Combustion Nitrogen Analyzers elementar Americas, Inc. SERA-IEG Annual Meeting June 21, 2009

Combustion Nitrogen Analyzers Agenda elementar Americas Inc. history and current organization elementar product line applications overview Analyzer technology and operation Chemistry / Process flow / Mechanical design Selecting an instrument design considerations choices - Rapid N cube / vario MACRO cube / vario MAX

elementar history Technology Development Organization 1868 - high temperature techniques developed in Hanau, Germany 1878 - Dennstedt Patent 1925 - Nobel prize for CHN analysis 1990 - first Macro scale elemental analyzer 1999 - first MAX analyzer 2006 - first cube platform analyzer introduced Organization 1868 - Heraeus 1993 - management buyout forms elementar GmbH 1999 - elementar Americas Inc formed 2008 - Isoprime Ltd acquired (Isotope Ratio Mass Spectrometers)

elementar Organization Manufacturing, R&D and applications labs elementar Analysensysteme GmbH CHNS/O Elemental Analyzers Located in Hanau, Germany (30 minutes from Frankfurt Airport) Isoprime Ltd Wholly owned subsidiary Isotope Ratio Mass Spectrometers Located near Manchester, U.K Sales, service, applications, and supplies elementar Americas, Inc. Responsible for sales and service in USA, Canada, Mexico and Central America based in Mt. Laurel, NJ (30 minutes from Philadelphia) Service from NJ, IN, CO, Toronto

elementar Elemental Analyzer Product Line Micro scale CHNS/O vario MICRO cube vario EL cube Macro scale CHNS/O vario MACRO cube vario MAX rapid N cube & rapid CS cube TOC liquiTOC vario TOC cube

Macro N/CN Elemental Analyzers vario MAX CN vario MACRO CN cube rapid N cube

Elemental Analyzer Technology and Operation Core Operations Combustion Gas separation Gas detection Chemistry Process Flow Diagram Other operations Sample preparation Autosampler and sample feeding Software

Elemental Analyzer Core Operations Combustion Sample combusts in furnace at 950 deg C to 1200 deg C Sample drops into crucible or is lowered into center of combustion tube Jet injection of oxygen via lance right over/at sample Creates turbulent flow around sample like blowing on a fire Three tube low voltage furnace with 10 year warranty 8 8

Elemental Analyzer Core Operations Gas Separation Helium or CO2 carrier gas pushes combustion gases through analyzer. C, H and S combustion gases are trapped in separate columns, then sequentially released (aka “purge and trap”). N2 gas is not trapped. It flows straight thru columns.

Elemental Analyzer Core Operations Gas Detection TCD – Thermal Conductivity Detector Utilizes a Wheatstone bridge circuit to compare relative thermal conductivity differences between the carrier gas and analyte gas Critical system component Elementar own design Larger dynamic range Very special thermistors which are not harmed by high oxygen content. Allows for suspension of carrier gas flow without any harm, even at operation temperature.

Elemental Analyzer Chemistry Combustion R-N + O2 ----> N2 + NOx + O2 + CO + CO2 + CH4 + X- + SOx + H2O Post Combustion CO + CH4 ---CuO & Pt --> CO2 + H2O Reduction NOx+O2 +SO2--tungsten--> N2+WO3 +CO (trace) CO + CuO --------> CO2

Elemental Analyzer More Chemistry Removal of other gases X- via reaction with silver wool H2O via condensation, membrane dryer and Sicapent trace S02 via reaction with tungsten Nitrogen detected by TCD Carbon Dioxide rapid N – “fades” into carrier gas vario MAX and vario MACRO – separated on purge and trap column, then released and detected by TCD.

CO + CH4 ---CuO & Pt --> CO2 + H2O Process Flow Diagram and Chemistry O2 C= 3.00% N= 2.00% Ash CO2 N2 N2 NOx CO2 sample Ash WO3 CO2 X- CO H2O CH4 O2 SO2 CO2 Oxidation ----> CO + CO2 + CH4 + N2 + NOx + SOx+ H2O + X- + O2 X X X X X X X R-N + O2 Post Oxidation CO2 column is heated. CO2 flows to TCD. Computer integrates peak and calculates CO2 percent. Gripper arm removes crucible with ash from combustion tube. Crucible deposited in recepticle for re-use Reduction Tube Excess oxygen reacts with Tungsten. SO2 is adsorbed by tungsten. Reduction Tube: Oxides of nitrogen reduce to nitrogen gas. Nitrogen flows to TCD. Computer integrates peak and calculates N2 percent. Combustion gasses are produced We are interested in N2 and CO2. Other gases must be converted or removed. Halogens are removed by reaction with silver wool in post combustion tube. Gripper Arm lowers crucible containing sample into combustion tube Oxygen is injected over sample Sample combusts Methane and carbon dioxide are oxidized in post combustion tube. Carbon dioxide flows through instrument and is trapped in column Water is removed by a three stage dryer: condensation membrane dryer Sicapent CO + CH4 ---CuO & Pt --> CO2 + H2O Reduction NOx + CH4+O2 +SO2--tungsten--> N2+WO3 +CO (trace)

Process Flow Diagram Comparison Replace robotic arm with Carousel and ball valve Add CF Hybrid vario MACRO cube CN Replace robotic arm with Carousel and ball valve CO2 Remove CO2 adsorber Rapid N cube

Elemental Analyzer Technology and Operation Core Operations Combustion Gas separation Gas detection Chemistry Process Flow Diagram Other operations Sample preparation Autosampler and sample feeding Software

Sample Preparation rapid N cube and vario MACRO cube 60 position open carousel - add samples at any time during run - optional 80 or 120 position carousel Variety of foils/capsules Sample Pressing Tool

rapid N cube and vario MACRO cube Ball Valve Sample Feed rapid N cube and vario MACRO cube rapid N cube and vario MACRO cube have slightly different designs. Both designs provide: inherent blank-free system reliable function keeps air out of the system very long lasting operation easy maintenance

rapid N Sample Introduction Ball valve with nickle flap flange Straight-through Ball Valve actuates. Sample falls to top of nickel flap flange. Nickel flap flange actuates magnetically.

vario MACRO cube patented zero-blank ball valve Position 1; Sample falls into ball valve cavity. Position 2; Ball valve cavity purged with helium. Position 3; Ball valve opens to combustion tube. More than 20 years ago we invented the ball valve technology for easy sample introduction. This patented technology is until now the best solution for this purpose. In combination with modern manufacturing and sealing materials it works without being noticed. Picture 1: Ambient air is kept from entering the combustion tube at all times. The sample is dropped into the ball valve. Picture 2: After one quarter turn of the ball it reaches the flush position. Ambient air inside the ball is flushed with the carrier gas (helium or argon) Picture 3: The ball valve rotates another quarter and the sample is dropped into the combustion zone. Ambient air is still reliably blocked from the system. Position #1 Position #2 Position #3

vario Max Sample preparation

vario MAX sample feeding

vario Max Sample Feeding Robotic “gripper arm” Lifts reusable crucible from carousel. Lowers crucible into the combustion tube (~1000o C) Lifts to removes crucible and ash Deposits the ash & crucible in catch bin

Analyzer Software intuitive interface easy editing view graph during analysis great export functionality 21CFR part11/LIMS/GLP conformity

Elemental Analyzer Technology and Operation Core Operations Combustion Gas separation Gas detection Chemistry Process Flow Diagram Other operations Sample preparation Autosampler and sample feeding Software

Macro sample N/CN Analyzer Selection maximum capacity (organic) and capability   1000 300 Sample Size 200 (mg Organic Content) 50 10 C S N CN CNS CHNS CHN O Cl Operating Mode vario MAX vario MAX Rapid N vario MAX vario MACRO Rapid CS vario EL vario TOC vario MICRO

Macro sample N/CN Analyzer Selection recommendations Vario MAX Best choice for CN or N samples that are non-homogeneous, very low in concentration, wet , high ash or difficult to handle. Vario MACRO cube Optimum economics for larger CN samples with easier handling characteristics (dry, semi-homogeneous). Capital cost lower than MAX CF Hybrid technology optimizes consumables cost Rapid N cube Optimum economics for larger N samples with easier handling characteristics. Capital cost lower than MACRO CO2 carrier gas reduces gas cost

vario MACRO cube Elementar´s answer to YOUR analytical needs The new cost-effective macro analyzer family for N/CN for protein, plant material or soil analysis CNS CHNS for plant and soil, environmental or oil samples CHN for the analysis of coal, biomass or combustible solid waste 27

Options: „Standard options:“ Capsule press for liquids Pressing tool IR Detectors for special applications: low level sulfur analysis low level oxygen analysis chlorine analysis VLS, vario liquid sampler Continuous flow Hybrid (CN only) 28

Options: Automatic liquid injector for the „cube“ family liquid sample feeder for 60 samples, plus flushing and waste positions easy setup, replaces standard ball valve and carousel can be used on: vario EL cube vario MICRO cube vario MACRO cube Launched in 2008, first installations successful The liquid injector marks a milestone in the „cube“ family of elemental analyzers. It serves as a tool for the injection of all kinds of liquids into the cube analyzers. Within a few minutes the vario Micro cube or the vario EL cube can be turned into fully funtional CHNS analyzers for liquids. The sample handling unit itself is mounted in the position of the solids automatic sample feeder. After exchanging the ball valve with a septum free injector port („Merlin-seal“) the sample feeder plate and attaching the gripper arm the unit is ready for operation. The entire procedure does not take longer than 10 minutes. This opens the world of liquid injections to your laboratory! 29

CF-Hybrid technique for CN mode The newly developed hybrid technology serves for longer lifetime of consumables. Only a fraction (approx 50%, adjustable) of the combustion gas is lead through the reduction tube in continuous flow mode, saving valuable reduction metal and expansion of uninterrupted operation time. Features: Easy to install and remove (1-2 minutes!), so the user can choose between highest sensitivity or highest throughput. Active flow control. Ideal for high-throughput laboratories with similar sample matrix. 30

Elementar thanks you for your attention ! For further information please contact us under: Web Page: www.CHNOS.com e-mail: info@elementar-inc.com