To whom it may concern Dear Madam/Sir, Resulting from the awareness about the impacts and the requirements to create an active substance dossier and for securing their business, four totally independent ozone equipment manufacturers have joined forces, which resulted in the foundation of the Ozone Registration Group (ORG). The members of the ORG are: Ozonia, Degrémont Technologies AG, hereinafter referred to as Ozonia, Xylem/Wedeco, Xylem Europe GmbH, hereinafter referred to as Xylem, ProMinent Dosiertechnik GmbH, hereinafter referred to as ProMinent, BWT Wassertechnik GmbH, hereinafter referred to as BWT The members of the ORG represent the largest fraction of the European and even global ozone markets. The global market share of all members altogether is approximately 75%. Ozone generation The technical predominant applied and dominating technologies are ozone generation from oxygen (always and only) contained in gas or in water. Two widely used methods to generate ozone from oxygen in gas are: (1) the dielectric barrier discharge (DBD) 1 (mostly used), and (2) UV irradiation. Ozone can also be generated from oxygen in water using electrolysis. More information about the different ozone generation processes can be found in Annex to this letter. Ozone AS dossier of the ORG The ORG plans to submit the Ozone AS dossier in early 2015 and is also in the process of offering Letter of Access to all ozone equipment manufacturers and/or operators, in any case, before September 2015. The following PT-groups are covered in the AS dossier of the ORG: PTs 2, 4, 5 and 11. This preselection of PTs made by the ORG represents the majority and most relevant ozone applications, as summarized in table 1. 1 There are three terms to name the process of generation of ozone in a plasma: corona discharge, dielectric barrier discharge (DBD) and silent barrier discharge. All three terms are naming the same physical process. DBD is the most accurate term. 1
Table 1: Examples for applications of included PTs Application PT Size of use Swimming pool water 2 small medium / private user Rinsing water for bottles in beverage industry 4 small large Drinking water 5 small large Circulation water of cooling towers 11 small large Other PT groups covering marginal markets (such as PT 3, PT 12, etc.) could be of interest for third parties, but are not of interest for the ORG for various reasons. In addition, domestic applications of ozone for hygiene purposes will not be supported by the ORG, which considers the safety margin of some of these applications too limited. The ozone AS dossier of the ORG is currently in its final stage of preparation and will be submitted in early 2015. Furthermore the ORG is in the process of setting up a non-profit organization called EurO 3zon (future website: www.euro3zon.org) which will be licensed for issuing letters of access (LoA) to third parties. It is expected to be ready selling LoAs by the beginning of 2015. The price setting of LoA will be determined in a fair, transparent and non-discriminatory manner. Please also note that the ORG does not seek to make profit from the sales of LoA rather than recovering incurred costs in result of the dossier efforts. For the applicants the LoA will be a good and manageable investment with much lower risks. Buying an LoA as they can benefit of the efforts and in-depth knowledge of the ORG for a minimum period of 10 years. Additionally the ORG understands that any party with more extensive needs for covering specialized PT groups, being not in the scope of the ORG dossier, it is possible to submit a subsequent dossier that is extending the scope of the dossier written by the ORG. Product authorization The members of the ORG will submit product authorizations using the Union authorization procedure. To the knowledge of the ORG ozone generated by all technologies described in this letter could be covered via one (1) single product authorization dossier. The motivation for this choice is that independent from the chosen technology ozone is always generated from oxygen, contained in a feeding gas or water. If this position is not appreciated by the CA meeting than a differentiation could be made between ozone generated from (1) gas (using the dielectric barrier discharge method or UV irradiation) or from (2) water (using electrolysis). Authorization holder Most of the ozone generating devices that are operated in the market are of small to medium size. For those end-users a single-point authorization - e.g. by the manufacturer of the device is desired in all cases. Consequently to the view of the ORG the majority of end-users of ozone generators (customers) can never be the authorization holder. This is practical unachievable and requires more resources and knowledge from the end-users than these can invest (irrelevant of the size of their operations). As outlined above and explained in more details in Annex there are devices in the market that can be operated with all kinds of feed gas containing oxygen (air, enriched oxygen 2
from air, and pure oxygen). So the authorization holder should be independent from the feed gas which is used, consequently the manufacturer of the device is better suited to fulfill this role. Otherwise, this will have an economic impact on the sector we can hardly oversee, and will again only harm the industry involved, especially to the numerous end-users. Additionally, to have the enduser as the authorization holder would create a non-handable workload to the Competent Authorities, responsible to issue such authorization. Moreover we have to keep in mind that ozone generating equipment is mostly operated to oxidize undesired organic and inorganic substances during purification of water streams, while disinfection is not the majority application in the oxidation market. The disinfection capability is in most applications only an indirect side-effect for which the majority of the end-users are even not interested in. Yours sincerely, Mr. Bernhard Paolini, Degrémont Technologies AG, Chairman Dr. Matthias Rothe, ProMinent Dosiertechnik GmbH Dr. Matthias Hoffmann, BWT Wassertechnik GmbH Dr. Jörg Mielcke and Dr. Tim Pühmeier, Xylem Water Solutions Representatives of the Ozone Registration Group 10 th November 2014 3
Ozone generation Ozone generated from oxygen in gas Ozone can be generated from oxygen using ambient air (Oxygen ~21%) or technical oxygen (Oxygen >93%) by the dielectric barrier discharge method (Figure 1). Ozone gas is always a mixture of the feedgas source plus the ozone generated from its contained oxygen. This is classified and measured using so called ozone concentration and ozone capacity. The ozone concentration is that in the gas phase and not to be mismatched with a concentration in solution where the ozone is applied. Cooling water Kühlwasser FI PI FI TI Cooling Ablauf Water discharge Kühlwasser Luft oder Sauerstoff Feedgas Air or O 2 Ozone containing gas ozonhaltiges Gas Ref.: TECHNICAL RULE DVGW W 625:1999-03 Ozone Electrodes for ozone generation by dielectric barrier discharge Ozonerzeugungselemente Figure 1: Ozone generation from oxygen using ambient air (Oxygen ~21%) or technical oxygen (Oxygen >93%) More details on one of the generation processes, namely the dielectric barrier discharge method that is converting oxygen containing gas to ozone product gas, are presented in the next figure. Here is dry oxygen containing gas passing through the discharge gap (Figure 2) inside an ozone generator. While passing through the discharge gap a part of the oxygen is transformed to ozone. Since not all of the electric energy supplied to the process cannot be utilized in the ozone forming reaction it has to be removed by forced cooling. Sufficient cooling of the ozone generator is important as heat itself will lead to ozone destruction (to oxygen). The ozone containing gas (short: ozone gas or ozone) leaving the ozone generator is then supplied to the point of use depending on the feed gas type and ozone concentration desired. 4
Ref.: TECHNICAL RULE DVGW W 625:1999-03 1 Power Source 2 High Voltage Connection 3 Discharge Gap 4 Dielectric Material 5 Ground Electrode Figure 2: Ozone generation from oxygen by dielectric barrier discharge using ambient air (Oxygen ~21%) or technical oxygen (Oxygen >93%) Figure 3 gives a complete process overview for (cooling) water treatment with ozone generated from oxygen contained in different feeding gases. Dosing of N 2 or Air (opt.) Figure 3: Ozone generated from oxygen in gas complete process overview Figure 4 represents a scheme with more details on the ozone injection process in water treatment. 5
Ref.: TECHNICAL RULE DVGW W 625:1999-03 Figure 4: Ozone generated from oxygen in gas complete process overview Figure 5 gives a view on ozone bubbling through to-be-treated water after injection. Figure 5: Ozone injection - where ozone meets the water to be treated (Ref.: Ozonia) Figure 6 gives a view on medium-sized devices in which ozone is generated from oxygen contained in feeding gas, including more details on the ozone generating module contained therein. 6
Figure 6: Ozone generated from oxygen contained in feeding gas view on medium-sized installation and the ozone generating device contained therein (Ref.: BWT) Figure 7 gives more examples of small and medium-sized ozone generating devices in which ozone is generated from oxygen contained in feeding gas. Figure 7: Examples of typical ozone generators with small and medium-sized ozone production capacity and in which ozone is generated from oxygen contained in feeding gas (Ref.: ProMinent and Xylem/Wedeco) Figure 8 gives a view on large-sized ozone-generating devices in which ozone is generated from oxygen contained in feeding gas, including the required power supply unit. Furthermore even large ozone-generating devices can be made transportable, e.g. by installing in a transportable container. 7
Figure 8: Examples of typical ozone generators with large ozone production capacity and in which ozone is generated from oxygen contained in feeding gas (Ref.: Xylem/Wedeco and Ozonia) Ozone generated from oxygen in water Figure 9 presents a basic scheme on how a electrolytic ozone generator cell works in order to generate ozone from (atomic) oxygen contained in water. Figure 9: Basic electrolytic cell for generating ozone from oxygen contained in water (Ref.: Ozonia) Figure 10 presents a view on the Membrel, an installation that generates ozone from water by electrolysis. The 3 electrolysis cells operating in parallel can be clearly distinguished. Figure 11 presents a process scheme for raw water treatment using a Membrel ozone electrolyser. 8
Figure 10: View on the Membrel, a device for generating ozone from water by electrolysis (Ref.: Ozonia) Figure 11: Ozone generated from water by electrolysis process scheme for raw water treatment including Membrel ozone electrolyser (Ref.: Ozonia) Half-life time of ozone It is also important to know that ozone is a non-persistent oxidant, with a typically very short half-live time. The half-live time for ozone dissolved in water (at ph 7 and various temperatures): Half-life time 30 minutes 15 C 20 minutes 20 C 15 minutes 25 C 12 minutes 30 C 8 minutes 35 C Temperature 9
Ozone destruction Off-gases from a process containing trace levels of un-reacted ozone must be passed through a thermal or catalytic type vent ozone destruct unit prior to its release into the atmosphere. More details on catalytic or thermal ozone destruction devices are presented in more details in figures 12 and 13. Ref.: TECHNICAL RULE DVGW W 625:1999-03 Figure 12: Catalytic ozone destruction Figure 13: Thermal vent ozone destruction unit (Reference: Ozonia) 10
Ozone applications This list is showing a non-exclusive list of applications. The largest use for ozone resides in the use of treatment of municipal drinking and waste waters. Municipal Drinking Water applications are including: taste and odor reduction, color removal, iron (Fe) and manganese (Mn) reduction, disinfection, micro pollutant removal. Ozone improves filtration and flocculation processes. Ozone is also used for the removal of difficult-to-treat pathogens such as Giardia and Cryptosporidium. Municipal Wastewater Treatment - Ozone has also been widely used in applications for municipal wastewater treatment including disinfection of wastewater effluent and treatment of sludge. Ozone can selectively remove pollutants such as TOC, COD, BOD, cyanides, phenols, color and odor. Recently pharmaceutical and residuals of personal care products come in the focus of ozone treatment. Sludge treatment can reduce the adverse effects of bulking sludge and minimize the use of chemicals. Todays, resulting water scarcity ozone is being considered effective treatment for water reuse applications that is recycling municipal wastewater for a variety of applications ranging from irrigation to indirect potable use. Industrial Wastewater - see also municipal applications. Cooling Water Treatment - Ozone has been widely used for the treatment of water in cooling water towers. It is a very effective and powerful. Additionally it is an environmentally friendly method that is replacing conventional biocides. Food and Beverage - Ozone generators are used a variety of applications for food and beverage processing. Applications include the treatment of bottled water and disinfection of bottles and caps. Aquaculture - Ozone is used to treat feed, process (recirculating aquaculture systems) and waste waters in the aquaculture industry. Swimming pools - Ozone can be used for any pools being private, municipal or commercially used Ozone, producing no undesired and harmful disinfection by-products, in contrast with chlorine, it offers therefore incredible health benefits as such problems are being reduced or eliminated. History of ozone use Ozone is used, as a biocide in water treatment applications and disinfection processes for decades. This is dating back to prior 1900 only few decades after it has been discovered by Schönbein (1840). France is considered as the cradle of ozonation. By 1990 over 700 ozonation plants were in operation in France, primarily for drinking water. Ozone remains the choice for drinking water disinfection in France with most major cities using this treatment. There many other examples of the use of ozone in full scale: 1906 - First Full Scale Ozone Plant by Marius Paul Otto in Bon Voyage, France. 1909 - Second full scale plant in Nice, France. 1911 - Ozone Generators started in St. Petersburg, 1950-136 Ozone Plants in France, England and Germany serving 8 MM people. From this beginning thousands of ozone generators have been installed in drinking water plants around the world by 1999. Today, there are approximately 3,000+ ozone full scale plants in the world in operation today; with over 1,500 in Europe and over 260 in the US (all of varying capacity). 11
Glossary & Terms Ozone concentration is showing gramms of ozone per standard qubic meters [g(o 3)/Nm³]) or its weight percent [wt%]. Today typical ozone system produce ozone gas from air with a range of 2-6 wt% and from oxygen with concentration from 7 wt% to over 20 wt%. Ozone capacity is the actual amount of ozone produced per time. This typically is in the range from a few gramms per hour to many hundred kilogramms per hour. Systems utilizing feedgas air are typically producing not over 100 kg/h of ozone and oxygen driven ozone genratros reach over 250 kg/h of ozone prodced. Ozone dose is the amount of ozone supplied to a process (e.g. proportional to flow). Ozone Dose [g/m³] = Mass of ozone [g/h] / Flow of water [m³/h] Ozone generation utilizing UV light: Rare gas excimer sources generally radiate in the ultraviolet (UV) and vacuum-ultraviolet (VUV) wavelength range. Their unique broad band emission characteristics, high internal efficiency and the high energy photons make them suitable for ozone generation and more other applications. VUV excimer can generate ozone from air, technical oxygen and direct in water. However this technology finds predominantly applications in smaller applications for lower ozone capacities. 12