HCl Mass Balance Results Q2 2020 - epawebapp.epa.ie

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Q1 2020 HCL Mass Balance Report April 9th 2020

page 1 of 21

HCl Mass Balance Results Q2 2020

1 Purpose [i]

The purpose of this document is to report results of the mass balance calculations using the

methods agree with the agency

2 Responsibilities [i]

Process owner: EHS Manager

Manager of necessary resources: Plant Manager

Implementation: Project Manager

3 Procedure [i]

3.1 IE Licence control and Monitoring Requirements.

The licence requirements are set out in Condition 6. Control and Monitoring of the IPPC Licence

PO376-02 as follows:

Condition 6.2

The licensee shall carry out such sampling, analyses, measurements, examinations,

maintenance and calibrations as set out below and as in accordance with Schedule C Control

& Monitoring, of this licence. IPCC Licence PO376

Condition 6.2.1

Analyses shall be undertaken by competent staff in accordance with documented

operating procedures.

Condition 6.2.2

Such procedures shall be assessed for their suitability for the test matrix and performance

characteristics shall be determined.

Condition 6.2.3

Such procedures shall be subject to a programme of Analytical Quality Control using control

standards with evaluation of test responses.

Condition 6.2.4

Where any analysis is sub-contracted it shall be to a competent laboratory.

Condition 6.3

The licensee shall ensure that:

(i) sampling and analysis for all parameters listed in the schedules to this licence; and

(ii) any reference measurements for the calibration of automated measurement

systems;

shall be carried out in accordance with CEN-standards. If CEN standards are not available,

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ISO, national or international standards that will ensure the provision of data of an equivalent

scientific quality shall apply.

Schedule B: Emission Limit Values

B.1 Emissions to Air:

Schedule C: Control & Monitoring:

C.1.2. Monitoring of Emissions to Air

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3.2 Key Measurement Equipment and Parameters

A mass balance is performed on the Multiple Hearth Furnace (MHF) and Shaft Kiln (SK)

systems, as per the figures below.

Figure 1: MHF Mass Balance Implementation Plan

Figure 2: SK Mass Balance Implementation Plan

Feed:

Current Frequency Continuously

3/day Measure % Solids Off Gas to Stack

3/day Measure Chloride Prosposed Frequency Off Gas No way to measure Dust Losses

Continuously Measure Gas Flow to MHF Prosposed Frequency (but very small)

1/week for Quarterly Report Calculate Off Gas Flow at 10% O2 1/week for Quarterly Report Calculate kg/hr. of chloride

Clarify Wet or Dry Basis 1/week for Quarterly Report Convert to HCl

Current Frequency Natural Gas

Continuously Measure Flowrate in nm3/hr

Calibrate Gas Meters.

Dust Returns

(No TM45E Extraction) Proposed Frequency

As per Tanker Measure TM45E removed by tankers

Continuously Measure Dust sent to TM45 / Techmag Storage (Level Indication in silo)

1/week Lab Days Measure Cl Content of Dust

1/week for Quarterly Report Calculate Cl kgs/hr removed with dust

Current Frequency

9/day Measure % Cl in CCM

Continuously Calculate Production

To Tankers

CCM Product

MHFFilter

Silo

Current Frequency Feed:

Continuously Calculate Feed Rate

9/day % Cl as in CCM

Current Frequency Off Gas

Continuously Measure Gas Flow to SK

1/week for Quarterly Report Calculate Off Gas Flow at 10% O2

Clarify Wet or Dry Basis

Current Frequency Natural Gas

Continuously Measure Flowrate in nm3/hr Prosposed Frequency Shaft Kiln Grits

Calibrate Gas Meters. 1/week for Quarterly Report Measure TPD Accurately (Investment)

1/week for Quarterly Report Measure %Cl (Extra Lab. work)

Off Gas

Prosposed Frequency Simatek Dust

1/week for Quarterly Report Measure TPD Accurately (Investment)

1/week for Quarterly Report Measure %Cl (Extra Lab. work)

Current Frequency DBM Product Off Gas to Stack

Continuously Accurate Weigh-Belt (Extra manpower) No way to measure Dust Losses

Assume 0% Cl Prosposed Frequency (but very small)

1/week for Quarterly Report Calculate kg/hr. of chloride

1/week for Quarterly Report Convert to HCl

Skips

Skips

Weighing Scales

Weighing Scales

SK

Drop Out Box

Filter

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Task How? Specification of Equipment

Accurately measure rate of feed to the MHFs

Flowmeter Electromagnetic Flowmeter, accuracy ±0.4% of the rate

Accurately weigh electro filter dust extraction

Level Indicators Bulk Solids Level radar, contactless. Accuracy ±0.03% Calculated from ±3mm accuracy.

Accurately weigh Simatek Dust

Load Cells Accuracy is 100kg +- 0.05kg = 0.05% accuracy.

Accurately weigh SK grits (drop out box)

Weighing Scales 10,000kg capacity and ±2kg accuracy.

Accurately weigh SK DBM Product

Weigh belt Solids Weigh belt with accuracy ±0.5-2%

Table 1: Equipment specifications for Mass Balance

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3.3 Standard Operating Procedures

The Standard Operating Procedure for the laboratory tests to perform this mass balance are

listed below, and can be found in the Laboratory Manual (QD2) to standard ISO 9001:

a. AT.21 – Chlorides in Solids

b. AT.30 – XRF Analysis by Pressed Pellet

The standard operating procedure for calculating the weekly reports that are collated quarterly

is named:

a. HCL Mass Balance SOP 001.

All these SOPs are included in the Appendices of this document.

3.4 Measurement Frequency

Measurement frequencies are displayed in Table 2 below.

Parameter Units Measurement Frequency

MHF production Rate kg/hr SCADA Continuously

SK Production Rate kg/hr SCADA Continuously

Cl in BP Cake (MgO basis) % Lab Shift 1/shift

Cl in DF Cake (MgO Basis) % Lab Shift 1/shift

Cl in CCM % Lab Shift 3/shift

BP MHF Feed kg/hr SCADA Continuously

DF MHF Feed kg/hr SCADA Continuously

Techmag production kg/hr SCADA Continuously

Cl in Techmag % Lab Days 1/week

SK Grits Production Rate kg/hr SCADA Continuously

Cl in SK Grits % Lab Days 1/week

Simatek Dust Production Rate kg/hr SCADA Continuously

Simatek Dust Production Rate kg/hr SCADA Continuously

Cl in Simatek Dust % Lab Days 1/week

Table 2: Frequencies of measurements. Green font indicates new test / reading.

3.5 Personnel Training Requirements

The SOPs quoted above are used for training personnel in the capturing and collating of the data for the quarterly reports.

Personnel on shift / production days are trained in the emptying of the vessel that collects the Simatek dust. The operations department are trained in the emptying of the Shaft Kiln Grits. The

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laboratory technicians are trained in the measuring of Chlorides in solids, and XRF analysis, as per the procedures quoted above.

3.6 Recording and Reporting Format

See SOP named HCL Mass Balance SOP 001, Appendix 4.3.

The spreadsheet to be completed weekly by the Process Department onsite with all the parameters logged, and mass balance calculated automatically – See Figure 3 and 4 below. This data is summarised and then submitted quarterly in a word document format to the EPA by the EHS Manager on site.

Figure 3: Snapshot of proposed recording spreadsheet MHF. Yellow indicates and input, green

indicates a calculated figure.

Figure 4: Snapshot of proposed recording spreadsheet SK. Yellow indicates and input, green

indicates a calculated figure.

See HCl Mass Balance SOP 001 for details on calculations.

These mass balance calculations form the basis of the report to be submitted to the EPA, collated into a word document.

The data reported to the EPA is in the form of Table 3 below.

Quarter HCl Total Emissions per Quarter (kg)

Average HCl Emissions Per hour (kg/h)

Standard Deviation (kg/h)

Maximum Emissions per hour (kg/h)

Notes / Comments

Q1

Q2

Q3

Q4

Table 3: Submission of Quarterly Data to the EPA.

Date

BP Feed

kg/day

CCM

BP Feed

%Cl

DF Feed

kg/day

CCM

DF Feed

%Cl

Cl to MHF

kgs/day

TM45E

kg/day

TM45E

%Cl

CCM

Product

kg/day

CCM %ClCl ex MHF

kgs/day

HCl in

Stack

kg/day

HCl in

Stack

kg/hr

Date

Pellet

Feed

kgs/day

% Cl in

pellets

Cl to SK's

kgs/day

Simatek

dust kgs/day

% Cl in

Simatek

Dust

SK Grits

kgs/day

% Cl in SK

Grits

DBM

Product

kgs/day

%Cl in

DBM

Cl ex SK's

kgs/day

HCl in

Stack

kg/day

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4. Summary of Results for Q1 & Q2 2020

Quarter / Year

HCl Total Emissions per Quarter (kg)



Maximum Emissions per hour (kg/h) Notes / Comments

Q1 2020 26144 11.97 5.78 34.96

Q1 2020 - only SKA was running during January 2020, and MHFA & SKA Feb and March.

Q2 2020 21986 10.07 9.20 38.10

Q3 2020

Q4

2020

5. Appendices

5.1 Appendix 1: AT.21 Chlorides in Solids (from Laboratory Manual)

CHLORIDES IN SOLIDS

METHOD NO. AT 21

Caustic magnesia, periclase, magnesium hydroxide solids, magnesium hydroxide filter cake.

PRINCIPLE

The sample is dissolved in nitric acid and water is added to make the solution between 0.5 and 1.5N with respect HN03. Silver nitrate is added in excess to precipitate all the chloride and the excess silver nitrate determined by back -titration with standard ammonium Thiocyanate using a solution of ferric ammonium sulphate as indicator.

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APPARATUS

I. 1 x Hot Plate/Magnetic Stirrer with follower

II. 1 x 500ml conical Flask

III. 1 x 100ml Measuring Cylinder

IV. 1 x 50ml Measuring Cylinder

V. 2 x 50ml Burettes

VI. Whatman 541 Filter Paper.

CHLORIDES IN SOLIDS

METHOD NO. AT. 21 (CONTD)

REAGENTS

a) Concentrated nitric acid (AR Grade)

b) Wash bottle with 1% nitric acid solution.

c) N Ammonium Thiocyanate (standardised) see Note 1.

d) N Silver Nitrate (Standardised).

e) Ferric Ammonium sulphate indicator - See note 2.

f) Potassium chromate indicator.

PROCEDURE

1. Weigh approx. 5grams of the sample to the nearest 0.01g.

2. Transfer the sample to a 500ml Erlenmeyer flask and add 200ml of deionised water (See

Note 3.) 3. Add concentrated nitric acid (15-16 ml for magnesium hydroxide; 17 -18 ml for magnesium

oxide and periclase).

4. Insert a 50mm magnetic stirring bar, place the flask on a hot place - cum stirrer, heat and

stir until the sample has virtually all dissolved.

5. A small residue of undissolved material is not important.

6. Add, from a burette, 20mls of 0.1N silver nitrate and stir on a stirrer for 1 minute.

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5.2 Appendix 2: AT.30 Chlorides in Solids (from Laboratory Manual)

XRF ANALYSIS BY PRESSED PELLET TECHNIQUE

METHOD NO. AT 30

LIMESTONE MAGNESIA

PRINCIPLE

The Bohr Concept of the atom states that all the electrons contained within an atom circulate on certain designated orbitals/shells around the central nucleus. The number of electrons in each shell is determined by the elements configuration in the periodic table and is based on the formula 2N2 where N is the shell number).

By the input of energy from an outside source (such as an x-ray tube) the electrons may be lifted to a higher energy level (shell or orbital). When this happens the excited atom (no longer at ground state) will try to rearrange itself to obtain its original configuration.

For instance, if an electron forms the K shell (N=1) is ejected to a higher level the K shell then has a “positive hole”. Generally speaking when excitation occurs the hole caused by its ejection is filled by an electron or combination of electrons from higher energy levels to restore the stability of the atom.

The initial cause of excitation is referred to as PRIMARY OR CONTINOUS RADIATION.

The energy released by demotion of higher level electrons to fill “Positive Holes” is called FLOURESCENT ENERGY OR CHARACTERISTIC RADIATION.

The fluorescent energy will be different for each element because of its individual or characteristic electronic configuration. Hence the term CHARACTERISTIC RADIATION.

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XRF ANALYSIS BY PRESSED PELLET TECHNIQUE

METHOD NO. AT 30 (contd)

Therefore, if a sample is bombarded with continuous radiation each element in the sample will emit a radiation which is characteristic of that particular element. The detection system within the instrument picks up and quantifies the characteristic radiation of each element contained within the sample.

The method of analysis is known as “X-RAY FLOURESCENCE”

There are two techniques used in preparing the sample for XRF.

1. Fused Bead Analysis

Where the sample is presented to the spectrometer in solid solution state.

2. Pressed Pellet Analysis

Where the sample is analysed in pressed tablet form held together with the aid of a binding agent.

With both techniques it is necessary to calibrate the XRF with known standards prepared in an identical manner to that used for the unknown samples

XRF Analysis by Pressed Pellet Technique

Method No. At. 30

Apparatus & Reagents

- Jaw Crusher (for granular samples)

- Disc Mill with puck and chamber of suitable composition to prevent sample of suitable

composition to prevent sample contamination - separate Lime/Magnesia chambers.

- Pellet Press (Herzog HTP 40) - Separate Lime/Magnesia Caps

- Top Pan Balance (3 decimal places)

- Whatman CF11 Cellulose Powder

- Tri Ethyl Amine Grinding Agent (T.E.A.)

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- Warning Commercial Blender (Model 32 BL 80) with 100ml stainless steel sample cup and

rubber lids - separate Lime/Magnesia cups

- Phillips PW 1480 XRF Spectrometer and sample holders.

Procedure

1. Grinding/Blending

1.1. Limestone 1.2. The normal limestone sample analysed in PPL is 2mm crushed quarry stone. This

should be split in Riffle box down to about 500g.

1.3. Place 20g (=/-0.01) of this well mixed sample in the cleaned colony grinding barrel and

add 5 drops T.E.A onto sample.

1.4. Grind limestone for 3 minutes (Setting 2 on the timer console)

1.5. Remove ground limestone and clean mill for next sample

1.6. Weigh out 5g (+/-0.01) of caustic and 2g (+/-0.01) of Whatman cellulose binder.

1.7. Transfer sample to caustic mini-blender bowl and firmly affix lid.


Method No. At. 30 (contd)

1.8. Mix at low speed for 10 seconds.

1.9. Remove bowl and shake vigorously for 10 seconds to homogenise.

1.10. Replace bowl and mix at low speed for a further 10 seconds.

1.11. Remove mixture and transfer to Pellet Press - press as normal.

1.12. Clean blender bowl thoroughly after each use to avoid contamination.

For pressing of Sample see Section 2.

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2. Caustic

2.1. Normal caustic does not require grinding.

Weigh out 5g (+/-0.1) of caustic and 2g (+/-/01) of Whatman cellulose binder.

2.2. Transfer sample to caustic mini-blender bowl and firmly affix lid.

2.3. Mix at low speed for 10 seconds

Remove bowl and shake vigorously for 10 seconds to homogenize.

2.4. Replace bowl and mix at low speed for a further 10 seconds.

2.5. Remove mixture and transfer to Pellet Press - press as normal. 2.6. Clean blender bowl thoroughly after each use to avoid contamination.

For pressing of Sample see Section 2.

3. Magnesium Hydroxide (Incl. Thickener, Effluent and Clarifier Underflows and Filter

Cake) 3.1. Filter and dry sample if necessary. (Washing if required according to Method AT. 3.2. Ignite about 10g of well-mixed sample at 70OoC. 3.3. Leave to cool in desiccator. 3.4. Proceed as for Caustic commencing Step. 1.2.2



4. PRESSING OF SAMPLE

4.1. Transfer blended sample to a sheet of paper

4.2. Place the sample into the pressing tool with care

4.3. Place pressing cover (die) on top of pressing tool ensuring die surface is cleaned.

4.4. Close crosspiece over pressing tool

4.5. Set potentiometer to 0)

4.6. Screw pressure screw down tightly and then loosen by ¼ turn.

4.7. Press green start button

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4.8. Pressing is complete when the operation lamp goes off on the front panel

4.9. Loosen pressure screw and open crosspiece

4.10. Set potentiometer to 3.

4.11. To remove pellet, press the green start button.

4.12. Remove die and sample from the top of the pressing too.

4.13. Clean pressing die thoroughly with a cloth

4.14. Pressing tool moves down automatically after 4 seconds

4.15. Instrument is now ready for next sample

4.16. Label sample clearly with date and time.

Comments - Schematic operation of Herzog Press displayed beside it - Settings for operation have been pre-set during original instrument installation

Pressure : 150 KN

Press Time : 5 Seconds



5. SPECTROMETER OPERATION

Samples should be analysed on XRF programs as displayed in XRF Room.

5.1. Ensure calibration labels are up to date.

5.2. Select correct program for sampled type. If sample chamber is closed type SLPO

(Sample Loading Position Open)

5.3. Place the sample in the sample holder and place in spectrometer.

Type in correct sample identification and press “Return”.

5.4. Sample will now be analysed

5.5. Record results from printout after analysing time is complete.

5.6. Remove sample from XRF. If no further samples are to run type SLPC. (Sample

Loading Position Closed)

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5.3 Appendix 3: HCl Mass Balance SOP 001

HCl Monitoring SOP

1 Purpose [i]

The purpose of this SOP is to outline the method in which HCl emissions are calculated by the

Mass Balance method and are reported to the EPA on a quarterly basis.

2 Area of validity [i]

EHS and Process Department

3 Responsibilities [i]

Process owner: EHS Manager

Manager of necessary resources: Plant Manager

Implementation: Process Engineer

4 Procedure [i]

4.1 Each week, the ‘HCl Mass Balance Report’ spreadsheet is updated by the Process department, on the basis of the following input parameters:

Parameter Frequency Data Source

MHF production Rate Continuously SCADA

SK Production Rate Continuously SCADA

Cl in BP Cake (MgO basis) 2/Shift Shift Lab Log

Cl in DF Cake (MgO Basis) 2/Shift Shift Lab Log

Cl in CCM 3/Shift Shift Lab Log

BP MHF Feed Continuously SCADA

DF MHF Feed Continuously SCADA

Techmag production Continuously SCADA

Cl in Techmag 1/week Lab Day Log

SK Grits Production Rate Continuously SCADA

Cl in SK Grits 1/week Shift Day Log

Simatek Dust Production Rate Continuously SCADA

Cl in Simatek Dust 1/week Shift Day Log

Table 1: Parameters and frequencies (green text indicates new measurement/test)

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4.2 The spreadsheet is in the following format, containing data on a daily basis as per Figure 1 and 2:

4.2.1 Multiple Hearth Furnaces

Figure 1: Snapshot of proposed recording spreadsheet MHF – Yellow indicates input figure,

green indicates calculated figure.

The following parameters are calculated in excel using the input data as follows:

Tons of caustic fed to the furnaces per day: The average flowrate of filter cake feed is measured in kg/h from both the belt presses and directly from the drum filters. The total feed is a sum of the two flowrates to the furnaces. The flowrate is converted to a weight by multiplying the flowrate by the specific gravity of the slurry. This is then converted to a rate per day by multiplying by 24. As we are interested in the solids, the mass rate must be multiplied by the % Solids content of the slurry. This results in the total feed of magnesium hydroxide (Mg(OH)2), as we are interested in magnesium oxide (MgO) we need to divide the mass rate by 1.45. The 1.45 is the stochiometric rate of conversion from the chemical reaction that occurs in our furnaces. This method of calculation is the same for both belt press feed and the drumfilters.

𝑇𝑃𝐷 𝐶𝐶𝑀 𝐹𝑒𝑒𝑑 =𝐹𝑙𝑜𝑤𝑟𝑎𝑡𝑒 × 24 × 𝑆𝑔 × % 𝑆𝑜𝑙𝑖𝑑𝑠

1.45

Mass rate of Chlorides to the Furnace (kg/day): This is calculated by multiplying the tons of caustic feed per day multiplied by a 1000 and the percentage chlorine in the filter cake

𝐶ℎ𝑙𝑜𝑟𝑖𝑑𝑒𝑠 𝑖𝑛 𝐹𝑒𝑒𝑑 = 𝑇𝑃𝐷 𝐶𝑀𝑀 𝐹𝑒𝑒𝑑 × 1000 × % 𝐶𝑙 𝑖𝑛 𝑐𝑎𝑘𝑒 Tons of TechMag sent to the Silo per day: The tons of TechMag produced per day is calculated by finding the change in silo level over 24 hours. From this we can calculate the weight of TechMag added to the silo by multiplying volume of TechMag by the specific gravity of TechMag. The amount of TechMag exported from the silos to tankers must also be accounted for. So, the total amount of TechMag produced is a summation of the two.

𝑇𝑜𝑛𝑠 𝑜𝑓 𝑇𝑒𝑐ℎ𝑀𝑎𝑔 = 𝐶ℎ𝑎𝑛𝑔𝑒 𝑖𝑛 𝑆𝑖𝑙𝑜 𝑙𝑒𝑣𝑒𝑙 × 𝐶𝑟𝑜𝑠𝑠 𝑆𝑒𝑐𝑡𝑖𝑜𝑛𝑎𝑙 𝐴𝑟𝑒𝑎 𝑜𝑓 𝑆𝑖𝑙𝑜 × 𝑆𝑔 + 𝑇𝑎𝑛𝑘𝑒𝑟 𝑇𝑜𝑛𝑠

Amount of Chloride Removed in TechMag (kg/day): This is calculated by multiplying the tons of TechMag sent to the silo per day by 1000 and then the percentage chlorides in the TechMag.

𝐶𝑙 𝑅𝑒𝑚𝑜𝑣𝑒𝑑 𝑖𝑛 𝑇𝑒𝑐ℎ𝑀𝑎𝑔 = 𝑇𝑜𝑛𝑠 𝑜𝑓 𝑇𝑒𝑐ℎ𝑀𝑎𝑔 × 1000 × % 𝐶𝑙 𝑖𝑛 𝑇𝑒𝑐ℎ𝑀𝑎𝑔 Total Amount of Caustic Produced per day (ton/day): The total amount of caustic produced is the difference between the total feed of caustic to the furnace and the total amount of TechMag sent to the silo

𝑇𝑜𝑡𝑎𝑙 𝐶𝐶𝑀 = 𝑇𝑃𝐷 𝐶𝐶𝑀 𝐹𝑒𝑒𝑑 − 𝑇𝑃𝐷 𝑇𝑒𝑐ℎ𝑀𝑎𝑔

Date

BP Feed

kg/day

CCM

BP Feed

%Cl

DF Feed

kg/day

CCM

DF Feed

%Cl

Cl to MHF

kgs/day

TM45E

kg/day

TM45E

%Cl

CCM

Product

kg/day

CCM %ClCl ex MHF

kgs/day

HCl in

Stack

kg/day

HCl in

Stack

kg/hr

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Total amount of Chlorine in the Caustic (kg/day): The total amount of chlorine in the caustic is calculated by multiplying the total amount of caustic produced per day by 1000 and then the percentage chlorides in the caustic.

𝐶𝑙 𝑖𝑛 𝐶𝐶𝑀 = 𝑇𝑜𝑡𝑎𝑙 𝐶𝐶𝑀 × 1000 × % 𝐶𝑙 𝑖𝑛 𝐶𝐶𝑀

Total amount of Chlorine emitted via the stack per day (kg/day): The total amount of chlorine sent to the stack is the difference between the total amount of chlorine in the feed minus the sum of the total amount of chlorine in caustic and the total amount of chlorine in the TechMag.

𝐶𝑙 𝑡𝑜 𝑠𝑡𝑎𝑐𝑘 = 𝐶𝑙 𝑖𝑛 𝐹𝑒𝑒𝑑 − 𝐶𝑙 𝑖𝑛 𝐶𝐶𝑀 − 𝐶𝑙 𝑖𝑛 𝑇𝑒𝑐ℎ𝑀𝑎𝑔 Total amount of Hydrogen Chloride emitted via the stack per day (kg/day): The total amount of HCl emitted via the stack is calculated by converting the Cl sent to the stack into HCl. This is done by multiplying the amount of Chlorine to the stack by the mass ratio of Cl to HCl, which is 36.5/35.5.

𝐻𝐶𝑙 𝑡𝑜 𝑠𝑡𝑎𝑐𝑘 = 𝐶𝑙 𝑡𝑜 𝑠𝑡𝑎𝑐𝑘 × 36.5

35.5

4.2.2 Shaft Kilns

Figure 2: Snapshot of recording spreadsheet SK – Yellow indicates input figure, green indicates

calculated figure.

The following parameters are calculated in excel using the input data as follows: Tons of Shaft Kiln Grits Produced per day:

The total amount of shaft kiln grits is measured using new equipment. Mass rate of Chlorides in the Shaft Kiln Grits (kg/day): This is calculated by multiplying the tons of shaft kiln grits extracted from the system per day multiplied by a 1000 and the percentage chlorine in the grits.

𝐶ℎ𝑙𝑜𝑟𝑖𝑑𝑒𝑠 𝑖𝑛 𝑆ℎ𝑎𝑓𝑡 𝐾𝑖𝑙𝑛 𝐺𝑟𝑖𝑡𝑠 = 𝑇𝑃𝐷 𝑆𝐾𝑔𝑟𝑖𝑡𝑠 × 1000 × % 𝐶𝑙 𝑖𝑛 𝑆𝐾𝑔𝑟𝑖𝑡𝑠 Tons of Simatek Dust Produced per day:

The total amount of Simatek dust is measured using new equipment. Mass rate of Chlorides in the Simatek Dust (kg/day): This is calculated by multiplying the tons of Simatek dust extracted from the system per day multiplied by a 1000 and the percentage chlorine in the filter dust.

𝐶ℎ𝑙𝑜𝑟𝑖𝑑𝑒𝑠 𝑖𝑛 𝑆𝑖𝑚𝑎𝑡𝑒𝑘 𝐷𝑢𝑠𝑡 = 𝑇𝑃𝐷 𝑆𝑖𝑚𝑎𝑡𝑒𝑘 𝑑𝑢𝑠𝑡 × 1000 × % 𝐶𝑙 𝑖𝑛 𝑆𝑖𝑚𝑎𝑡𝑒𝑘 𝑑𝑢𝑠𝑡

Date

Pellet

Feed

kgs/day

% Cl in

pellets

Cl to SK's

kgs/day

Simatek

dust kgs/day

% Cl in

Simatek

Dust

SK Grits

kgs/day

% Cl in SK

Grits

DBM

Product

kgs/day

%Cl in

DBM

Cl ex SK's

kgs/day

HCl in

Stack

kg/day

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Tons of Shaft Kiln Feed (Caustic pellets) per day: This is calculated as 95% of the Dead Burned Magnesia produced from the shaft kilns. This percentage is calculated from historical data. From the historical data the losses from the systems are equal to 5%. These losses are volatiles that are burnt off in kiln, and dust and grits losses.

𝑇𝑃𝐷 𝐹𝑒𝑒𝑑 =𝑇𝑃𝐷 𝐷𝐵𝑀

0.95

Mass rate of Chlorides in the Shaft Kiln Feed (kg/day): This is calculated by multiplying the tons of shaft kiln feed (caustic) per day multiplied by a 1000 and the percentage chlorine in the caustic feed.

𝐶ℎ𝑙𝑜𝑟𝑖𝑑𝑒𝑠 𝑖𝑛 Feed = 𝑇𝑃𝐷 𝐹𝑒𝑒𝑑 × 1000 × % 𝐶𝑙 𝑖𝑛 𝑐𝑎𝑢𝑠𝑡𝑖𝑐 Total amount of Chlorine emitted via the stack per day (kg/day): The total amount of chlorine sent to the stack is the difference between the total amount of chlorine in the feed minus the sum of the total amount of chlorine in the shaft kiln grits and the total amount of chlorine in the Simatek dust

𝐶𝑙 𝑡𝑜 𝑠𝑡𝑎𝑐𝑘 = 𝐶𝑙 𝑖𝑛 𝐹𝑒𝑒𝑑 − 𝐶𝑙 𝑖𝑛 𝑆𝐾𝑔𝑟𝑖𝑡𝑠 − 𝐶𝑙 𝑖𝑛 𝑆𝑖𝑚𝑎𝑡𝑒𝑘 𝑑𝑢𝑠𝑡 Total amount of Hydrogen Chloride emitted via the stack per day (kg/day): The total amount of HCl emitted via the stack is calculated by converting the Cl sent to the stack into HCl. This is done by multiplying the amount of Chlorine to the stack by the mass ratio of Cl to HCl, which is 36.5/35.5.

𝐻𝐶𝑙 𝑡𝑜 𝑠𝑡𝑎𝑐𝑘 = 𝐶𝑙 𝑡𝑜 𝑠𝑡𝑎𝑐𝑘 × 36.5

35.5

4.3 Quarterly, the totals calculated in the HCl Mass balance spreadsheet is collated and put into the word document to be submitted to the EPA by the EHS Manager.

Quarter HCl Total Emissions per Quarter (kg)



Maximum Emissions per hour (kg/h)

Notes / Comments

Q1

Q2

Q3

Q4

Table 2: Parameters and data sources (green font indicates new measurement/test)

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5.4 Appendix 4: Excel Spread Sheet Containing Q2 2020 HCL Mass Balance Report for The MHF’s

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5.5 Appendix 5: Excel Spread Sheet Containing Q2 2020 HCL Mass Balance Report for The Shaft Kilns.

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Documents

HCl Mass Balance Results Q2 2020 - epawebapp.epa.ie