User’s Manual Titrilyzer® Total Hardness (caco3) Series Of On-line Hardness (caco3)analyzers

User’s Manual TitriLyzer® Total Hardness (CaCO3) Series of on-line Hardness (CaCO3)Analyzers

Serial number: 012.1189.1708.148

User’s Manual TitriLyzer® Total Hardness (CaCO3) Series of on-line Hardness (CaCO3) Analyzers

© 2017 – AppliTek NV – Printed in Belgium All rights reserved. No part of this manual may be reproduced, stored in a retrieval system or transmitted in any form or by any means - electronic, mechanical, photocopying, recording or otherwise - without the prior written permission of AppliTek NV. The content of this document is entirely a non-binding external opinion. Neither AppliTek NV nor any of its employees can be held liable for damages to people, third parties, goods and assets that may result from implementing the content.

CONTENTS Preface – Documents and safety..........................................................................................10 Installation of the analyzer – Overview .............................................................................11 1. Installation of the analyzer ........................................................................................12 1.1 Dimensions of the analyzer ...............................................................................12 1.2 Location and ambient conditions .......................................................................13 1.3 Mounting instructions ........................................................................................13 2. Power and signals ....................................................................................................14 2.1 Power................................................................................................................14 2.2 Signals ..............................................................................................................14 3. Utilities ......................................................................................................................15 3.1 Overview ...........................................................................................................15 3.2 Sample feed ......................................................................................................15 3.3 Drain .................................................................................................................16 3.4 Overflow............................................................................................................16 3.5 Reagents & Calibration/validation solutions feed ...............................................16 3.6 Instrument air ....................................................................................................16 4. Power up & components test ....................................................................................17 4.1 Analyzer design ................................................................................................17 4.2 Wet chemical components ................................................................................18 4.3 Analog output ....................................................................................................21 4.4 Analog input ......................................................................................................21 5. Analyser method .......................................................................................................22 5.1 Specifications ....................................................................................................22 5.2 Analysis ............................................................................................................22 5.3 Calibration .........................................................................................................22 5.4 Validation ..........................................................................................................23 5.5 Cleaning ............................................................................................................23 5.6 Prime ................................................................................................................23 6. Reagent preparation .................................................................................................24 6.1 Reagent consumption .......................................................................................24 6.2 Storage and quality of chemicals and solutions .................................................24 6.3 Acid solution (0.5 M) .........................................................................................25 6.4 Buffer Ca Mg solution ........................................................................................25 6.5 Buffer Ca solution (NaOH 1M)...........................................................................26 6.6 Color solution ....................................................................................................26 6.5 EDTA solution (0.01 M) .....................................................................................27 6.6 Calibration standard solution .............................................................................28 6.7 Validation standard solution ..............................................................................28 6.8 Cleaning solution...............................................................................................29 7. Start-up of the analyser.............................................................................................30 7.1 Access ..............................................................................................................30 7.2 Reagents ..........................................................................................................30 7.3 Analysis procedure............................................................................................31 7.4 Calibration .........................................................................................................35 7.5 Cleaning ............................................................................................................36 7.6 Time List ...........................................................................................................36 7.7 Data and results ................................................................................................37 7.8 Analyzer settings ...............................................................................................38 7.9 Start-up the analyser for on-line measurement..................................................40 8. Maintenance .............................................................................................................41 8.1 Check for leaks and abnormal conditions ..........................................................41 8.2 Check for alarms ...............................................................................................41

8.3 Prepare reagents and fill the reagent containers ...............................................41 8.4 Run the calibration program ..............................................................................42 8.5 Run the cleaning program .................................................................................42 8.6 Replacement of the micropump’s duckbills .......................................................42 8.7 Replacement of the peristaltic pump tubing .......................................................42 8.8 Shutdown of the analyzer for a longer period ....................................................43 9. Troubleshooting ........................................................................................................43 10. Spare Parts ...........................................................................................................43 Addendum ........................................................................................................................44 Addendum 1: Analysis Procedure.....................................................................................44 1.1 Main Method – Analysis ....................................................................................44 1.2 Main Method – Cleaning (optional) ....................................................................44 1.3 Main Method – Priming (optional)......................................................................45 1.4 Ca Hardness Method – Analysis .......................................................................45 1.5 Total Hardness Method – Analysis ....................................................................46 Addendum 2: Analyzer Configuration ...............................................................................48 2.1 Digital Outputs ..................................................................................................48 2.2 Digital Inputs .....................................................................................................48 2.3 Analog Inputs ....................................................................................................48 2.4 Analog Outputs .................................................................................................49 2.5 Communication ports ........................................................................................49 2.6 Results ..............................................................................................................49 2.7 Results Calibration ............................................................................................49 2.8 Results Calculation ...........................................................................................49 2.9 Results Analog output .......................................................................................51 2.10 Result Alarms....................................................................................................51 2.11 Results Graph ...................................................................................................51 2.12 Algorithms .........................................................................................................51 2.13 Alarm and message table..................................................................................53 2.14 Group DO .........................................................................................................53 Addendum 3: Alarms and signals .....................................................................................54

Preface – Documents and safety Thank you for purchasing this high quality analytical instrument. The analyzer is designed for installation in industrial environments and intended for professional use. On delivery the analyzer does not offer readily available end-user functionality. The analyzer needs to be installed and configured by competent staff prior to use by the end user. Information about the exact specifications, necessary connections, utilities and maintenance schedules is given in the accompanying GENERAL SAFETY BOOK (8 languages). General safety instructions AppliTek and/or its affiliates use their best efforts to deliver a high quality analytical instrument and reliable software packages. AppliTek nor its affiliates cannot be held responsible for any damage that may result from the incorrect use of the software and hardware, use outside the scope of the analyzer’s specification, misinterpretation of the safety instructions, errors or deliberate modifications made to the analyzer; in addition, any warranty issued by AppliTek becomes void. •

Knowledge of the basic safety regulations is essential for the safe handling and disruption-free operation of the unit. Therefore, please read the entire manual before setting up the analyzer. Pay attention to danger and caution statements;

•

These operating instructions contain the most important guidelines necessary in order to safely oversee the unit’s operation;

•

All persons working on the unit should take note of these operation instructions, and especially those relevant to safety;

•

Protect the analyzer from impacts causing corrosion or preventing components from working properly;

•

Have faulty parts of the analyzer replaced immediately;

•

Spare parts must comply with the technical requirements determined by AppliTek;

•

When malfunctioning, take the analyzer out of operation. Repair the malfunctions immediately. Failure to do so could result in serious injury to persons or damage to the equipment;

•

On top of this, all rules and regulations pertinent to accident prevention, which are applicable at the measuring site, are to be followed.

•

It is the operator’s responsibility to allow only those persons to work on the unit who are familiar with the regulations concerning safe handling and have been informed how to work with the instrument;

Safety devices Before any initialization of the unit, all safety devices must be properly mounted and functional. Safety devices can only be removed: •

During maintenance and repair work by trained personnel or when the unit has been disconnected from the electrical mains.

•

After the unit has been safeguarded against renewed operation.

Electrical dangers Work on the unit’s power supply and electronics can only be carried out by a qualified electrician. The mains switch must be switched off during work on electrical components.

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Installation of the analyzer – Overview

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1. Installation of the analyzer 1.1 Dimensions of the analyzer

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1.2 Location and ambient conditions The analyzer is designed for installation at indoor environmental conditions. Install the analyzer where the temperature is maintained as stable as possible between 10 and 30 °C (range 4°C) and is not subject to sudden temperature changes. The analyzer should be installed as close as possible near the sampling point. If this is not the case, a fast loop sampling system has to be installed because a long distance between the analyzer and the sampling point will increase the response time of the analyzer. Do not mount the analyzer in direct sunlight! This can affect the visibility of the screen and the analyzer, its components and reagents. Other points of attention are:

- humidity: 5 – 95 % non-condensing - avoid corrosive atmospheres

Variation of these conditions can seriously affect the analyzer results and damage the analyzer and its components!

1.3 Mounting instructions The analyzer is designed for wall mounting and intended for permanent installation. Make sure the location is easy accessible. The dimensions of the analyzer are given on the previous page. The indicated footprint is a strict minimum and doesn’t take into account the space needed for tubing and cables. The analyzer has four mounting holes for screws M8x10mm at the back of the cabinet. These bolts are fastened into/onto the supporting structure from the inside of the electrical cabinet at the back. This analyzer has to be installed by qualified technical personnel to ensure adherence to all applicable electrical plumbing requirements.

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2. Power and signals 2.1 Power First open the electrical cabinet door by pulling the two levers and unhook them. Make provisions for removing power to the analyzer during servicing. The AC power cable enters on the left side of the cabinet at the back through the upper left cable gland. The terminals for the power and ground are located at the upper left hand corner of the cabinet at the back, as you face the unit. Connect your wiring to the upper side of the terminals. Connect the AC feed as follows: -

The protective ground at the yellow/green terminal block. The hot/line (L) and neutral (N) wire are to be connected at the circuit breaker.

Terminal Protective Ground (PE) Hot/line (L) Neutral (N)

North American wire color Green Black White

European wire color Green/yellow Brown Blue

2.2 Signals External 24Vdc power supply Note: If additional AO, DI or DO connections are required, extra terminals will be present. Connections: AO1-AO2: Analog Outputs 4-20mA, active current, max. load 500R FCT1-FCT5: Free ConTacts (digital output) Relay output, contact loading max. 24VDC/0,5A PCT1-PCT4: Power ConTacts (digital outputs) 24VDC/0,5A output INP1-INP4: INPut (digital input) 24VDC, to trigger with external potential free contact

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CONTACT AO1 AO2 AO3 AO4 FCT1 FCT2 FCT3 FCT4 FCT5 PCT1 PCT2 PCT3 PCT4 INP1 INP2 INP3 INP4

INPUT/OUTPUT AO1 AO2 AO3 AO4 DO25 DO26 DO27 DO28 DO29 DO21 DO22 DO23 DO24 DI1 DI2 DI3 DI4

NAME Result Tot Hard STR1 Result Ca Hard STR1 Result Tot Hard STR2 Result Ca Hard STR2 Malfunction

EXT SV STR1 EXT SV STR2

3. Utilities 3.1 Overview Consumption/ analysis

Consumption/28 days (1 analysis/10 min)

Sample

~ 80 ml

~ 350 L

Rinse

(for cleaning)

N.A.

Vent

/

/

Reagents

See Chapter 6

See Chapter 6

Comment Atmospheric pressure Atmospheric pressure Free Atmospheric pressure

Connection 1/8” 1/8” 1/4” 1/8”

3.2 Sample feed The sample feed to the analyzer must be at atmospheric pressure if the analyzer uses a peristaltic pump for sampling. The sample feed to the analyzer must be higher than the sample flow in the analyzer. It is recommended to use a small overflow vessel (next to the analyzer) from which the analyzer will take fresh sample. Thus the sample in the overflow vessel should be continuously refreshed. If the size of the solids present in the sample is too high, it is recommended to filter the sample. Connection: 1/8” OD tubing (PFA) Location: Left side of the analyzer The analyzer is not designed for use with samples that are explosive or flammable. If a solution other than water is used, this solution should be tested to test the compatibility with the instrument!

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3.3 Drain The analyzer needs a drain to discharge both sample and reagents after analysis. A floor or sink drain is satisfactory, but it must be unrestricted and located at a lower level than the analyzer so that gravity will carry away the liquid. The drain must have a vent to the atmosphere and the drain tube from the analyzer must not be submerged. Pay attention that the drain line is never blocked. A water connection is also recommended so that the drain sink and piping is regularly flushed with clean water in order to avoid clogging due to crystallization. Steepness of the draining pipe must be sufficient. Drain piping: recommended diameter of 32 mm Connection: 1/4” OD tubing (PFA) Location: Bottom side of the analyzer Although the chemical reagents are diluted, the user has to check that the external drain/overflow system is appropriate for reagents and corrosive wastes! Used reagents shall be treated for disposal according to national or local regulations!

3.4 Overflow The analyzer needs an overflow tube in order to drain the analysis compartment in case of leakage of sample fluids, reagent fluids (and combination of both) in the compartment. A floor or sink drain is satisfactory, but it must be unrestricted and located at a lower level than the analyzer so that gravity will carry away the liquid. The overflow tube from the analyzer must not be submerged. Pay attention that the overflow line is never blocked. Steepness of the overflow pipe must be sufficient. Connection: 3/8” OD tubing (PFA) Location: Bottom side of the analyzer

3.5 Reagents & Calibration/validation solutions feed Connections have to be made between the reagent containers and the dispensers, the micro pumps and the cleaning valve. The calibration/validation solutions can be connected to the REF1 or REF2 selection valve. Connection: 1/8” OD tubing Location: Bottom or left side of the analyzer Although the chemical reagents are diluted, the user has to check that the external drain/overflow system is appropriate for reagents and corrosive wastes! Used reagents shall be treated for disposal according to national or local regulations!

3.6 Instrument air The instrument air must be dry and dust free (according to ISA-S7.0.01-1996). The minimal pressure of the instrument air necessary for the analyzer is 1 bar (100 kPa or 15.5 psi). Instrument air is used for purging the analyzer in order to prevent corrosion by corrosive gases such as chlorine gas from outside the analyzer. Connection: 1/4” OD tubing (PFA)

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4. Power up & components test The analyzer and its components must be tested before the unit can be put into online service. Make sure that all necessary connections were made before testing the following components. Switch on the analyzer by means of the circuit breakers lever in the electrical compartment and (if present) the external power switch. When connecting the power of the analyzer, the software is started up. First, the initial startup screen appears. While this screen is visible, the parameters are loaded (loading of methods, configuration …) and the dispensers are initialized. Next, the MAIN screen (F1) becomes visible automatically.

Initial startup screen

MAIN screen

4.1 Analyzer design

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4.2 Wet chemical components Menu path: → F2

In the Visualization (F2) submenu, the wet chemical components (reagent pumps, stirrer, dispenser…) can be controlled manually. Press the icons on the screen to control the components. A control panel appears on the right side of the screen. By use of this panel, the chemical components can be controlled. Check if these components are working properly. 1. Stirrer Press the stirrer icon. Switch the stirrer ON/OFF by pressing the ‘ON/OFF’ button. It is also possible to turn the stirrer ON for a specified time. Insert the time (in seconds) and press the ‘Start’ button.

2. Micropump Press the micropump icon. Insert the number of pulses. Press ‘Pulse’ to start the micropump. Press the ‘Stop’ button to stop the micropump.

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3. Drain pump and Drain/Level valve The drain/level valve is used in combination with the drain pump for draining or leveling the analysis vessel. When the drain pump is started and the drain/level valve is not activated, the analysis vessel is drained. Press the pump icon. Switch the pump ON/OFF by pressing the ‘ON/OFF’ button. It is also possible to turn the pump ON for a specified time. Fill in the time (in seconds) and press the ‘Start’ button. The ‘Group’ function is implemented for safety reasons. If for example a valve must be opened before a pump is started, the group action can be used, if programmed. Press the valve icon. Activate/deactivate the valve by pressing the ‘ON/OFF’ button. It is also possible to activate the valve for a specified time. Fill in the time (in seconds) and press the ‘Start’ button. When the pinch valve and the drain pump are activated, the level action takes place: the excess of sample is removed from the analysis vessel. The level action is used to make sure that the amount of sample in the analysis vessel is equal for each analysis.

4. Sample pump The sample pump is used in combination with the SV1, REF1, REF2 or Cleaning valve for sampling. Press the pump icon. Switch the pump ON/OFF by pressing the ‘ON/OFF’ button. It is also possible to turn the pump ON for a specified time. Fill in the time (in seconds) and press the ‘Start’ button. The ‘Group’ function is implemented for safety reasons. If for example a valve must be opened before a pump is started, the group action can be used, if programmed.

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When the sample enters because one or more valves are switched, it is necessary to switch these valves on before the sample pump is started. Press the icon of the corresponding valve. Switch the valve ON/OFF by pressing the ‘ON/OFF’ button. It is also possible to turn a valve ON for a specified time. Fill in the time (in seconds) and press the ‘Start’ button. Next, press the sample pump and start the sample pump.

Components that are not visible on the visualization screen can be controlled in the DO submenu. Menu path:

Select the digital output by use of the Edit (E) button.

The value of the digital output can be toggled manually with the ‘ON/OFF’ button. After entering an activation time (seconds), the ‘START’ button can be pressed to activate the digital output. The digital output will then be active during the inserted number of seconds. After entering a number of pulses, the digital output will give the set number of pulses. Press ‘Stop’ to stop any action of the DO. Press the arrow keys at the top of the screen to select another DO. Press ‘Back’ to quit the screen.

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4.3 Analog output Menu path:

Press the EDIT (E) button to control the selected analog output. Use a multimeter to check if the analog output signal is working.

Insert a value by use of numeric keyboard and confirm. Press Accept to update this value. Check if this value corresponds to the value the multimeter is giving. Check the ‘Installation Manual’ to make the right connections.

4.4 Analog input Menu path:

Check if all analog inputs are responding correctly. Press the EDIT (E) button to control the selected analog input.

4.4.1 Photometer The calibration of the photometer performed in distilled water (media 1)

is

Press enter to start calibration Put sensor in media 1 and enter Stabilizing, press enter to continue Update calibration data

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5. Analyser method 5.1

Specifications

Specifications are subject to change without notice.

Method:

Colorimetric titration

Wavelength:

610 nm

Parameter:

Total Hardness (as mg/L CaCO3) and Ca Hardness

Range:

50 – 1000 mg/L CaCO3

Precision:

< 2 % of full scale range (with standard solutions)

Analysis time:

< 10 minutes

Sample requirements:

Atmospheric pressure, flow rate between 10 and 30 ml/minute, sample temperature between 5 and 60 °C

Sample dilution:

pump head and sample valves for sampling dispenser for internal dilution

Stream selection:

Channel1: Channel2: Channel8: Channel10:

5.2

stream 1 (Sample valve and EXT SV1) stream 2 (Sample valve and EXT SV2) validation (REF2 valve) REF2 (REF2 valve)

Analysis

The analysis vessel is cleaned and filled with fresh sample. After sampling, the acid, buffer (buffer Ca Mg) and color solution are added to the sample. Next, the photometric titration (610 nm) with EDTA is performed and the calcium and magnesium concentrations in the sample are determined (Total Hardness as mg/L CaCO3). When measuring the Ca hardness the buffer (buffer Ca) changes the pH to 12. The Mg settles and when the EDTA is added, the calcium concentration in the sample is only determined. The acid solution is added to dissolve all carbonates (CaCO3 dissolves into Ca2+ and (CO3)2which is removed as CO2 in acidic environment). The buffer solution is added to reach an alkaline pH in which the color solution forms a purplish-blue color. The color changes to red when contacting free calcium or magnesium. The color changes to blue when EDTA is added to the sample. The change from the red to blue color is measured.

5.3

Calibration

The calibration procedure measures a REF2 or 1000 mg/l CaCO3 solution (channel 10 – REF2 valve) to correct for any deviation in the results by external influences (sample volume, micropump volume, reagent concentration).

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5.4 Validation The validation method is used to verify the functioning of the analyzer with a standard solution. The validation procedure measures a standard solution with a known CaCO3 concentration (channel 8 – REF2 valve) to validate the analyzer.

5.5

Cleaning

The cleaning procedure should prevent any build-up of chemicals in the analyzer. To obtain an effective cleaning procedure one has to test the cleaning solution and the cleaning interval for each application. Perform the cleaning procedure with the selected cleaning solution and interval for a trial period, check then the effectiveness of the procedure and change if necessary.

5.6

Prime

The prime procedure can be used when starting up the analyzer or after a shutdown of the analyzer: the reagent tubings are flushed with fresh reagent solution and the sample tubing and the analysis vessel are flushed with fresh sample.

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6. Reagent preparation

!

Warning: Some of the chemicals used are corrosive or harmful! All operating personnel should wear protective gloves, goggles and acid-proof clothing! Check the MSDS before starting to handle the chemicals.

The information in this document is based on the present state of our knowledge and is applicable to the products with regard to appropriate safety precautions. It does not guarantee any of the properties of the products. AppliTek shall not behold liable for any damage resulting from handling or from contact with any product described in this manual.

6.1 Reagent consumption In the tables below, the products that are needed to prepare the reagents are listed. The product name, the formula, the molecular weight, the CAS No. and the amount needed to prepare 1 liter of the reagents is given. Check the consumption of the reagents (28 days) to adapt the volumes needed. Product Acid solution

Consumption/analys is ~ 0.5 ml

Buffer Ca solution ~ 1 ml Buffer Ca Mg ~ 0.5 -0.75 ml solution Color solution ~ 0.75 ml

Consumption/28 days (1 analysis/10 min) < 2.5 L

Recommandable conatiner (L) Plastic – 2.5L

<5L

Plastic – 5L

<5L

Plastic – 5L

<5L

Plastic – 5L

EDTA solution

Concentration dependent

Concentration dependent

Plastic – 10L

Calibration solution REF2

~ 80 ml

N.A.

N.A.

6.2 Storage and quality of chemicals and solutions Quality of chemicals: All chemicals should be of ACS grade or better. We recommend the use of pro analysis chemicals. Quality of water: Reagent grade, de-ionized water (calcium- and magnesium-free) must be used to prepare the chemical solutions and for rinse purposes. Laboratory equipment: Reagent and solutions should be prepared and kept in plastic vessels. Avoid the use of glassware.

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6.3 Acid solution (0.5 M) Product

Formula

MW (g/mol)

CAS No.

Product number

Hydrochloric acid (0.5 M)

HCl

36.46

7647-01-0

318957 (Sigma-Aldrich)

Hydrochloric acid 0.5 M

Hazard statement(s): H290:

May be corrosive to metals.

Precautionary statement(s): None

This solution is stable for several months.

6.4 Buffer Ca Mg solution Product

Formula

MW (g/mol)

CAS No.

1 liter solution

Ammonium chloride

NH4Cl

53.49

12125-02-9

54 g

Ammonia solution 25%

NH4OH

35.05

1336-21-6

350 ml

Mg-EDTA*

C10H12MgN2Na2O8·4H2O

430.56

29932-54-5

5g

*ethylenediaminetetraacetic acid magnesium disodium salt tetrahydrate

Ammonium chloride

Hazard statement(s): H302: H319:

Harmful if swallowed. Causes serious eye irritation.

Precautionary statement(s): P305 + P351 + P338: IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continue rinsing.

Ammonia solution 25%

Hazard statement(s): H302: H314: H335: H400:

Harmful if swallowed. Causes severe skin burns and eye damage. May cause respiratory irritation. Very toxic to aquatic life.

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Precautionary statement(s): P261: Avoid breathing vapours. P273: Avoid release to the environment. P280: Wear protective gloves/ protective clothing/ eye protection/ face protection. P305 + P351 + P338: IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continue rinsing. P310: Immediately call a POISON CENTER or doctor/ physician.

Mg-EDTA (ethylenediaminetetraacetic acid magnesium disodium salt tetrahydrate) Not a hazardous substance or mixture according to Regulation (EC) No. 1272/2008. This substance is not classified as dangerous according to Directive 67/548/EEC.

Preparation: Dissolve 54 g of ammonium chloride (NH4Cl) in de-ionized water using a volumetric flask of 1000 ml. Add 350 ml of 25% ammonium hydroxide solution (NH4OH). Add 5 g Mg-EDTA, dissolve completely and fill up to 1 liter with de-ionized water. This solution is stable for 1 month.

6.5 Buffer Ca solution (NaOH 1M) Product

Formula

MW (g/mol)

CAS No.

1 liter solution

Sodium hydroxide

NaOH

40.00

1310-73-2

40 g

Sodium hydroxide (pellets)

Hazard statement(s) H314:

Causes severe skin burns and eye damage

Precautionary statement(s) P280: Wear protective gloves/ protective clothing/ eye protection/ face protection. P305 + P351 + P338: IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continue rinsing. P310: IF exposed or if you feel unwell: immediately call a POISON CENTER or doctor/physician.

Preparation: Dissolve 40 g of sodium hydroxide (NaOH p.a., > 99 %) in 500 ml of demineralized water and dilute to 1 liter with demineralized water.

6.6 Color solution Product

Formula

MW (g/mol)

CAS No.

1 liter solution

Calmagite

HOC10H5[N=NC6H3(OH)CH3]SO3H)

358.37

3147-14-6

0.2 g

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Calmagite

Hazard statement(s): H315: H319: H335:

Causes skin irritation. Causes serious eye irritation. May cause respiratory irritation.

Precautionary statement(s): P261: Avoid breathing dust/ fume/ gas/ mist/ vapours/ spray. P305 + P351 + P338: IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continue rinsing.

Preparation: Dissolve approximately 0.2 g Calmagite (HOC10H5[N=NC6H3(OH)CH3]SO3H) in 400 mL degassed de-ionized water using a volumetric flask of 1L. Fill up to the grade mark with deionized water. This solution is stable for 1 month.

6.5

EDTA solution (0.01 M)

Product

Formula

MW (g/mol)

CAS No.

1 liter solution

EDTA*

C10H14N2Na2O8.2H2O

372.2

6381-92-6

3.722 g

C10H14N2Na2O8

336.21

139-33-3

100 ml

OR EDTA-Na2** 0.1M

*ethylenediaminetetraacetic acid disodium salt dihydrate **ethylenediaminetetraacetic acid disodium salt solution

EDTA (ethylenediaminetetraacetic acid disodium salt dihydrate)

Hazard statement(s) H319:

Causes serious eye irritation.

Precautionary statement(s) P305 + P351 + P338: IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continue rinsing. EDTA (ethylenediaminetetraacetic acid disodium salt solution) Not a hazardous substance or mixture according to Regulation (EC) No. 1272/2008. Not a hazardous substance or mixture according to EC-directives 67/548/EEC or 1999/45/EC.

Preparation: Dissolve accurately 3.722 g ethylenediaminetetraacetic acid disodium salt dihydrate (C10H14N2Na2O8.2H2O) in 500 ml degassed de-ionized water and fill up to 1000 ml.

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OR Dilute a 0.1 M EDTA stock solution by taking exactly 100 ml of the 0.1 M EDTA solution using a volumetric flask of 1000 ml and adding de-ionized water up to the mark grade. This solution is stable for 1 month.

6.6

Calibration standard solution

Product

Formula

MW (g/mol)

CAS No.

1 liter solution

Calcium chloride dihydrate

CaCl2.2H2O

147.02

10035-04-8

3.668 g

Calcium chloride dihydrate

Hazard statement(s): H319:

Causes serious eye irritation

Precautionary statement(s): P305 + P351 + P338: IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continue rinsing.

Preparation: 1000 mg/L Ca stock solution Prepare a stock solution of 1000 mg/L CaCO3: dissolve accurately 3.668 g calcium chloride dihydrate (CaCl2.2H2O) in 200 ml degassed de-ionized water (DI water), using a volumetric flask of 1000 ml. Add de-ionized water up to the mark grade. 1000 mg/L CaCO3 calibration standard solution Prepare a standard solution of 1000 mg/L CaCO3: take accurately 400 ml of the 1000 ppm Ca stock solution and transfer a volumetric flask of 1000 ml. Add de-ionized water up to the mark grade.

6.7

Validation standard solution

Product

Formula

MW (g/mol)

CAS No.

1 liter solution

Calcium chloride dihydrate Magnesium chloride hexahydrate

CaCl2.2H2O

147.02

10035-04-8

3.668 g

MgCl2.6H2O

203.30

7791-18-6

8.365 g

Calcium chloride dihydrate

Hazard statement(s):

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H319:

Causes serious eye irritation

Precautionary statement(s): P305 + P351 + P338: IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continue rinsing.

Magnesium chloride hexahydrate Not a hazardous substance or mixture according to Regulation (EC) No. 1272/2008. This substance is not classified as dangerous according to Directive 67/548/EEC.

Preparation: 1000 mg/L Ca stock solution Dissolve accurately 3.668 g calcium chloride dihydrate (CaCl2.2H2O) in 200 ml de-ionized water, using a volumetric flask of 1000 ml. Add de-ionized water up to the mark grade. 1000 mg/L Mg stock solution Dissolve accurately 8.365 g magnesium chloride hexahydrate (MgCl2.6H2O) in 200 ml deionized water, using a volumetric flask of 1000 ml. Add de-ionized water up to the mark grade. Preparation validation standard solution 250 mg/l CaCO3 : Take accurately 50 ml of the 1000 ppm Ca stock solution and 30 ml of the 1000 ppm Mg stock solution and transfer into 200 ml de-ionized water, using a volumetric flask of 1000 ml. Add de-ionized water up to the mark grade. This solution contains the equivalent of 100 mg/l Ca or 250 mg/l CaCO3.

6.8 Cleaning solution The cleaning procedure should prevent any build-up of chemicals in the analyser. To obtain an effective cleaning procedure one has to test the cleaning solution and the cleaning interval for each application. Perform the selected cleaning solution and interval for a trial period, check then the effectiveness of the procedure and change if necessary.

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7. Start-up of the analyser 7.1 Access Menu path: → F1 → User → Enter Access password Press the black box next to ‘User:’ to change the userlevel by use of the corresponding password.

Depending on the userlevel some menus are accessible and some are not. Normally, when the analyzer is started up, the ‘Automatic’ userlevel appears. This level is also used in online situations. The analyzer is locked, which means that the METHOD (F4) and CONFIG (F5) menu are not accessible. If modifications of the software are needed, higher userlevels can be used. The access to certain crucial parameters is only given if the ‘Administrator’ password is used. Enter the password by pressing the ‘Enter Access password’ button. Default passwords: User Automatic User1 User2

Password a b

7.2 Reagents Menu path: → F1 → 1.Method → Priming Select the method with the navigation buttons at the bottom of the MAIN (F1) screen. The method screen appears.

If all wet chemical components are working properly, the reagents can be connected to the analyser. Press the ‘Priming’ button to fill up all tubings to the analysis vessel with reagent 30

Make sure there is no air present in the tubings. Also, make sure there is no air present in the dispenser, the tubing to the dispenser and the tubing from the dispenser to the analysis vessel.

7.3 Analysis procedure Follow the procedure below to start the method. It is recommended to run the method several times and to make sure the measurements are stable before a calibration of the analyzer is performed. Make sure all flushing times are set correctly before the analyzer is started for on-line measurement. Menu path: → F1 → 1.Method Select the method with the navigation buttons at the bottom of the MAIN (F1) screen. The method screen appears.

Menu path: → F1 → Method → Playlist → Automatic sequence Press the Playlist button. Press the Automatic sequence button and insert the desired module, channel and number of analysis. Press Accept to confirm. Press Back to quit the window without saving the changes. Start parameters: Module: CH: # Runs: Comment:

Analysis, Preconditioning, Cleaning, Priming, Init, and Exit. Automatic sequence or channel 1 to 10 Insert the number of runs of the module (0 = Continuous analysis) Add a comment concerning the analysis (Optional). This comment will also be displayed in the data table.

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7.3.1 Single stream analysis -

Module: CH:

select Analysis insert the number of the stream (Sample = stream 1 – 8; REF1 = stream 9; REF2 = stream 10) insert the desired number of runs (=1 for single stream analysis)

-

#Runs:

-

Continuous analysis: Fixed number of analysis:

insert 0 as #Runs in the method main screen insert the desired #Runs in the method main screen

For example: - The third sample stream needs to be analyzed - Insert ‘3’ as channel (CH) and 1 as #Runs 7.3.2 Single stream analysis with cleaning -

Module: CH:

-

#Runs:

select the desired module (Analysis or Cleaning) insert the number of the stream (Sample = stream 1 – 8; REF1 = stream 9; REF2 = stream 10) (For cleaning, always use channel 1) insert the desired number of runs (=1 for single stream analysis)

Repeat for each stream that needs to be analyzed. -

Continuous analysis: Fixed number of analysis:

insert 0 as #Runs in the method main screen insert the desired #Runs in the method main screen

For example: There one streams that need to be analyzed. After 10 analysis, a cleaning is needed. Insert ‘Analysis’ as Module, ‘1’ as channel and ‘10’ as #runs Insert ‘Cleaning’ as Module, ‘1’ as channel and ‘1’ as #runs (For cleaning, always use channel 1) 7.3.3 Multiple stream analysis -

Module: CH:

-

#Runs:

select Analysis insert the number of the stream (Sample = stream 1 – 8; REF1 = stream 9; REF2 = stream 10) insert the desired number of runs (=1 for single stream analysis)

Repeat for each stream that needs to be analyzed.

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-

Continuous analysis: Fixed number of analysis:

insert 0 as #Runs in the method main screen insert the desired #Runs in the method main screen

For example: - There are five streams that need to be analyzed. - Insert ‘1’ as channel and 1 as # runs - Insert ‘2’ as channel and 1 as # runs - Insert ‘3’ as channel and 1 as # runs - Insert ‘4’ as channel and 1 as # runs - Insert ‘5’ as channel and 1 as # runs 7.3.4 Multiple stream analysis with cleaning -

Module: CH:

-

#Runs:

select the desired module (Analysis or Cleaning) insert the number of the stream (Sample = stream 1 – 8; REF1 = stream 9; REF2 = stream 10) (For cleaning, always use channel 1) insert the desired number of runs (=1 for single stream analysis)

Repeat for each stream that needs to be analyzed. -

Continuous analysis: Fixed number of analysis:

insert 0 as #Runs in the method main screen insert the desired #Runs in the method main screen

For example: - There are two streams that need to be analyzed. Next, a cleaning is needed. - Insert ‘Analysis’ as Module, ‘1’ as channel and ‘1’ as #runs - Insert ‘Analysis’ as Module, ‘2’ as channel and ‘1’ as #runs - Insert ‘Cleaning’ as Module, ‘1’ as channel and ‘1’ as #runs (For cleaning, always use channel 1)

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7.3.5 Start the method Menu path: → F1 → 1.Method1 → Playlist → Start

7.3.6 Stop the method

Menu path: → F1 → 1.Method1 → Stop Press the ‘Stop’ button. The method will be finished and the analyzer will stop (status will change from ‘Run’, to ‘Stopped’ and then ‘Ready’).

Menu path: → F1 → 1.Method1 → Abort Press the ‘Abort’ button to stop the method immediately after confirmation.

Menu path: → E-Stop In case of emergency, all methods can be stopped directly by pressing the E-STOP button (SOFTWARE emergency stop) at the bottom of the screen.

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7.3.7 Remote control Menu path: → F1 → 1.Method1 → Is Master

Press the ‘Is Master’ button. The following instruction screen appears. Press ‘Toggle’ to put the analyzer in ‘Is Slave’ position. If the method is in this position, it is impossible to start the method manually. The method can only be started remotely i.e. by a digital input, by Modbus communication, by a sequence… Press Abort to stop the method. Press the ‘Is Slave’ button to put the analyzer in ‘Is Master’ position again.

7.4 Calibration When the analysis results are stable, the analyzer can be calibrated. Menu path: → F1 → Method → Calibrate

Press the ‘Calibrate’ button. The calibration procedure will start automatically after confirmation. The calibration procedure consists of following steps: -

Number of runs (REF1): Number of runs (REF2):

3x 3x

stream 9 stream 10

The concentration of the REF1 and REF2 solution and the number of runs is programmable in the Configuration (F5) menu (See Configuration Manual for more information). Press the ‘Calibration history’ button to get an overview of the previous calibration data.

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7.5 Cleaning Menu path: → F1 → Method → Cleaning

To clean the analyzer (the analysis vessel) press the ‘Cleaning’ button. The cleaning subroutine will be executed and the analyzer is stopped. When the analyzer is on-line, the cleaning procedure starts after the Analysis subroutine is finished. The analyzer is started again for on-line measurements after the Cleaning subroutine is finished.

7.6 Time List Menu path: → F1 → Method → Time list Press the Time list button to configure the time list. An overview of the configured time tables is displayed. Scroll through the list by use of the arrow keys.

Press the Edit (E) button to configure the selected time table. Every time table can be turned ON or OFF by pressing the toggle (T) button. Make sure the ‘Direct’ button is selected to guarantee the proper functioning of the Time list. Press Back to quit the screen.

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7.6.1 Configuration of the time list Only a configured time list can be used. Make sure the time list is turned ‘ON’ and the ‘Direct’ button is selected. Refer to the Configuration manual for additional information about the configuration of the time list. Press Accept to confirm. Press Back to quit the screen. Example: An automatic calibration on stream 1 of method 1 is needed, every day at 12 o’clock. -

HH: 12 Channel: 1 Start function: Calibration Index: Method1

7.7 Data and results Menu path: → F3 → Database

The analysis results of every method are displayed in the ‘Database’ submenu. A method can be selected by use of the arrow keys at the right side of the screen. Press the Edit (E) button to view the result for the selected method. The arrow keys on the right side of the screen can be used to scroll through the list. The file can be exported to a memory stick by pressing the ‘Export’ button. The data are exported to a CSV-file that can be opened for example in EXCEL.

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Menu path: → F6

The course of a titration can be followed in the F6 submenu. Select the titration algorithm by use of the dropdown menu. The graph can be appointed by use of the alphanumeric keyboard. The screen can be copied to an USB stick by pressing the Export button. Press the orange arrow key to view the titration data table. The titration algorithm can be selected by use of the dropdown menu.

7.8 Analyzer settings Adjustments to the analyzer configuration are made in the Configuration (F5) menu. We recommend you to read the instructions very carefully before making adjustments to the analyzers configuration: the functioning of the analyzer may be disturbed! For more information about the analyzer settings, refer to the Configuration Manual. 7.8.1 Adaptation of flushing intervals Menu path: → F5 → Software → CH Interval

The time set in a channel interval is channel dependent. Change this time in order to extend/reduce for example the flush time of the sample through the analysis vessel. Repeat for every channel (sample stream) if necessary.

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7.8.2 Adaptation of constant values Menu path: → F5 → Software → Constants

Constant values are used in the calculation of the results. Change these values if necessary. 7.8.3 Adaptation of group DO times Menu path: → F5 → Software → Group DO → E (Edit) Group actions are implemented to run several actions simultaneously. Be careful when changing the ‘group DO’ settings, the functioning of the analyzer may be disturbed.

Select the ‘group DO’ by use of the arrow keys and press the Edit button to change the settings.

The times are entered in millisecond (ms). To avoid problems with analyzer functioning, only change the time with the greatest value. Press Accept to save the settings. Test the changes before starting the analyzer for on-line measurements.

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7.8.4 Adaptation of algorithms Menu path: → F5 → Software → Algorithms Settings for algorithms are configured in the AppliTek lab with standard solutions. Depending on the problems that occur in the field, other settings need to be adapted. For more information about the algorithm settings, refer to the Configuration Manual.

7.9 Start-up the analyser for on-line measurement The analyser is now set-up and ready to go online. Make sure all analyser components are working properly and all settings are correct before the analyser is started.

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8. Maintenance Task Check for leaks and abnormal conditions Check for alarms Prepare reagents and fill the reagent containers Run the calibration program Replace the duckbills Replace all peristaltic pump tubing Replace all pinch valve tubing Replace all tubing

Daily

Weekly

Monthly

Quarterly

Annually

X

X

X

X

X

X

X

X

X

X

X

X

X

(X)

(X)

X X

X

X

X X

Perform a regular inspection of the analyzer to ensure proper performance.

8.1 Check for leaks and abnormal conditions It is recommended that the instrument and preconditioning system is inspected visually on a regular basis in order to guarantee the correct functioning of the system and to check the integrity of the output. • Check for alarms on the instrument display • Check all the components in the analysis compartment, the outside connectors and tubings for leaks. • Confirm sample flow by checking the constant delivery of the sample • Check the liquid levels in the reagent and standard solution containers • Check if all the components in the analyzer cabinet are functioning (pumps, valves, dispensers, photometer/electrode and stirrer). The photometer/electrode can be checked by checking if the measurement values are normal. If not, double-check by performing a calibration. • Check the air pressure.

8.2 Check for alarms Check the alarm page on the touch screen PC for alarms.

8.3 Prepare reagents and fill the reagent containers Use reagents supplied by AppliTek or a qualified company or prepare them yourself by following the instructions in chapter 6. Refill the reagent containers with the fresh made reagents or use supplied reagents. Make sure that the tubings reach the bottom of the reagent containers. Never pour the fresh reagents in containers with old reagents! Dispose the old reagents before pouring new reagent into its specific container.

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8.4 Run the calibration program Refer to chapter 7.4 if analysis results are not as expected.

8.5 Run the cleaning program Refer to chapter 7.5 to perform a manual cleaning. Refer to chapter 7.6 to program the automatic cleaning procedure.

8.6 Replacement of the micropump’s duckbills • Open the electrical cabinet of the analyzer. • Disconnect the micropump and remove the old duckbill valves. Keep in mind their original position. • Place the new duckbill valves in the same position as the previous duckbills. Be careful the duckbills are tightened well when reconnecting the micropump.

8.7 Replacement of the peristaltic pump tubing • Unfasten the wingnuts that fix the peristaltic pumps onto the electric motor coupler. • Remove the pump head. • Separate the front pump half from the back half. Hold the pump axle and the back pump half together (1a). • Remove the tubing. Keep in mind the length of both endings coming out of the pump head. • Cut new tubing of the same size at the same length of the old one. • Assemble the tube in the exact same way the old one was placed and push it down the back pump half in front of the pump axle rollers. Then twist the pump axle a bit while you keep pushing the tubing down so it is pressed between the pump housing and the pump axle rollers (1b +1c). • Join the two pump halves and make sure the tubing is not squeezed between the two halves (1d). • Place back the pump head and align the pump axle with the motor axle by pushing it against the motor axle while turning the pump axle with a screwdriver. • Fasten the wingnuts. • Activate the pump and check if it is running properly.

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8.8 Shutdown of the analyzer for a longer period If the analyzer is stopped for a longer period (more than 3 days), it is recommended to rinse the sample tubing, the reagent tubing, the dispensers and the analysis vessel with demineralized water or a cleaning solution. In order to increase the lifetime of the electrodes, it is recommended to take out the electrodes and store them with the original electrode cap. To prevent evaporation of the electrolyte in the electrode, the electrode cap has to be filled with electrolyte. Storage of the electrodes in de-mineralized water will significantly decrease the lifetime of the electrodes.

9. Troubleshooting If analysis results are unstable the following items should be checked: a) Micropumps: make sure the reagents are dosed correctly and that no air is present in the tubings b) Peristaltic pumps: check if the drain and sample pump are working correctly c) Valves: make sure the sample/REF1/REF2/Clean valves are working correctly d) Stirrer: check if there is a magnetic stirrer bar in the analysis vessel and if the solution is stirred during analysis e) Check the positioning of the tubings inside the analysis vessel • The drain tubing must be positioned at the back side of the analysis vessel and in the ringlets. • Other tubing should be positioned above the liquid level. f) Check the reagents. Prepare a new set of reagents when the reagent containers are empty. Flush/Prime all tubing before performing a measurement.

10.

Spare Parts

See Material Date Sheet with corresponding analyzer serial number.

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Addendum Addendum 1: Analysis Procedure Remark: Adjustments to the methods are made in the METHOD (F4) menu. We recommend you to read the ‘Configuration Manual’ carefully before making adjustments to the method: the functioning of the analyzer may be disturbed.

1.1

Main Method – Analysis

Streamselection Channel 1 (sample) Channel 2 (sample) Channel 8 (validation) Channel 10 (calibration) Nr 1 2 3 4 5 6 7

1.2 Nr 9 10 11 12 13 14 15 16 17 18 19 20

Step Name PROGMOD1: Analysis Run: Ca Hardness Wait for Method Run: Total Hardness Wait for Method Write to database Waiting

Channel DO Sample (STR1) Sample (STR2) REF2 REF2 Interval

Volume

Pulses

1s 1800 s 1s 1800 s 1s Variable: Waiting

Main Method – Cleaning (optional) Step Name PROGMOD3: Cleaning Clean ON DP CCW Interval Sample Group Drain Group Sample Group Stirrer ON Waiting Drain Group Clean OFF Write to database Waiting

Interval

Volume

Pulses

50 ms 30 s 8000 ms 16000 ms 8000 ms 50 ms 60 s 16000 ms 50 ms 1s 1s

44

1.3 Nr 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40

1.4 Nr 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19

Main Method – Priming (optional) Step Name PROGMOD4: Priming DP CCW ON Acid pulses Buffer Ca pulses Buffer CaMg pulses Color pulses EDTA pulses SP CW ON Clean Interval REF2 Interval Spare Interval Sample Interval SP CW OFF Waiting DP CCW OFF Rinse Group Drain Group Rinse Group Drain Group Waiting

Interval

Volume

50 ms 1s 1s 1s 1s 150 s 50 ms 15 s 15 s 15 s 15 s 50 ms 30 s 50 ms 10000 ms 16000 ms 10000 ms 16000 ms 1s

Pulses

150p 150p 150p 150p 150p

Ca Hardness Method – Analysis Step Name PROGMOD1: Analysis Streamselection ON Stirrer ON DP CCW Interval ABS Meas. ABS drain Calc. SP CW ON DP CCW ON Flushing SP CW OFF Waiting DP CCW OFF Sample Group Drain Group Sample Group Drain Group Sample Group Level Group Streamselection OFF

Interval

Volume

Pulses

50 ms 50 ms 30 s 5s 1s 50 ms 50 ms Variable: Flushing 50 ms 5s 50 ms 8000 ms 16000 ms 8000 ms 16000 ms 8000 ms 11000 ms 50 ms 45

20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51

1.5 Nr 1 2 3 4 5 6 7 8 9

ABS Meas. ABS sample Calc. Sample Detection Calc. Waiting Sub procedure 0 Drain / Level OFF Stirrer ON Acid pulses Waiting Buffer Ca pulses Color pulses Waiting Hardness Algorithm Waiting Algorithm check Calc. ml. infl Ca Calc. Ca Hardness Calc. Write to database Drain Group Streamselection ON Rinse Group Drain Group Rinse Group Drain Group Streamselection OFF Waiting Sub procedure 1000 Drain / Level OFF Ca Hardness Calc. Write to database Streamselection OFF Waiting

5s 1s 1s 15 s 0s 50 ms 50 ms 9s 60 s 18 s 12 s 5s 1200 s 1s 1s 1s 1s 1s 16000 ms 50 ms 10000 ms 16000 ms 10000 ms 16000 ms 50 ms Variable: Waiting 0s 50 ms 1s 1s 50 ms 1s

9p 18p 12p

Total Hardness Method – Analysis Step Name PROGMOD1: Analysis Streamselection ON Stirrer ON DP CCW Interval ABS Meas. ABS drain Calc. SP CW ON DP CCW ON Flushing

Interval

Volume

Pulses

50 ms 50 ms 30 s 5s 1s 50 ms 50 ms Variable: Flushing

46

10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51

SP CW OFF Waiting DP CCW OFF Sample Group Drain Group Sample Group Drain Group Sample Group Level Group Streamselection OFF ABS Meas. ABS sample Calc. Sample Detection Calc. Waiting Sub procedure 0 Drain / Level OFF Stirrer ON Acid pulses Waiting Buffer CaMg pulses Color pulses Waiting Hardness Algorithm Waiting Algorithm check Calc. ml. infl TH Calc. Total Hardness Calc. Write to database Drain Group Streamselection ON Rinse Group Drain Group Rinse Group Drain Group Streamselection OFF Waiting Sub procedure 1000 Drain / Level OFF Total Hardness Calc. Write to database Streamselection OFF Waiting

50 ms 5s 50 ms 8000 ms 16000 ms 8000 ms 16000 ms 8000 ms 11000 ms 50 ms 5s 1s 1s 15 s 0s 50 ms 50 ms 9s 60 s 15 s 12 s 5s 1200 s 1s 1s 1s 1s 1s 16000 ms 50 ms 10000 ms 16000 ms 10000 ms 16000 ms 50 ms Variable: Waiting 0s 50 ms 1s 1s 50 ms 1s

9p 15p 12p

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Addendum 2: Analyzer Configuration See also ‘Material Date Sheet’ with corresponding analyzer serial number. Software: PP65 UPA V3.06.70

2.1

Digital Outputs

Nr 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 21 22 25

Name SP CW SP CCW DP CW DP CCW Drain / Level Stirrer Acid Buffer Ca Buffer CaMg Color EDTA Spare REF2 Clean Rinse Sample EXT SV STR1 EXT SV STR2 Malfunction

2.2

Digital Inputs

Nr 1 2 3 4

2.3 Nr 1

Name INP1 INP2 INP3 INP4

Analog Inputs Name ABS

48

2.4 Nr 1 2 3 4

2.5

Analog Outputs Name Result Tot Hard STR1 Result Ca Hard STR1 Result Tot Hard STR2 Result Ca Hard STR2

Communication ports

Nr 1

Name COM1

2.6

Results

Nr 1 2 3 4 5 6 7 8 9 10 11

2.7

Function 0

Name Sample Detection ABS drain Ca ABS sample Ca ml. infl Ca Algorithm check Ca Hardness Total Hardness ABS ml. infl TH ABS drain TH ABS sample TH

Databit 8

Parity 0

Stopbit 1

Unit N.A. mAU mAU ml N.A. ppm ppm mAU ml mAU mAU

Results Calibration

Name A1 Total Hardness 7,15776 Ca Hardness 7,21652

Min A1 0 0

Name Conc. Ref2 Total Hardness 1000 Ca Hardness 1000

Runs Ref2 3 3

2.8

Baudrate 9600

Max A1 20 20

Results Calculation

Sample Detection 1 M1 - M2 2 IF R1 < 100 THEN Set alarm byte: 1 Value: 1 3 IF R1 >= 100 THEN Set alarm byte: 1 Value: 0 4 IF R1 < 100 THEN goto subprocedure 1000 5 IF R1 >= 100 THEN goto subprocedure 0 6 R1 End of calculation

49

ABS drain Ca 1 M1 End of calculation ABS sample Ca 1 M2 End of calculation ml Infl. Ca 1 M3 End of calculation Algorithm check 1 IF M-Alarm3 = 1 THEN GOTO R3 2 0 End of calculation 3 IF 0 = 0 THEN goto subprocedure 1000 4 1 End of calculation Ca Hardness 1 M3 write to calibration 2 M3 / Factor a1 3 R2 * Conc. ref2 4 R3 End of calculation Total Hardness 1 M6 write to calibration 2 M6 / Factor a1 3 R2 * Conc. ref2 4 R3 End of calculation ABS 1

ABS End of calculation

ml Infl. TH 1 M6 End of calculation ABS drain TH 1 M4 End of calculation ABS sample TH 1 M5 End of calculation

50

2.9

Results Analog output

Result Ca Hardness Ca Hardness Total Hardness Total Hardness

Channel 1 2 1 2

Analog output Result Ca Hard STR1 Result Ca Hard STR2 Result Tot Hard STR1 Result Tot Hard STR2

Value 4mA 0 0 0 0

Value 20mA 1000 1000 1000 1000

2.10 Result Alarms Result Ca Hardness Total Hardness

Channel

Low alarm DO

High alarm DO

Low value

High value

0

0

1500

0

0

1500

2.11 Results Graph Result Ca Hardness Total Hardness

Channel 0 0

Low value 0 0

High value 1000 1000

2.12 Algorithms Name: Sensor: Pauze Pauze drift: Pauze Max time: Pauze Min time: Initial dosing Init steps: Init time: Init Volume: Init Speed: Dynamic dosing Dyn. slope: Dyn. speed: Dyn. refill speed: Dyn. min step: Dyn. max step: Dyn. min time: Dyn. max time: Dyn. drift: Dyn. nr of points: EP minimum: EP peak:

Ca Hardness ABS 0 0 0 3 5 0,1 30 5 30 60 0.1 0.2 5 6 0 5 0,05 2

51

EP filter: EP threshold: EP1 M-position: Window-low: Window-high: Threshold: Stop Stop volume (ml) Stop at measured value: Drift: Number of EP: Dosed volume after EP: Stop time: Graph Graph Low: Graph High:

Name: Sensor: Pauze Pauze drift: Pauze Max time: Pauze Min time: Initial dosing Init steps: Init time: Init Volume: Init Speed: Dynamic dosing Dyn. slope: Dyn. speed: Dyn. refill speed: Dyn. min step: Dyn. max step: Dyn. min time: Dyn. max time: Dyn. drift: Dyn. nr of points: EP minimum: EP peak: EP filter: EP threshold: EP1 M-position:

6 50 3 0 2000 250 10 2900 0 1 0.1 1200 0 2500

Total Hardness ABS 0 0 0 3 5 0,1 30 5 30 60 0.1 0.4 5 10 0 5 0 2 6 0 6

52

Window-low: Window-high: Threshold: Stop Stop volume (ml) Stop at measured value: Drift: Number of EP: Dosed volume after EP: Stop time: Graph Graph Low: Graph High:

0 2000 250 10 2900 0 1 0.1 1200 0 2500

2.13 Alarm and message table Nr 0 1 2 3 4 5 6

Type None Alarm Alarm Alarm Alarm Alarm Alarm

Apply Global Global Global Global Global Global Global

Function Emergency stop Direct alarm Calibration failure SensorABS M-Alarmml infl. Titration algorithm Titration algorithm

Message E-stop/Reinitialize the dispensers! No sample detected Calibration error Sensor ABS error Inflection point not found Titration Ca error Titration TH error

Reset Automatic Automatic Automatic Automatic Automatic Automatic Automatic

2.14 Group DO

Sample Drain Level Rinse

Action 1 2 1 2 1 2 1 2

DO1 SP CW SP CW DP CCW DP CCW Drain/Level DP CCW Rinse Rinse

Status On On On On Continue On On On

DO2 Stirrer Stirrer Stirrer Stirrer Stirrer

Status Off On On Off Off

Stirrer Stirrer

Off On

Time (ms) 3000 4000 5000 10000 1000 9000 3000 6000

53

Addendum 3: Alarms and signals 3.1

Alarms

Introduction All alarms are implemented as follows: • •

Closed contact: Open contact:

the alarm is off and the Analyzer is On-line the alarm is active

Alarm list •

Malfunctioning alarm: Every alarm activates the malfunctioning alarm output (contact is opened). o Emergency stop When the emergency stop is activated, the analyzer shall stop immediately. o Leak detection There is a sensor installed inside the analyzer cabinet to detect leaks. When a leak is detected, the malfunctioning alarm is triggered and the analyzer is stopped (optional). A message box appears on the main screen. o Sensor When there is a problem with one of the sensors, the malfunctioning alarm is activated. A massage appears in the message or history submenu. o Titration alarm When there is a problem during the titration (titration out of time, no inflection points detected…) the malfunctioning alarm is activated. A massage appears in the message or history submenu.

•

Maintenance alarm: When the maintenance mode is active after pressing the MAINTENANCE ON/OFF button, a digital output is activated (maintenance contact is opened) to indicate remotely that the analyzer is not running on-line. When the maintenance mode is active, the analyzer is always in the local control mode: the analyzer can only be started manually.

3.2

Signals

The standard signal is an active 4-20 mA signal. RS232/MODBUS are optional, but can be programmed and used if the proper remote IO is installed.

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Warranty 1. Warranties AppliTek NV/SA warrants that its products are free from defects in materials and workmanship (under normal conditions of use and service) for a period one (1) year from date of shipment to original purchaser. 2. Limited warranty and liability On principle, the “General terms of and conditions of sale and delivery” of the company AppliTek apply. All warranty and liability claims made for damage to persons or property are invalid when they prove to have as a cause one or more of the following: • • • • • • • • •

Operating the unit for reasons other than its designed purpose Improper assembly, initializing, operating or maintenance of the unit Operating the unit when any safety or protection devices are defect or non-functioning Non-adherence of any instruction in the operating manual Unauthorized constructional alterations to the measuring unit Unauthorized constructional alterations to the utilities (for example instrument air supply). Incorrect maintenance of unit components Maintenance and repair work improperly carried out Catastrophes caused by outside interference, natural disaster, labor unrest, acts of war, terrorism, civil strife or acts of any governmental jurisdiction.

Warranty also does not cover: Freight charges on expedited or express shipment of warranted parts or product Travel fees associated with on-site warranty repair 3. Inspection and claims Claims for damage in shipment must be filed immediately with delivering carrier. Claims for shortages, shipping errors or any claim that the goods do not conform with the terms of the contract must be submitted to the AppliTek NV/SA in writing within five (5) days of receipt. If buyer fails to comply with the term ‘within 5 days of receipt’, the goods shall be deemed to conform with contract terms, and buyer shall accept and pay for the goods in accordance with the contract. Buyer waives any right to revoke acceptance after such five days period. All claims must be accompanied by a copy of the shipment note. 4. Indemnity for products manufactured according to customer’s requirements In the event AppliTek NV/SA provides products in accordance with drawings, models or samples provided by the customer, customer shall indemnify AppliTek NV/SA from any liability, cost or expense suffered by AppliTek NV/SA as a result of the violation of any law or regulation or the infringement of any industrial property right or other right of third parties. 5. Notification of product hazards and recall of products Customer will inform AppliTek NV/SA immediately in writing about any events which indicate any hazards connected with the product. Upon written notice of the AppliTek NV/SA about hazards in connection with the products or unfitness for use of the products and recall of products, the customer will immediately cease using the products for any reason, the customer, as its sole remedy shall be entitled compensation equivalent to the current value of the used product, but in no event more than the purchase price. AppliTek NV/SA shall not be liable for buyer’s loss of profit or incidental consequential or special damages of any kind.

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