It’s Not A Bomb!
A Safe, Selective, High Performing
Alternative to Chlorine Oxidants
Wayne Buschmann, Ph.D., Chief Technology Officer
Clean Chemistry, Inc. | cleanchemi.com
[email protected] |(303) 440-8329
© 2017 Clean Chemistry, Inc.
A Safe, Selective, High Performing
Alternative to Chlorine Oxidants
Abstract
Clean Chemistry recently brought to market a new, patented, advanced oxidation
chemical technology as a replacement for more dangerous and polluting chemical
oxidants.
The PeroxyMAXTM technology provides performance that no other chemistry offers
because it is based on delivering bulk quantities of reactive oxygen species (ROS) in a
liquid form. The performance, safety, pollution prevention and low cost of ownership
of this technology creates new opportunities to reduce or replace chlorine oxidants
and their associated hazards in industrial sectors including energy, pulp & paper and
mining.
Two of the most widely used industrial oxidants are chlorine and chlorine dioxide,
which are highly corrosive, flammable and hazardous to produce, ship, store and use.
Byproducts of chlorine oxidants and disinfectants can be highly toxic and persistent
in the environment. PeroxyMAXTM is inherently safer because it is produced as an
aqueous solution on-demand near the point of use in a safe, automated process from
stable, non-flammable feedstocks. PeroxyMAXTM is significantly less corrosive than
chlorine oxidants, has low volatility and is non-flammable. The system platform is
small and has minimal power consumption.
Over the past year, PeroxyMAXTM has been successfully used to treat over 1 billion
gallons of water for reuse and is becoming a preferred oxidant in the upstream oil &
gas sector for customers who have experienced unacceptable safety and corrosion
incidents using chlorine oxidants.
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Introduction
Clean Chemistry has introduced a new advanced oxidation chemical technology,
PeroxyMAXTM , to the marketplace creating new opportunities to achieve greater
efficiency, safety, water reuse and pollution prevention in industrial sectors historically reliant on chlorine oxidants.
Specific advantages of the PeroxyMAXTM technology include significantly improved
safety from reduced human and environmental exposure hazards; reduction of toxic,
persistent chlorinated oxidation byproducts; reduced sludge waste for disposal; and
reduced corrosion damage to equipment and infrastructure.
PeroxyMAXTM is safer because it is produced as an aqueous solution (less than 6%
active ingredient) on-demand near the point of use in a safe, automated process from
stable, non-flammable feedstocks. The technology delivers a mixture of reactive
oxygen species (ROS) not previously available in bulk quantities including singlet
oxygen,1 superoxide2 and hydroperoxyl radicals. PeroxyMAXTM provides source
reduction of pollutants by minimizing toxic organic halide formation during water
treatment and bleaching processes, by not forming bromate during treatment of
seawater and groundwater containing bromide and by reducing waste sludge volume
for disposal. PeroxyMAXTM minimizes its environmental impact potential by naturally
degrading in a short period of time to non-toxic, rapidly biodegradable residuals.
The oxidant is also less corrosive and has low volatility and odor relative to common
industrial oxidants including chlorine, chlorine dioxide, ozone and peracetic acid.
Technology Development and Performance
The patented chemistry behind PeroxyMAXTM was discovered in an effort to develop
new and improved methods of generating safer oxidant systems enhanced by reactive
oxygen species (ROS) in liquid formulations. Of particular interest were practical and
economic methods to generate elevated concentrations of ROS that are useful in
highly contaminated and saline environments including singlet oxygen,1 superoxide
radical,2 hydroperoxyl radical and other beneficial radical species or combinations.
These ROS were of particular interest because there were no industrially practical
methods to generate them in bulk quantities and they had yet to be exploited significantly.
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The primary active ingredient for PeroxyMAXTM is produced by reacting three stable,
non-flammable feedstocks together in a specific process. The oxidant solution is then
applied to the treatment objective where it is consumed within minutes to hours
as it generates ROS. The byproducts of the oxidant chemistry are non-toxic, readily
biodegradable and generally regarded as safe.
Figure 1. Comparison of clarification performance on produced water.
Untreated
Chlorine Dioxide
Hydrogen Peroxide
PeroxyMAXTM
Performance, safety and low capital and operating costs are critical features that
make PeroxyMAXTM competitive and often superior to chlorine, chlorine dioxide,
hydrogen peroxide and peracetic acid in a number of applications. For example, large
Table 1. Produced water treatment
scale, cost effective water reuse is enabled by PeroxyMAXTM in oilfield operations,
for oilfield reuse
which reduces demand on freshwater resources and limited disposal well capacity;
Parameter
Raw
Treated
6
7.2
400
670
Chloride
(mg/L)
56,900
55,000
Calcium
(mg/L CaCO3)
1,250
1,000
Magnesium
(mg/L CaCO3)
365
355
Iron
(mg/L)
12.3
2
TSS
(mg/L)
515
8
APB
(cells/mL)
100-1,000
<1
SRB
(cells/mL)
100k-1MM
1-10
pH
ORP
(mV vs SHE)
minimizes sludge waste and disposal costs; and reduces water transport and associated truck traffic, fuel consumption, emissions and road repair costs. Reducing
corrosion of equipment by using PeroxyMAXTM significantly reduces operating and
maintenance costs. Oil separation and recovery is a revenue-generating capability.
PeroxyMAXTM can significantly reduce chemical costs and the amount of sludge
waste for disposal during water treatment and clarification. Produced water typically
contains significant levels of scaling minerals (calcium, magnesium, strontium, barium),
which consume large quantities of water softening chemicals and generate excessive
solids and sludge for disposal. In practice, reuse of produced water for oilfield operations rarely requires significant softening. Results for selective clarification of iron
and total suspended solids (TSS) from produced water with PeroxyMAXTM are shown
in Table 1. For comparison, clarification of this water with softening by pH adjustment
alone produced 3.5 times more sludge for landfill disposal.
The bacteria load (acid producing and sulfate reducing bacteria, APB and SRB) was
significantly reduced by the clarification process, which can reduce the amount
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of expensive and environmentally persistent conventional biocides (aldehydes,
quaternary ammonium compounds) used by 50-90%. Further testing has shown
that PeroxyMAXTM has antimicrobial performance superior to chlorine bleach and
competitive to chlorine dioxide in contaminated oilfield water without clarification of
solids.
Separating crude oil and gas condensates from produced water recovers valuable
hydrocarbons that would otherwise be removed as impurities from the water
Figure 2. Relative corrosion rates
phase creating additional sludge for disposal. PeroxyMAXTM can be used in small
of carbon steel exposed to solution
amounts for hydrocarbon separation in place of more expensive and environmentally
phase (top) and vapor phase (bottom)
persistent demulsifiers. As an example, rapid oil separation driven by PeroxyMAXTM
enabled a 97% recovery of oil from a produced water in the Utica formation containing 0.26% wt/vol free and emulsified oils. Oil recovery reduced the potential
waste sludge mass by about 50% and generated about 60 barrels of oil from 30,000
barrels of produced water, which represents a meaningful revenue stream.
For groundwater and seawater treatment applications, bromate formation is an
important environmental and human health issue. Bromate is a highly toxic oxidation
byproduct of bromide salts, a well-known issue for oxidants such as ozone,3 peracetic
acid4 and elevated concentrations of chlorine. PeroxyMAXTM was demonstrated to
have undetectable bromate formation potential in brackish and saline water containing bromide salts under conditions known to promote bromate formation.3,4
The corrosivity of PeroxyMAXTM is lower than most oxidants in the solution phase
and vapor phase, which reduces equipment damage and replacement costs. Figure
2 shows the relative corrosion rates of PeroxyMAXTM and conventional oxidants
relative to oxygen in air on carbon steel. PeroxyMAXTM is compatible with stainless
steel in contrast to chlorine bleach, which causes pit corrosion. Reducing vapor phase
corrosion is important in paper making and water treatment facilities where the
integrity of steel structures and equipment can be compromised over time. Reduced
vapor phase corrosion for PeroxyMAXTM is a direct result of its low volatility, which
dramatically reduces maintenance and capital replacement costs.
Using PeroxyMAXTM is significantly safer than chlorine and chlorine dioxide. Chlorine
and ClO2 are highly corrosive, toxic and flammable gases. Chlorine dioxide is also
an explosive gas. Chlorine and ClO2 gases are heavier than air so their release can
quickly impact large numbers of people over large areas. Chlorine and ClO2 have
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vapor pressures greater than 1 atm and very limited solubility in water, near 0.8% wt/
vol at 20o C, and rapidly off-gas from water. Chlorine and ClO2 are NIOSH listed as
immediately dangerous to life or health at 29 and 13.8 mg/m3, respectively, concentrations that are easily achieved in the head space of tanks.
PeroxyMAXTM is composed of a dilute solution of a peroxide salt. Salts, in general,
have very low vapor pressures compared to liquids and gases. Potential exposure
to PeroxyMAXTM solution is limited to direct contact with liquid solution. Oxygen
is slowly released from any unconsumed oxidant leaving non-toxic, biodegradable
residuals.
In practice, open water tanks treated with excess chlorine dioxide in oilfield operations regularly off gas at rates that can trigger shut downs of operations and cause
exposure to personnel. Chlorine dioxide generating equipment periodically fails,
which sometimes results in severe injuries or death. Chlorine dioxide that is stored
and used in pulp mills poses severe exposure hazards if not properly contained
and safeguarded.6 In agricultural, food and dairy processing operations significant
numbers of workers are regularly exposed and injured during accidental releases of
chlorine dioxide and chlorine gases.6,7 Large volumes (i.e., rail cars) of chlorine that
are transported through and stored in major metropolitan areas for water treatment
and other uses pose a potentially catastrophic hazard to life and property.8 Chlorine
dioxide cannot be transported in large quantities due to its instability, therefore, it is
generated and stored on the location it is used. The PeroxyMAXTM technology creates
a viable alternative to reduce or eliminate the above hazards thereby protecting the
health and safety of personnel and nearby populations.
Technology Commercialization
Full scale deployment of PeroxyMAXTM units has occurred in several states, with the
largest number of units located in the Permian Basin. Over the past year, PeroxyMAXTM has been successfully used to treated over 25 million barrels (1.05 billion
gallons) of water for reuse. Clean Chemistry has grown its market share in oilfield
water treatment despite being at the bottom of the most recent market cycle because
of the low total cost of ownership for PeroxyMAXTM treatment. The commercial
generation and dosing systems are safe, have a very small footprint, and require
fewer operators per unit than other treatment methods.
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Figure 3. PeroxyMAXTM chemical
Treatment units (Figure 3) are self-contained and are capable of treating water at
treatment system
rates up to 7000 gpm. Mobile units are housed in cargo trailers and fixed units are
installed on-site. Treatment units are powered by a single 15A, 120V wall outlet
(less than 1800 W) and are outfitted with sensors, safety interlocks and secondary
containment.
Intelligent, tunable dose control also allows for a reduction in chemical and labor
costs. The high ORP response of PeroxyMAXTM has been leveraged to create
automated dose adjustments and real-time water quality monitoring, assuring high
quality treatment regardless of fluctuating water quality. The user interface is a touch
screen control panel, which is accessible through wireless networking for remote
monitoring, operation and real-time quality control of the product and treatment
process and supply chain management. Treatment systems can be operated safely
and reliably by trained service company partners allowing for rapid deployment and
growth of PeroxyMAXTM in the upstream oil and gas environment.
PeroxyMAXTM is an important advance in oxidation technology. Its high performance,
increased worker and public safety, pollution prevention, reduced corrosion, automation, and low capital and operating costs enable it to replace chlorine oxidants at
industrial scales.
The PeroxyMAXTM chemistry, synthesis methods and applications are covered by
multiple pending and issued patents in the US and other regions.
References:
1. DeRosa, M.C., Crutchley, R.J.; “Photosensitized singlet oxygen and its applications,” Coord.
Chem. Rev., 2002 (233-234), 351-371.
2. Bielski, B.H.J., Cabelli, D.E., Arudi, R.L., Ross, A.B.; “Reactivity of HO2/O2- Radicals in Aqueous
Solution,” J. Phys. Chem. Ref. Data, 1985, 14(4), 1041-1100.
3. Von Gunten, U.; Hoigné, J.; “Bromate Formation During Ozonation of Bromide-Containing
Waters: Interaction of Ozone and Hydroxyl Radical Reactions,” Environ. Sci. Technol., 1994 (28),
1234-1242.
4. Shah, A.D.; Liu, Z.Q.; Salhi, E.; Höfer, T.; Von Gunten, U.; “Peracetic Acid Oxidation of Saline
Waters in the Absence and Presence of H2O2: Secondary Oxidant and Disinfection Byproduct
Formation,” Environ. Sci. Technol., 2015 (49), 1698-1705.
5. “Pulp and Paper Capacities Survey 2015-2020,” Food and Agriculture Organization of the
United Nations; Rome 2016. Available at: http://www.fao.org/forestry/statistics/81757/en/
6. U.S. Department of Labor, Occupational Safety and Health Administration; accident report
database search at: https://www.osha.gov/pls/imis/AccidentSearch.search?acc_keyword=%22Chlorine%22&keyword_list=on
7. Fidis, A. “Pulp Fiction, Chemical Hazard Reduction at Pulp and Paper Mills,” U.S. PIRG Education
Fund; Washington, DC; August 2007.
8. Jones, R., MD; Wills, B., DO; Kang, C., MD; “Chlorine Gas: An Evolving Hazardous Material
Threat and Unconventional Weapon,” West J Emerg Med., 2010 May; 11(2): 151–156.
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