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The BioTector COD TOC TN analyzer
and patented Two Stage Advanced Oxidation process
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BioTector Analytical Systems Ltd.
Training Course BioTector Analytical Systems Ltd.
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BIOTECTOR SUMMARY Complete oxidation of the sample with hydroxyl radicals. Representative sample without any filtration (up to 2mm soft particulates). Self cleaning technology. High reliability: 86,000 measurements per annum and over 99% on-line time. Low Maintenance: 6 month service intervals. No calibration requirement between services. No interference from salts or Calcium. Automatic range selection and multi-streaming. Programmable Analysis Modes: TIC & TOC, TC, VOC, TC-TIC, TN and in addition TPR, TP modules are available. Analyse wide range of effluents containing fats, oils, salts, de-icing chemicals, particulates, fibrous materials.
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PRESENTATION OUTLINE Introduction to the BioTector COD TOC TN analyzer. Problems associated with On-Line TOC measurement. Existing TOC Technologies and Limitations. The patented Two Stage Advanced Oxidation Process. Self Cleaning Technology and Intelligent Diagnostics. Operation of the TN module. Oxidation Chemistry and Recoveries. The effect of Salt. Analyzer Applications, Advantages and Disadvantages. Summary.
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Introduction to the BioTector COD TOC TN analyzer.
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The BioTector TOC analyzer
316SS and PFA wetted parts. Separate Electronics & Analysis Section Self Cleaning Technology Uptime > 99% Results in 6 minutes Multi-range capability Single & Multi-Stream capability TN module available. TP module available. If installed, it increases the enclosure height by 250mm. Measurement parameters, TIC & TOC, TC, VOC, TC-TIC, TN and in addition TPR, TP modules are available. After correlation, COD, BOD.
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The BioTector Plus TOC analyzer
Hastelloy C276 or PTFE and PFA wetted parts. Separate Electronics & Analysis Section Self Cleaning Technology Uptime > 99% Results in 6 minutes Multi-range capability Single & Multi-Stream capability TN module available. TP module available. If installed, this extends the lower enclosure by 250mm. Measurement parameters, TIC & TOC, TC, VOC, TC-TIC, TN and in addition TPR, TP modules are available. After correlation, COD, BOD. The BioTector series 4 plus should be used where corrosive materials are present in the sample, or where the sample matrix is not known.
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Power Supply, Motors and Valves
The main components inside the upper compartment of the BioTector TOC/TN analyzer. Power Supply, Motors and Valves Isolator and Power PCB Mains terminals Power Supply, Processor Relay terminals 4-20ma terminals 4-20ma isolators Relay PCB Ozone PCB Stream Expansion PCB Signal PCB RS232 cable
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The main components inside the lower compartment of the BioTector TOC/TN analyzer.
Ozone generator MV7 Injection valve Ozone destructor MV1 Exhaust valve Cooler Regulator, 350mabr Mass Flow Controller CO2 Analyser TN Module MV4 Sample In (ARS) valve MV6 Acid valve Oxidized Fluid Catch-pot TN valves P2 Circulation pump N pump P3 Acid, P4 Base pump Sample pump P1 Reactor MV5 Sample Out valve Pinch valves: Manual Sample valve Zero Water valve Cleaning valve
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Problems associated with On-Line TOC measurement
Problems associated with On-Line TOC measurement. Existing TOC Technologies and Limitations.
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PROBLEMS ASSOCIATED WITH ONLINE TOC MEASUREMENT:
Manufacturers have struggled to build reliable TOC analyzers. Existing Technologies not flexible enough to overcome problems and limitations such as: Contamination and drift resulting in high maintenance. Requirement for filtration and micro-sampling systems resulting in unrepresentative TOC and system failure. Analyzer failure due to salts or calcium in the sample. Difficulty in analyzing volatile organics.
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EXISTING TOC TECHNOLOGIES: THERMAL OXIDATION
Rotometer Carrier gas and CO2 from reaction CO2 Free Carrier gas (measuring) Reactor with Platinum Catalyst. Sample In Inorganic Carbon Acid Degassing Cooler & Filter CO2 Analyzer Carrier gas (stripping) As the sample typically enters and exits through the top of the reactor, this results in material being trapped in the reactor. Salts coat the inside of the reactor, and create problems with recovery by coating the catalyst. Sample Tubes can be as small as 0.5 mm. Sample filtering is typically <200 micron. Sample Volume < 10 micro-litres.
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THERMAL OXIDATION: SAMPLE INJECTION
Injection using a slider valve: Contaminated Sample Line Reactor Slider Valve Sample Bypass To flush the old sample from the valve, the sample is pumped through the upper port of the slider valve (as shown). The centre of the slider valve then moves down, and the sample is flushed into the reactor. As the valve is made from ceramic, salts can crystallize around the slider mechanism, causing it to seize. It can also be difficult to clean the line from the valve going into the reactor.
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EXISTING TOC TECHNOLOGIES: UV PERSULFATE
High TOC levels can cause scaling of the UV light. In the event of a TOC exceedance, the analyser may automatically disconnect itself from the sample. As the sample typically enters through the base of the reactor, and exits through the top, this results in material being trapped in the reactor. Salts, as low as 0.5% can inhibit the persulfate oxidation mechanism, resulting in a low or zero TOC result. Turbid or dirty samples can block the UV light, effectively preventing oxidation of the sample. Sample filtering is typically <200 micron.
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The patented Two Stage Advanced Oxidation process.
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Compliance with European Norm EN 1484
BioTector Series 4 Compliance with European Norm EN 1484 Section 4: Principle states: “Oxidation of organic carbon in water to carbon dioxide by combustion, by the addition of an appropriate oxidant, by UV radiation or any other high energy radiation.” “The final determination of CO2 is carried out by a number of different procedures, for example infrared spectrometry, titration, thermal conductivity, conductometry, coulometry, CO2 sensitive sensors and flame ionization detection.”
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BioTector Series 4 Compliance with US EPA 415.1
Section 2.0: Summary of Method states: “Organic carbon in a sample is converted to carbon dioxide (CO2) by catalytic combustion or wet chemical oxidation. The CO2 formed can be measured directly by an infrared detector or converted to methane (CH4) and measured by a flame ionization detector. The amount of CO2 or CH4 is directly proportional to the concentration of carbonaceous material in the sample.”
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Compliance with ASTM D5173-97
BioTector Series 4 Compliance with ASTM D Standard Test Method for: “On-Line Monitoring of Carbon Compounds in Water by Chemical Oxidation, by UV Light Oxidation, by Both, or by High Temperature Combustion Followed by Gas Phase NDIR or by Electrolytic Conductivity (of the released CO2 gas).”
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THE PATENTED TWO STAGE ADVANCED OXIDATION PROCESS:
SUMMARY OF THE ON-LINE OPERATION SAMPLING: A representative unfiltered sample is taken containing fats, salts, particulates, suspended fibres and colloidal material. TIC PHASE: The inorganic carbon content is removed by an acid reagent. The CO2 gas is sparged by oxygen and measured by an infrared CO2 analyser. BASE OXIDATION: Ozone generated by the corona-discharge method is applied to a high pH reagent to promote the production of hydroxyl radicals which results in the effective and complete oxidation of the sample. TOC PHASE: An acid reagent is added to remove the total organic carbon content of the oxidized sample as CO2 gas, and this is measured by an infrared CO2 analyser. RANGE SELECTION: Automatic selection of the optimum sample volume for the TOC range.
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Operation of the COD TOC TN analyzer: TOC or Oxidation (OXP) phase.
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GENERAL LAYOUT TOC - TN P2 Circulation Pump Glass beads
MFC Mass Flow Controller MV51 Purge OXYGEN O2 Regulator MV7 Injection EXHAUST MV1 Exhaust CO2 Analyzer Ozone Destructor MV4 Sample In SAMPLE OUT Cooler Ozone Generator Oxidized Fluid Catch-pot TN Module MCR Reactor P2 Circulation Pump Glass beads Cleaning DRAIN P4 Base Pump BASE MV6 Acid P3 Acid Pump ACID MV5 Sample Out Zero Manual P1 Sample ZERO MANUAL SAMPLE IN
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GAS FLOW (ANALYZER ZERO)
MFC Mass Flow Controller MV51 Purge OXYGEN O2 Regulator MV7 Injection EXHAUST MV1 Exhaust CO2 Analyzer Ozone Destructor MV4 Sample In SAMPLE OUT Cooler Ozone Generator Oxidized Fluid Catch-pot TN Module MCR Reactor P2 Circulation Pump Glass beads Cleaning DRAIN P4 Base Pump BASE MV6 Acid P3 Acid Pump ACID MV5 Sample Out Zero Manual P1 Sample ZERO MANUAL SAMPLE IN The gas flows through the MFC, ozone generator, reactor and cooler to purge the CO2 analyzer. The BioTector sets its zero for the next reaction.
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SAMPLE BYPASS P2 Circulation Pump Glass beads
MFC Mass Flow Controller MV51 Purge OXYGEN O2 Regulator MV7 Injection EXHAUST MV1 Exhaust CO2 Analyzer Ozone Destructor MV4 Sample In SAMPLE OUT Cooler Ozone Generator Oxidized Fluid Catch-pot TN Module MCR Reactor P2 Circulation Pump Glass beads Cleaning DRAIN P4 Base Pump BASE MV6 Acid P3 Acid Pump ACID MV5 Sample Out Zero Manual P1 Sample ZERO MANUAL SAMPLE IN The sample pump runs, transporting the sample into the BioTector and through the ARS Sample In valve. This flushes any old sample from the sample line, and ensures a fresh sample for analysis.
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SAMPLE INJECTION <2000mg TOC
MFC Mass Flow Controller MV51 Purge OXYGEN O2 Regulator MV7 Injection EXHAUST MV1 Exhaust CO2 Analyzer Ozone Destructor MV4 Sample In SAMPLE OUT Cooler Ozone Generator Oxidized Fluid Catch-pot TN Module MCR Reactor P2 Circulation Pump Glass beads Cleaning DRAIN P4 Base Pump BASE MV6 Acid P3 Acid Pump ACID MV5 Sample Out Zero Manual P1 Sample ZERO MANUAL SAMPLE IN The ARS Sample-In valve turns 90’ (M-V setting in the software),
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SAMPLE INJECTION <2000mg TOC
MFC Mass Flow Controller MV51 Purge OXYGEN O2 Regulator MV7 Injection EXHAUST MV1 Exhaust CO2 Analyzer Ozone Destructor MV4 Sample In SAMPLE OUT Cooler Ozone Generator Oxidized Fluid Catch-pot TN Module MCR Reactor P2 Circulation Pump Glass beads Cleaning DRAIN P4 Base Pump BASE MV6 Acid P3 Acid Pump ACID MV5 Sample Out Zero Manual P1 Sample ZERO MANUAL SAMPLE IN The sample pump runs, and injects the sample into the reactor. The sample volume injected depends on the TOC range, a low range requires a large, 8ml sample.
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SAMPLE INJECTION <2000mg TOC
MFC Mass Flow Controller MV51 Purge OXYGEN O2 Regulator MV7 Injection EXHAUST MV1 Exhaust CO2 Analyzer Ozone Destructor MV4 Sample In SAMPLE OUT Cooler Ozone Generator Oxidized Fluid Catch-pot TN Module MCR Reactor P2 Circulation Pump Glass beads Cleaning DRAIN P4 Base Pump BASE MV6 Acid P3 Acid Pump ACID MV5 Sample Out Zero Manual P1 Sample ZERO MANUAL SAMPLE IN The ARS Sample-In valve turns 90’ (M-V setting in the software),
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TIC ACID INJECTION <2000mg TOC
MFC Mass Flow Controller MV51 Purge OXYGEN O2 Regulator MV7 Injection EXHAUST MV1 Exhaust CO2 Analyzer Ozone Destructor MV4 Sample In SAMPLE OUT Cooler Ozone Generator Oxidized Fluid Catch-pot TN Module MCR Reactor P2 Circulation Pump Glass beads Cleaning DRAIN P4 Base Pump BASE MV6 Acid P3 Acid Pump ACID MV5 Sample Out Zero Manual P1 Sample ZERO MANUAL SAMPLE IN The acid pump and injection valve flush the sample into the reactor with acid. The circulation pump mixes the acid with the sample. The pH in the reactor is <1.
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SAMPLE INJECTION >2000mg TOC
MFC Mass Flow Controller MV51 Purge OXYGEN O2 Regulator MV7 Injection EXHAUST MV1 Exhaust CO2 Analyzer Ozone Destructor MV4 Sample In SAMPLE OUT Cooler Ozone Generator Oxidized Fluid Catch-pot TN Module MCR Reactor P2 Circulation Pump Glass beads Cleaning DRAIN P4 Base Pump BASE MV6 Acid P3 Acid Pump ACID MV5 Sample Out Zero Manual P1 Sample ZERO MANUAL SAMPLE IN The ARS Sample-In valve turns 180’ (M-F180 setting in the software), and the sample injected by the TIC acid is the sample contained within the valve when it turns. Several fixed volumes are available, from 0.12ml (10,000mg TOC) to 0.02ml (up to 100,000mg TOC with extended oxidation).
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TIC ACID INJECTION >2000mg TOC
MFC Mass Flow Controller MV51 Purge OXYGEN O2 Regulator MV7 Injection EXHAUST MV1 Exhaust CO2 Analyzer Ozone Destructor MV4 Sample In SAMPLE OUT Cooler Ozone Generator Oxidized Fluid Catch-pot TN Module MCR Reactor P2 Circulation Pump Glass beads Cleaning DRAIN P4 Base Pump BASE MV6 Acid P3 Acid Pump ACID MV5 Sample Out Zero Manual P1 Sample ZERO MANUAL SAMPLE IN The acid pump and injection valve flush the sample into the reactor with acid. The circulation pump mixes the acid with the sample. The pH in the reactor is <1.
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TIC SPARGING P2 Circulation Pump Glass beads
MFC Mass Flow Controller MV51 Purge OXYGEN O2 Regulator MV7 Injection EXHAUST MV1 Exhaust CO2 Analyzer Ozone Destructor MV4 Sample In SAMPLE OUT Cooler Ozone Generator Oxidized Fluid Catch-pot TN Module MCR Reactor P2 Circulation Pump Glass beads Cleaning DRAIN P4 Base Pump BASE MV6 Acid P3 Acid Pump ACID MV5 Sample Out Zero Manual P1 Sample ZERO MANUAL SAMPLE IN The ARS Sample-In valve turns 180’. Any TIC in the sample reacts with the acid liberating CO2 gas. This is sparged from the liquid with the sparge gas, and is measured in the CO2 analyser.
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TOTAL INORGANIC CARBON
REACTION GRAPH The reaction graph screen on the BioTector records the CO2 gas as it is sparged from the acidic liquid in the reactor and measured in the CO2 analyzer. The accurate Mass Flow Controller provides a stable gas flow for the sparging process, and the microprocessor in the BioTector calculates the total quantity of CO2 gas released from the liquid to provide an accurate result. If the BioTector detects an unexpected high TIC reading, it automatically extends the TIC time until all the TIC is sparged.
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SELF CLEANING SAMPLE LINE
MFC Mass Flow Controller MV51 Purge OXYGEN O2 Regulator MV7 Injection EXHAUST MV1 Exhaust CO2 Analyzer Ozone Destructor MV4 Sample In SAMPLE OUT Cooler Ozone Generator Oxidized Fluid Catch-pot TN Module MCR Reactor Glass beads Cleaning DRAIN P4 Base Pump BASE MV6 Acid P3 Acid Pump ACID MV5 Sample Out Zero Manual P1 Sample ZERO MANUAL SAMPLE IN While the TIC is sparging, the cleaning valve operates and the sample pump runs in reverse. The spent acid from the previous reaction is used to clean the sample line back to the sample inlet point.
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BASE INJECTION Glass beads
MFC Mass Flow Controller MV51 Purge OXYGEN O2 Regulator MV7 Injection EXHAUST MV1 Exhaust CO2 Analyzer Ozone Destructor MV4 Sample In SAMPLE OUT Cooler Ozone Generator Oxidized Fluid Catch-pot TN Module Glass beads Cleaning DRAIN P4 Base Pump BASE MV6 Acid P3 Acid Pump ACID MV5 Sample Out Zero Manual P1 Sample ZERO MANUAL SAMPLE IN Sodium hydroxide is injected into the reactor with the base pump, and the pH is increased to >13.
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BASE OXIDATION P2 Circulation Pump Glass beads
MFC Mass Flow Controller MV51 Purge OXYGEN O2 Regulator MV7 Injection EXHAUST MV1 Exhaust CO2 Analyzer Ozone Destructor MV4 Sample In SAMPLE OUT Cooler Ozone Generator Oxidized Fluid Catch-pot TN Module P2 Circulation Pump Glass beads Cleaning DRAIN P4 Base Pump BASE MV6 Acid P3 Acid Pump ACID MV5 Sample Out Zero Manual P1 Sample ZERO MANUAL SAMPLE IN The ozone generator is switched on, and this converts the oxygen into ozone. At pH>13, the ozone reacts with the hydroxide ions and forms hydroxyl radicals. These oxidise the organic carbon into carbonate or oxalate. This oxidation process completely cleans the reactor of organic material.
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TOC ACID INJECTION Glass beads
MFC Mass Flow Controller MV51 Purge OXYGEN O2 Regulator MV7 Injection EXHAUST MV1 Exhaust CO2 Analyzer Ozone Destructor MV4 Sample In SAMPLE OUT Cooler Ozone Generator Oxidized Fluid Catch-pot TN Module Glass beads Cleaning DRAIN P4 Base Pump BASE MV6 Acid P3 Acid Pump ACID MV5 Sample Out Zero Manual P1 Sample ZERO MANUAL SAMPLE IN After oxidation is complete, the acid valve and acid pump operates, and acid is injected into the reactor. The pH is reduced to <1.
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TOC 2nd STAGE OXIDATION P2 Circulation Pump Glass beads
MFC Mass Flow Controller MV51 Purge OXYGEN O2 Regulator MV7 Injection EXHAUST MV1 Exhaust CO2 Analyzer Ozone Destructor MV4 Sample In SAMPLE OUT Cooler Ozone Generator Oxidized Fluid Catch-pot TN Module P2 Circulation Pump Glass beads Cleaning DRAIN P4 Base Pump BASE MV6 Acid P3 Acid Pump ACID MV5 Sample Out Zero Manual P1 Sample ZERO MANUAL SAMPLE IN At pH<1, two reactions take place. In the first, the ozone generator remains on and ozone oxidizes the manganese in the acid. The oxidized manganese reacts with the oxalate to produce CO2 gas, which is sparged and measured as TOC. The oxidized manganese produces the pink colour in the liquid in the reactor.
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TOC SPARGING P2 Circulation Pump Glass beads
MFC Mass Flow Controller MV51 Purge OXYGEN O2 Regulator MV7 Injection EXHAUST MV1 Exhaust CO2 Analyzer Ozone Destructor MV4 Sample In SAMPLE OUT Cooler Ozone Generator Oxidized Fluid Catch-pot TN Module P2 Circulation Pump Glass beads Cleaning DRAIN P4 Base Pump BASE MV6 Acid P3 Acid Pump ACID MV5 Sample Out Zero Manual P1 Sample ZERO MANUAL SAMPLE IN In the second simultaneous reaction, the acid reacts with carbonate to produce CO2 gas, which is sparged and measured as TOC. Ozone is not required for this process.
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TOTAL ORGANIC CARBON REACTION GRAPH
The reaction graph screen on the BioTector records the gas as it is sparged from the acidic liquid in the reactor and measured in the CO2 analyzer. The TOC result is the total quantity of CO2 gas released from the liquid, from both the simultaneous oxalate and carbonate reactions. If the BioTector detects an unexpected high TOC reading, it automatically extends the TOC time until all the CO2 is sparged.
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REACTOR PURGE Mass Flow Controller SAMPLE OUT P2 Circulation Pump
MFC Mass Flow Controller MV51 Purge OXYGEN O2 Regulator MV7 Injection EXHAUST MV1 Exhaust CO2 Analyzer Ozone Destructor MV4 Sample In SAMPLE OUT Cooler Ozone Generator Oxidized Fluid Catch-pot TN Module MCR Reactor P2 Circulation Pump Glass beads Cleaning DRAIN P4 Base Pump BASE MV6 Acid P3 Acid Pump ACID MV5 Sample Out Zero Manual P1 Sample ZERO MANUAL SAMPLE IN The MFC increases the gas flow to 80 LPH, the exhaust valve is closed and the sample out valve opened. The acidic, oxidized fluid in the reactor is purged, and collected in the oxidized fluid catch-pot, where its characteristic pink colour generated by the oxidized manganese should be visible.
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ANALYZER PURGE P2 Circulation Pump Glass beads
MFC Mass Flow Controller MV51 Purge OXYGEN O2 Regulator MV7 Injection EXHAUST MV1 Exhaust CO2 Analyzer Ozone Destructor MV4 Sample In SAMPLE OUT Cooler Ozone Generator Oxidized Fluid Catch-pot TN Module MCR Reactor P2 Circulation Pump Glass beads Cleaning DRAIN P4 Base Pump BASE MV6 Acid P3 Acid Pump ACID MV5 Sample Out Zero Manual P1 Sample ZERO MANUAL SAMPLE IN The gas flows through the MFC, ozone generator, reactor and cooler to purge the CO2 analyzer.
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Self Cleaning Technology and Intelligent Diagnostics.
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SELF CLEANING SAMPLE LINE
MFC Mass Flow Controller MV51 Purge OXYGEN O2 Regulator MV7 Injection EXHAUST MV1 Exhaust CO2 Analyzer Ozone Destructor Glass beads MV4 Sample In SAMPLE OUT Cooler Ozone Generator P2 Circulation Pump Oxidized Fluid Catch-pot TN Module MCR Reactor Cleaning DRAIN P4 Base Pump BASE MV6 Acid P3 Acid Pump ACID MV5 Sample Out Zero Manual P1 Sample ZERO MANUAL SAMPLE IN While the TIC is sparging, the cleaning valve operates and the sample pump runs in reverse. The spent acid from the previous reaction is used to clean the sample line back to the sample inlet point.
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SELF CLEANING SAMPLE LINE
The outside surface of the sample tubing is covered with fatty material in a dairy plant. The internal surface of the tubing is kept clean with the self cleaning technology.
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HIGH AND LOW RANGE TOC MEASUREMENTS with SELF CLEANING TECHNOLOGY
Stream 1 (10,000) 9656.9 9819.3 10064 Stream 2 (50) 53.7 50.1 49.6 59.1 50.4 50 (2000) 2039.7 1974.5 1957.7 2064.1 2000.9 1998 50.2 49.8 49.0 50.3 49.2
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AUTOMATIC PRESSURE TEST
MFC Mass Flow Controller MV51 Purge OXYGEN O2 Regulator MV7 Injection EXHAUST MV1 Exhaust CO2 Analyzer Ozone Destructor Glass beads MV4 Sample In SAMPLE OUT Cooler Ozone Generator P2 Circulation Pump Oxidized Fluid Catch-pot TN Module MCR Reactor Cleaning DRAIN P4 Base Pump BASE MV6 Acid P3 Acid Pump ACID MV5 Sample Out Zero Manual P1 Sample ZERO MANUAL SAMPLE IN Every reaction, and on start-up, the gas flows through the MFC and pressurizes the analyser. If there is no leak, the flow through the MFC will drop below its pass level, and the pressure test will pass.
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AUTOMATIC FLOW TEST Glass beads P2 Circulation Pump
MFC Mass Flow Controller MV51 Purge OXYGEN O2 Regulator MV7 Injection EXHAUST MV1 Exhaust CO2 Analyzer Ozone Destructor Glass beads MV4 Sample In SAMPLE OUT Cooler Ozone Generator P2 Circulation Pump Oxidized Fluid Catch-pot TN Module MCR Reactor Cleaning DRAIN P4 Base Pump BASE MV6 Acid P3 Acid Pump ACID MV5 Sample Out Zero Manual P1 Sample ZERO MANUAL SAMPLE IN Every day, and on start-up, the MFC sets a high flow through the exhaust valve and independently through the sample out valve. If the flow drops by <10%, the flow test passes.
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PREDICTOR FEATURE By monitoring the height of the CO2 peak generated by the TOC sparging, the Biotector can estimate the overall TOC result, and give advanced warning of a spill or plant upset.
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Operation of the COD TOC TN analyzer: TN or Liquid Phase Analysis (LQP) phase.
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Operation of the TN module.
Operation of the TN module, a brief summary: -When the BioTector oxidises organic carbon it also oxidises nitrite, ammonia and bound nitrogen into nitrate, NO3-. -The TN module collects the BioTectors TOC sample out fluid, and analyses it for the presence of NO3-. The TN result is available about 2 minutes after the TOC result. -After measurement, the TN module returns the sample out fluid to the BioTectors cleaning cycle vessel so that it can be used for reverse wash cleaning. -The overall reaction time with the TN module is typically <9 minutes.
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GENERAL LAYOUT TN MODULE
N Pump DRAIN DRAIN LV3 Cleaning 217nm detector CLEANING LV2 DIW DIW 265nm detector LV1 Sample in SAMPLE OUT Detector module. Oxidized Fluid Catch-pot To OXP Cleaning valve To OXP Sample out valve
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OXIDATION FLUID CATCH-POT FILL
N Pump DRAIN DRAIN LV3 Cleaning 217nm detector CLEANING LV2 DIW DIW 265nm detector LV1 Sample in SAMPLE OUT Detector module. Oxidized Fluid Catch-pot To OXP Cleaning valve To OXP Sample out valve At the end of the OXP reaction, the acidic oxidized fluid from the OXP reactor is purged, and collected in the oxidized fluid catch-pot. This liquid contains all forms of nitrogen oxidised by the BioTector to NO3-.
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MEASURING CELL FILL N Pump DRAIN DRAIN LV3 Cleaning 217nm detector CLEANING LV2 DIW DIW 265nm detector LV1 Sample in SAMPLE OUT Detector module. Oxidized Fluid Catch-pot To OXP Cleaning valve To OXP Sample out valve The N pump runs, pumping the oxidized fluid from the catch-pot into the cell.
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TN MEASURE N Pump DRAIN DRAIN LV3 Cleaning 217nm detector CLEANING LV2 DIW DIW 265nm detector LV1 Sample in SAMPLE OUT Detector module. Oxidized Fluid Catch-pot To OXP Cleaning valve To OXP Sample out valve The Flash Lamp is activated, and the TN in the form of NO3- is measured. The measuring frequency is 217nm, the through-cell reference is 265nm and this data is used with the cell zero readings to calculate the TN result. Typically, three separate measurements are carried out, with the N pump running for 2 seconds between each measurement.
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MEASURING CELL EMPTY N Pump DRAIN DRAIN LV3 Cleaning 217nm detector CLEANING LV2 DIW DIW 265nm detector LV1 Sample in SAMPLE OUT Detector module. Oxidized Fluid Catch-pot To OXP Cleaning valve To OXP Sample out valve The N pump runs in reverse, returning the oxidized fluid from the cell to the catch-pot. The OXP sample pump then uses the oxidized fluid in its reverse cleaning process, emptying the oxidized fluid catch pot. Note: If the OXP sample pump reverse time is not set, for example if a span calibration is run, then the oxidized fluid is pumped to drain by the N pump, not into the oxidized fluid catch pot (not shown on presentation).
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MEASURING CELL CLEAN N Pump DRAIN DRAIN LV3 Cleaning 217nm detector CLEANING LV2 DIW DIW 265nm detector LV1 Sample in SAMPLE OUT Detector module. Oxidized Fluid Catch-pot To OXP Cleaning valve To OXP Sample out valve The N pump runs, bringing cleaning fluid into the cell. This is typically carried out every reactions, to clean the cell and guarantee that the cell and tubes will never require any physical cleaning or maintenance.
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MEASURING CELL CLEAN N Pump DRAIN DRAIN LV3 Cleaning 217nm detector CLEANING LV2 DIW DIW 265nm detector LV1 Sample in SAMPLE OUT Detector module. Oxidized Fluid Catch-pot To OXP Cleaning valve To OXP Sample out valve The N pump runs in reverse, cleaning the tube to the catch-pot, and additionally puts a few drops of cleaning fluid into the catch-pot to clean the base of the catch-pot. This is later removed by the OXP sample pump.
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MEASURING CELL CLEAN N Pump DRAIN DRAIN LV3 Cleaning 217nm detector CLEANING LV2 DIW DIW 265nm detector LV1 Sample in SAMPLE OUT Detector module. Oxidized Fluid Catch-pot To OXP Cleaning valve To OXP Sample out valve The N pump runs, bringing cleaning fluid back out of the catch-pot tube.
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MEASURING CELL CLEAN N Pump DRAIN DRAIN LV3 Cleaning 217nm detector CLEANING LV2 DIW DIW 265nm detector LV1 Sample in SAMPLE OUT Detector module. Oxidized Fluid Catch-pot To OXP Cleaning valve To OXP Sample out valve The N pump runs in reverse, pumping the cleaning fluid to drain.
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GENERAL LAYOUT TN MODULE
MEASURING CELL CLEAN GENERAL LAYOUT TN MODULE N Pump DRAIN DRAIN LV3 Cleaning 217nm detector CLEANING LV2 DIW DIW 265nm detector LV1 Sample in SAMPLE OUT Detector module. Oxidized Fluid Catch-pot To OXP Cleaning valve To OXP Sample out valve The OXP Sample Pump runs reverse for 2 second to empty the Oxidized Fluid Catch-pot.
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MEASURING CELL WASH N Pump DRAIN DRAIN LV3 Cleaning 217nm detector CLEANING LV2 DIW DIW 265nm detector LV1 Sample in SAMPLE OUT Detector module. Oxidized Fluid Catch-pot To OXP Cleaning valve To OXP Sample out valve The DIW wash is carried out after every cleaning reaction. Typically there are two consecutive washing cycles after each cleaning. The N pump runs, bringing DIW into the cell.
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MEASURING CELL WASH N Pump DRAIN DRAIN LV3 Cleaning 217nm detector CLEANING LV2 DIW DIW 265nm detector LV1 Sample in SAMPLE OUT Detector module. Oxidized Fluid Catch-pot To OXP Cleaning valve To OXP Sample out valve The N pump runs in reverse, washing the tube to the catch-pot, and additionally puts a few drops of DIW into the catch-pot to wash the base of the catch-pot. This is later removed by the OXP sample pump.
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MEASURING CELL WASH N Pump DRAIN DRAIN LV3 Cleaning 217nm detector CLEANING LV2 DIW DIW 265nm detector LV1 Sample in SAMPLE OUT Detector module. Oxidized Fluid Catch-pot To OXP Cleaning valve To OXP Sample out valve The N pump runs, bringing DIW back out of the catch-pot tube.
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MEASURING CELL WASH N Pump DRAIN DRAIN LV3 Cleaning 217nm detector CLEANING LV2 DIW DIW 265nm detector LV1 Sample in SAMPLE OUT Detector module. Oxidized Fluid Catch-pot To OXP Cleaning valve To OXP Sample out valve The N pump runs in reverse, pumping the cleaning fluid to drain.
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GENERAL LAYOUT TN MODULE
MEASURING CELL WASH GENERAL LAYOUT TN MODULE N Pump DRAIN DRAIN LV3 Cleaning 217nm detector CLEANING LV2 DIW DIW 265nm detector LV1 Sample in SAMPLE OUT Detector module. Oxidized Fluid Catch-pot To OXP Cleaning valve To OXP Sample out valve The OXP Sample Pump runs reverse for 2 second to empty the Oxidized Fluid Catch-pot. The process is now repeated for a second wash cycle.
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DIW MEASURE (ZERO) The N pump runs, bringing DIW into the cell. N Pump
DRAIN DRAIN LV3 Cleaning 217nm detector CLEANING LV2 DIW DIW 265nm detector LV1 Sample in SAMPLE OUT Detector module. Oxidized Fluid Catch-pot To OXP Cleaning valve To OXP Sample out valve The N pump runs, bringing DIW into the cell.
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DIW MEASURE (ZERO) N Pump DRAIN DRAIN LV3 Cleaning 217nm detector CLEANING LV2 DIW DIW 265nm detector LV1 Sample in SAMPLE OUT Detector module. Oxidized Fluid Catch-pot To OXP Cleaning valve To OXP Sample out valve The Flash Lamp is activated, and the cell zero is measured. The measuring frequency is 217nm, the through-cell reference is 265nm.
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DIW MEASURE (ZERO) N Pump DRAIN DRAIN LV3 Cleaning 217nm detector CLEANING LV2 DIW DIW 265nm detector LV1 Sample in SAMPLE OUT Detector module. Oxidized Fluid Catch-pot To OXP Cleaning valve To OXP Sample out valve The N pump runs in reverse, pumping the DIW to drain.
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REACTION STOP CONDITION
N Pump DRAIN DRAIN LV3 Cleaning 217nm detector CLEANING LV2 DIW DIW 265nm detector LV1 Sample in SAMPLE OUT Detector module. Oxidized Fluid Catch-pot To OXP Cleaning valve To OXP Sample out valve When the BioTector stops, the measuring cell is filled with DIW, and the N pump stops.
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Operation of the BioTector COD TOC TN analyzer: COD calculation
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COD calculation is carried out using the following Algorithm:
COD = {Overall Factor * [(TOC Factor * TOC) + (TN Factor * (TN - NO3))] } + Offset Factor The TOC factor is the factor used for the TOC contribution to the COD . The TN factor is the factor used for the TN contribution to the COD. The NO3 is a fixed factor which can be used if the NO3 level is such that it can have an effect on the overall COD result. The Overall factor and Offset factor are used to finalize the COD correlation.
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Oxidation Chemistry and Recoveries.
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The patented Two Stage Advanced Oxidation chemistry.
In the TIC phase, the pH is lowered to <1pH. A reaction between acid and carbonate forms carbon dioxide gas. CO32- (aq) --> (H+) --> CO2 (g) In the oxidation phase, the pH is raised to >13pH, and the ozone generator is switched on. Ozone and hydroxyl ions react to form hydroxyl radicals. Both carbon (TOC) and nitrogen (TN) are oxidised in this phase. TOC Oxidation. CxHy (aq) --> (O3 and OHº) --> CO3 2- (aq) (major product, carbonate) CxHy (aq) --> (O3 and OHº) --> C2O4 2- (aq) (minor product, oxalate) TN Oxidation: N-Bound (aq) --> (O3 and OHº) --> NO3 - (aq) NH4 (aq) --> (O3 and OHº) --> NO3 - (aq) NO2- (aq) --> (O3 and OHº) --> NO3 - (aq) In the TOC phase, the pH is lowered to <pH1. Acid and carbonate react to form carbon dioxide gas. Ozone oxidises the manganese, which reacts with oxalate to form carbon dioxide gas. C2O42- (aq) --> (Mn+++) --> CO2 (g)
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Ozone/Hydroxyl Radical Oxidation V’s Two Stage Advanced Oxidation
Test Results Solvents Tested Oxidation (recovery) rates Ozone/Hydroxyl Radical (ie without catalyst) 2 Stage Advanced Oxidation (ie with catalyst) HCOOH Formic Acid 100% H3COH Methanol Dimethylformamide H2N-CH2-CH2NH2 Ethylene diamine 92% CH2-OH-CH2OH Ethylene glycol 90% Propylene glycol 80% C6H12O6 Glucose 76% H3C-CO-CH3 Acetone 72% H3C-(CH2)2-CH2OH Butanol H3C-CH2OH Ethanol H3C-COOH Acetic Acid H3C-(CH2)4-CH2OH Hexanol 71% H3C-(CH2)4-COOH Hexanoic acid H3C-(CH2)2-COOH Butyric acid C6H5OH Phenol 66% Potassium hydrogen phtalate 64% Sodium oxalate 32% Acrylonitrile N-Methly-2-Pyrrolidone
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Oxidation Potentials of Oxidizing Agents.
The sulfate radical is use in UV persulfate analysers. Permanganate and Dichromate are used in COD analysers.
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Oxidation levels at varying oxidation times.
The typical oxidation time is 150 seconds
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Oxidation levels at varying oxidation times.
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Oxidation levels at varying salt levels.
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Analyzer Applications, Advantages and Disadvantages.
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Advantages and Disadvantages of the BioTector.
Self cleaning oxidation without filtration. Rugged sampling with a minimum 3 mm ID sample tube capable of handling particulates up to 2 mm. Constructed using robust materials such as Hastelloy, Teflon, and Kalrez. This enables the BioTector to withstand a wide variety of corrosive and toxic process fluids. The BioTector can operate safely in hazardous environments: i) It can analyse toxic process fluids without venting them to atmosphere. ii) The BioTector can be purged for classified areas. iii) The BioTector can analyse high pressure samples. Disadvantage: More expensive to manufacture.
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BioTector installations.
Industries, which have been using the Two Stage Advanced Oxidation technology for more than 10 years (over 600 units installed worldwide to date 2009) Dairy processing plants where the effluents are high in fats, sugar and protein. Chemical plants and applications where the process streams are high in salt and contain volatile organics. Refineries where wastewaters contain oil, calcium and salts. Municipal treatment plants where the wastewaters have high turbidity and particulates. Airports where the surface water contains de-icing chemicals, particulates and salts (extremely high Organic loads). Pulp and paper industries where wastewater contain fibrous materials and particulates. Pharmaceutical industries where the waste streams contains a wide variety of chemicals.
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Typical external connections.
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BioTector installation in Diageo (Guinness) Ireland.
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BioTector installation in an Airport.
Photo required
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Typical analyser house.
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SUMMARY Complete oxidation of the sample with hydroxyl radicals.
Representative sample without any filtration (up to 2mm soft particulates). Self cleaning technology. High reliability: 86,000 measurements per annum and over 99% on-line time. Low Maintenance: 6 month service intervals. No calibration requirement between services. No interference from salts or Calcium. Automatic range selection and multi-streaming. Programmable Analysis Modes: TIC & TOC, TC, VOC, TC-TIC, TN and in addition TPR, TP modules are available. Analyse wide range of effluents containing fats, oils, salts, de-icing chemicals, particulates, fibrous materials.
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BioTector Installations
There are over 750 BioTector’s installed world wide, many of which are in applications which would not have been possible with conventional technologies.
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