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Advanced Oxidation

OriginClear’s AOx™ is a next-generation Advanced Oxidation Process. It has been shown to achieve real-time sanitation and reduction of micro-contaminants in potable and near-potable waters.

 

Endocrine disrupting chemicals have been implicated in numerous adverse health outcomes, including… infertility… early puberty, breast and prostate cancer, thyroid disorders, Alzheimer’s and Parkinson’s disease, attention-deficit hyperactivity disorder, obesity, diabetes, asthma, immune disorders, and more.

The Endocrine Disruption Exchange

What are These Contaminants?

There are a great many micro-contaminants, and OriginClear maintains a complimentary database (click here to view preview site).

But the greatest threat to human and animal health may be EDCs: Endocrine Disrupting Chemicals.

These chemicals include pesticides and herbicides, hormones, pharmaceutical and recreational drugs, and industrial solvents.


Filtration Is Not Enough

No water treatment solution can achieve 100% effectiveness. Micro-contaminants remain, even after multi-stage filtration and reverse osmosis. Filters are selective as to what they filter out; and they can become less effective over time. In addition, water filters have been shown to create their own bacterial populations.

For instance, a study published in the journal Environmental Science: Water Research & Technology concluded that activated carbon block-based point-of-use drinking water filters “significantly alter the bacterial abundance and composition of drinking water.”

Existing systems for potable water treatment need a final barrier to catch these last fractions of micro-contaminants.

Potable Water in GM-free Scotland

Source: GM-free Scotland


The Answer

The answer is OriginClear’s next-generation Advanced Oxidation Process, AOx:

  • AOx positions as a final electrochemical barrier to effectively reduce many of these contaminants when earlier steps have missed them.
  • AOx treats the last fraction of micro-contaminants in potable water, missed by virtually all other solutions.
  • AOx can prevent bacterial contamination from filters by acting as an electrochemical sanitizing agent.
  • AOx can help attain a new water standard, Super Toxin Free™.

 

 

Applications

In 2016, OriginClear announced that it successfully developed and proven its unique Advanced Oxidation process, AOx, to complement its breakthrough water cleanup system, Electro Water Separation™, or EWS.

University laboratory tests have shown that EWS, combined with Advanced Oxidation (EWS:AOx™), can now also address dissolved contaminants, which are otherwise difficult to remove without chemicals such as chlorine.

“EWS already generates 370mg per second of gas, which is more than twice the amount needed for the removal by electro-flotation of a 2000 mg/l solids contents wastewater. Now, we have confirmed that EWS with Advanced Oxidation also produced more than 330 g/m3 of mixed ROS species, such as hydrogen peroxide, for a similar average energy consumption of 1 kWh per m3 of treated water.”
Dr. Luis Edgar Cabrales Arriaga, assistant professor at the Department of Physics and Engineering at CSU Bakersfield.

AOx for Fouled Water Applications

Extremely dirty, oily waters, such as landfill runoff and agricultural effluents, require our industrial water treatment process, Electro Water Separation™ (EWS).

In these applications, AOx can be combined with EWS, for final sanitation, further reduction of miscible contaminants, and microtoxin reduction.

Disinfection and Decontamination

AOx technology is an evolution of known Advanced Oxidation processes. The AOx reactor module is specifically designed to focus on the generation of Reactive Oxygen Species (ROS) such as ozone, hydrogen peroxide and hydroxyls.

Early laboratory studies carried out by the Company in partnership with California State University at Bakersfield (CSU Bakersfield) indicated the effectiveness of EWS:AOx, as measured by Reactive Oxygen Species (ROS) generation.

ROS are the strongest oxidants that can be used in water and can degrade virtually any contaminant. Their confirmed presence indicates the degree to which the system is able to remove organics from water without chlorine-generated Disinfection By-Products (DPB), which are considered harmful in a wastewater treatment system.

“For example, in China, we have been asked to clean up the ‘black water’ contaminants coming out of landfills, which can be so thick that they can clog up any filter. We have shown that EWS:AOx can do the job, and I’m happy to report that we are now in the commercial negotiation phase after a successful demonstration.”
Jean-Louis Kindler, President,
OriginClear Technologies

The AOx reactor takes water that is largely clear of suspended solids and oils. In the EWS stage, this water has begun to acquire disinfecting and decontaminating oxidants, known as Reactive Oxygen Species or ROS.

In the AOx reactor, reaction with the anode surface inside the reactor causes on-site generation of an additional large amount of ROS. Targeted cathode material selection triggers other complementary reactions occurring at the cathode surface, addressing contaminants that cannot be oxidized.

At this stage, the few remaining fine micron-sized suspended solids as well as the dissolved or miscible contaminants will be oxidized or reduced. The resulting elements after these chemical reactions will either precipitate and sink to the bottom of the AOx tank for removal, or dissipate as off-gas that can be scrubbed and treated if needed.

Depending on the application requirements, AOx can be implemented in tube-shaped inline Advanced Oxidation Reactors or in an Advanced Oxidation tank – or in combination – both featuring OriginClear’s trade-secret reactor designs. AOx can also generate other compounds including chlorine, to neutralize specific contaminants such as ammonia.

 

OriginClear's Advanced Oxidation reactors.

OriginClear’s Advanced Oxidation (AOx) reactors.

Effective disinfection without adding chemicals.

Being solely composed of oxygen and hydrogen, in-situ generated ROS introduce no additional hazardous element in the water. It is a major benefit for operators wanting to avoid HAZMAT logistics issues, not only when having to treat the concentrated waste, but also because there is no need to bring in and inject oxidants such as Hydrogen Peroxide, as is often required in conventional Advanced Oxidation processes.

Dramatic reduction in total organic compounds.

Overall, the system has shown a dramatic reduction in Total Organic Compounds which includes all forms of organic contamination, solids, miscible or dissolved, to  meet new stringent global discharge requirements.

Even prior to this innovation, EWS, combined with an iSep ultrafiltration membrane, demonstrated up to a 99.9% removal of dispersed oil, 99.5% removal of suspended solids as well as successful treatment of chemical oxygen demand (COD), including specific contaminants such as ammonia, phosphorus and hydrogen sulfide. These results were presented at the International Water Conference in 2015.

In 2016 and 2017, OriginClear filed for patents to protect the new AOx process and system configuration.

 

Standalone AOx Operation

Potable or near-potable water is typically free of particulates and oils. In such applications, EWS is not needed, and operators can deploy AOx by itself, as a next-generation AOP.

In 2017, OriginClear showed that AOx could be used on a standalone basis to treat potable and near-potable waters for micro-contaminants. In laboratory research, AOx has been shown to be extremely effective in treating micro-contaminants in potable or near-potable water.

OriginClear is now scaling up to field pilot and demonstration, while testing continues on a series of contaminants and water samples.

An OriginClear lab technician tests micro-toxin levels

OriginClear Engineer Ayush Tripathi
tests for glyphosate reduction.

Patents

The first patent for standalone AOx operation was filed in March, 2016. We filed two subsequent patent filings in the summer of 2017, which further refined the technology for real-world drinking water applications (See Intellectual Property.)

Validation

Laboratory scale testing in the summer and fall of 2017 focused on the marker contaminant, glyphosate (the key ingredient in Monsanto’s Roundup, and the world’s most-used herbicide).

These developments make it possible to treat water with very low concentrations of contaminants while eliminating the need for salt injection, making it possible to locate systems in commercial and domestic environments.

Next Steps

The validation process continues and is explained here.

We are interested in research and development partners to continue to explore the exciting potential of next-generation AOx.

For more information, please contact Technology Partnerships.

Effectiveness

Introduction

Electrolysis Components

OriginClear’s core Advanced Oxidation Process, AOx™, removes minute contaminants that remain in potable water after treatment. AOx is an effective electrochemical barrier to remove the last fractions of microtoxins, after all other methods have been used.

For our purposes, potable water is any water which has no suspended solids or oils, and has been treated with filtration and other final-stage methods. It may include:

  • Domestic drinking water (tap water)
  • Bottled waters
  • Agricultural irrigation water
  • Water in hot tubs and pools.

We call these contaminants “microtoxins”, because, even in low doses, many have the potential to affect the immune and endocrine systems in humans and animals.

A wide array of these compounds exists. We are currently validating AOx on the most widely-known microtoxins, following best practices for scientific sampling. We will continue to publish results of our testing as it progresses.


Method

We work with two types of testing samples:

  1. Artificially high in contaminants (as used in laboratory animal testing), or
  2. In very low concentrations as is typically found in the food chain or in our drinking water.

We implement AOx in original designs which use two kinds of electrochemical reactions to treat microtoxins: Direct Oxidation (DO) and Indirect Oxidation (IO).

 

OriginClear Advanced Oxidation Components

Direct Oxidation

Using Direct Oxidation (DO) in a configuration related to our latest innovation, we have successfully treated microtoxins in as little as 45 seconds, achieving real-time and inline processing.

We use our internally-developed inline reactors for DO. These are arrays of tubes with the anode nested inside the cathode. The gap between anode and cathode is very small, which makes for an effective reaction even without treating the water for conductivity.

Procedure:

  1. Fill feed tank with test solution.
  2. Pump solution into inline reactor array.
  3. Control flow to obtain between 45 seconds and three minutes of residence time.
  4. Solution may be recirculated multiple times to approximate real-world results at scale, where mazes of reactor tubes are used to enable longer residence time.

  Advanced Oxidation Electrodes

Indirect Oxidation

Indirect Oxidation (IO) is a lengthier method. This may be required for waters contaminated with stubborn toxins such as cryptosporidium cysts. It is often deployed in addition to Direct Oxidation.

While Direct Oxidation uses continuous tubes for reaction, IO employs a reactor cell with a proprietary design for mesh electrodes lining the bottom of a treatment tank. Through hydrolysis, the electrodes produce a gaseous cloud which contains an effective concentration of oxidizing agents.

Procedure:

  1. Fill the reactor cell with test solution.
  2. Power the reactor, and treat for between 30 and 90 minutes. There is no recirculation.
  3. Take samples quarterly within the allotted test time. For example, if we treat for 60 minutes, we sample every 15 minutes. Our test series will determine the optimum residence time.

Synergistic Effect

We deploy both reaction types to test each contaminant. In the lab, we test DO and IO separately to benchmark relative efficiency. Field designs may combine DO and IO for maximum effectiveness under challenging operating conditions.

We test continuously using our in-house chemical tests, or our mass spectrometer. In addition, we utilize a certified laboratory to analyze the results of each major test before it is published.

These third party tests have confirmed the effectiveness of AOx in reducing low-concentration microcontaminants to the non-detectable level, potentially making them Microtoxin Free™.

 

OriginClear Advanced Water Purification Unit

The Test Series

This test series focuses on a series of contaminants present in drinking water at a microscopic level.

Glyphosate is world’s most-used pesticide and the key ingredient in Monsanto’s Roundup®. Because its toxicity is still controversial, many filtration manufacturers omit treatment claims for glyphosate. To remedy this omission, we began with this contaminant, which is present in up to 70% of US drinking water.

Reports on the full test series follow. We welcome your suggestions — please use this contact form and we will respond quickly.

Click to view the microtoxin test series now.

 

Technical Details

OriginClear’s innovative AOx™ is an emerging, next-generation AOP. It features two methods, both catalytic, for reducing pollutants through oxidation. These methods may be used singly or in combination, according to the application.

The oxidizing agents include Oxygen (O), Chlorine (Cl), Hydrogen Peroxide (H2O2) and Ozone (O3).

Hydroxyl Radical (OH•) is the most powerful oxidizing agent available, produced by the reaction of Hydrogen Peroxide and Ozone.

Direct and Indirect Oxidation

The first method is direct, by exchange of electrons between the anode and the pollutants.

The second is indirect, by generating strong reactive oxygen species (ROS) — most especially OH• — on the anode surface, i.e. in-situ generation of oxidizing species.

The presence of chloride ions in the treated solution may facilitate indirect bulk oxidation by the in situ electro-generation of active chlorines like hypochlorite, chlorine dioxide and chlorine, which could greatly enhance the overall electrochemical incineration of the organic pollutants.

Non-Reactive Contaminants

Advanced Oxidation Processes are at their most effective when they generate the highly-reactive Hydroxyl Radical (OH•). However, not all contaminants are reactive to OH•.

A dual solution is needed, which AOx achieves by combining electro-oxidation processes:

  1. Anodic oxidation by generating the full range of reactive oxygen species (ROS), especially OH•.
  2. Oxidation with active chlorine (“mediated oxidation”), which complements OH• where it is ineffective.

In this scenario, AOx forms large quantities of anodically generated active chlorine species such as Cl2, HClO/ClO‾ and ClO2‾.

These can oxidize the organics in competition with ROS by direct electron transfer (DET) reactions (e.g., fluorinated organics).

Hydroxyl Radical (OH•) Scavenging

AOPs suffer from decreased efficiency in natural waters due to OH• scavenging. Presence of bicarbonate ions (HCO3−) can appreciably reduce the concentration of OH• due to scavenging processes that yield H2O and a much less reactive species, •CO3−.

AOx solves this issue. The design uses water oxidation to produce an acidic boundary layer at the anode surface; so that in this region, HCO3– is protonated to H2CO3 and therefore prevents OH• scavenging associated with HCO3–present in natural waters.

 

Compare AOx

Advanced Oxidation Processes use strong oxidizing agents to reduce pollutants and sanitize water.

As outlined in an industry article, existing methods include injection, catalysis or irradiation, separately or in combination, under mild temperature and pressure conditions.

 

The Differences

Here’s how AOx compares with the existing technologies:

  1. Injected AOP has a high operating cost, due to the need to continuously input expensive chemical reagents proportional to the quantity of contaminants to be removed; and the related labor.
    • Unlike injection, AOx does not require input of expensive reagents, and can operate unattended.   
  2. Catalytic AOP often needs salt to bring about a reaction, and may not be a real-time process.
    • Unlike many other typical processes, AOx requires no salt or other mineral, and treatment can be continuous and real-time, depending on requirements.     
  3. Irradiation AOP produces ozone, which by itself does not produce hydroxyl radical, the strongest oxidant used in water treatment.
    • Unlike injection, AOx does not require input of expensive reagents, and can operate unattended. Unlike irradiation, AOx generates a wide range of ROS, including the all-important Hydroxyl Radical (OH•).

Conclusion: AOx is the effective technology for Advanced Oxidation Processing.

 

Introducing AOxPlus

The Fenton process is well known as a way to clean up the toughest water problems – in the lab! AOxPlus™ is the Fenton process for the 21st Century. OriginClear Technology President “JL” Kindler shows off how the high production of hydroxyls is a reality and talks about a new partnering relationship in Oman with a major oil producer.

 

14 Sep 2018: Application Engineer, Ayush Tripathi, joins CEO Eckelberry to discuss the AOxPlus breakthrough and what it means. He also discusses field rollouts of the technology.

 

AOxPlus™

A Breakthrough Advanced Oxidation Process

AOxPlus™ is a revolutionary method to produce hydroxyl radicals in large quantities to treat highly-contaminated wastewater.

In today’s era of steadily worsening states of water and disease generating or even fatal contaminants, AOxPlus “air breathing” contaminant reduction technology, is a significant technical breakthrough with a wide range of applications.

Hydroxyl Radical and Toxic Contaminants

The highly-reactive hydroxyl radical (•OH), delivers more than twice the oxidation, or cleansing power, of chlorine, without the toxic byproducts.

Based on laboratory testing, OriginClear engineers estimate that the new AOxPlus can produce roughly 10,000 times more hydroxyl radical molecules than the original AOx technology, which primarily outputs free chlorine. The two technologies can be used in tandem to deliver the one-two punch of chlorine and hydroxyl radical molecules, for class-leading contaminant breakdown.

To generate these new levels of hydroxyl radical in AOxPlus, the OriginClear research team used a special air-breathing membrane in a new reactor, disintegrating hard-to-remove contaminants. AOxPlus does not require chemical injection, or clear water (as with Ultra-Violet or UV), and is highly cost-effective when compared with, for example, diamond electrodes. It can offer a more efficient treatment solution to sectors that produce highly-contaminated wastewater, such as the pharmaceutical and food industries.

An important aspect of the AOxPlus technology is its scalability, which distinguishes it as a stand-alone water purification technology which can be applied to remedy most of the “invisible poisons” complicating the treatment of publicly consumed commercial, industrial and municipal water.

Depending on the application requirements, AOxPlus can be implemented in tube-shaped inline Advanced Oxidation Reactors or in an Advanced Oxidation tank – or in combination – both featuring OriginClear’s trade-secret reactor designs.

Transmitting Cell, Plus Electricity

AOxPlus is so elegantly simple that it can be reduced to two components, a transmitting cell and an electric current. However, due to its solid scientific technical grounding, the basic formulas and theoretical principles of AOxPlus are equally sound when applied to applications on commercial, industrial and municipal scale. This factor enables a wide scope of uses for AOxPlus.

In a syndicated television interview of September 14, 2018, Senior Engineer Ayush Tripathi described the innovation:

“What we call persistent organics compounds (POCs), are difficult to oxidize by an oxidizing molecule such as chlorine or hydrogen peroxide, so we produce and activate this hydrogen peroxide inside the reactor, which then are further converted into OH radicals. These OH radicals instantly react with the compounds and mineralize them to carbon dioxide, water and carbon.

“Since this technology uses only electricity to promote these reactions it is very scalable because it requires only electricity and a cell which can be manufactured on a much larger scale and because it is very efficient in producing these oxidants it can easily be scaled to larger, industrial sized reactors.”

OriginClear Research Team Heralds Breakthrough

 

Operational Parameters

Flow Rate: 150 – 200 mL/min
Current: 0.25 – 1 A
Total Volume = 256 mL
Cathode Volume = 128 mL~ 50s in the cathode chamber

  • Rapid H2O2 production accomplished in 50s
  • Can be quantitatively controlled with current
  • Current Efficiencies from 79% to 98%
  • Significant quantities of H2O2 produced at low currents
  • Significant activation of H2O2 to form hydroxyl radical (•OH)
Prognosis
  • Systems shows significantly higher hydroxyl radical
    production than competitive technologies
  • Almost 10,000x more
  • Electrodes are a fraction of the cost

Dramatic reduction in total organic compounds.

Overall, the system has shown a dramatic reduction in Total Organic Compounds which includes all forms of organic contamination, solids, miscible or dissolved, to meet new stringent global discharge requirements.

Lab Test Results: Oxidant Production driven by Cathodic Peroxide Production

Historical Background

AOxPlus™ is based on a historic scientific breakthrough known as the Fenton process, developed in the 1890s by Henry Fenton, which is very well known in the science world and academia as the fundamental theory and technology governing the production of OH radical molecules (the most powerful oxidants that can be found in water). It involved the mixing of hydrogen peroxide and ferrous sulfide for the production of these hydroxyl radicals. These reactions invariably take place, but slowly.

However, unlike the synthetic Fenton process whose scientific advancement has not kept pace with or been developed in the atomic and digital technology age and involves the potentially dangerous employment of hydrogen peroxide and ferrous sulfides, the AOxPlus water treatment module utilizes an organic electrolysis process to generate hydrogen peroxide inside the cell. This hydrogen peroxide will then react with iron, also released inside the cell, to produce extremely high levels of hydroxyl radical molecules, known as the superior purifying agent for waterborne microbiological contaminants and toxins.

AOxPlus introduces no additional hazardous element in the water. It is a major benefit for operators wanting to avoid HAZMAT logistics issues, not only when having to treat the concentrated waste, but also because there is no need to bring in and inject oxidants such as Hydrogen Peroxide, as is often required in conventional Fenton-based Advanced Oxidation processes.

Industrial-scale AOxPlus unit triggers development of home add-on unit

Due to growing concerns over cancer causing waterborne micro-contaminants such as Bayer-Monsanto’s Roundup® that are commonly found in municipally provided water supplies and are not easily removed by ordinary processes, OriginClear’s AOxPlus technology has become a potentially high-demand solution to advanced disinfection problems.

The nature of its genetically altered, synthetic chemical composition make Roundup and other similar manmade toxins and complex contaminants extremely difficult to remove from water sources. However, they can be “reacted out” with electrically produced hydroxyl radicals, which ionically and chemically decompose this class of extreme bio-toxins. AOxPlus oxidizes the contaminants in water at such an extreme level that it destroys all bio-toxic water contaminants. AOxPlus generates at one level free chlorine and at a much higher level, AOxPlus generates a significantly more oxidizing, denser cloud of hydroxyl radicals, or •OH.

This characteristic of the AOxPlus unit’s “air-breathing” and hydroxyl generating extreme oxidation technology has forecast the development of a household and small commercial use add-on product to supplement and augment smaller scale water treatment systems. This AOxPlus add-on, now in development, could provide a reliable micro-disinfection unit, that destroys this “Roundup class” of malicious bio-toxins, and be sold into the home water system installer network in America.

 

Water Tech Network

OriginClear licenses its core technologies to forward-looking and innovative technology companies and offers a limited number of exclusive partnerships to proven water industry professionals that are driving the advancement of solutions and water treatment systems to fill the urgent need of the people of our planet for clean and reliable water. Find out if your company or operation qualifies to join our Water Tech Network™. Become part of the team that operates Above and Beyond Clear Water™. Complete the form at bottom of page HERE.

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