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Ballast Water Treatment Systems Electrochlorination NaOCl Active Ingredient Hydrogen By-product Management Discussion Document

Prepared by Ian Perrett Consultant ISPC i_perrett@isp-c.co.uk

ISPC specialises as a technical consultancy service in the field of Electrochlorination Package (ECP) Engineering, primarily as utilised within Land Based and Offshore applications. As with maritime seawater system anti-fouling control Electrochlorination has been widely, safely and effectively utilised for decades in the LB and OS industries. From published test data, marketing material and discussions viewed there did not appear to be a wide coverage of Hydrogen by-product management available in the public domain when the electrolysis of seawater or brine solutions is utilised to supply the active ingredient of NaOCl (Sodium Hypochlorite) in BWTS’s. This discussion document therefore endeavours to translate the principles and understandings of Hydrogen by-product management, as applied within the LB and OS industries, to the relatively new application of ECP’s as generating systems for BWTS’s. It also addresses whether the historical experience of installation and operating of ECP’s for shipboard cooling water system fouling protection can be translated to their use for BWTS.

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Content

1) 2) 3)

Electrochlorination Historical Shipboard Application BWTS Electrochlorination a. Direct Injection Ballast Tank Natural Aspiration of Hydrogen Byproduct b. Indirect Injection with pre-dosing Hydrogen Dis-entrainment

4) 5)

Electrolyser Installation Comments

Appendices
1) 2) 3) 4) BWTS - Hydrogen Calculations Direct Injection BWTs - Hydrogen Calculations Indirect Injection BWTS Indirect NaOCl Injection Hazardous Area Calculations BWTS Indirect NaOCl Injection Hazardous Area Calculations

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1) Electrochlorination The application of Electrochlorination is a well understood method of controlling marine bio-fouling in a seawater system, utilising readily available seawater for partial conversion of the NaCl and H 2O media by electrolysis to a low concentration NaOCl solution to accommodate the dosing requirements of the seawater system. With the advent of BWTS’s utilising this technology the question occurs whether existing electrochlorination experience in the marine environment can be applied to BWTS? The focus of attention herein is the management of the Hydrogen generated as one of the by-products of that electrolysis. The volume of Hydrogen by-product can be determined by a factor of 0.316 m 3 @ 0°C @ 1 bara for every 1 kg of NaOCl production, the volume adjusted for the applicable design temperature. The hypothetical examples explored within this document include:BWT 01/02 which describes systems where a 10,000m3 ballast tank is filled at a rate of 1,250m3/h treated to 10 mg/l NaOCl for a design ambient air temperature of 25°C. NaOCl kg/h NaOCl kg/h NaOCl kg/h = = = (Flow m3/h x NaOCl mg/l) ÷ 1000 (1,250 x 10) ÷ 1000 12.5 kg/h

Therefore the rate of Hydrogen production can be calculated as:H2 m3/h H2 m3/h Fill duration Fill duration Total H2 = = = = = NaOCl kg/h x 0.316 x ((273 + Design Temp °C) ÷ 273) 4.31 m3/h (355 g/h) 10,000 m3 ÷ 1250 m3/h 8h 34.6 m3 (2.84kg)

2) Historical Shipboard Applications Historically electrochlorination as a means of controlling marine bio-fouling has largely been in the application of cooling systems water treatment. Using a side stream of the seawater system the electrolyser installation main equipment would consist of an Electrolyser assembly and a Transformer Rectifier to convert the on board AC supply utility to a DC supply for the electrolyser cells. Typically the electrolyser seawater carrier stream NaOCl discharge would be directly manifolded to the various sea chests for injection to the suction side of the seawater pumps, with flows adjusted and balanced for the fixed electrolyser mass balance of which the NaOCl production is variable by DC current control, which once set will be of a single NaOCl product concentration, i.e. production of the sum of the user weight demands with respective flow adjustment to the users.
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The NaOCl dosing regime would typically be governed by monitoring the overboard discharge(s) for a trace residual chlorine concentration. This has proven adequate to ensure the seawater system as a hostile environment for marine organisms with the result that the system remains clear of marine fouling. There are many publications that correctly identify these thousands of installations as of proven success but can this success with cooling water treatment be wholly translated to BWTS? In a cooling water system the residence time is brief and the overboard discharge residual chlorine is not indicative of a sterile solution, it is only indicative that a trace chlorine residual exists after a brief period of time, i.e. the dosing regime does not necessarily satisfy the complete chlorine demand of the seawater. The seawater cooling system dosing regime for NaOCl is typically in the region of 0.5-1 mg/l whereas the dosing regime for BWTS is generally far higher and with much longer residence times in which the active NaOCl is effective, that dosing regime is targeted more at sterilisation which is not necessarily achieved, nor required, for once through cooling system protection from marine fouling. Similarly Hydrogen management on historical Electrochlorination cooling water system applications has typically been reliant on the solubility of Hydrogen in seawater maintaining the Hydrogen in solution throughout the system until it is safely released at the overboard discharge. This has been acceptable where the dosing regime and subsequent Hydrogen content is relatively low and the seawater is not exposed to atmospheric pressure and Hydrogen release within the confines of the seawater system. Again where a higher NaOCl dosing regime is employed for BWTS then the forgoing argument for Hydrogen retention as a solute would no longer be applicable. 3) BWTS Electrochlorination Electrochlorination applied as part of a BWTS basically supplies the active ingredient of NaOCl and the discussions herein are not related to its efficacy, they relate only to the installation and Hydrogen management where it is employed. There are two main electrochlorination practices employed for BWTS. a) By direct injection where the electrolysis cells are configured either in the ballast water stream or by direct injection from a seawater side stream. b) Indirect injection by means of a side stream seawater supply to the Electrolyser assembly and introduction of an inter stage Hydrogen degassing system between the Electrolyser assembly and dosing points. NB It should be noted that Electrochlorination systems which are also installed on FPSO’s could well be subject to existing requirements of a classified area, whether this is to a self-generated Hydrogen gas group or reflect an existing hazardous area assessment and whether that gas group classification includes Hydrogen would be considered on an individual basis..

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Hydrogen as a highly flammable gas is an inherent by-product in the electrochlorination of seawater or any brine solution. The argument that has to be considered is whether the potential exists for it to escape to atmosphere within the NaOCl generating system or application and thus self-generate a classified (hazardous) area. Both the Hydrogen and NaOCl are generated within the electrolyser stream(s) reaching a maximum concentration at the discharge of the electrolyser assembly. It is custom and practice to report the LEL of Hydrogen as 4% in Air, this level is in reality the LFL with an UFL of 75%, the actual LEL of Hydrogen in Air is 17% and the UEL is 56%. Typically dilution of the Hydrogen by-product of the electrolysis of seawater is to 1% in Air by forced draught ventilation which is then considered safe to discharge into an unclassified area without changing the classification of that area. It is generally and instinctively accepted that Hydrogen is a hazardous gas and as a reminder of the potential hazard some of its properties are listed below Molecular weight [g/mol] Diffusion coefficient @ NTP (2) [m2/s] Diffusion velocity @ NTP (2) [m/s] Buoyant velocity [m/s] Specific heat (constant p) of gas @ NTP (2) [kJ/(kg K)] gas @ STP (1) [kJ/(kg K)] Flammability limits in air [vol%] Detonability limits in air [vol%] Minimum ignition energy [J] for detonation Auto-ignition temperature in air [K] Hot air jet ignition temperature [K] Gross heat of combustion or HHV [kJ/mol] @ 15 °C Net heat of combustion or LHV [kJ/mol] @ 15 °C Flame temperature [K] Laminar burning velocity in air [m/s] Visible laminar flame speed [m/s] Deflagration pressure ratio Adiabatic flame temperature [K] Detonation velocity [m/s] Energy release [MJ/kg mixture] TNT equivalent [g TNT/g] 2.01594 0.61*10-4 < 0.02 1.2 - 9 14.85 14.304 4.0 - 75.0 (4) 13 - 70 (5) 1.9*10-5 ~ 10,000 793 – 1023 (858) 943 286.1 241.7 2318 2.65 - 3.25 18.6 8.15 2318 1480 - 2150 2.82 26.5

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a. Direct Injection Ballast Tank Natural Aspiration of Hydrogen Byproduct In Land Based and Offshore applications of ECP’s Hydrogen management is effected primarily by either forced draught air dilution (vented tanks) or by naturally aspirated (effectively open topped) Hydrogen dis-entrainment tanks before the media is utilised for dosing a seawater system. In respect of a direct injection BWTS a comparison can be drawn to naturally aspirated land based degassing tanks. A generally accepted proviso for naturally aspirated tanks would be that they have minimal ullage for Hydrogen concentration at the media surface therein and also inherit a Zone 0 C rating. The tank would typically be designed with a top cover and screened side vents to prevent wind borne debris ingress, with the side vents of equal area to the media surface to facilitate unrestricted Hydrogen escape to atmosphere and the tank physically located such that no pockets of hydrogen could be collected in adjacent structures. However a ballast tank has a large ullage decreasing as the periodic fills progress, arguably presenting a large but decreasing volume vented through a top vent only. The ballast tank will therefore differ by virtue of not presenting the large venting facility associated with land based naturally aspirated tanks with the Hydrogen by-product released at the rate at which it is produced into a relatively confined space. Whilst there is no forced draught air dilution there would be an exhaust by ullage air volume displacement as the ballast tank fill progresses, therefore the natural buoyancy of Hydrogen in Air has to be considered with respect to the actual Hydrogen in Air concentration that exists in the ballast tank ullage at any given time. An extract from a mathematical model BTW-02 is appended to this document which explores a theoretical equilibrium for the Hydrogen in Air concentration for a direct NaOCl injection example related to the forgoing. Available data for Hydrogen solubility in water has been utilised and whilst data for Hydrogen solubility in seawater is not readily available it is understood that solubility is less in chloride solutions. Again it should be appreciated that what has not been predicted in the theoretical model, based on equilibrium against solubility in a liquid mass subject to a rate of change, is the impact Hydrogen’s buoyancy in air would have through natural aspiration via the tank vents during the fill cycle. Also an incremental theoretical model is subject to some minor inaccuracies as the sum of the increments, particularly in the final minutes of fill where it reports increases of the Hydrogen content in excess of the actual quantity of Hydrogen produced by the electrolysis. The absolute results however correspond well with the by-product quantity calculated separately by Faradays Law. Given the forgoing argument regarding the natural buoyancy of Hydrogen in Air empirical data has also to be considered to draw conclusions on the actual hazard potential. The theoretical model also takes into account the Hydrogen solute during the fill cycle and that which will be dis-entrained on completion of the ballast fill cycle. Again the residence time for complete dis-entrainment on fill completion would have to be subject to empirical data as the equilibrium based model is a worst case result where continuing dis-entrainment after ballast fill completion is a function of both the Hydrogen solute and bubble rise velocity from the bottom fill.
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NB. The theoretical models are based on a continuous ballast fill cycle and consequently the continuous ullage Air/Hydrogen mixture displacement which forms part of the dilution reports of the theoretical equilibrium models. Should however a pause in the ballast fill occur then the dis-entrainment of the entrained Hydrogen and Hydrogen Solute will continue for a period of time with the probability of an increase over and above the theoretical concentrations recorded below in the absence of this displacement. A risk assessment should also consider any potential for the vents to be restricted which would similarly present the potential for an increase in Hydrogen in Air concentration within the tank.

b. Indirect Injection with pre-dosing Hydrogen Dis-entrainment By means of an inter-stage Hydrogen disengagement system such as a degassing tank or a hydro-cyclone assembly the electrolyser product stream is subject to entrained Hydrogen removal prior to its utilisation for dosing of the ballast water. Utilising forced draught air dilution blowers these systems are typically argued to remove 99% of the Hydrogen product from the NaOCl media. More accurately they are argued to reduce the Hydrogen in Air concentration to 1% for safe discharge to atmosphere, therefore given that the atmosphere adjacent to the media surface is 1% Hydrogen in Air a certain amount of Hydrogen will remain as a solute in the media used for dosing. Based on this criterion an extract of a further mathematical model BWT-01, based on equilibrium, exploring the theoretical Hydrogen in Air concentrations in the ballast tank during the fill cycle is appended. The forgoing arguments relating to the model are also applicable to this model.

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4) Electrolyser Installation The other area necessary for examination is the electrolyser installation. It has been argued above that where there is a potential for Hydrogen to escape from the process equipment the electrolyser installation has a potential for selfgeneration of a hazardous area. For the purposes of simplifying this discussion the potential for self-generation of a hazardous area can be viewed as dependent on the NaOCl product concentration prior to Hydrogen dis-entrainment as the ratio would be consistent. In the cases discussed above this would be either from the point of production to the ballast tank in the case of direct NaOCl injection or between the point of production up to and including the Hydrogen dis-entrainment facilities. These two cases are explored in the appended Hazardous Area Assessments, one for each case of the above mentioned systems. These example hypothetical studies have been conducted to EN-60079-10 with similar design / operating parameters applied. The variable design conditions include the temperature which has been applied @ 55°C as a maximum, the ventilation velocity as a minimum for machinery spaces, and the pressures utilised are estimates of operating pressures at the low end of the scale. With the potential leak sized for 0.2mm2 as will be noted the hazardous area envelopes indicated vary considerably, but by this assessment they do exist. With regard to the pressure variable utilised it has been considered that plastic type piping would be utilised for the higher NaOCl concentrations generated by indirect injection as is standard within the industry. Careful consideration should be given to the pressure temperature relationship of these materials at the design temperature of 55°C and the potential for leakage. In indirect systems where a degassing tank is employed the interconnecting piping should also be assessed for similar hazards if, for example, flange connections are utilised in the interconnecting piping where the electrolyser assembly and the degassing tank are remote from each other. Another factor for consideration where an inter stage degassing tank is employed is the residence time the Electrolyser media discharge requires in the degassing tank for Hydrogen dis-entrainment. Typically 5 minutes this represents an H2 volume in this hypothetical example of 0.4m3 at any given time which in the event of power failure would result in its undiluted release to the discharge vent at varying concentrations of Hydrogen in Air if redundant means of dilution are not employed. In the writers experience there has been reference made that Electrochlorination Packages do not change an areas’ classification in which case it would be supported by Notified Body Certification to that effect. This would equally apply where an Electrochlorination Package is certified for installation in a hazardous area, but not necessarily certificated not to change that area classification if the pre-existing applicable gas group did not include Hydrogen.

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5) Comments In the LB and OS OEM supply there are differing schools of thought regarding Hazardous area zoning of Electrolyser installations but a relatively common understanding of Hydrogen dis-entrainment tank classification. In the cases under discussion and with regard to the Ballast Tank treatment it is arguable that during the fill cycle that the surface of the seawater would be at least Zone 2 C based on its intermittent operation, Zone 0 C at the surface during the fill cycle. It is also arguable that the vented discharge mixture could contain a content of flammable gas above LEL and strict application could advocate a Zone 2 C rating for that area. Given that this is a marine environment rather than LB or OS the concentration criteria and application suggests that a different approach may be appropriate. If empirical testing suggests that a hazard presented by a theoretical model does not exist in practice then a judgement call is necessary, qualified by consideration of the forgoing arguments and any means of mitigation employed. It should be noted from the models however that a significant weight of H2 could theoretically be present in the relatively confined ballast tanks with the concentrations indicated by the equilibrium model impacted by the natural buoyancy of H2 in Air. Whilst endeavouring to offer an objective assessment of the above mentioned hypothetical examples this discussion document and related documents are not to be taken as ISPC advocacy of any area classification. Primarily it is an aide memoir for consideration by others to their particular project parameters. Not dealt with in this discussion document are the subjects of corrosion and sedimentation. The corrosive effects of the relatively dilute NaOCl media are well understood, less well understood is that for any electrolytic process is the necessity for process DC current containment to avoid media borne stray current corrosion of inline metallic piping and fittings. Similarly the electrolysis of seawater also has insoluble by-products which are typically managed by maintenance of line velocity and tank agitation to avoid their precipitation, i.e. settlement is avoided by process design.

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Appendix 1

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ISPC Electrochlorination Package Engineering Title Document Revision Date Project Client Page 7 of BWTS - Hydrogen Calculations Direct Injection BWT 02 A 26-Oct-12 Various - Marine Environment TBA 13

Ballast Tank Atmosphere Calculations Tank Volume Ballast Pump Duration = Ballast Pump Hydrogen Rate of Release 4.31 m /h
3

10000 1250 8.000 1250

m h

3 3

m /h

20.83 48

m /min x 10 min increments m /min m /min Hydrogen Solute as a Ullage Volume Hydrogen Solute g 0.025 0.099 0.226 0.405 0.640 0.932 1.283 1.696 2.172 2.715 3.326 4.008 when Released m
3 3 3

3

Rate of Vent Air + H2 Discharge from Tank m /h
3

20.83 0.072

Hydrogen Solute as a Volume incremental increase m
3

Volume Increment Mins Start 1 2 3 4 5 6 7 8 9 10 11 12 10 20 30 40 50 60 70 80 90 100 110 120 Water m
3

Volume Ullage m
3

Volume Hydrogen m interval 0.72 0.72 0.72 0.72 0.72 0.72 0.71 0.71 0.71 0.71 0.71 0.71
3

Weight Hydrogen g interval 59.17 59.09 59.06 59.00 58.95 58.90 58.85 58.79 58.73 58.67 58.61 58.54

Hydrogen Conc % Increase 0.0073% 0.0075% 0.0076% 0.0078% 0.0080% 0.0082% 0.0084% 0.0086% 0.0088% 0.0090% 0.0092% 0.0095%

Hydrogen Conc % Cumulative 0.0073% 0.0148% 0.0225% 0.0303% 0.0383% 0.0465% 0.0548% 0.0634% 0.0722% 0.0812% 0.0904% 0.0999%

Hydrogen Vented g Increment 1.26 2.54 3.86 5.20 6.57 7.97 9.41 10.88 12.38 13.93 15.51 17.14

Hydrogen Vented g Cumulative 1.26 3.80 7.66 12.86 19.42 27.39 36.80 47.67 60.06 73.98 89.49 106.63

Hydrogen Ullage g 59.17 117.00 173.52 228.67 282.42 334.75 385.63 435.01 482.87 529.16 573.84 616.88

Hydrogen Solubility g/l 0.000000 0.000000 0.000000 0.000000 0.000001 0.000001 0.000001 0.000001 0.000001 0.000001 0.000001 0.000002

Hydrogen Volume m
3

208 417 625 833 1042 1250 1458 1667 1875 2083 2292 2500

9792 9583 9375 9167 8958 8750 8542 8333 8125 7917 7708 7500

0.72 1.42 2.11 2.78 3.43 4.06 4.68 5.28 5.86 6.43 6.97 7.49

0.00 0.00 0.00 0.00 0.01 0.01 0.01 0.02 0.02 0.03 0.04 0.04 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.01 0.01 0.01

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Hydrogen Solute as a Ullage Volume Increment Mins Start 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 42 130 140 150 160 170 180 190 200 210 220 230 240 250 260 270 280 290 300 310 320 330 340 350 360 370 380 390 400 410 420 Water m
3

Hydrogen Solute as a Volume incremental increase m
3

Volume Hydrogen Solute g 4.766 5.601 6.518 7.521 8.612 9.798 11.083 12.473 13.973 15.590 17.331 19.204 21.219 23.385 25.714 28.219 30.913 33.815 36.944 40.322 43.976 47.938 52.246 56.947 62.099 67.775 74.070 81.108 89.060 98.167 when Released m
3

Volume Ullage m
3

Volume Hydrogen m interval 0.71 0.71 0.71 0.71 0.71 0.71 0.70 0.70 0.70 0.70 0.70 0.70 0.70 0.69 0.69 0.69 0.69 0.69 0.68 0.68 0.68 0.67 0.67 0.67 0.66 0.66 0.65 0.64 0.63 0.62
3

Weight Hydrogen g interval 58.47 58.40 58.33 58.25 58.17 58.08 57.99 57.90 57.79 57.69 57.57 57.45 57.32 57.18 57.03 56.87 56.70 56.51 56.30 56.07 55.82 55.54 55.22 54.86 54.45 53.97 53.40 52.72 51.88 50.82

Hydrogen Conc % Increase 0.0097% 0.0100% 0.0103% 0.0106% 0.0109% 0.0113% 0.0117% 0.0121% 0.0125% 0.0129% 0.0134% 0.0140% 0.0145% 0.0151% 0.0158% 0.0166% 0.0174% 0.0183% 0.0193% 0.0204% 0.0217% 0.0231% 0.0248% 0.0266% 0.0288% 0.0315% 0.0346% 0.0384% 0.0432% 0.0494%

Hydrogen Conc % Cumulative 0.1096% 0.1196% 0.1299% 0.1405% 0.1515% 0.1627% 0.1744% 0.1865% 0.1989% 0.2119% 0.2253% 0.2392% 0.2538% 0.2689% 0.2847% 0.3013% 0.3187% 0.3370% 0.3563% 0.3767% 0.3984% 0.4215% 0.4463% 0.4729% 0.5018% 0.5332% 0.5678% 0.6062% 0.6494% 0.6988%

Hydrogen Vented g Increment 18.81 20.52 22.29 24.11 25.99 27.92 29.92 31.99 34.13 36.35 38.65 41.05 43.54 46.14 48.85 51.70 54.68 57.82 61.13 64.64 68.36 72.33 76.57 81.15 86.10 91.49 97.43 104.02 111.43 119.90

Hydrogen Vented g Cumulative 125.43 145.96 168.25 192.36 218.35 246.27 276.19 308.19 342.32 378.67 417.32 458.37 501.91 548.05 596.90 648.60 703.29 761.11 822.24 886.88 955.24 1027.57 1104.14 1185.29 1271.39 1362.88 1460.31 1564.32 1675.75 1795.65

Hydrogen Ullage g 658.22 697.81 735.62 771.57 805.63 837.72 867.79 895.76 921.56 945.12 966.34 985.14 1001.41 1015.06 1025.95 1033.97 1038.97 1040.80 1039.28 1034.22 1025.40 1012.58 995.47 973.76 947.06 914.93 876.84 832.13 780.00 719.40

Hydrogen Solubility g/l 0.000002 0.000002 0.000002 0.000002 0.000002 0.000003 0.000003 0.000003 0.000003 0.000003 0.000004 0.000004 0.000004 0.000004 0.000005 0.000005 0.000005 0.000005 0.000006 0.000006 0.000006 0.000007 0.000007 0.000008 0.000008 0.000009 0.000009 0.000010 0.000010 0.000011

Hydrogen Volume m
3

2708 2917 3125 3333 3542 3750 3958 4167 4375 4583 4792 5000 5208 5417 5625 5833 6042 6250 6458 6667 6875 7083 7292 7500 7708 7917 8125 8333 8542 8750

7292 7083 6875 6667 6458 6250 6042 5833 5625 5417 5208 5000 4792 4583 4375 4167 3958 3750 3542 3333 3125 2917 2708 2500 2292 2083 1875 1667 1458 1250

7.99 8.47 8.93 9.37 9.78 10.17 10.54 10.88 11.19 11.48 11.73 11.96 12.16 12.32 12.46 12.55 12.62 12.64 12.62 12.56 12.45 12.29 12.09 11.82 11.50 11.11 10.65 10.10 9.47 8.73

0.05 0.06 0.07 0.08 0.10 0.11 0.12 0.14 0.16 0.17 0.19 0.21 0.24 0.26 0.29 0.31 0.34 0.38 0.41 0.45 0.49 0.53 0.58 0.63 0.69 0.75 0.82 0.90 0.99 1.09

0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.03 0.03 0.03 0.03 0.03 0.04 0.04 0.04 0.05 0.05 0.06 0.06 0.07 0.08 0.09 0.10

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Hydrogen Solute as a Ullage Volume Increment Mins Start 43 44 45 46 47 48 430 440 450 460 470 480 Water m
3

Hydrogen Solute as a Volume incremental increase m
3

Volume Hydrogen Solute g 108.792 121.511 137.335 158.303 189.647 0.000 Max when Released m
3

Volume Ullage m
3

Volume Hydrogen m interval 0.60 0.58 0.54 0.49 0.37 2.11 33.77
3

Weight Hydrogen g interval 49.43 47.52 44.67 39.96 30.45 173.74 2780.92

Hydrogen Conc % Increase 0.0576% 0.0692% 0.0868% 0.1164% 0.1775% 0.0000%

Hydrogen Conc % Cumulative 0.7564% 0.8257% 0.9124% 1.0289% 1.2064% 0.0000%

Hydrogen Vented g Increment 129.79 141.67 156.56 176.54 206.99 0.00 2607.18

Hydrogen Vented g Cumulative 1925.44 2067.10 2223.66 2400.19 2607.18 0.00

Hydrogen Ullage g 648.93 566.66 469.67 353.07 206.99 0.00

Hydrogen Solubility g/l 0.000012 0.000013 0.000015 0.000017 0.000019 0.000000

Hydrogen Volume m
3

8958 9167 9375 9583 9792 10000

1042 833 625 417 208 0

7.88 6.88 5.70 4.29 2.51 0.00

1.21 1.35 1.53 1.76 2.11 0.00 2.11

0.12 0.14 0.18 0.23 0.35 -2.11

Final Increment

48 Volume Water

In 1 Minute Increments Ullage Volume Ullage m
3

Hydrogen Hydrogen Solute g 189.647 196.086 203.308 211.532 221.092 232.515 246.731 265.588 293.712 349.575 Solute Released m
3

Volume Hydrogen m
3

Weight Hydrogen g interval 30.45 5.92 5.92 5.92 5.92 5.92 5.92 6.46 6.46 6.46 6.46

Hydrogen Conc % Increase 0.1775% 0.0383% 0.0431% 0.0493% 0.0575% 0.0690% 0.0862% 0.1149% 0.1724% 0.3448% 3.5921%

Hydrogen Conc % Cumulative 1.2064% 1.2447% 1.2878% 1.3371% 1.3945% 1.4635% 1.5497% 1.6647% 1.8371% 2.1819% 5.7741%

Hydrogen Vented g Increment 206.99 21.36 22.10 22.94 23.93 25.11 26.59 31.18 34.41 40.87 108.14

Hydrogen Vented g Cumulative 2607.18 2628.54 2650.64 2673.58 2697.50 2722.62 2749.21 2780.38 2814.79 2855.66 2963.80

Hydrogen Ullage g 206.99 192.21 176.77 160.59 143.56 125.55 106.36 93.53 68.81 40.87 10.38

Hydrogen Solubility g/l 0.000019 0.000020 0.000021 0.000021 0.000022 0.000023 0.000025 0.000027 0.000029 0.000035 0.000093

Hydrogen Volume m
3

Increment As Above 1 2 3 4 5 6 7 8 9 10

Mins 470 471 472 473 474 475 476 477 478 479 480

m

3

9792 9813 9833 9854 9875 9896 9917 9938 9958 9979 10000

208 188 167 146 125 104 83 63 42 21 2

0.37 0.07 0.07 0.07 0.07 0.07 0.07 0.07 0.07 0.07 0.07

2.51 2.33 2.15 1.95 1.74 1.52 1.29 1.04 0.77 0.45

2.11 2.18 2.26 2.35 2.46 2.59 2.74 2.95 3.27 3.89

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Water volume = Volume Ullage = Volume Hydrogen = Hydrogen Weight = Hydrogen Conc. % Increase= Hydrogen Conc. % Cumul've= Hydrogen Vented g increment = Hydrogen Vented g cumulative = Hydrogen Ullage g = Hydrogen Solubility g/l = Hydrogen Volume = Hydrogen Solute = Hydrogen Solute m = Hydrogen Solute increment m =
3 3

Increment Minutes x ballast Pump flow per minute Tank volume - water Volume Incremental volume of Hydrogen discharged to tank at NaOCl production rate and at design temperature - equivalent volume of solute incremental weight gain Incremental weight of Hydrogen discharged to tank at NaOCl production rate and at design temperature Ullage Volume / Hydrogen volume increment discharge Hydrogen increment % increase + previous increment % concentration m per increment (83) x increment cumulative % concentration x Hydrogen density at design temperature Incremental vented Hydrogen weight + preceding cumulative hydrogen weight vented Current Hydrogen Weight in current increment ullage @ current cumulative concentration ((0.978 x H2 % incremental Conc)/1228)x 2.015 (Henry) Ullage volume x Hydrogen cumulative % at design temperature Water volume x 10^3 x increment hydrogen solubility Hydrogen volume at design temperature if atmosphere at 0% Hydrogen concentration Increment of Hydrogen production retained in solute and not discharged to tank during that increment
3

BWTS NaOCl Hydrogen management

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ISPC © 2012

Appendix 2

BWTS NaOCl Hydrogen management

Page 15

ISPC © 2012

ISPC Electrochlorination Package Engineering Title Document Revision Date Project Client Page 7 of BWT - Hydrogen Calculations Indirect Injection BWT 01 A 26-Oct-12 Various - Marine Environment TBA 13

Ballast Tank Atmosphere Calculations Tank Volume Ballast Pump Duration = Ballast Pump Hydrogen Rate of Release 0.04 m /h
3

10000 1250 8 1250

m

3 3

m /h h m /h
3

20.83 48 20.83 0.001

m /min x 10 min increments m /min m /min Hydrogen Solute as a Ullage Volume Hydrogen Solute g 0.000 0.001 0.002 0.004 0.006 0.009 0.013 0.017 0.022 0.027 0.033 0.040 0.048 when Released m
3 3 3

3

Rate of Vent Air + H2 Discharge from Tank

Hydrogen Solute as a Volume incremental increase m
3

Volume Increment Mins Start 1 2 3 4 5 6 7 8 9 10 11 12 13 10 20 30 40 50 60 70 80 90 100 110 120 130 Water m
3

Volume Ullage m
3

Volume Hydrogen m
3

Weight Hydrogen g interval 0.65 0.65 0.65 0.65 0.65 0.65 0.65 0.65 0.65 0.65 0.65 0.65 0.65

Hydrogen Conc % Increase 0.0001% 0.0001% 0.0001% 0.0001% 0.0001% 0.0001% 0.0001% 0.0001% 0.0001% 0.0001% 0.0001% 0.0001% 0.0001%

Hydrogen Conc % Cumulative 0.0001% 0.0001% 0.0002% 0.0003% 0.0004% 0.0005% 0.0005% 0.0006% 0.0007% 0.0008% 0.0009% 0.0010% 0.0011%

Hydrogen Vented g Increment 0.01 0.03 0.04 0.06 0.07 0.09 0.10 0.12 0.14 0.15 0.17 0.19 0.21

Hydrogen Vented g Cumulative 0.01 0.04 0.08 0.14 0.21 0.30 0.40 0.52 0.66 0.81 0.98 1.17 1.37

Hydrogen Ullage g 0.65 1.28 1.90 2.50 3.09 3.66 4.22 4.76 5.29 5.80 6.29 6.77 7.23

Hydrogen Solubility g/l 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000

Hydrogen Volume m
3

208 417 625 833 1042 1250 1458 1667 1875 2083 2292 2500 2708

9792 9583 9375 9167 8958 8750 8542 8333 8125 7917 7708 7500 7292

0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01

0.01 0.01 0.02 0.03 0.03 0.04 0.05 0.05 0.06 0.06 0.07 0.08 0.08

0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00

BWTS NaOCl Hydrogen management

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ISPC © 2012

Hydrogen Solute as a Ullage Volume Increment Mins Start 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 43 140 150 160 170 180 190 200 210 220 230 240 250 260 270 280 290 300 310 320 330 340 350 360 370 380 390 400 410 420 430 Water m
3

Hydrogen Solute as a Volume incremental increase m
3

Volume Hydrogen Solute g 0.056 0.066 0.076 0.087 0.099 0.112 0.126 0.141 0.158 0.176 0.195 0.215 0.238 0.262 0.288 0.315 0.345 0.378 0.413 0.452 0.493 0.539 0.589 0.644 0.705 0.774 0.851 0.940 1.044 1.168 when Released m
3

Volume Ullage m
3

Volume Hydrogen m
3

Weight Hydrogen g interval 0.65 0.65 0.65 0.65 0.65 0.65 0.65 0.65 0.65 0.65 0.65 0.65 0.65 0.65 0.65 0.65 0.65 0.65 0.65 0.65 0.65 0.65 0.65 0.65 0.65 0.65 0.65 0.65 0.65 0.65

Hydrogen Conc % Increase 0.0001% 0.0001% 0.0001% 0.0001% 0.0001% 0.0001% 0.0001% 0.0001% 0.0001% 0.0001% 0.0001% 0.0001% 0.0002% 0.0002% 0.0002% 0.0002% 0.0002% 0.0002% 0.0002% 0.0002% 0.0002% 0.0003% 0.0003% 0.0003% 0.0003% 0.0004% 0.0004% 0.0005% 0.0006% 0.0007%

Hydrogen Conc % Cumulative 0.0012% 0.0013% 0.0014% 0.0015% 0.0016% 0.0018% 0.0019% 0.0020% 0.0021% 0.0023% 0.0024% 0.0026% 0.0027% 0.0029% 0.0031% 0.0033% 0.0034% 0.0036% 0.0039% 0.0041% 0.0043% 0.0046% 0.0049% 0.0052% 0.0055% 0.0059% 0.0064% 0.0069% 0.0074% 0.0081%

Hydrogen Vented g Increment 0.23 0.25 0.27 0.29 0.31 0.33 0.35 0.38 0.40 0.43 0.45 0.48 0.51 0.54 0.57 0.61 0.64 0.68 0.72 0.77 0.81 0.86 0.92 0.97 1.04 1.11 1.19 1.28 1.39 1.52

Hydrogen Vented g Cumulative 1.60 1.85 2.11 2.40 2.70 3.03 3.39 3.76 4.17 4.59 5.05 5.53 6.04 6.58 7.16 7.77 8.41 9.10 9.82 10.59 11.40 12.26 13.18 14.15 15.19 16.30 17.49 18.78 20.17 21.69

Hydrogen Ullage g 7.67 8.09 8.49 8.87 9.23 9.57 9.88 10.18 10.45 10.69 10.91 11.10 11.26 11.40 11.50 11.57 11.61 11.61 11.57 11.49 11.37 11.21 10.99 10.72 10.39 10.00 9.53 8.99 8.35 7.60

Hydrogen Solubility g/l 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000

Hydrogen Volume m
3

2917 3125 3333 3542 3750 3958 4167 4375 4583 4792 5000 5208 5417 5625 5833 6042 6250 6458 6667 6875 7083 7292 7500 7708 7917 8125 8333 8542 8750 8958

7083 6875 6667 6458 6250 6042 5833 5625 5417 5208 5000 4792 4583 4375 4167 3958 3750 3542 3333 3125 2917 2708 2500 2292 2083 1875 1667 1458 1250 1042

0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01

0.09 0.09 0.09 0.10 0.10 0.11 0.11 0.11 0.12 0.12 0.12 0.12 0.13 0.13 0.13 0.13 0.13 0.13 0.13 0.13 0.13 0.12 0.12 0.12 0.12 0.11 0.11 0.10 0.09 0.08

0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01

0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00

BWTS NaOCl Hydrogen management

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ISPC © 2012

Hydrogen Solute as a Ullage Volume Increment Mins Start 44 45 46 47 48 440 450 460 470 480 Water m
3

Hydrogen Solute as a Volume incremental increase m
3

Volume Hydrogen Solute g 1.322 1.525 1.824 2.406 0.000 Max when Released m
3

Volume Ullage m
3

Volume Hydrogen m
3

Weight Hydrogen g interval 0.65 0.65 0.65 0.65 0.00 30.36

Hydrogen Conc % Increase 0.0009% 0.0011% 0.0017% 0.0034% 0.0000%

Hydrogen Conc % Cumulative 0.0090% 0.0101% 0.0119% 0.0153% 0.0000%

Hydrogen Vented g Increment 1.68 1.90 2.22 2.87 0.00 30.36

Hydrogen Vented g Cumulative 23.37 25.27 27.49 30.36 0.00

Hydrogen Ullage g 6.73 5.69 4.44 2.87 0.00

Hydrogen Solubility g/l 0.000000 0.000000 0.000000 0.000000 0.000000

Hydrogen Volume m
3

9167 9375 9583 9792 10000

833 625 417 208 0

0.01 0.01 0.01 0.01 0.00 0.34

0.07 0.06 0.05 0.03 0.00

0.01 0.02 0.02 0.03 0.00 0.03

0.00 0.00 0.00 0.01 -0.03

Final Increment

48 Volume Water

In 1 Minute Increments Ullage Volume Ullage m
3

Hydrogen Hydrogen Solute g 2.406 2.471 2.545 2.628 2.725 2.840 2.983 3.173 3.455 4.015 Solute Released m
3

Volume Hydrogen m
3

Weight Hydrogen g interval 0.65 0.06 0.06 0.06 0.06 0.06 0.06 0.06 0.06 0.06 0.06

Hydrogen Conc % Increase 0.0034% 0.0004% 0.0004% 0.0005% 0.0006% 0.0007% 0.0009% 0.0011% 0.0017% 0.0034% 0.0359%

Hydrogen Conc % Cumulative 0.0153% 0.0157% 0.0161% 0.0166% 0.0172% 0.0179% 0.0187% 0.0199% 0.0216% 0.0251% 0.0610%

Hydrogen Vented g Increment 2.87 0.29 0.30 0.31 0.32 0.33 0.35 0.37 0.40 0.47 1.14

Hydrogen Vented g Cumulative 30.36 30.65 30.95 31.26 31.58 31.92 32.27 32.64 33.05 33.52 34.66

Hydrogen Ullage g 2.87 2.64 2.42 2.18 1.93 1.67 1.40 1.12 0.81 0.47 0.11

Hydrogen Solubility g/l 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000001

Hydrogen Volume m
3

Increment As Above 1 2 3 4 5 6 7 8 9 10

Mins 470 471 472 473 474 475 476 477 478 479 480

m

3

9792 9813 9833 9854 9875 9896 9917 9938 9958 9979 10000

208 188 167 146 125 104 83 63 42 21 2

0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00

0.03 0.03 0.03 0.02 0.02 0.02 0.02 0.01 0.01 0.01

0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.04 0.04 0.04

BWTS NaOCl Hydrogen management

Page 18

ISPC © 2012

Water volume = Volume Ullage = Volume Hydrogen = Hydrogen Weight = Hydrogen Conc. % Increase= Hydrogen Conc. % Cumul've= Hydrogen Vented g increment = Hydrogen Vented g cumulative = Hydrogen Ullage g = Hydrogen Solubility g/l = Hydrogen Volume = Hydrogen Solute = Hydrogen Solute m = Hydrogen Solute increment m =
3 3

Increment Minutes x ballast Pump flow per minute Tank volume - water Volume Incremental volume of Hydrogen discharged to tank at NaOCl production rate and at design temperature - equivalent volume of solute incremental weight gain Incremental weight of Hydrogen discharged to tank at NaOCl production rate and at design temperature Ullage Volume / Hydrogen volume increment discharge Hydrogen increment % increase + previous increment % concentration m per increment (83) x increment cumulative % concentration x Hydrogen density at design temperature Incremental vented Hydrogen weight + preceding cumulative hydrogen weight vented Current Hydrogen Weight in current increment ullage @ current cumulative concentration ((0.978 x H2 % incremental Conc)/1228)x 2.015 (Henry) Ullage volume x Hydrogen cumulative % at design temperature Water volume x 10^3 x increment hydrogen solubility Hydrogen volume at design temperature if atmosphere at 0% Hydrogen concentration Increment of Hydrogen production retained in solute and not discharged to tank during that increment
3

BWTS NaOCl Hydrogen management

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ISPC © 2012

Appendix 3

BWTS NaOCl Hydrogen management

Page 20

ISPC © 2012

ISPC Electrochlorination Package Engineering Document BWT 05 Revision A Date 29-Oct-12 Project Electrochlorination Assembly Client Standard - BWTS Indirect NaOCl Injection Page 3 of 7 Electrochlorination Package Data Ambient Design Temperature Electrolyser Duty Streams Electrolyser Standby Streams Electrolyser Seawater Carrier Stream Inlet Pressure Electrolyser Seawater Carrier Stream Outlet Pressure Electrolyser Seawater Carrier Stream Flowrate Total ECP Flowrate Electrochlorination Package Capacity Electrolyser Stream Capacity Hypochlorite Concentration Number of Electrolysers per Stream Electrolyser Line Size Leakage Orifice Size Leakage Orifice Diameter Space Estimates Length Width Height Occupancy Ventilation Estimate Velocity Required (Typical) Calculated Velocity Air Changes per Hour (4-12 Typical) Vz Radius 55 1.00 1.00 2.50 2.00 12 12 12.50 12.50 1000 1.00 3.00 0.20 0.50 ºC Qty Qty barg barg m3/h m3/h kg/h kg/h mg/l Qty mm mm2 mm EN DN 8861

Standard ISO 5167-1 : 1991

15.00 15.00 15.00 50% 28638 0.10 0.10 16.97 1265

m m m

m3/h m/sec m/sec mm

EN DN 8861

BWTS NaOCl Hydrogen management

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ISPC © 2012

Appendix 4

BWTS NaOCl Hydrogen management

Page 22

ISPC © 2012

ISPC Electrochlorination Package Engineering Document BWT 04 Revision A Date 29-Oct-12 Project Electrochlorination Assembly Client Standard - BWTS Direct NaOCl Injection Page 3 of 7 Electrochlorination Package Data Ambient Design Temperature Electrolyser Duty Streams Electrolyser Standby Streams Electrolyser Seawater Carrier Stream Inlet Pressure Electrolyser Seawater Carrier Stream Outlet Pressure Electrolyser Seawater Carrier Stream Flowrate Total ECP Flowrate Electrochlorination Package Capacity Electrolyser Stream Capacity Hypochlorite Concentration Number of Electrolysers per Stream Electrolyser Line Size Leakage Orifice Size Leakage Orifice Diameter Space Estimates Length Width Height Occupancy Ventilation Estimate Velocity Required (Typical) Calculated Velocity Air Changes per Hour (4-12 Typical) Vz Radius 55 1.00 1.00 2.50 2.00 1250 1250 12.50 12.50 10 1.00 3.00 0.20 0.50 ºC Qty Qty barg barg m3/h m3/h kg/h kg/h mg/l Qty mm mm2 mm EN DN 8861

Standard ISO 5167-1 : 1991

15.00 15.00 15.00 50% 28638 0.10 0.10 16.97 303

m m m

m3/h m/sec m/sec mm

EN DN 8861

BWTS NaOCl Hydrogen management

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ISPC © 2012