the produced water in the settling and pretreatment pits. Fig. 2 Square tube bundle

Reaction Zone

Figure 3, Flow diagram of the

reaction zone.

Fig. 4 Weir tank

Fig. 5 Removed SolidsAfter the water has been cleaned, a biocide is added when it is pumped from the weir tank to

the storage pit. CoilChem is using their BC 1000 biocide a t a dosage rate of 100 ppm. This acts as a preservative to prevent bacteria growth until the water is used.

When we arrived on location we were met by Danny Wesley the president of CoilChem. I asked him to walk us through the treatment process from where the produced water enters Brigham’s recycle pits, flow though the pits, processing by CoilChem and stora ge in the primary recycle pit.

In my opinion

, CoilChem’s water treatment technology is sound for removal of suspended solids, iron, sma ll amounts of oil, iron sulfide, hydrogen sulfide and bacteria from produced water. The processed water should be compatible with most pressure pumping company’s sli ck fracturing chemistry. As can be seen in Figure 1 the treated water is very clear and Figure 7 shows the iron
has been reduced from 2

. 86 mg/l to .01 mg/l and the total suspended solids have been reduced from 1312 mg/l to .34 mg/l. No other support has been provided to show removal of other
contaminants or bacteria.

CoilChem representatives told me that their water treatment process can be combined with other technologies to make the processed water compatible with any type of frac chemistry. For

instan ce, their process can be combined with Dow’s boron removal technology (Amberlite IRA

743 ion exchange media ) to process produced water for use where operators are doing borate cross linked gel completions and the produced water contains boron above 50 ppm. I have seen the Amberlite remove boron from produced water to levels less than 1 ppm; however, I have seen other vendors use the product and not be successful in having their fluid work with the frac
vendors. I have also seen water processed and the Amb erlite used where the frac chemistry worked just fine. If CoilChem is going to market the more complex water treatment processes then they will have to show positive results from pilot tests and frac vendors chemistry.

The following appendi ces provide mor e detailed information about CoilChem’s treatment process and pictures of the test site we visited.

Acknowledgement: I would not have been able to write this assessment without the generous help of Jerry Noles and David Essman with CoilChem, LLC. Fig. 6 Water treatment flow diagramFig. 7 Basic water chemistry before and after treatment

## Appendix 1

CoilChem Technology Write

- Up Jerry Noles, CEO CoilChem, LLC

CoilChem process for treating Oilfield waters: injection, frac recycle, p roduced w aters, f lowback or pit waters

- The water treatment process introduced by CoilChem is very simple, consisting of 5 process steps:

1. Oxidation

– CoilChem selected H ydrogen Peroxide as the oxidant to accomplish the key changes in the water quality to ensure consistently successful treatment for suspended solids and oil removal (to < 1NTUs and less than detectable Oil & Grease).

2. Reaction Time

– a few minutes of “organized” turbulence inside a specially design

Reactor

.

3. Coalescence

– A simply constructed chamber with widely available plastic media separates clean oil from, the water, leaving the solids behind.

4. Separation

– Ultra

- clean water is produced by pumping the water through a separation tank where specially designed wei rs allow suspended solids to gravitationally separate. Directional changes and decreased velocity aid in particle separation. This process is accelerated by the particle destabilization that occurs by the shift in p H and the oxidizer
introduction in the r eactor phase.

5. Passive Solids Dewatering

– removed every hour from the system by purging from a bottom manifold incorporated within the separation tank. The solids are allowed to settle and the water is drawn off of a specially design dewatering roll

- off

– ready for disposal.

The fol lowing provides some brief explanations of the core steps in the CoilChem water
treatment process

– why it works, why it works so well, why it meets cost reduction objectives
for our clients in this difficult environment.



### Oxidation

The CoilChem process for treating oilfield and other waters begins with the addition of hydrogen peroxide. The hydrogen peroxide accomplishes several important tasks, as shown in the table

below:

### Oxidizing Iron

Converting Iron divalent to trivalent cation s

– The first step in removing suspended solids is to neutralize the surface, electrical charges which prevent them from combining to form larger particles. Most particles, encountered in water systems, have mixed charge sites on the surface
but are net ne gatively charged

– preventing the particles from joining and becoming larger. The charge neutralization process is called Coagulation. “Chemical Coagulants” are positively charged chemicals added to effect the neutralization of the predominantly negative charges on suspended particles. Such products include ferric chloride, ferrous sulfate or even aluminum sulfate or polyaluminum chloride. Electrocoagulation (EC) adds iron by corroding steel anodes (or aluminum for Al 3+ ).

Almost all Produced Waters cont ain iron, by adding hydrogen peroxide, the iron already in the water is oxidized to a trivalent cation. Rather than buying iron coagulants (chemicals or EC) and then having to pay to dispose of that same iron

– the CoilChem process uses the iron already

pr esent.

The reaction with divalent iron is as follows:

Fe 2+ + H 2 O 2 → Fe 3+ + HO• + OH

Additional and significant benefit to the full treatment is provided by the formation of the hydroxyl radical. 

## Oxidizes Hydrogen Sulfide

Many wells are contaminated with hydrogen sulfide which poses a health risk to personnel working at the site. Because the CoilChem process adds hydrogen peroxide and controls the feed of the peroxide to maintain a given Oxidation Reduction Potential (ORP), any sulfide contaminants, (H 2 S, FeS, etc.) in the water are removed. CoilChem process eliminates sulfides in

oilfield waters.

Hydrogen sulfide removal is very fast with hydrogen peroxide. Chlorine dioxide is much more expensive than hydrogen peroxide and more readily consumed when sulfides are present:Oxidant Lbs. Oxidant per pound of H 2 S

Chlorine Dioxide 1.5 to 3.4 Lbs. ClO 2 / Lb. H 2 S Hydrogen Peroxide 1.0 Lbs. H 2 O 2 / Lb. H 2 S

Hydrogen peroxide is typically shipped as a 30% or 50% solution and fed neat. Chlorine dioxide typically requires onsite generation using either two or three reagents

– all presenting handling concerns. At roughly half of the price of most chlorine dioxide costs

– hydrogen peroxide is an excellent choice and a powerful oxidizer.


### Breaks Residual Polymers

The standard means of breaking the organic polymers used in Fracing and Completions is by
oxidation

– with bleach or other oxidant (inorganic or organic peroxides). The polymers coming back with water to be treated will materially impair the performance of m ost, current, water treatment process technologies. Using hydrogen peroxide oxidation as the first step in the CoilChem process means that the process can take 100% Flowback or other waters heavily contaminated with polymers like guar or p

- acrylamides. By controlling the dosage rate of the peroxide to maintain a specified ORP, the process automatically ensures the polymers have been sufficiently degraded.

CoilChem process can easily manage waters with high concentrations of oilfield polymers.



### Kills Bacteri a

Hydrogen peroxide is an excellent bactericide. Even waters with significant levels of biological activity are made effectively sterile by the peroxide addition.

CoilChem process reduces or eliminates feed of biocides


### Destabilizes Dissolved Organics

The s tandard means of removing dissolved organics is by oxidation followed by particulate filtration. Flotation cells are commonly used in refinery wastewater treatment. Water going to the flotation cell is typically treated with chemical oxidant followed by a coagulant or floccul a nts

. The dissolved organics when destabilized form a particulate which is readily removed by gravitational separation, flotation or filtration.

Some particularly, environmentally problematic species, like phenols, are safely destroye d by oxidation reducing any associated long

- term liability for their discharge.



### CoilChem Reaction Zone

– the “Coil” in CoilChem

The “Coil” in CoilChem is a specially designed, patented, serpentine tube bundle for mixing of chemicals evenly throughout the fluid body, the bundle is designed to prevent the oxidizer from boiling out of the water while maximizing mixing and turbulence o f the passing water. Ensuring effective mixing and contact of the various reagents in the water with their respective targets,reactions are driven to completion quickly. The “Coils” were designed, and remain quite popular,

as hydration units to maximize polymer efficiencies in fracing and completion applications. Full polymer hydration is achieved in only a few minutes versus hours in stagnant or lightly mixed
make

- down tanks.

In the CoilChem Reaction Zone , the oxidation and coagulation reactions are completed and process of flocculation has begun. Tiny floc particles ar e visible in the weir system just
downstream of the Reaction Zone

. Depending on the application, the pipe coil Reactor , is made of mild carbon steel, PVC or other
material.



### Coalescence

Downstream of the Reaction Zone, the water enters the Coalescer where, by passing the forward flow through high surface area, plastic media, droplets of oil are brought together and separated from the water. From Wikipedia:

Coalesce nce (physics) , the merging of two or more droplets, bubbles or particles into one

The Separation velocity (V s ) of oil droplets from water is described by the following equation (Stoke’s Law) Reaction Zone

– demonstrated performance

in rapid & full polymer hydration ensure efficient oxidation reactions go to complet ion

. Patented performance...We learn from that equation that the delta in density between the fluid and the droplet is not

nearly as important as the particle size in determining separation velocity. V s increases with the square of the particle size

– the coalescer causes the oil particles to combine forming larger particles

– dramatically increasing the rate of separation.

The picture above is the media in the CoilChem coalescer

– not the many channels through which the fluids must pass

– the constant directional changes encourage collosions of droplets.



### Solids

Solids are dra wn off of the separation (weir) tank and collected in phase separating roll

- offs as pictured below. This material primarily composed of Iron and Suspended solids is purged from the bottom of the separation tank once every 30 min to one hour. The solids a ccumulate and are vacuumed out and disposed of in land fill applications by the customer. The volume of the solids is typically between 30 to 40 yards per week.

## Appendix 2

P hoto Log of the CoilChem/Brigham Pilot Test Site

Pecos County Texas August 19, 2015

Water flowing into Brigham’s settling pit from their gathering system.

### Brigham’s settling pit. Note the material which has dropped out of the water. Truck unloading station at Brigham’s settling pit.

### Brigham’s pretreatment pit.

CoilChem water treatment equipment.

### CoilChem chemical mixing equipment (center)

CoilChem weir tank (center)

### CoilChem dewatering box for collecting solid waste.

Suspended solids removed from produced water.

### Square tube bundle

– “Reaction Zone” where chemicals are mixed into the water.

Chemical totes connected to “Reaction Zone” tube bundle. Reaction Zone

### Chemical tote containing Caustic Soda connected to the “Reaction Zone”

Chemical tote containing Hydrogen Peroxide connected to the “Reaction Zone”

### Top of weir tank with covers removed showing weirs working.

Top of weir tank with covers removed showing coalescing media on the right.
Note there is no oil in the water to be recovered.

Coalescing Media

### Final Product

– clean water from dirty produced water.