Galvanizing
Galvanizing
Galvanizing
Emission estimation
technique manual
for
This manual may be reproduced in whole or part for study or training purposes subject to the
inclusion of an acknowledgment of the source. It may be reproduced in whole or part by those
involved in estimating the emissions of substances for the purpose of National Pollutant
Inventory (NPI) reporting. The manual may be updated at any time. Reproduction for other
purposes requires the written permission of the Department of Sustainability, Environment,
Water, Population and Communities, GPO Box 787, Canberra, ACT 2601, e-mail:
[email protected], web: www.npi.gov.au, phone: 1800 657 945.
Disclaimer
The manual was prepared in conjunction with Australian states and territories according to the
National Environment Protection (National Pollutant Inventory) Measure.
While reasonable efforts have been made to ensure the contents of this manual are factually
correct, the Australian Government does not accept responsibility for the accuracy or
completeness of the contents and shall not be liable for any loss or damage that may be
occasioned directly or indirectly through the use of, or reliance on, the contents of this
manual.
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EMISSION ESTIMATION TECHNIQUES
FOR
GALVANIZING
TABLE OF CONTENTS
DISCLAIMER ..................................................................................................................... I
1 INTRODUCTION ................................................................................................... 1
1.1 Process for NPI reporting ......................................................................... 1
1.2 Information required to produce an annual NPI report ............................ 2
1.3 Additional reporting materials ................................................................. 2
2 PROCESS DESCRIPTION..................................................................................... 3
3 EMISSION SOURCES ........................................................................................... 4
4 THRESHOLD CALCULATIONS ......................................................................... 6
5 TECHNIQUES FOR ESTIMATING EMISSIONS ............................................... 7
5.1 Direct measurement.................................................................................. 8
5.2 Mass balance ............................................................................................ 9
5.3 Engineering calculations .......................................................................... 9
5.4 Emission factors ....................................................................................... 9
5.5 Approved alternative .............................................................................. 10
6 TRANSFERS OF NPI SUBSTANCES IN WASTE ............................................ 11
8 REFERENCES ...................................................................................................... 14
APPENDIX A: DEFINITIONS AND ABBREVIATIONS ............................................. 15
APPENDIX B: EMISSION FACTORS ........................................................................... 16
APPENDIX C: MODIFICATIONS TO THE GALVANIZING EMISSION ESTIMATION
TECHNIQUE (EET) MANUAL (VERSION 2.0 JULY 2012) ........................................ 25
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GALVANIZING
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1 Introduction
The purpose of all emission estimation technique (EET) manuals is to assist
Australian manufacturing, industrial and service facilities to report emissions of listed
substances to the National Pollutant Inventory (NPI). This manual describes the
procedures and recommended approaches for estimating emissions and transfers from
Australian galvanizing operations.
Note that the ANZSIC code is part of NPI reporting requirements. The NPI Guide
contains an explanation of the ANZSIC code.
This manual has been developed through a process of national consultation involving
state and territory environmental agencies and key industry stakeholders. Particular
thanks are due to the Galvanizers Association of Australia (GAA)
Step 2: Determine the emission sources for your Refer to: Section 3
facility “Emission sources”
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1.2 Information required to produce an annual NPI report
The following information is needed for the reporting period:
• Amount of acid, zinc and other NPI substances used at the facility during the
reporting period.
If any fuel burning equipment has been used on the facility, including on-site
vehicles, additional data will need to be collated:
• type and amount of fuel burned
• pollution control devices employed, and
• volume and throughput of fuels or organic liquids stored on-site.
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2 Process description
Galvanizing is a process undertaken to coat ferrous metals and metal products in a
layer of zinc to prolong their life. The metal to be coated requires pre-treatment prior
to being immersed into the zinc bath in order to remove rust, grease and other
materials, and therefore to promote the galvanizing process. Pre-treatment can include
treatment of the metal with an alkaline degreasing solution, an acid pickling solution,
water rinse, and a pre-flux solution. The pre-flux solution is usually comprised of zinc
ammonium chloride (ZnCl2.3NH4Cl), and is used to promote the zinc-metal bond.
After pre-treatment, the metal is immersed in molten zinc followed by a quench bath.
1 shows a basic galvanizing flow diagram and some expected emission points. As
each galvanizing facility in Australia is unique, you are encouraged to develop flow
diagrams for your operation that detail the input of materials and NPI listed
substances and the emissions resulting from the operation of each process.
Figure 2: The basic galvanizing process steps and likely emission points
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For example, ash and dross are generally processed on site to extract zinc which is
then remelted into galvanizing bath or recycled off-site and made into zinc powders
which go into other products, such as paint, make-up, etc.
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3 Emission sources
This section describes the raw material inputs, the equipment used and the processes
employed that result in emissions of NPI listed substances in the galvanizing process.
This section also provides a concise description of the potential fate (to air, land, and
water) of these emissions.
Waste liquids may be generated from spent pre-treatment solutions and sometimes
from quenching activities after galvanizing; it is expected that pollutants are captured
on site and transferred off-site under a trade waste agreement or via approved waste
disposal contractors (i.e. no emissions are expected). The process tanks usually
contain metal salts, acids, bases, and dissolved base materials.
The galvanizing process also generates solid wastes. Solid wastes include a zinc oxide
ash that is periodically removed from the surface of the galvanizing bath and zinc iron
alloy dross removed from the bottom of the galvanizing bath, as well as solids in
spent solutions and wastewater treatment sludge. Characterisation of these wastes
may be required when estimating emissions using the mass balance approach (see
Section 5).
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Table 1 summarises the raw material inputs and the emissions of NPI substances that
could be generated during the galvanizing process.
Galvanizing may involve the use and handling of a number of NPI listed substances.
These substances commonly include zinc and compounds (e.g. zinc ammonium
chloride), chromium (VI) compounds, hydrochloric acid, sulfuric acid, chlorine, and
ammonia.
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Table 1 - Material inputs and emissions from galvanizing processes
Process Material Emissions to air Solid waste emissionsB General Management of
input Emissions
Degreasing Substrate to be galvanised, alkaline degreasing • VOCs Process sludges Sludges disposed of as
solution • steamA Caustic sludge containing controlled/prescribed wastes
zinc
Pickling Substrate to be galvanized • hydrochloric acid Process sludges Spent acid disposed of as
Acid pickling solution, hydrochloric acid • sulfuric acid controlled/prescribed wasteC
sulfuric acid
Water rinses Rinse water and substrate to be galvanised Zinc and other metal Sludges disposed of as
sludges controlled/prescribed wastes
Pre-flux Substrate to be galvanized • ammonia, Zinc and other metal Sludges disposed of as
Zinc ammonium chloride • ammonium chloride sludges controlled/prescribed wastes
ammonia solution • steamA
Galvanizing bath Substrate to be galvanized • hydrochloric acid, Zinc oxide ash, zinc iron Reprocessing of ash and dross for
Zinc, alloys, metal salts, acids • ammonia, alloy dross zinc contentD
• ammonium chloride,
• zinc oxide,
• zinc chloride,
• particulate matter,
• lead oxide,
• copper oxide,
• chlorine
Quenching Sodium dichromate • SteamA Zinc and other metal Sludges and solutions disposed of
sludges as controlled/prescribed wastes
Heating of Fuel • VOCs, Released to atmosphereE
galvanizing bath • oxides of nitrogen,
• particulate matter,
• sulfur dioxide
Source: Queensland Department of Environment and Heritage, 1998.
A. Non NPI substance
B. May result in the transfers of NPI substances
C. There is some but limited collection and treatment of acid fumes and spent acid up to this manual's date.
D. A number of facilities also have a hood over the galvanizing bath capturing emissions to air
E. Some facilities recycle heat to other parts of the galvanizing process
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4 Threshold calculations
The NPI has six different threshold categories. The NPI Guide outlines each of these.
Further information on these thresholds can be found in the NPI Guide.
The following example demonstrates how thresholds are related to the reporting
requirement for Category 1. The usage of each of the substances listed as Category 1
under the NPI must be estimated to determine whether the 10 tonnes reporting
threshold is exceeded. If the threshold of a Category 1 substance is exceeded,
emissions of that substance from the facility (for all sources) must be reported, even if
the emissions of the substances are very low or zero.
In addition, the facility combusts 18,000,000 MJ natural gas to heat the zinc
galvanizing bath.
From the NPI Guide, based on the NPI categories and their associated thresholds, the
facility is required to estimate and report:
The facility is not required to report emissions of chromium VI and compounds as use
of this substance does not exceed the reporting threshold (10 tonnes per year).
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5 Techniques for estimating emissions
Emissions to air, land and water for every NPI substance that trips a threshold must be
reported from all point and fugitive sources at the facility. These are reported as “total
point” and “total fugitive” emission sources. The NPI Guide provides detailed
information on thresholds and identifying emission.
There are five types of emission estimation techniques (EETs) that may be used to
estimate emissions from your facility. These are:
• sampling data or direct measurement
• mass balance
• fuel analysis or engineering calculations
• emission factors, or
• an approved alternative.
Generally, galvanizing facilities report emissions for hydrochloric acid using the
emission factor method, however some facilities report hydrochloric acid emissions
using direct measurement, engineering calculations, mass balance calculations or by
an approved alternative technique. The emission factor method, engineering
calculation and mass balance calculations are briefly described in this section.
Information on the other emission estimation techniques can be found in the NPI
Guide.
If you estimate emissions by using any of these EETs, your data will be displayed on
the NPI database as being of “acceptable reliability”. Similarly, if your state or
territory environmental agency has approved the use of EETs that are not outlined in
this manual, your data will also be displayed as being of acceptable reliability.
This manual seeks to provide the most effective emission estimation techniques for
the NPI substances relevant to the galvanizing industry. The absence of an EET for a
substance in the manual does not imply that an emission should not be reported to the
NPI. The obligation to report on all relevant emissions remains if reporting thresholds
have been exceeded.
You should note that the EETs presented in this manual relate principally to average
process emissions. Emissions resulting from non-routine events are rarely discussed
in the literature, and there is a general lack of EETs for such events. However, it is
important to recognise that emissions resulting from significant operating excursions
and/or accidental situations (e.g. spills) will also need to be estimated. Emissions to
land, air and water from spills must be estimated and added to process emissions
when calculating total emissions for reporting purposes.
The emission resulting from a spill is the net emission, i.e. the quantity of the NPI
reportable substance spilled, less the quantity recovered or consumed immediately
(within 24 hours) during clean up operations.
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5.1 Direct measurement
Direct measurement involves monitoring and recording emissions of a particular
substance at either a point in time or on a continual basis. Many facilities are required
to directly measure specific substances as a result of their licensing requirements of
their state/territory environment agency. Stack sampling test reports often provide
emissions data in terms of kg/hr or grams/m³ STP dry (dry standard cubic metre).
Annual emissions for NPI reporting can be calculated from this data using
Equations 1 or 2 below.
Stack tests for NPI reporting should be performed under representative (i.e. normal)
operating conditions, and in accordance with the methods, or standards, approved by
the relevant environmental authority. Tests conducted specifically for the NPI may
differ from stack tests undertaken for a State or Territory licence condition, which
may require the test be taken under maximum emissions rating (i.e. where emissions
are likely to be higher than when operating under normal operating conditions).
However, the acceptability of using existing monitoring program data and test
methods should be checked with your local environmental regulatory authority.
This Section shows how to calculate emissions in kg/hr based on stack sampling data,
and how to convert this to an annual emission figure. Calculations involved in
determining PM₁₀ emissions are used as an example, although the same general
methodology is applicable for most of the substances listed on the NPI.
Equation 1
Equation 2
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Any facility using direct measurement may use this data as the basis of their NPI
report.
Efficiency rates for different control devices can be found in the NPI Emission
estimation technique manual for combustion in boilers.
Example 2 illustrates the use of emission factors and control efficiencies in estimating
emissions using Equation 3.
Equation 3
where :
Ekpy,i = annual emissions of pollutant i, kg/yr
A = activity rate, tank/yr
EFi = uncontrolled emission factor of pollutant i, kg/tank
CEi = Control efficiency for substance i (%)
Modern galvanizing plants with properly shielded acid baths may use a control
efficiency of 75% for acid emissions.
Tables 3 and 4 in Appendix B provide emission factors for the hot dip galvanizing
process.
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Example 2: Calculating emissions using emission factors
From example 1, Facility A has determined that they have a requirement to report
emissions and transfers of hydrochloric acid and zinc and compounds, as well as
emissions of Category 2a substances.
Hydrochloric acid:
The facility operates three acid tanks which have a surface area each of 20 m2, using
hydrochloric acid at an average concentration of 12%w/v. The ambient temperature of
the solution in the acid tank is 25°C. The facility has proper shielding on the acid
tanks to reduce emissions.
Using Equation 3:
Category 2a substances:
The facility burns natural gas using a boiler with capacity <30MW. Using the
Combustion in Boilers EET manual, the facility estimates emissions of the Category
2a substance.
As the facility exceeded the reporting threshold for hydrochloric acid (10 tonnes) and
zinc and compounds (10 tonnes), the facility must also consult Section 6 to determine
if it is necessary to report transfers of waste for these substances.
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6 Transfers of NPI substances
The NPI requires the mandatory reporting of NPI substances that are transferred in
waste to a final destination. Transfers are required to be reported if a Category 1,
Category 1b or Category 3 reporting threshold is exceeded. For example, if the
threshold has been exceeded for a Category 1 substance as a result of use onsite,
transfers to a final destination of that substance, as well as emission are reportable.
Both emissions and transfers are reportable in kilograms.
A containment destination may be on site, for example a tailings storage facility on-
site, or off-site, for example waste going to landfill. The transport or movement of
substances contained in waste to a sewerage system is also included.
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Table 2: Transfers reporting requirements
Waste stream containing NPI Reporting requirements
substances
Liquid waste discharged to sewer system Reporting is mandatory
Discharge of NPI substance to a
mandatory reporting transfer destination.
Solid waste sent to landfill Reporting is mandatory
Discharge of NPI substance to a
mandatory reporting transfer destination.
Waste sent for recycling or reprocessing Reporting is voluntary
Reuse of waste containing NPI
substances, reporting is voluntary
If your facility has exceeded the threshold and is required to report transfers, only the
amount of the actual substance(s) transferred is reportable. You should report only the
amount of NPI substances in the waste, not the total waste, for example, a facility
generates 1 ton of a waste slurry which is sent off-site for treatment for destruction.
The waste slurry contains 1kg of lead oxide with the rest of the slurry made up of
non-NPI substance. This means that the facility would need to report 1kg of lead
oxide, rather than the entire mass of waste slurry.
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7 Additional reporting information
This manual has been written to reflect the common processes employed in
galvanizing activities. To ensure a complete report of the emissions and transfers of
waste for your facility, it may be necessary to refer to other EET manuals. These
include but are not limited to:
• Combustion in Boilers
• Combustion Engines
• Fuel and Organic Liquid Storage, and
• Fugitive Emissions
For details on how to report substance emissions and transfers from your facility, refer
to NPI Guide.
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8 References
ANZSIC: Australian and New Zealand Standard Industrial Classification, Australian
Bureau of Statistics and Statistics New Zealand 2006, ABS Catalogue 1292.0
Eastern Research Group. November 1996. Final Report: Preferred and Alternative
Methods for Estimating Fugitive Emissions From Equipment Leaks. Morrisville, NC,
USA.
Perry, R. and Green, D., 1997, Perry’s Chemical Engineers’ Handbook, 7th Ed.,
McGraw-Hill, New York, USA.
USEPA. October 1992. VOC / PM Speciation Data System - Version 1.50. United
States Environmental Protection Agency, Office of Air Quality Planning and
Standards. Research Triangle Park, NC, USA.
The following Emission Estimation Technique Manuals can be downloaded from the
NPI homepage, (http://www.environment.gov.au/epg/npi/home.html) or obtained
from your local environmental protection agency (see the front of the NPI Guide for
details):
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Appendix A: Definitions and abbreviations
Term Definition
Facility any building or land from which a substance may be emitted, together
with any machinery, plant, appliance, equipment, implement, tool or other
item used in connection with any activity carried out at the facility
kg kilogram
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Appendix B: emission factors
Table 3: Emission factors - acid pickling - hydrochloric acid A,B,C,D
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Acid Tank Solution Emission Factor Emission Factor
Concentration Size Temperature (kg/tank (kg/tank
(% w/v) (m²) (°C) /year) /month)
10 5 20 28.4 2.4
10 5 25 41.4 3.5
10 5 30 60.2 5
10 10 20 56.8 4.7
10 10 25 82.7 6.9
10 10 30 120.4 10
10 15 20 85.2 7.1
10 15 25 124.1 10.3
10 15 30 180.6 15.1
10 20 20 113.6 9.5
10 20 25 165.5 13.8
10 20 30 240.8 20.1
10 25 20 142.1 11.8
10 25 25 206.8 17.2
10 25 30 301 25.1
12 5 20 63.4 5.3
12 5 25 92.4 7.7
12 5 30 134.6 11.2
12 10 20 126.9 10.6
12 10 25 184.8 15.4
12 10 30 269.1 22.4
12 15 20 190.3 15.9
12 15 25 277.2 23.1
12 15 30 403.6 33.6
12 20 20 253.7 21.1
12 20 25 369.6 30.8
12 20 30 538.2 44.9
12 25 20 317.2 26.4
12 25 25 462 38.5
12 25 30 672.7 56.1
14 5 20 140.8 11.7
14 5 25 205.2 17.1
14 5 30 299 24.9
14 10 20 281.6 23.5
14 10 25 410.4 34.2
14 10 30 597.9 49.8
14 15 20 422.4 35.2
14 15 25 615.6 51.3
14 15 30 896.9 74.7
14 20 20 563.2 46.9
14 20 25 820.8 68.4
14 20 30 1195.9 99.7
14 25 20 704 58.7
14 25 25 1026 85.5
14 25 30 1494.8 124.6
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Acid Tank Solution Emission Factor Emission Factor
Concentration Size Temperature (kg/tank (kg/tank
(% w/v) (m²) (°C) /year) /month)
16 5 20 310.8 25.9
16 5 25 453.1 37.8
16 5 30 660.6 55.1
16 10 20 621.5 51.8
16 10 25 906.2 75.5
16 10 30 1321 110.1
16 15 20 932.3 77.7
16 15 25 1359.3 113.3
16 15 30 1981.6 165.1
16 20 20 1243 103.6
16 20 25 1812.5 151
16 20 30 2642.1 220.2
16 25 20 1553.8 129.5
16 25 25 2265.6 188.8
16 25 30 3302.6 275.2
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Table 4: Emission factors - acid picking - sulfuric acid
Substance Uncontrolled emission factor EF Emission factor
(kg/per tank/year) rating
Sulfuric acid 134 U
Derived from Texas Commission on Environmental Quality (TCEQ), Calculations Package, Hot Dip
Galvanizing
Assumptions:
Tank size is approximately 21 square metres in size
Tank operating temperature is ambient
Acid concentration is approximately 16%
Emissions factors are per tank per year.
Emission factors are uncontrolled. If controls are used (such as suppressants, hoods of other
abatement), the emission factor should be adjusted by the percentage efficiency of any such control.
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Appendix C: Modifications to the galvanizing emission estimation
technique (EET) manual (Version 2.0 July 2012)
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