DGMK

Research Report

616-2

AdBlue as a Reducing Agent for the Decrease of NOx Emissions

from Diesel Engines of Commercial Vehicles

Part 2: Laboratory and Field Testing of AdBlue

AdBlue Logistics

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German Society for Petroleum and Coal Science and Technology

DGMK-Research Report 616-2

AdBlue as a Reducing Agent for the Decrease of NOx Emissions from Diesel Engines of Commercial Vehicles

Part 2: Laboratory and Field Test Results of AdBlue

AdBlue Logistics

Abstract: In order to comply with stringent exhaust gas emission standards issued by the European Union for 2005 and 2008 for diesel engines of HD (heavy duty) commercial vehicles, the European automobile industry has chosen the „selective catalytic reduction“ (SCR) technology. By this method, nitrogen oxide (NOx) emissions can be reduced by 60 % vis-à-vis current standards. In addition they agreed to use „AdBue“, an aqueous solution of urea, as a reducing agent, which is needed to reduce the oxides of nitrogen into elementary nitrogen. The first vehicles equipped with this new technology will be launched in January 2005.

This report explains the mechanism of the SCR/urea technique and outlines production as well as physical, chemical and environmental properties of urea and AdBlue. It summarises the results of laboratory and field tests, which were run in order to investigate the technical and logistical requirements of this new technique, and it describes first experiences gained at public service stations, which have been equipped with an AdBlue filling station. Finally, the report reflects on what is needed for the build-up of an AdBlue distribution network.

Length of the report: 27 pages, 3 tables, 4 figures, 4 annexes, 13 references Duration: 2003 – 2004 Author: Dr. Wolf-Peter Trautwein, Hamburg Project Coordination: Dr. B.-R. Altmann, DGMK, Hamburg DGMK Committee: Storage, Transportation and Distribution DGMK Division: Refining and Product Application Published: Hamburg, February 2005

Projectadvisors: A. Aehle, ELAFLEX Tankstellentechnik GmbH, Hamburg

M. Angelopoulos, ESSO Deutschland GmbH, Hamburg E. Auer, AMI Agrolinz Melamine International GmbH, A – Linz Dr. K. E. Austmeyer, HORN GmbH & Co. KG, Flensburg J.-U. Brandis, UNITI e.V. , Hamburg J. Ebner, Daimler Chrysler AG, Stuttgart H. T. Ebner, VDA Verband der Automobilindustrie e.V., Frankfurt G. Emmerling, MAN Nutzfahrzeuge AG, Nürnberg M. Frankrone, Yara Industrial GmbH, Oberhausen A. Graf Bülow, BfT e.V., Bonn M. Günther, Tankschutz Bott GmbH, Bad Brückenau L. Hahn, OMV Deutschland GmbH, Landshut J. Heise, Union Technik GmbH & Co. KG, Duisburg P. Jagnow, Dresser Europe GmbH, Einbeck H.-J. Kalisch, ESSO Deutschland GmbH, Hamburg F.-J. Kersting, Gilbarco GmbH & Co KG, Salzkotten S. Kunter, FAFNIR GmbH, Hamburg B. Krause, Umweltbundesamt, Berlin H. Maahsen, TOKHEIM GmbH, München M. Øverlie, Yara International ASA, N - Oslo P. Pröhl, SKW Stickstoffwerke Piesteritz GmbH, Lutherstadt Wittenberg G. Sasse, Mineralölwirtschaftsverband e.V., Hamburg M. Schmidt, Shell Global Solutions (Deutschland) GmbH, Hamburg P. Schnell, Total Deutschland GmbH, Berlin B. Scholtissek, Deutsche BP AG ARAL Forschung, Bochum Dr. B. Schulwitz, GMA-Ges. für Mineralöl-Analytik und Qualitätsmanagement mbH + Co. KG, Hamburg Dr. J. Seiler, VDA Verband der Automobilindustrie e.V., Frankfurt T. Spietczack, Shell Deutschland Oil GmbH, Hamburg Dr. M. Stöckli, Iveco Motorenforschung GmbH, CH – Arbon P.M.J. Thomassen, Kuwait Petroleum Research & Technology B.V., NL – Hoogvliet Dr. K. von Kurnatowski, SKW Stickstoffwerke Piesteritz GmbH, Lutherstadt Wittenberg F. Weidner, BASF AG, Ludwigshafen

Deutsche Wissenschaftliche Gesellschaft

für Erdöl, Erdgas und Kohle e.V.

DGMK-Forschungsbericht 616-2

AdBlue als Reduktionsmittel für die Absenkung der NOx-Emissionen aus Nutzfahrzeugen mit Dieselmotor

Teil 2: AdBlue-Erprobung in Labor- und Feldtesten AdBlue-Logistik

Kurzfassung: Um die verschärften Abgasnormen für Dieselmotoren schwerer Nutzfahrzeuge zu erfüllen, die die Europäische Union für die Jahre 2005 und 2008 (Euro 4 bzw. 5) erlassen hat, hat die europäische Automobilindustrie sich auf das Verfahren der „selektiven katalytischen Reduktion“ (SCR-Verfahren) geeinigt. Mit dieser Methode ist es möglich, die Stickoxid-Emissionen um die erforderlichen 60 % gegenüber den heutigen Standards zu reduzieren. Außerdem hat sie sich darauf geeinigt, „AdBlue“, eine wässrige Harnstoff-Lösung, als Reduktionsmittel zu verwenden, das benötigt wird, um die Stickoxide in elementaren Stickstoff umzusetzen. Die ersten, mit der SCR-Technologie ausgerüsteten Nutzfahrzeuge werden ab 2005 auf den Markt gebracht.

Dieser Forschungsbericht erläutert die Wirkungsweise der SCR/Harnstoff-Technologie und beschreibt Produktion sowie physikalische, chemische und ökologische Eigenschaften von Harnstoff und AdBlue. Er fasst die Ergebnisse von Labor- und Feldtesten zusammen, die durchgeführt wurden, um die technischen und logistischen Anforderungen der neuen Technologie zu untersuchen, und schildert erste Erfahrungen, die an öffentlichen Tankstellen mit einer AdBlue-Zapfanlage gewonnen wurden. Schließlich schildert er, was für den Aufbau eines europaweiten, flächendeckenden Verteilungsnetzes für AdBlue erforderlich ist.

Berichtsumfang: 27 Seiten, 3 Tabellen, 4. Abbildungen, 4 Anhänge Laufzeit: 2003 – 2004 Autor: Dr. Wolf-Peter Trautwein, Hamburg Projektkoordination: Dr. B.-R. Altmann, DGMK, Hamburg DGMK-Fachausschuss: Lagerung, Transport und Verteilung DGMK-Fachbereich: Verarbeitung und Anwendung Veröffentlichung: Hamburg, Februar 2005

Projektbegleitung: A. Aehle, ELAFLEX Tankstellentechnik GmbH, Hamburg

M. Angelopoulos, ESSO Deutschland GmbH, Hamburg E. Auer, AMI Agrolinz Melamine International GmbH, A – Linz Dr. K. E. Austmeyer, HORN GmbH & Co. KG, Flensburg J.-U. Brandis, UNITI e.V. , Hamburg J. Ebner, Daimler Chrysler AG, Stuttgart H. T. Ebner, VDA Verband der Automobilindustrie e.V., Frankfurt G. Emmerling, MAN Nutzfahrzeuge AG, Nürnberg M. Frankrone, Yara Industrial GmbH, Oberhausen A. Graf Bülow, BfT e.V., Bonn M. Günther, Tankschutz Bott GmbH, Bad Brückenau L. Hahn, OMV Deutschland GmbH, Landshut J. Heise, Union Technik GmbH & Co. KG, Duisburg P. Jagnow, Dresser Europe GmbH, Einbeck H.-J. Kalisch, ESSO Deutschland GmbH, Hamburg F.-J. Kersting, Gilbarco GmbH & Co KG, Salzkotten S. Kunter, FAFNIR GmbH, Hamburg B. Krause, Umweltbundesamt, Berlin H. Maahsen, TOKHEIM GmbH, München M. Øverlie, Yara International ASA, N - Oslo P. Pröhl, SKW Stickstoffwerke Piesteritz GmbH, Lutherstadt Wittenberg G. Sasse, Mineralölwirtschaftsverband e.V., Hamburg M. Schmidt, Shell Global Solutions (Deutschland) GmbH, Hamburg P. Schnell, Total Deutschland GmbH, Berlin B. Scholtissek, Deutsche BP AG ARAL Forschung, Bochum Dr. B. Schulwitz, GMA-Ges. für Mineralöl-Analytik und Qualitätsmanagement mbH + Co. KG, Hamburg Dr. J. Seiler, VDA Verband der Automobilindustrie e.V., Frankfurt T. Spietczack, Shell Deutschland Oil GmbH, Hamburg Dr. M. Stöckli, Iveco Motorenforschung GmbH, CH – Arbon P.M.J. Thomassen, Kuwait Petroleum Research & Technology B.V., NL – Hoogvliet Dr. K. von Kurnatowski, SKW Stickstoffwerke Piesteritz GmbH, Lutherstadt Wittenberg F. Weidner, BASF AG, Ludwigshafen

Table of Contents Summary 1

Zusammenfassung 3

1 Introduction: Reason and Objective 5 1.1 Euro standards for the reduction of exhaust gas emissions 5 1.2 The technology of selective catalytic reduction 6 1.3 Technical and logistic requirements 8

2 Properties of Urea and AdBlue 9 2.1 Urea 9 2.2 AdBlue 9

3 Laboratory and Field Testing of AdBlue 11 3.1 Stability tests 11 3.2 Field tests 12 3.3 Compatibility with other materials 12 3.4 Emulsion test 12 3.5 Result 12

4 Field Tests with SCR Vehicles 13 4.1 Functional tests of DaimlerChrysler 13

4.1.1 Winter tests in Rovaniemi, Finland, early 2003 13 4.1.2 Winter tests in Rovaniemi, Finland, winter of 2003/04 14 4.1.3 Summer tests in Spain in 2004 14 4.1.4 Result 15

4.2 Functional tests by MAN 15 4.2.1 Summer tests in 2003 and 2004 15 4.2.2 Winter tests in 2003/04 15

5 AdBlue Testing at Public Service Stations 17 5.1 OMV service station at Dingolfing, Bavaria 17 5.2 Total service stations at Berlin and Stuttgart 18

6 Logistics 21

7 Conclusions 23

8 References 25

9 Attachments 27

1

Summary The Parliament of the European Union has issued stricter emission standards (Euro 4 and 5) for HD diesel engines for the years 2005 and 2008. Compared to current limits, an emission reduction of 60 % for nitrogen oxides and of 80 % for particulate matter will be required. After testing and comparing various technical options, the European manufacturers of HD commercial vehicles have agreed on one method for meeting these standards: the „selective catalytic reduction“ (SCR technology), which, in the presence of a reducing agent, converts nitrogen oxides into nitrogen and water, which are natural components of our atmosphere. The European automobile industry has also agreed on one reducing agent: an aqueous solution of urea, which will be distributed under the trade name „AdBlue“. This report describes the mechanism and advantages of the SCR/urea technology. The main reason for the decision of the manufacturers of HD vehicles was the fact that this technique, according to current knowledge, appears to be the only method, which enables the necessary decrease of all exhaust gas emissions to the level of Euro 5, while maintaining engine optimization with regard to performance and fuel economy. Furthermore this method can be applied to all types of engines. In addition this report describes properties and environmental impact of urea as well as its aqueous solution. According to the European product classification guideline, AdBlue poses no serious risk to humans, animals or the environment, if properly handled. Materials used in direct contact with AdBlue must be checked for compatibility with this product. For production, transportation and storage of AdBlue very stringent quality requirements have to be observed, in order to avoid impairment of the efficiency of the SCR catalyst. Within the scope of this project, a number of pilot and laboratory tests has been conducted, to investigate storage and thermal stability as well as compatibility of AdBlue with other materials. Under correct storage conditions, AdBlue is a stable, easy to handle solution, which does not attack highly alloyed steel, various plastic materials or seals and which does not form stable emulsions with fuel. In extended vehicle tests, the European automobile industry has investigated the suitability of the SCR technology for decreasing NOx emissions and of AdBlue as a reducing agent. This report describes test results which were achieved under extreme climatic conditions thus confirming the suitability of the method. In the course of 2003, the first public service stations have been equipped with AdBlue filling devices. The experiences, gained since then, have confirmed good storage stability and easy handling of the product. The important European manufacturers of commercial vehicles will offer HD trucks equipped with the SCR/urea technology starting in January 2005. With an AdBlue tank of 100 l capacity, such vehicles have a travelling range of about 6,000 km. In Germany, two thirds of the HD trucks are refuelled at private filling stations of the larger fleet owners, where they could also refuel AdBlue. For an area covering Europe-wide supply of the other vehicles, it would be sufficient, if the mineral oil trade would equip a number of their public service stations with AdBlue filling devices along the main expressways. Starting in 2006, it is planned to also offer lighter trucks and busses with SCR technique. At that time, private filling stations of larger fleet owners

2

and some public service stations along the main expressways alone may not be sufficient for an area covering AdBlue supply. In the meantime AdBlue filling equipment is offered, ranging from smaller mobile filling systems to fully integrated filling stations with storage tank, heated pipes, pumps and standardized filling nozzles. The European producers of AdBlue have entered into contracts with distributors of chemicals to establish a Europe-wide distribution network for AdBlue. Thus the area covering supply of HD vehicles with AdBlue should be secured – at least for the initial phase.

3

Zusammenfassung Das Parlament der Europäischen Union hat für die Jahre 2005 und 2008 verschärfte Abgasnormen für Dieselmotoren von schweren Nutzfahrzeugen verabschiedet, die für die Emission von Stickoxiden eine Reduktion um insgesamt 60 % und die von Partikeln um 80 % gegenüber den zur Zeit geltenden Grenzwerten verlangen (Euro 4 und Euro 5). Nach Erprobung und Vergleich verschiedener technischer Möglichkeiten haben sich die europäischen Hersteller der schweren Nutzfahrzeuge auf ein Verfahren zur Einhaltung dieser Grenzwerte geeinigt: die „selektive katalytische Reduktion“ (SCR-Verfahren), bei der die Stickoxide in Gegenwart eines Reduktionsmittels in Stickstoff und Wasserdampf, also natürliche Bestandteile unserer Atmosphäre, umgesetzt werden. Die europäische Automobilindustrie hat sich ferner darauf verständigt, einheitlich eine wässrige Lösung von Harnstoff als Reduktionsmittel einzusetzen, die unter der Bezeichnung „AdBlue“ vertrieben werden soll. Im vorliegenden Bericht werden Wirkungsweise und Vorteile der SCR/Harnstoff-Technologie beschrieben. Maßgeblich für den Beschluss der Nutzfahrzeughersteller ist die Tatsache, dass diese Technik nach heutiger Kenntnis das einzige Verfahren darstellt, welches die erforderliche Absenkung aller Abgasemissionen auf das Niveau von Euro 5 bei gleichzeitiger Optimierung des Motors hinsichtlich Leistungsverhalten und Kraftstoffverbrauch ermöglicht. Außerdem ist dieses Verfahren bei allen Motoren anwendbar. Der Bericht beschreibt außerdem Eigenschaften und Umweltverhalten sowohl des Harnstoffs als auch seiner wässrigen Lösung. AdBlue ist gemäß den europäischen Einstufungsrichtlinien bei ordnungsgemäßer Verwendung ungefährlich für Mensch, Tier und Umwelt. Beim Umgang mit AdBlue sind Werkstoffe mit entsprechender Chemikalienbeständigkeit zu verwenden. An Produktion, Transport und Lagerung von AdBlue werden außerdem besonders strenge Qualitätsanforderungen gestellt, damit der SCR-Katalysator durch das Reduktionsmittel nicht in seiner Wirksamkeit beeinträchtigt wird. Im Rahmen dieses Projektes wurden einige Pilot- und Laborteste durchgeführt, mit denen die Lager- und thermische Stabilität sowie die Verträglichkeit von AdBlue mit anderen Materialien untersucht wurden. AdBlue ist unter normalen Lagerungsbedingungen eine stabile Lösung, die sich gut handhaben lässt, hochlegierte Stähle sowie eine Reihe von Kunststoffen und Dichtungsmaterialien nicht angreift und mit Kraftstoffen keine stabilen Emulsionen bildet. Die europäische Automobilindustrie hat in ausgedehnten Fahrzeugtesten die Eignung der SCR-Technologie zur Herabsetzung der NOx-Emissionen sowie der AdBlue-Lösung als Reduktionsmittel untersucht. Der Bericht beschreibt die Testergebnisse, die vor allem unter extremen klimatischen Bedingungen ermittelt wurden und die Eignung dieses Verfahrens bestätigten. Im Laufe des Jahres 2003 wurden die ersten öffentlichen Tankstellen mit einer AdBlue-Zapfanlage ausgerüstet. Die hierbei gemachten Erfahrungen bestätigten die gute Lagerstabilität und leichte Handhabbarkeit des Produktes. Mehrere große, europäische Hersteller von Nutzfahrzeugen werden ihre schweren LKWs ab Januar 2005 in einer SCR-Version anbieten. Mit einem AdBlue-Tank von 100 l Kapazität ausgerüstet, haben solche Fahrzeuge eine Reichweite von rund 6000 km. Zwei Drittel der schweren LKWs in Deutschland werden an betriebseigenen

4

Tankstellen betankt, wo sie dann auch mit AdBlue versorgt werden könnten. Für eine flächendeckende europaweite Versorgung der übrigen Fahrzeuge würde es ausreichen, wenn die Mineralölwirtschaft entlang der Hauptverkehrsrouten einige Tankstellen mit entsprechenden AdBlue-Zapfsäulen ausrüsten würde. Ab 2006 werden auch leichtere LKWs (ab ca. 6 t zGG) und Busse mit SCR-Technik auf den Markt kommen. Für diese Fahrzeuge reichen dann betriebseigene Tankstellen der Fuhrparks und wenige öffentliche Tankstellen entlang der Hauptverkehrswege allein nicht mehr für eine flächendeckende AdBlue-Versorgung aus. Inzwischen werden AdBlue-Zapfanlagen angeboten, die von einfachen mobilen Füllsystemen bis zu voll integrierten Tankanlagen mit Lagertank, beheizten Leitungen, Pumpen und standardisierten Zapfpistolen reichen. Die europäischen Hersteller von AdBlue haben internationale Kooperationsverträge mit Vertriebspartnern, die sich auf die Distribution von Chemikalien spezialisiert haben, abgeschlossen. Damit sollte zumindest für die Anlaufphase die flächendeckende Versorgung der schweren Nutzfahrzeuge mit AdBlue europaweit gesichert sein.

5

1 Introduction: Reason and Objective

1.1 Euro standards for the reduction of exhaust gas emissions

DGMK Research Report 616 – 1 of September 2003 dealt with the issue: „AdBlue as a reduction agent for the decrease of nitrogen oxide emissions (NOx) from diesel engines of commercial vehicles“ [1]. As described there, at the end of 1999, the parliament of the EU has issued stricter exhaust gas limit values for diesel engines of heavy duty (HD) commercial vehicles. According to these new standards, NOx emissions have to be reduced in two steps in 2005 (Euro 4) and 2008 (Euro 5), respectively, each time by 30 % vis-à-vis the current limits of Euro 3. Significantly tighter limits apply to the other pollutants, as well: for carbon monoxide (CO), unburned hydrocarbons (HC) and most importantly for particulate matter (PM) (table 1 and 2). Pollutant Euro 3

from 2001 Euro 4

from 2005 Euro 5

from 2008 Nitrogen oxides (NOx) 5.0 3.5 2.0 Carbon monoxide (CO) 2.0 1.5 1.5 Unburned hydrocarbons (HC) 0.66 0.46 0.46 Particulate matter (PM) 0.1 0.02 0.02 Tab. 1: Exhaust gas limits of the EU standard 99/96/EG for HD commercial

vehicles (> 3.5 t; > 85 kW) in g/kWh Tab. 2: Exhaust gas limits for HD commercial vehicles in percent vis-à-vis

the current standard (Euro 3)

020406080

100

Perc

ent

NOx PM CO HC

Exhaust Gas Limits

Euro 3Euro 4Euro 5

6

Whereas the limit values of Euro 4 can still be met with various methods, such as exhaust gas recirculation in combination with a particle filter, the simultaneous reduction of NOx and particle emissions to the values of Euro 5 poses a technical problem, which, according to current knowledge, can only be solved with one specific method described in the following paragraph [3].

1.2 The technology of selective catalytic reduction

After testing and comparing different technical options, the European manufacturers of HD commercial vehicles have agreed on one method for compliance with stricter NOx limit values: the “selective catalytic reduction” (SCR method) [4]. Ammonia (NH3) is used as a reducing agent; however, due to its aggressiveness and toxicity, it is not applied as such, but in the form of an innocuous substance, which releases NH3 in the exhaust gas stream, only. The European automobile industry has agreed to use a 32.5 % by weight aqueous solution of urea as a reducing agent, which is distributed under the trade name “AdBlue”. When using the SCR technology, the engine can be operated under optimal conditions, thus minimising fuel consumption and therefore CO2 emissions as well as the discharge of all pollutants except NOx. After the combustion gases have left the engine, they first run through a pre-oxidation catalyst where unburned hydrocarbons, carbon monoxide and particulate matter are oxidised as completely as possible. NO is oxidized partly to NO2, because the subsequent reduction proceeds fastest at a mixing ratio of NO:NO2 of 1:1. Then a pump, which is controlled by a monitoring unit, injects AdBlue from a separate tank into the hot exhaust gas stream, where it hydrolyses to NH3 and CO2. In the actual selective reduction, NH3 reacts with the NO/NO2 mixture to form nitrogen and water (steam), which are regular components of our breathing air. This chemical reaction takes place on a catalytic converter consisting of transition metal compounds on a ceramic carrier. Small unused amounts of NH3 can be oxidised in a subsequent oxidation catalyst (figure 1):

7

Chemical reactions: • Partial oxidation: 2 NO + O2 → 2 NO2 • Urea hydrolysis: (NH2)2CO + H2O → 2 NH3 + CO2 • Selective reduction: NO + NO2 + 2NH3 → 2N2 + 3H2O

Fig. 1: Scheme of a combined deNOx system for exhaust gas treatment on the basis of the SCR method [4] The European manufacturers of commercial vehicles have agreed to use SCR/urea technology, because this method offers a number of advantages, which no other method known at this time can provide [5]:

• The engine can be operated at optimal conditions, because the nitrogen oxides formed in the process are converted into elementary and therefore innocuous nitrogen in a second step behind the engine.

• The optimal engine adjustment results in a better efficiency (about 5 % less fuel consumption) and therefore in less CO2 emissions.

• The discharge of all pollutants (NOx, PM, CO and CH) is minimised, thereby complying with the stringent requirements of Euro 4 and 5.

• The SCR/urea technology is applicable to all types of engines and functions with diesel fuels of varying qualities.

• The SCR method is maintenance-free and designed for the entire lifespan of the vehicle.

• SCR has no influence on service and oil change intervals of the vehicles. • In some European countries, SCR equipped vehicles are eligible for certain

financial incentives, such as reduced expressway fees (10 instead of 12 cent/km in Germany, starting in 2005, planned in Switzerland and Austria), lower taxes or more favourable depreciation rates.

In the medium- and long-term, a technical and economical alternative to the SCR technology for compliance with the Euro 5 standard is not in sight. This method offers the most cost-efficient solution with regard to environmental protection and efficiency.

8

1.3 Technical and logistic requirements

After the European car manufacturers had committed themselves to the SCR/urea technology, they then expected that mineral oil industry and trade will provide the required AdBlue - possibly in the same way like fuels – through the public service station net in a Europe-wide and area-covering manner. This expectation resulted in a number of unresolved issues with regard to technical and logistic requirements:

• Standardisation and quality assurance of AdBlue (from product delivery by the producer to sale at the dispense pistol)

• Supply and storage of AdBlue at the service station • Temperature effects (crystallisation, hydrolysis) and storage stability • Compatibility with other materials (metals, concrete pavement, seals) • Behaviour in an oil separator • Interface filling nozzle/filler neck for the AdBlue fuelling

The automobile and mineral oil industry have run various laboratory, service station and vehicle tests, in order to resolve these questions. The results are described in this research report 616-2 (chapter 3 to 5). In addition, this report contains some considerations about the Europe-wide supply of HD commercial vehicles with AdBlue (chapter 6).

9

2 Properties of Urea and AdBlue

2.1 Urea

In view of the importance of urea for the application of the SCR method, this chapter summarises the most important properties of this substance and its aqueous solution (see also DGMK Research Report 616-1 and the literature quoted there). Urea is a colour- and odourless, crystalline substance, which is produced synthetically in large amounts from ammonia and carbon dioxide. It is used mainly in agriculture as a fertiliser and feed additive, but also in the plastic, textile, pharmaceutical and particle board industry. Urea as well as its aqueous solutions (e. g. AdBlue) are of low acute toxicity and do not act as a skin or eye irritant; sensitising, carcinogenic or mutagenic effects are unknown. Therefore, urea is not listed as a dangerous substance according to the Hazardous Substances Ordinance and does not require any labelling according to the Chemicals Act. Urea poses only a small risk to surface waters and is easily biodegradable. According to transport regulations, the aqueous solution of urea is classified as a non-hazardous material and not subject to the Hazardous Incident Ordinance. Urea is classified by the Consulting Committee for environmentally relevant, existing substances of the Society of German Chemists in group III, comprising products which represent a low endangering potential for the general population and the environment according to current knowledge [6].

2.2 AdBlue

AdBlue is a 32.5 % by weight solution of technically pure urea in demineralized water. This concentration was chosen, because at this urea content, the crystallisation point reaches a minimum of minus 11 °C (eutectic mixing ratio). High demands are made on the purity of the solution, not only during production, but also during handling, transportation and storage. AdBlue must be kept free of any metal ions (e.g. Na, K, Mg, Ca, Al and especially heavy metals), because their salts can clog the pores of the ceramic carrier material or poison the active centres of the catalyst thereby rendering it ineffective [7]. AdBlue is not inflammable, but can release ammonia under heat exposure. According to the European product classification guideline 67/548/EU, AdBlue poses no serious risk to humans, animals or the environment [8]. However, it should be stored separately from nitrates and nitrites. Urea solution corrodes certain materials, such as copper, zinc and unalloyed steels. Therefore containers, pipes and pumps must be made of stable materials, such as highly alloyed austenitic steels, different plastic materials (polyethylene, -propylene, -isobutylene and -fluoroethylene, Viton etc.) and plastic coated metal containers. Unalloyed and galvanised steels as well as copper and its alloys are not suited. In view of the crystallisation of AdBlue, which starts at minus 11 °C, storage tanks, filling stations and valves must be insulated and heated during the winter, if necessary. Within Cefic, the European producers of urea have prepared a “quality assurance guidance document”, which describes recommended practices for handling, transport and storage of the aqueous urea solution to ensure that the AdBlue quality is maintained from production to the sale to the end-user. This document is shown in

10

attachment 9.1 of this report, dated 15.07.2004. The newest version can be obtained from the internet [8]. As the European urea producers guarantee, their production capacities are sufficient to cover the AdBlue demand in Europe, which, according to the latest forecast of ACEA, will increase from about 280,000 t in 2006 to almost 4 million t in 2012 (information of ACEA from 2. Nov. 2004).

Tab. 3: AdBlue demand in the European Union according to an estimate of

ACEA, November 2004

0

500,000

1,000,000

1,500,000

2,000,000

2,500,000

3,000,000

3,500,000

4,000,000

4,500,000

2005 2006 2007 2008 2009 2010 2011 2012Year

AdB

lue

Dem

and

[t/ye

ar]

Total AdBlue Demand (EU-25)

Total AdBlue Demand (EU-15)

Total AdBlue Demand (10 new EU states)

11

3 Laboratory and Field Testing of AdBlue In 2003, the Research Department of Aral, Bochum, has carried out the following tests within the scope of DGMK Research Project 616: 1. Stability tests

• Storage stability • Thermal stability

2. Field tests

• Handling: filler nozzle/spills/ drippings/cleaning • Winter operation (temperatures between –4 and –8 °C) • Summer operation (temperatures up to 32 °C)

3. Compatibility with other materials

• Concrete • Metals and plastic material • Seals

4. Emulsion test

• Separation of fuel/AdBlue mixtures These tests have shown the following results:

3.1 Stability tests

AdBlue was stored at room temperature; after half a year, the solution showed no significant changes of the quality characteristics defined by DIN V 70 070. At the end of the test, all specified values were within the limits of the DIN standard. In storage stability tests at higher temperatures, slightly different results were achieved: At a storage temperature of 50 °C, only very small amounts of ammonia were developed; after about 100 hours at 70 °C, the NH3 concentration of the AdBlue solution increased beyond the limit value of 0.2 % by weight as specified by the DIN standard, and it reached a value of 1.4 % by weight NH3 after 350 hours (attachment 9.2). Based on these tests of Aral, AdBlue is relatively stable at storage temperatures of up to 50 °C; at higher temperatures, however, an increasing hydrolysis of urea takes place.

12

3.2 Field tests

For these tests, Aral installed an ‘intermediate bulk container’ (IBC), which was filled with AdBlue. Handling of the urea solution turned out to be without any problems. Stains of smaller drops, which resulted from filling AdBlue with a filler nozzle, could be removed easily. Lasting stains developed only, if these drops were not removed from the concrete floor (B35) within a few days. Summer operations at temperatures of up to 30 °C confirmed the lab tests about the thermal stability of AdBlue. Apart from very minor smells, no significant changes or nuisance factors could be attributed to AdBlue (the odour threshold value of NH3 is between 10 and 20 ppm [9]. Winter operations could not be run, since ambient temperatures did not fall below –8 °C and therefore did not reach the crystallisation point of AdBlue of –11 °C. No problems were observed at a temperature of –8 °C, which prevailed for a few days,.

3.3 Compatibility with other materials

B 35 concrete cubes and plates were exposed to AdBlue and water for six weeks. Subsequently, the solutions were analysed for their calcium content. It was demonstrated that AdBlue does not extract more Ca than water from the concrete, which is used as a pavement at service stations. Tests about the compatibility of AdBlue with various metals and plastic materials confirm the data as shown in DIN V 70 070. Polysulfide was investigated as an example for seals, and it was found to be stable.

3.4 Emulsion test

Mixtures of AdBlue and diesel fuel were investigated according to an Aral in-house test method, in order to check, if AdBlue forms stable emulsions with petrol or diesel fuel, which could impair the function of the oil separator of a service station. For this purpose, an AdBlue/diesel fuel mixture was stirred in a Turax for 30 seconds at 11,000 rpm. The emulsion formed in the Turax was then centrifuged for 5 minutes at 1,600 rpm. Thereafter, the emulsion had completely separated into an aqueous and a hydrocarbon layer. According to Aral’s experiences, these test results show, there are no problems to be expected with emulsion formation in an oil separator.

3.5 Result

The results of the above mentioned pilot and lab tests of the Aral Research Department can be summarized as follows: AdBlue is a stable solution, even under extended time periods, if stored properly. It can be handled without difficulties, does not attack concrete, highly alloyed steels, plastic materials and seals, and it does not form stable emulsions with fuel oils.

13

4 Field Tests with SCR Vehicles

4.1 Functional tests of DaimlerChrysler

Already prior the decision for the SCR method, DaimlerChrysler had tested ten Mercedes-Benz commercial vehicles over a distance totalling 3.2 million kilometres [10]. The specific purpose of this report is to describe more recent field tests, which were mainly carried out to test the suitability of the method under extreme climatic conditions.

4.1.1 Winter tests in Rovaniemi, Finland, early 2003 The results of the first winter tests with regard to the vehicles can be summarised as follows:

• The components have proven their suitability for winter conditions. • The heating of the AdBlue system with cooling water was successful. • The total system of the vehicles needs further optimisation; especially the

heating system under extreme conditions requires improvement. • For the assessment of the total system, additional investigations in a cooling

cell and further tests are planned. The results of these winter tests with regard to the AdBlue filling stations yielded the following:

• In the cooling cell, vehicles could be refuelled at temperatures down to –20 °C without any problems.

• During subsequent field tests in Finland, the content of the tank was heated to more than 10 °C. Nevertheless, filling nozzle and pump occasionally failed.

• The outdoor version of the AdBlue filling station worked satisfactorily at temperatures to –20 °C. At temperatures between –30 and –34 °C, pipes and pumps froze up, resulting in a rupture of an impeller gear tooth. The filling station worked satisfactorily again, after exchange of the impeller gear and raising the temperature over 24 °C by intensified heating.

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4.1.2 Winter tests in Rovaniemi, Finland, winter of 2003/04 After initial tests of four vehicles and two filling stations, the vehicles were parked from Dec. 15, 2003 to Jan. 22, 2004. Four freezing cycles with complete freezing and thawing were carried out during this time. No problems were experienced during the subsequent start and operation, but the heating by cooling water required about two hours to thaw the content of a large, completely frozen AdBlue tank. However, by appropriate design of the heating pipes, it was possible, to pump AdBlue out of the tank already after a heating period of about 15 minutes. Since it takes two to three days, until an AdBlue tank is completely frozen – even at very low temperatures – these heating times should not pose any problem in practise, because commercial vehicles are usually operated without any breaks, and therefore, the tank filling is kept at sufficiently high temperatures by the heated cooling water of the engine. Successful driving tests with twelve Euro 4 vehicles at temperatures down to –20 °C were carried out from Jan. 23 to Feb. 16, 2004. Heated mobile filling stations of Bott (1000 l IBC) and Ucon (1000 l container) were used for refuelling. The Elaflex filling nozzle was equipped with a magnetic lock; its final cut-off system needs further improvement (too much dripping).

4.1.3 Summer tests in Spain in 2004 Fifteen Euro 4 trucks (Actros, Axor and Atego as well as two city buses, one Unimog and one Econic) were tested in Granada from July 5 to August 2, 2004 at ambient temperatures between +30 °C and +40 °C. The test vehicles covered a distance of almost 100,000 km. No functional failures and no breakdown of the exhaust gas after-treatment occurred. Again, filling stations of Bott and Ucon with filling nozzles of Elaflex were used. AdBlue had been produced by Yara. A total of 1,400 l AdBlue were consumed during these tests. The heavier vehicles consumed between 1.4 and 2.0 l/100 km, the smaller ones 0.8 to 1.4 l/100 km; this corresponds to 4 – 5 % of diesel consumption. The investigation was focussed on the following crucial points:

• Function of the dosage unit: The control of the dosage unit worked satisfactorily. There were no leaks. Smaller leaks at other locations could be eliminated.

• Testing of the AdBlue tank unit on board the vehicles under extreme heat and

road conditions: The vehicles were equipped with aluminium tanks (AlMg3 alloy); their capacity ranged from 25 to 110 l. There were no malfunctions of the tank unit, even when the tanks on the vehicle were exposed to direct sun light, thus reaching temperatures of 40 to 50 °C. There were no leaks at the tanks and no nuisances by odours during the venting of tanks.

15

• Measurements at the SCR unit at high ambient temperatures: The unit functioned troublefree. All temperatures measured were at target value. Neither the catalytic converter nor the adjacent components reached inadmissible temperatures.

• Testing the refuelling process: The refuelling unit had a pump delivery rate of

30 l/min. After optimisation of the filling nozzle by Elaflex, the cut-off system of the pump worked correctly, when the tank was full. However, the discharge of remaining amounts of liquid after cut-off were too high despite the magnetic cut-off. There were no nuisance factors caused by odours during the refuelling process.

4.1.4 Result In summary, it can be stated that the SCR technology is a reliable method for the reduction of NOx emissions; it functions satisfactorily – even under the extreme conditions of a winter in Finland or a summer in southern Spain.

4.2 Functional tests by MAN

MAN conducted the following vehicle tests with AdBlue:

4.2.1 Summer tests in 2003 and 2004 A truck equipped with SCR technology was driven through Spain for three weeks during the summer of 2003. A plastic tank filled with AdBlue was installed on the vehicle. Refuelling did not pose any problems despite high temperatures. There were no noticeable odours. The test was repeated in southern Spain, starting July 7, 2004. Again there were no technical problems or any nuisance factors by odour.

4.2.2 Winter tests in 2003/04 An SCR vehicle was driven through Sweden for three weeks during the winter of 2003/04. It was refuelled at a container service station without any problems – even at temperatures of –32 °C. The heating of the AdBlue tank by the cooling water of the engine was sufficient to keep the AdBlue solution liquid, also at ambient temperatures below –30 °C. Remark: MAN has decided to comply with the requirements of Euro 4 by measures alternative to the SCR technology. For this purpose MAN uses a further developed system of cooled exhaust gas recirculation in combination with a particle filter in the muffler made of high alloyed steel.

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17

5 AdBlue Testing at Public Service Stations The first three public service stations were equipped with an AdBlue filling station in Germany during the year 2003:

• OMV service station in Dingolfing, Bavaria. Opening March 3, 2003 • Total service station in Berlin. Opening Oct.10, 2003 • Total service station in Stuttgart. Opening on Nov. 19, 2003

In 2004, OMV, Austria, opened the first Austrian service station with AdBlue at the Inn autobahn in Vomp, Tyrol. In the meantime, OMV has opened further public service stations at an autobahn: Schnelldorf in Germany and Prostejov in the Czech Republic. Additionally, OMV has announced plans to equip 67 service stations with AdBlue filling units throughout Europe by the end of 2007. The company also plans to offer AdBlue in 10 litre cans at 81 autobahn service stations in ten countries, starting in January 2005. The following is a summary of the experiences and test results gained while handling AdBlue.

5.1 OMV service station at Dingolfing, Bavaria

In early 2003, OMV, Vienna, had agreed to equip the service station in Dingolfing, Bavaria, with an AdBlue filling unit for a field test within the scope of the DGMK Research Project 616-2. On March 3, 2003, the AdBlue test station of Bott was commissioned, which had already been used during the field tests of DaimlerChrysler in Finland (chapter 4.1). The AdBlue unit consists of an above ground IBC plastic container, which was filled with 1000 l AdBlue produced by AMI Agrolinz Melamine GmbH, and a filling unit with a filling nozzle made by Elaflex. In total, eleven trucks were refuelled until Oct. 7, 2003. On Feb. 16, 2004, the IBC was replaced by another one filled with fresh AdBlue.

Figure 2: OMV Service Station in Dingolfing

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For quality control of the AdBlue solution, samples were taken as required: directly at the producer and with the filling nozzle from the IBC of the service station at Dingolfing. The results of these samples show that even after one year of storage, all analytical characteristics of the AdBlue solution remained essentially unchanged and within the limits of the DIN standard (attachment 9.3). These trials demonstrated the suitability of the Bott refuelling unit and the stability of the AdBlue solution. No smell of ammonia was observed, but some minor deposits of crystals showed up at locations, where water could evaporate from the solution, such as the filling nozzle and the filler neck.

5.2 Total service stations at Berlin and Stuttgart

Total opened the first fully integrated AdBlue filling system at a service station in Berlin in October 2003, and one month later another one in Stuttgart (figure 3 and 4). Construction work was done by Union Technik. AdBlue is stored in coated under ground tanks. Pipes leading to the dispensing unit are heated. The integrated filling system was developed by Dresser-Wayne. According to the results of the monthly investigations of the filling units by Dresser and Union Technik, both units are working satisfactorily. .

Figure 3: Service Station TOTAL, Berlin Alt-Mahlsdorf

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Figure 4: Service Station TOTAL, Stuttgart Ulmenstraße SKW Piesteritz provided the AdBlue solution and took monthly AdBlue samples from both tanks for analysis (attachment 9.4). As the results show, all analytical characteristics remained practically constant and within the limits of the DIN V 70 070 standard. There was no hydrolytic degradation; the content of heavy metals was below detection limit. This demonstrates that AdBlue is stable for more than one year, if stored appropriately.

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6 Logistics Some of the truck manufacturers will start to launch the SCR/urea technology for their HD diesel vehicles at the beginning of 2005. For a successful market introduction, the automobile industry expects the mineral oil business to provide the required AdBlue in sufficient amounts and of adequate quality – eventually in an area covering Europe-wide manner. They expect a stepwise introduction: first mainly at privately owned filling stations of larger fleets, later at filling stations along expressways in Europe, and finally through the existing network of public filling stations for truck fuelling. The set-up of such an infrastructure, especially in its last phase, would require considerable investments by the mineral oil business for installation of additional dedicated tanks, pipes, pumps and filling units at the service stations. Therefore, this chapter describes a few considerations on what is needed to supply AdBlue for HD commercial vehicles throughout Europe. Here are some facts about the situation in Germany: In 2003, diesel fuel consumption amounted to 27.9 million t, 25.1 million t of that in road traffic. About 70 % of the total diesel fuel (corresponding to 20 million t) is consumed by commercial vehicles. There are 3.6 million commercial vehicles in Germany (10 % thereof have a load capacity of over 6 t). Approximately two thirds of the operators of these cars refuel at 3,500 privately owned service stations. About 20 % of the commercial vehicles are refuelled at truck stops and only 10 % at public service stations [11]. The normal HD commercial vehicle has a diesel fuel tank size of 1,000 l and an average fuel consumption of 34 l/100 km. It can cover a distance of almost 3,000 km, corresponding to a trip from Copenhagen to Palermo or from Paris to Moscow. The AdBlue consumption amounts to ca. 5 % of the diesel fuel consumption. With an AdBlue tank of 100 l capacity, this vehicle could travel the route Copenhagen – Palermo both ways, without the need to refuel AdBlue. Even at smaller tank capacities, the routes of trucks are planned such that refuelling outside the own refuelling station is unnecessary. In addition, DaimlerChrysler have announced that they will equip their long-distance trucks with extra large AdBlue tanks with a capacity of 145 l for the interim period, in which AdBlue is not offered everywhere; this would allow a travel distance of almost 10,000 km [12]. These considerations show that about two thirds of all HD trucks in Germany can cover their AdBlue demand at their private service stations – even for trips across Europe, provided the fleet owner has made the necessary investments for AdBlue fuelling. For this purpose, a number of companies (such as Bott and Ucon) are offering AdBlue dispensing equipment comprising:

• Containers with pump systems, heating and filling nozzles and • Filling units with heating, flow meters and accounting systems..

This equipment was used successfully in the field tests of the car manufacturers (chapter 4).

22

The remaining third of commercial vehicles, which refuelles at truck stops and public service stations, will also require AdBlue at these locations. However, since these vehicles have the same driving range as the other ones, their AdBlue supply should be sufficiently guaranteed by service stations along the main expressways. This puts the request of the automobile industry into perspective for an AdBlue supply at practically all public service stations in the third and last phase. The mineral oil business could considerably reduce the investment cost by focussing on the service stations along the main traffic routes. In June 2004, four important European urea producers (AMI, BASF, SKW Piesteritz and Yara Intern.), five manufacturers of commercial vehicles (DAF, DaimlerChrysler, Iveco, Renault and Volvo) and three mineral oil companies (CEPSA, OMV and Total) have committed themselves in a joint press release to the concept of the SCR/urea technology. According to their statement it ideally combines economic and ecological advantages [13]. AdBlue producers (AMI, BASF, SKW Piesteritz and Yara) have announced co-operations with distributor companies (OMV, Penta Chemicals and ERC Techology, Kruse Chemie and Brenntag AG) for the set-up of a German or European AdBlue infrastructure, which could guarantee the supply of the private as well as public service stations. The following supply alternatives are offered:

• in a 10 litre can, especially as a reserve tank or emergency supply, • in a 1000 litre IBC, which can be equipped with pump, heating, filling nozzle or

complete dispensing unit as well as flow meter and accounting system and • in bulk by tank car for filling 1,000 to 30,000 litre tanks, which can be equipped

with heating, insulation, liquid level indicator, complete encasement, filling nozzle or complete dispensing unit, flow meter and accounting system.

The AdBlue demand of HD diesel vehicles can thus be guaranteed in an area covering Europe-wide manner by the privately owned service stations of the fleet operators and the service stations at truck stops and main expressways. There is no need for equipping those service stations, which are not frequented by trucks with SCR systems, with AdBlue filling units.

23

7 Conclusions The stricter exhaust gas regulatios of the EU, Euro 4 and 5, apply to new types of HD commercial vehicles in 2005 and 2008, respectively, and they become effective for all newly commissioned vehicles one year later. The technology of selective catalytic reduction has proven to be a reliable and safe method for meeting these rigid regulations in a number of field tests, not only in stationary, but also mobile applications – even under extreme climatic conditions. Starting in 2005, the car manufacturers will offer their customers HD trucks equipped with this technique. The European urea producers will provide the AdBlue needed for the SCR method in sufficient amounts and of required quality, and they have announced co-operations with distributor partners for the set-up of an AdBlue distribution network. Two thirds of all HD trucks in Germany will cover their AdBlue demand at the service stations of their truck depots, provided the fleet owners have made the necessary investments for AdBlue tanking. The other vehicles can be supplied at truck stops and public service stations. In the meantime, some mineral oil companies have started to equip their first service stations with AdBlue filling systems. Others plan to offer AdBlue in 10 litre cans at their stations. Due to the relatively small AdBlue consumption of less than 2 l/100 km, vehicles equipped with an AdBlue tank of 100 l capacity can criss-cross Europe without the need to refuel the reducing agent. Therefore the AdBlue distribution network does not need to be too tight. In view of these facts, the stepwise expansion of the SCR technology should be on the right target in the very near future.

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25

8 References [1] DGMK Research Report 6161-1: AdBlue as a reducing agent for the decrease

of NOx emissions from diesel engines of commercial vehicles, Hamburg, September 2003

[2] Directive 1999/96/EU of the European Parliament and the Council of 13

December 1999 on the approximation of the laws of the Member States relating to measures to be taken against the emission of gaseous and particulate pollutants from compression ignition engines for use in vehicles, and the emission of gaseous pollutants from positive ignition engines fuelled with natural gas or liquefied petroleum gas for use in vehicles and amending Council Directive 88/77/EEC

[3] Selective Catalytic Reduction (Final Report), ACEA, Brussels, 23.06.2003 [4] Scheme of a combined system for exhaust gas treatment on the basis of the

SCR method, information by Shell Global Solutions GmbH, 2003 [5] ACEA Statement on the Adoption of SCR Technology to Reduce Emissions

Levels of Heavy Duty Vehicles, ACEA, Brussels, 05.07.2003 [6] BUA Stoffbericht No. 76, October 1991, Gesellschaft Deutscher Chemiker,

Verlag Chemie, Weinheim [7] DIN V 70070:2003, Deutsches Institut für Normung e.V., Berlin, published by

Beuth Verlag, Berlin [8] CEFIC: Automotive Grade Urea – Quality Assurance Guidance Document,

European Chemical Industry Council, Brussels, 15.07.2004. Newest version under http://www.petrochemistry.net/Product & sector groups/ Automotive grade urea

[9] Threshold limit value list ammonia, supplement of 1986 and W. S. Ferguson et

al, J. occup. Med. 19, 319 (1977) [10] VDI nachrichten of 06.09.2002 [11] A. Münch, Brennstoffspiegel, Oct. 2004, S.34 [12] Press release of DaimlerChrysler of 21.6.2004, Wörth [13] Joint press information about AdBlue: manufacturers of urea and commercial

vehicles and of the mineral oil industry under http.//www.BASF.de

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9 Attachments 9.1 CEFIC: Automotive Grade Urea – Quality Assurance Guidance Document:

http://www.petrochemistry.net/Product & Sector Groups/Automotive Grade Urea

9.2 Thermal stability of AdBlue at 70 °C – investigations by Aral Research

Department 9.3 AdBlue analytical results and diagram of storage stability of AdBlue at the

OMV service station at Dingolfing, Bavaria, investigations by AMI Agrolinz Melamine International GmbH

9.4 AdBlue analytical test results of the Total service stations at Berlin and

Stuttgart, investigations by SKW Stickstoffwerke Piesteritz GmbH

Attachment 9.1

~‚

~

L

AUTOMOT!VE GRADE UREA

Version 1.0

AUS 32Accord~ng to D~N V 70070

Quallity AssuranceGuidance Docurnent

1 15 JuIy 2004

Attachment 9.1

Contents

Version 1.0

1.1.1

lntroductionObiectives

1.2 lntroduction1 .3 Distribution cham

Quality RequirementsIntluences on the catalysts lifetime

2.2 Quality reguirements for AUS 32

3.3 Physical conditions during storage and transportation3.4 Shelf Life3.5 Cleanliness of materials in contact with AUS 323.6 Quality control by ampling, testing and monitoring

SamplingFilling of IBC‘sFilling of Small ContainersLoading of Bulk AUS 32TestingQuality Control and MonitoringContainer and Bulk Product Entrance CheckProduct Release and Handling of Non-conforming productReturnecl ProductTraceabilitv and Renewed Certification of AUS_32

3.9 Docurnentation3.9.1 Duration of Safekeeping of Quality Documentation and Samples3.10 Audits

4.4.1

Tank Storage of AUS 32General

4.2 Basic design and construction4.2.1 Construction Materials4.2.2 Coating4.2.3 Heating and Insulation4.3 Tank storage Recjulations4.4 Cleaninp and Maintenance

5.5.1

Loading of AUS 32General

WARNINGIn order to be sure you are using the latest version of this document, please makesure to visit http:/Iwww.petrochemistrv.net / Product & sector groups 1 Automotive

grade urea, tor any possible updates.

2.2.1

3.3.1

General Characteristics of AUS 32 Distribution ChamDistribution cham .. loaistics

3.2 Use of materials compatible w~th~~~AUS 32

3.6.13.6.1.13.6.1.23.6.1.33.6.23.6.33.6.3.13.73.7.13.8

2 15 July 2004

Attachment 9.1

Version 1.0

5.2 Basic Concegt and Design5.3 Loading Reciulations

6. BuIk Transport of AUS 326.1 General6.2 Basic Design and Construction6.2.1 Trucl~Railway/Container6.3 Previous and Simultaneous Product Loads6.4 Cleaning

7. Unloading of AUS 327.1 General7.2 Basic Concegt and Design7.3 Unloading Regulations7.4 Dispensing Units

8. Päckaging, Filling of AUS 328.1 General Conditions8.2 Eguipment Parts in Contact with AUS 328.3 Container Specifications8.3.1 IBCs/Drums8.3.2 Smali Piastic Containers8.4 Eguipment and Unloading Procedures8.5 Packaging and Filling Systems8.6 Cleaning8.7 Labelling, Sampling, Quality Control and Analysis Attestation8.8 Storage of Containers8.9 Loading for Shipment

9. Environmental issues9.1 Properties of AUS 329.1.1 Enyironmental Aspects on Waterand Soil9.1.2 Enyironmental Aspects on Atmospbere9-2 Cleaning and Waste Disposal

AttachmentsAttachment 1: Product information — AUS 32Attachment 2: Specifications AUS 32. according to DIN V 70070Attachment 3: Material CompatibilityAttachment 4: Allowed Previous LoadingsAttachment 5: AUS 32 Logistics — Flow Diagram

3 lSJuIy2004

Attachment 9.1

Version 1.0

1. Introduction

1.1 ObjectivesThis technical guidance document describes the recommended handling anddistribution of 32.5% aqueous urea solution AUS 32 DIN V 70070 grade to preservethe quality of the solution from production via storage and distribution to the end-user.

This document covers- product handling- quality assurance- safety measures- environmental protection

lt identil9es all participants in the distribution cham (producers of AUS 32, logisticspartners, public filling and truck stations) and draws their attention to commonguidelines concerning handling in such a way that the intended high quality ofAUS 32 will be maintained fron~ the point of production to the point of end-use.

The participants in the distribution cham are encouraged to set down all operations inthe form of operating instructions according to the SO 9001:2000 standard.All staff engaged in production, handling and distribution must be fully familiar withthe relevant operational standards and regulations and recommendations given inthis document and they rnust all be given training on a regular basis. The training hasto be documented, according to ISO standards.

To niaintain product quality and proper functioning of the dispensing units regularmaintenance is essential. This issue is not addressed in this guidance document.Fleet owners and service station operators should consult their AUS 32 suppliers forfurther guidance on this issue.

1.2 IntroductionAfter evaluating different concepts to meet the Euro IV (10/2006) and Euro V(10/2009) standards for heavy-duty vehicles, the automotive industry has decided touse the SCR-technology with AUS 32, as reducing agent for most of these vehicles.The 8CR technology has demonstrated the capability to reduce NOx emissions fromheavy duty trucks in test cycles and in on-the-road operation. The combination offuel-economy-optimised engines with bw particulates and SCR is able to meet theEURO IV and V regulation.

The 8CR technobogy with AUS 32 as reducing agent has already been appliedsuccessfully to stationary applications, waste incinerators, power plants and to mobileDiesel engines in applications such as ships and locomotives.

The basic chemical reaction of the urea SCR process is as follows:

AUS 32 is injected into the hot exhaust gas and is hydrolysed above approx. 180°Cforming arnmonia (NH3) according the following reaction equation:

Hydrolysis reaction: (NH2)2C0 + H20 2 NH3 + CO2

At the homogeneous extruded, base metal 8CR catalyst the following reaction takesplace to convert NOx with NH3 from the hydrolysis reaction to nitrogen and water.

SCRreaction: 4NH3 ÷ 4N0 ~O2 -‚ 4N2 +6H20

4 15July2004

Attachment 9.1

Version 1.0

SNH3 + 6N02 -* 7N~ +121120

For the SCR after-treatment technology to remain effective it is essential te avoid anycontamination of AUS 32 caused by foreign compounds and matter and by anyphysical conditions out of the limits specified.

1.3 Distribution Cham

Quality assurance processescovered in this document

For a more detailed process f]ow chart see attachment 5.

Distribution to be based on dedicated equipment tor storage, handling anddistribution.

5 15 JuIy 2004

Attachment 9.1

Version 1.0

2. Quality Requirements

2.1 lnfluences an the Catalyst‘s LifetimeThe catalysts used in the 5CR after-treatment system consist of catalytically activetransition metal campounds, which are fixed onto ceramic carriers. The ability of the5CR after-treatment system to convert NO, into N2 and H20 depends to a largeextent on the actual activity of these active centres, and an the width of the pores inthe ceramic carrier. Pore size influences the diffusion rate of the exhaust gases mbthe catalyst.To ensure a high activity af the 5CR after-treatment system over a lang periad of birnethe quality af AUS 32 has to be cantrolled very strictly, as rnany af the camponentswith limit values in DIN V 70070 irreversibly hamm the catalyst system by physicalblocking af the pores, or deactivatian of the reactive centres. Paar activity of the 5CRafter-treatment system due ta inactive catalysts may 1) result in an increase in NOxemission, and 2) cause secandary darnage in the engine itself due ta an exhaust gaspressure increase.

2.2 Qualit~‘ Reguirements for AUS 32The quality requirements far AUS 32 are defrned in the German pre-standard DINV 70070 (see attachment 2), together with the test methods. The specification Iaid outin this standard has ta be maintained frorn praductian thraughout the entiredistribution system to the end-user.

The pre-standsrd csn be obtained via:Beuth Verlag GmbHBurggrafenstraße 610787 BerlinTelefon +49 (0)30 2601-0Telefax +49 (0)30 2601-1260postmaster@beuth.de

3. General Characteristics of AUS 32 Distribution Cham

3.1 Distribution Cham - LopisticsTa maintain quality thraughout the distribution cham the following technical andpracedural requirements must be niet:- Use af materials compstible with AUS 32 (~ 3.2)- Physical canditians during starage and transportation (~ 3.3)- Shelf Life (~ 3.4)- Cleanliness af materials in contact with AUS 32 (~ 3.5)- Quality contral by sampling, testing and rnonitaring (~ 3.6)- Praduct release and handling of nanconfarming praduct (~ 3.7)- Traceability of AUS 32 (~ 3.8)- Dacumentation (~ 3.9)- Audits (~ 3.10)

3.2 Use of Materials Compatible with AUS 32All materials used far the construction af tanks and containers including tubes, valvesand fittings for storage, transportatian and handling must be compatible with AUS 32

6 15July2004

Attachment 9.1

Version 1.0

to avoid any contamination of AUS 32 antI corrosion of devices used (Details onmaterials recommended see attachment 3). Materials used for sampling devices,sample storage containments and canisters have to be compatible with the ureasolution.

3.3 Physical Conditions During Storage antI TransportationTo avoid any impairment of quahty of AUS 32 during storage antI transportation thefollowing physical conditions have to be met:- Storage temperature below 25 °C is recommended to maintain shelf life.- Storage temperature above minus 11 °C is recommended to avoid crystallisation,

which starts at minus 11.5°C- Sun light protection (to avoid growth of algae)- Weil closed containments to protect the containment as weil as the solution from

any contamination.- prolonged storage above 30 °C will cause hydroiysis to occur, with the

consequent formation of ammonia and pressure rise.

3.4 Shelf LifeBecause of this tendency to hydrolyze AUS 32 has a sheif üfe of approximately6 months provided the above mentioned storage conditions are obeyed. Afterexpiration of the shelf life the batch has to be tested for a decision about further use.

3.5 Cleanliness of Materials in Contact willi AUS 32All materials in contact with AUS 32 have to be free from foreign matter such as fuel,oil, greases, detergents, dust, antI any chemicals and natural products.Prior to the first use with AUS 32 any material has to be cleaned and flnally rinsedwith demineralised water — dont use tap water 1 — or AUS 32 until a representativesample of the used rinsing water used for the cieaning shows that the system isclean. in case of storage antI transportation facilities this has to be verifledanalyticaliy according to attachment 2. The use of any detergent is forbidden forcleaning because of contamination.The use of non-dedicated equipment has to be regarded as the first use.Compartments filled with AUS 32 have to be seaied.

3.6 Quality Control by Samplina, Testing antI MonitoringTo be released for shipment antI when received at its destination all batches ofAUS 32 must be checked according to the procedures described below. A batchmeans a well-defined.and traceable quantity of AUS 32 (see also 3.7).These checks must be duly noted in writing antI kept on file by the production sites,terminals, and at the traders/contractors.

At every transfer of AUS 32 from production- antI intermediate storage tanks thetraceability of batches has to be guaranteed to enable proper monitoring of theproduct quahty. Appropriate regulations concerning taking antI keeping samples haveto be flxed in-house and/or to be agreed between different partners involved.

lf the recommended shelf life (~ 3.4) is exceeded at any point in the distribution chamthe material must be retested prior to use.

The following paragraphs will describe the minimum requirements pertaining tosampling, testing/checking antI monitoring of bulk or packaged shipments.

7 lSJuly 2004

Attachment 9.1

Version 1.0

Furthermore, the procedures for renewed quality certiflcatiori in case of intermediarymanipulations (iG. intermediate tank storage, filling or re-filling) are described.

3.6.1 SamplingFor sampling the following rules apply:• Written instruction about how samples shall be taken and stored must always be

available.• All samples must be representative of the batch to be sampled and correctly

labelled.• The samples must be Iabelled with the following information: Product name, batch

or charge code, containment taken from, part of the containment where thesample has been taken from, date of sampling.

o The samples must be taken and kept in clean odourless containers made ofHDPE or other suitable materials (See attachment 3). Devices used for samplingmust likewise be clean and suitable.

• Prior to the analysis the samples must be stored according to § 3.3 at the rightconditions.

• The minimum quantity of sample material must be 1 litre, i.e. at least double thatrequired for complete verification of AUS 32 specifications.

3.6.1.1 Filling of 1BC‘sIf dedicated ISC‘s are filled no sampling of the filled compartrnents is necessary.

If non-dedicated ISC‘s are filled from a defined batch of AUS 32 samples must betaken from every container according to a standard procedure. The individualsamples should be combined and kept as retention aamples.

3.6.1.2. Filling of SmaIl ContainersSmall containers are defined as drums and canisters. To avoid any possiblecontamination the use of new or dedicated containers is strongly recommended.During the filling of small containers with AUS 32 of a defined batch, during one shift,samples have to be taken according to a standard procedure. As a minimum 0.5 litresamples have to be taken from the firat and the last container. The samples have tobe combined and kept as retention samples.

3.6.1.3 Loading of Bulk AUS 32After loading a means of transportation (ship, tank truck, iso-container, rail tank) asample has to be taken from the means of transport. This must be done according toa standard procedure that ensures that the sample is representative. For dedicatedmeans of transportation an analysis of this sample is not necessary. If non-dedicatedmeans of transportation are used this sample must be tested (See § 3.5).

3.6.2 TestingEach AUS 32 batch produced has to be tested according to the standard DIN V70070. lt is recommended, that only laboratories taking part in round robin tests forAUS 32 are used for this testing.

3.6.3 Quality Control and MonitoringFor each batch a quality certificate (e.g. inspection certificate 3.‘I.B. according tostandard EN10204 or equivalent) must be issued by a laboratory certilied accordingto lSO quality management standards. The methods to determine characteristicproduct parameters comprise tests (i.e. defined in the DIN V 70070 standard, seeattachment 2) by which AUS 32 can be clearly identified and possible contaminationdiscovered.

8 l5July2004

Attachment 9.1

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Typical properties to be determined for the sake of product identification are forinstance solution density and refractive index. A minimum contamination test must atleast include visual checking of the solution colour, suspended particulates andodour. These tests are to be performed every time AUS 32 15 transferred from onecontainer to another.Principles of quality control procedures in the different steps of the supply cham aregiven below.

3.6.3.1 Container and Bulk Product Entrarice CheckWhen bulk product is received at any point of the distribution cham, lt has to beidentified by means of checking delivery documents and quality certificates;Before the bulk product can be unloaded lt is required to analyse lt - according to astandard procedure - to check the identity eg. by measuring density and refractiveIndex, if the compartment has not been sealed by the supplier. Should there, as aresult of this procedure, be any doubt about the quality of the product proceed as 15given in paragraph 3.7.

3.7 Product Release and Handling of Non-conforminci ProductProduct batches are released for further use when the resuits of testing fully conformwith the specification of the standard. Shouid there be any parameter off-spec or snydoubt about the quality of the product, the batch must be withheld and storedseparately and labelled properly. Further investigations must then be carried out.If product should not be in accordance with the product sales specification (i.e.contaminated and/or wrongly labelled material) lt must be Iabelled as such and storedseparateiy to prevent lt from entering the distribution cham.In such case product quality must be re-checked. If the analysis resuits require, theshipment and possibly the entire batch must be recalled.

3.7.1 Returned ProductAUS 32 that for any reason has been returned must not ha allowed to re-enter thedistribution cham unless a quality check has been carried out to ensure that all qualitystandards are upheld. To minimize the risk of overlooking an unidentified contaminantlt 15 recommended that such returned product is downgraded to technical grade ureasolution.

3.8 Traceability and Renewed Certification of AUS 32To secure product traceability a system that can identify product whereabouts all theway from the production site to the end-user has to be established, going backte theoriginally produced batch of AUS 32. In oase a batch is mixed with more than 5%wt.Iwt. of another batchan additional retainment sample has to be taken and keptaccording to 3.6.1. All links in the distribution cham must be included soas to enableimmediate recall of faulty product. Every shipment must be properly labelled withproduct name and batch number.In the oase of any gap in the traceability cham of batches renewed certification 15necessary for the quantity of AUS 32 concerned. A sample has to be analyzedaccording to DIN V 70070 and a new batch number has tobe assigned.

3.9 DocumentationAll procedures and all records of the distribution cham, concerning production,product delivery, loading, storage, sampling, testing, product release and handlinghave to be documented according to the guidelines of quality management standardlSO 9001 :2000.

9 l5July 2004

Attachment 9.1

Version 1.0

3.9.1 Duration of Safekeeping of Quality Documentation and SamplesQuality documents must be kept on file according to actual European product liabilityregulations (EU regulations require 10 years). The samples, on which the quahtydocument tor a given batch 15 based, must be kept safe for at least the shelf life Dt thebatch. Storage must be under adequate physical conditions (see paragraph 3.3).

3.10 AuditsAll parties involved in any link of the AUS 32 distribution cham must submit toindependent audits by 150 certified auditors to determine and document that relevantrulea and regulations including this document are obeyed.lt is recomn‘iended, that the producers of AUS 32 carry out their own audits,according to defined ISO procedures, down the supply cham on a regular basis.lf needed, action has to be taken to reaolve any problems identified. The properexecution of such action plans must be carefully surveyed and documented accordingto the quality management standard 180 9001 :2000.

4. Tank storage of AUS 32

4.1 GeneralThe product specific characteristics and physical conditions recommended (seeparagraph3.3) have to be taken into consideration to ensure that the quality ofAUS 32 throughout the storage is not impaired and that its shelf life is not shortened.

During the fihling of the storage systems down the distribution cham, as weil as duringthe loading or unioading of tank trucks or any other product transfer measures haveto be taken to avoid the contamination of AUS 32 with dust or soil. To avoid anycontamination during the storage intermediate storage tanks have to be equippedwith air particie filter systems for the venting system.

4.2 Basic Design and ConstructionThe whoie storage system, consisting of tanks, pipea, pumps, filters, fihhing stationsetc., has to be used soieiy for AUS 32 to prevent cross-contamination with otherchemicals. Storage facihities tor AUS 32 shouid be protected from temperatures ofmore than 30°C and below -11°C. Especially free-standing storage facilities have tobe insulated to protect AUS 32 from being damaged quahity wise. Depending on theregional climate the tanks have to be equipped with heating and/or coohing.The storage system of distributors, situated at any point in the distribution cham hasto comply with all demands of this guidehine.

4.2.1 Construction MaterialsFor the recommended materials for the entire storage system for AUS 32 refer toattachment 3.

4.2.2 CoatingAs an alternative to stainless steel tanks it is possible to use carbon steel coated withan AUS 32-compatible material (see attachment 3).

4.2,3 Heating and InsulationThe storage temperature should not exceed 30 °C of AUS 32. The effects of directsolar radiation have to be avoided. Depending on the regional climate heating orinsulation must be employed. Heat exchangers/cooiers in contact with the product

10 l5July 2004

Attachment 9.1

Version 1.0

must be made of stainless steel (refer to attachment 3) and should preferably beoperated with water. If electric heating coils or heat exchangers operated with highpressure steam in direct contact with AUS 32 are used — local overheating must beavoided due to the potential for increased formation of ammonia and carbon dioxide.

4.3 Tank Storape RegulationsPrior to the first use with AUS 32 any storage System has to be cleaned and flnallyrinsed•with demineralised water — dont use tap water 1 — or AUS 32 until arepresentative sample of the used rinsing water used for the cleaning shows that thesystem is clean if tested according to DIN V 70070. During the storage of AUS 32 allrelevant regulations must be followed, and an operating manual must be available tothe operators. Quality checks must be carried out according to chapter 3 of thisdocument.

4.4 Cfeaning and MaintenanceAll cleaning and maintenance of AUS 32 storage and handling systems have to becarried out according to standard procedures and be documented in writing. All tasksmust be performed in such a manner that contamination of the product is prevented.Prior to a re-start the equipment must be rinsed with AUS 32 of sales specifications.

5. Loading of AUS 32

5.1 GeneralAUS 32 is not classified as a hazardeus material. lt can therefore be loaded into tankervehicles, containers, railway tank wagons etc. without any specific risks arising either forpersonnel or the environment. The systems and equipment which are used for thetransport of AUS 32 are to be designed and utilised in such a way that the quality of theproduct is not impaired in any way, and no damage can be caused to personnel or theenvironment.

5.2 Basic Concept and DesignThe loading equipment tobe used has tobe dedicated for the handling of AUS 32 andhas to be identified accordingly. The loading area must be kept clean and the potentialfor any form of contamination of the solution must be minimized during loading. All thecomponents of the loading system should be emptied, cleaned, and closed oft after use.This is necessary in order to prevent contamination of AUS 32 by dust and other foreignsubstances. They have to be closed after each use and handled and stored in acontrolled manner in order to avoid misuse and contamination.Loading itself has to be carried out in a loadingfunloading compartment area whichconforms to national water resource Iaws.

5.3 Loadinq RequlationsAll loading operations are to be set down according to the QA in the form of operatinginstructions. A loading checklist has to be used. This list should be signed by a personresponsible for the loading procedure and the truck driver and kept safely by the loadingdepartment. Particular attention is required in order to avoid errors when fliling AUS 32.The following inspections are to be regarded as the minimum requirements:- Visual inspection for cleanliness of the transport equipment, ancillary equipment,

and systems

11 15.Ju1y2004

Attachment 9.1

Version 1.0

- Cleanliness of the loading equipment- Proper function of the connection between the loading and transport equipment- Proper closure of all valves and apertures after completion of the loading

procedure and sealing oftransport

6. BuIk transport of AUS 32

6.1 GeneralTo prevent any kind of contamination lt is necessary to employ the highest qualityassurance standards when transporting AUS 32 in bulk. Therefore, everytransportation contractor has to certify that he will meet such standards referring toquality management systems like 150 9001:2000.Contracts with transportation companies must explicitly state that sub-contractors arenot permitted to be used unless the subcontractor has provided the producer withadequate proof of quality management.Transfer of AUS 32 fron, one means of transport to another is only allowed, ifadequate cleaning procedures and checks according to chapter 3.5 and 6.4 havebeen run to prevent any contamination. lt this is not possible this solution has tobedowngraded to technical grade urea solution.

6.2 Basic Design and ConstructionAll construction materials including any gaskets must be compatible with AUS 32 (seeattachment 3). Openings and hoses have to be stored and secured in such a way,that impurities from the surroundings are not able to contaminate the product itselt.

6.3 Previous and Simultaneous Product LoadsDedicated means of transportation should be the standard for transportation ofAUS 32 to minimise any risk of contamination.

If the means of transportation has not exclusively been used for AUS 32 a specialcleaning procedure has to be used, a certificate of cleanliness issued by a companycertified according to SO 9001:2000 has tobe presented and the nature of the lastthree transported goods must be documented and presented before filling. Besidesthat the outlet, the nIet, and the interior of the tank has to be checked visually.

6.4 CleaningProper cleaning of all means of transportation is of utmost importance and beforeevery loading all parts of the system that could come into contact with AUS 32 mustbe adequately cleaned. The cleaning process and its results must be clearlydocumented, the documentation being kept to be presented on demand. Anattestation of the cleaning operation must be given in writing and the nature of the lastthree goods transported previously must be stated. Means of transportation which areexclusively used for transporting AUS 32 do not have to be cleaned before reloadingwith AUS 32, provided all valves, openings and hoses have been closed and handledproperly, and this has been confirmed by a visual inspection at the filling station.

7. Unloading of AUS 32

7.1 General

12 l5July2004

Attachment 9.1

Version 1.0

Every unloading and transfer of AUS 32 from one compartment into another has tobeplarined in such a way that the product quality remains assured. The recommendationsgiven in Section 3 are to be respected.

7.2.1 Basic Concent and DesignThe unloading equipment to be used has to be ciedicated for the use of AUS 32 and hastobe identified accordingly. All the components of the unloading system should beemptied, cleaned, and closed off after use. This is necessary in order to preventcontamination of AUS 32 by dust and other foreign substances. Hoses have to beclosed after each usa and handled and stored in a controlled manner in order to avoidniisuse and contamination.Unloading itseif has to be carried out in an area which conforms to national waterresource laws.

7.3 Unfcading RegulationsOnly sealed contsiners should be unloaded. lt any seal is broken or missing the suppliershould be immediately contacted for advice.All bulk unloading operations — including multi drop deliveries - are to be set downaccording to the Quality Assurance in the form of operating instructions.Before unloading, all hoses and couplings are to be checked tor defects, faults, andcleanliness. The product which is to be unloaded has to be checked for identity inaccordance with the delivery documents and, if appropriate, a sarnple has to be takentor any examinations which rnay be required. lf any irregularities occur, unloading has tobe stopped immediately, the sarriple taken must be analyzed, and further actiondetermined on the basis of the analysis results.

7.4 Dispensing unitslt is recomrnended, that any dispensing unit has to be cleaned on a regular basis tomaintain proper functioning.

8. Packaging, filling af AUS 32

8.1 General conditionsAt the sites where packaging and tilling of AUS 32 is being carried out adequateprecautions must be taken to prevent any contamination of AUS 32.

8.2 Eguipment Parts in Contact with AUS 32All equipment in direct contact with AUS 32 (i.e. pipelines, hoses, pumps, etc.) mustbe in accordance with aftachment 3.

8.3 Container SpecificationsThe handling of empty containers (IBC‘s, drums, canisters) must be considered as animportant element of the AUS 32 distribution cham. Consequently, the followingregulations must be paid dose attention to:1. Every container must be labelled in accordance with § 3.8 50 that it can be tracedback to the supplier.2, The cleanliness of the container‘s inside must be checked according to a writtenprocedure.

13 l5July2004

Attachmerit 9.1

Version 1.0

3. Containers and seals must be made of materials compatible with AUS 32 (seeattachment 3).

8.3.1 IBC‘s/DrumsAUS 32 may also be supplied in IBC‘s, which typically have a volume of Im3 or indrums. The ISC‘s are designed as a closed system, which prevents AUS 32 fromcontamination. After filling they have to be sealed

8.3.2 Small Plastic ContainersOnly one-way small containers should be used. These are primarily intended as acontingency supply tor end users with limited demand and intermediate distributorsand are easy to handle.

8.4 Eguinment and Unloadinp ProceduresThe site of unloading must be easily accessible for the means of transportation.Proper labelling and foolproof connections must be ernployed so as to minimize thepossibility of mistakes and contamination. Before unloading, product quality must bechecked, if the container is not sealed (~ 7.3).

8.5 Packaging and Filling SystemsAll equipment used has to be dedicated for AUS 32. Packaging and filling operationsmust take place in a clean environment. Precautions rnust be taken to prevent anycontamination of AUS 32.

8.6 CleaningDedicated containers may be filled without cleaning, if the seals of the container areunbroken. Proper cleaning of the containers is of utmost importance and before everyloading all parts of the system that could get in contact with AUS 32 must beadequately cleaned. In the final cleaning step the IBC must be rinsed withdemineralised water — don‘t use tap water! — or AUS 32 and completely ernptied. Thecleaning procedure must be clearly documented.

8.7 Labelling, Sampling, Quality Control and Analysis AttestationThe batch number and the container identification number must enable completetraceability and ensure that the operator, date of filling and the origin of the AUS 32can be determined.

8.8 Storage of ContainersTo be able to manage AUS 32‘s shelf life any product movement in and out ofstorage must be on the principle of „first in — first out‘. The recommendations in § 3.3must be obeyed.

8,9 Loading for ShipmentThe Ioading of trucks must be done according to a written checklist that at the end ofthe operation must be checked in order to elirninate any Ioading mistakes. The checkand package lists must be signed by the person responsible for the operation.

14 l5JuIy 2004

Attachment 9.1

Version 1.0

9. Environmental Issues — Cleaning & Waste DisposalThis Information is for guidance purposes only. For up-to-date information pleaseconsult your suppilers MSDS.

9.1 Properties of AUS 32AUS 32 is harmless in all aspects according to EU Directive 67/548/EEC onchemicals.

9.1.1 Environmontal Aspects an Water and SollAUS 32 is classified as a compound with bw risk to water and soll. Additionalinformation 15 availabbe from the producers of AUS 32.

9.1.2 Environmentai Aspeets on AtmosphereAUS 32 is an aqueous solution. lt AUS 32 is handled as outlined in this document noimpact on the atmosphere is to be expected.In the oase of fire; containments of AUS 32 should be cooled by spraying of water toavoid pressure rise and bursting of containments. At elevated temperatures AUS 32will decompose rapidly to form carbon dioxide and ammonla.

9.2 Cieaning and Waste DisposalSpillecl product should be transferred into a suitable containment by pumping orcovering with absorbent material and transferred into a container tor controlleddisposal. The containments have to be labelled properly to avoid any mixing withAUS 32. Do not release into surface water. Do not empty into drains.Contact the local authorities for waste disposal. For recycling of unused productcontact the manufacturer.Remaining traces of spilled AUS 32 can be rinsed with plenty of water into the dram.

Recommended waste classification according to EWC:06 1099 (Fertilizer residues — Waste, non harmful)

Wastes from cleaning procedures should be handled like spilled product.

15 lSJuIy2004

Attachment 9.1

Version 1.0

Attachment 1 -

Product information - AUS 32

Chemically, AUS 32 is an aqueous solution of 32.5 % by weight of urea. The product 15 ofvew high purity and ta consistent quality is secured through the industrial standardDIN V 70070.

1. General data related to AUS 32Chemical composition: urea in waterCAS-Number (urea): 57-13-6 (CAS: Chemical Abstracts Service)EINECS-Number (urea): 200-315-5COMMON SYNONYMES (urea): Carbamide, Carbonyldiamide, Carbon acid

diamidGerman: Harnstoff,Spanish: Urea,French: Uräe,Latin: Carbamidum; Urea pura; Ureum.

2. Physical characteristics of AUS 32Solubility of AUS 32 in water: unlimitedAppearance: clear and colourlessSmeil: no or slightly like ammoniaCrystallization point: — - 11.5 °CViscosity (at 25°C): ca. 1.4 mPa sHeat conductivity (at 25 °C): ca. 0.570 W/m KSpecific heat (at 25 °C): ca. 3.40 kJ/kg KSurface tension: min. 65 mN/m

3. Classification / hazardsWater hazard dass (Germany): 1R-phrases/ S-phrases: not applicableTransport regulations: According to the ADR/RID transport regulations

AUS 32 5 classified as a non-hazardousmaterial.

Hazards: Posing no serious risk to humans, animals or theenvironment if properly handled, AUS 32 is nothazardous according to the European productciassification guideline. However, direct contactwith other chemical should be avoided,particularly with nitrates and nitrites.

16 15Ju1y2004

Attachment 9.1

Version 1.0

- Attachment 2..

Specificafions AUS 32, according to DIN V 70070

Specification:Urea 31.8~- 33.3 % by weightAlkalinity as NH3 0.2 % by weightCarbonate as C02 0.2 %Biuret 0.3 %Insolubles < 20 mg/kgForrnaldehyde 10 mg/kgPhosphate (P04 )* 0.5 mg/kgCalcium* 0.5 mg/kgIron* 0.5 mg/kgCopper* 0.2 mg/kgZinc* 0.2 mg/kgChromium* 0.2 mg/kgNickel* 0.2 mg/kgMagnesium* 0.5 mg/kgSodiumt 0.5 mg/kgPotassium* 0.5 mg/kgDensity at 20°C 1.0870 - 1.0920 g/cm3Refreetive index at 20°C 1.3817 - 1.3840 (-)

The analytical methods are defined in DIN V 70070.

As of August 2003

* Contents have to be analytically checked for non-dedicated containers prior to fllling

17 15Ju1y2004

Attachment 9.1

Version 1.0

- Attachment 3-

fv[aterial Compatibility

Materials to be used in direot contact with AUS 32— HighIy allcyed austenitic Cr-Ni-steels and Cr-Ni-Mo-steels act. to DIN EN 10088-1 to —3

(i.e. 1.4541 und 1.4571), worked according industrial standard— HD-Polyethylene— HD-Polypropylene— Polyfluorethylen— Polyvinylidenedifluoride— PoIy(perf]uoroalkoxy) PFA— Polyisobutylene— Titanium- EPDM— Viton

Any other material not cited in this attachment must be tested regarding corrosion resistanceand possible influences on the product specification Iisted above.

18 15July2004

Attachment 9.1

Version 1.0

- Attachment 4

AiloedPrevioüsLo~dings

Dedicatecl means of transportation is defined as follows:

The compartment is empty, and the last preloading has been AUS 32.

Non-dedicated means of transportation ja defined as follows:

Any other means of transportatiort

They are only allowed, if

1. a certificate of cleanliness, issued from a approved and 150 9001-certified cleaningcompany 5 presented, or

2. the compartment ja empty, and the last preloading has been— technical grade urea solutions, or deionised water

and a visual inspection from the top does not show any impurity and a sample takenat the outlet doesn‘t show by visual inspection any foreign matter.

19 15Ju1y2004

Attachment 9.1

- Attachnient 5 -

AUS 32 Logistics - FIow diagram

Pro duction

Version 1.0

Check storage conditions,arnount of AUS 32 in Um

inlermediate storage tank,sampling

Check berore loadingMilling

Certuticate of analysis

‘jrTransportation

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• Internat documentation

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