UPTEC-F11061 Examensarbete 30 hp December 2011

Environmental analysis of zirconium alloy production

Mikael Lundberg Abstract Environmental analysis of zirconium alloy production

Mikael Lundberg

Teknisk- naturvetenskaplig fakultet UTH-enheten The generation of electricity in light water nuclear power plants uses Besöksadress: zirconium alloys as the primary Ångströmlaboratoriet Lägerhyddsvägen 1 containment and cladding of the nuclear Hus 4, Plan 0 fuel. The environmental impacts of the production of zirconium alloys have been Postadress: analyzed form a lifecycle perspective. Box 536 751 21 Uppsala From the mining of the zirconium-bearing mineral zircon to the finished zirconium Telefon: alloy tube. A qualitative study 018 – 471 30 03 indentifying the production processes

Telefax: and their potential environmental 018 – 471 30 00 impacts have been performed. A quantitative study to perform a Hemsida: lifecycle analysis of the zircon mining http://www.teknat.uu.se/student and mineral separation was carried out. The life cycle analysis for the zircon mining was compared to the current lifecycle analysis (LCA) in Vattenfall's Forsmark nuclear power plant environmental product declaration (EPD). The results showed that the additional impact on Forsmark's EPD, when including the mining of zircon, is below 0.1% of the current levels for all parameters analyzed. A lifecycle analysis for the production of zirconium metal and zirconium alloy tube could not be performed due to lack of data from the zirconium metal industry. The major direct emissions from the zircon mining industry are related to the use of fossile fuels in machinery. The major direct emissions from the zirconium metal manufactoring industry are related to the use of acids.

Handledare: Lasse Kyläkorpi Ämnesgranskare: Mattias Lantz Examinator: Thomas Nyberg ISSN: 1401-5757, UPTEC-F11061 Sponsor: Vattenfall AB 0.1 Popul¨arvetenskaplig sammanfattning

Zirkoniumlegeringen zircalloy anv¨andssom konstruktionsmaterial vid tillverkn- ing av k¨arnbr¨ansleti dagens k¨arnkraftverk av l¨attvattentyp. Legeringen zircal- loy som anv¨andsf¨oratt innesluta uranet som ¨arsj¨alva k¨allantill energiutvinnin- gen i ett k¨arnkraftverk. Vid tillverkningen av k¨arnbr¨ansleplaceras uran i form av sm˚akutsar i l˚angar¨orav zircalloy, dessa r¨ormonteras sedan ihop paket om ett hundratal r¨orf¨oratt bygga upp ett br¨ansleelement. Det ¨ardessa br¨ansleelement som laddas in i k¨arnkraftveken varje ˚arvid revisionsavst¨allningen. Br¨ansle- inkapslingen av zicalloy har tv˚ahuvudsakliga funktioner, dels att h˚allaurankut- sarna p˚aplats, dels att fungera som en barri¨arf¨oratt f¨orhindraspridning av radioaktiva ¨amnen. Anledningen till att zirkoniumlegeringar anv¨andssom br¨ansleinkapsling ¨aratt zirkonium ¨armotst˚andskraftigtmot korrosion samt att det l¨attsl¨apper igenom de neutroner som bildas vid k¨arnklyvningar och som kr¨avsf¨oratt uppr¨atth˚allaklyvningen av uranatomerna.

Denna rapport syftar till att unders¨oka milj¨oaspekterna av tillverkningen av zirkoniumlegeringar, fr˚angruvbrytning av den zirkoniuminneh˚allandemineralen zirkon till tillverkningen av de zircalloy-r¨orsom anv¨andsf¨ork¨arnbr¨ansletillverkning. Rapporten behandlar inte sj¨alva tillverkningen av k¨arnbr¨ansled¨arurankutsar monteras i zircalloy-r¨orf¨oratt bilda br¨ansleelement. Fokus i rapporten ligger p˚aatt kvalitativt beskriva hur gruvbrytningen och tillverkningsprocessen g˚ar till samt att kvantitativt beskriva hur stora de utsl¨appsom f¨orekommer ¨ar.

Zirkonium utvinns ur mineralen zirkon som ¨aren zirkonium-kisel-oxid som ¨ar vanligt f¨orekommande i naturen. Mineralen f¨orekommer i l˚agakoncentrationen i vulkanisk berggrund. N¨arberggrunden eroderar frig¨orsmineraler som sand- korn som sprids med vatten och vind. P˚agrund av att zirkon ¨artyngre ¨an den vanlig kiseloxid sand sedimenteras och koncentreras zirkonsanden i sand- bankar p˚astr¨anderoch sanddyner tillsammans med andra tyngre metaller som titan, uran, torium och s¨allsynta jordartsmetaller. Dagens gruvbrytning sker fr˚anfyndigheter d¨arzirkonsanden koncentrerats under perioderna mellan de senaste istiderna. Den st¨orsta delen av brytningen sker fr˚annuvarande eller historiska havsstr¨ander. De l¨andermed de st¨orstafyndigheterna och st¨orsta produktionen ¨arAustralien och Sydafrika som tillsammans st˚arf¨orca 2/3 av b˚adefyndigheterna och produktionen.

Gruvbrytningen sker fr˚anoftast fr˚ansanddyner som ˚aterfinnsett flertal me- ter under markytan, d¨armedbeh¨over de ¨ovrejordlagren flyttas. Detta sker vanligtvis med lastmaskiner, dumpers och bulldozers men om grundvatten- f¨oruts¨attningarna¨arde r¨attasanv¨andsen mudderteknik d¨arsanden blandas med vatten och sugs upp. Marken ˚aterst¨allskontinuerligt i takt med att bryt- ningen f¨oljermalmkroppen fram˚at.Sanden f¨orstill ett anrikningsverk som kon- centrerar den tunga mineralsanden. Denna process bygger enbart p˚afysikalisk separering, inga kemikalier anv¨ands. Zirkonet anrikas genom sedimentering, elektrostatiskt och magnetisk separation. Den stora milj¨op˚averkan fr˚anbryt- nings och anrikningsprocesserna kommer ifr˚ande stora markytorna som sk¨ovlas f¨oratt komma ˚atmalmen och fr˚ande utsl¨appsom sker fr˚anf¨orbr¨anning av fos- sila br¨ansleni de maskiner som anv¨ands.Uran och toriumhalten i mineralerna medf¨or¨aven radiologiska krav p˚aarbetsmilj¨o˚atg¨arder.

3 Det anrikade zirkonet skeppas sedan till producenterna av zirkonium metall d¨arsanden genomg˚aren serie kemiska processer f¨oratt separera zirkonium fr˚an kisel och sedan zirkonium fr˚anhafnium. F¨oratt avl¨agsnakisel anv¨andsen h¨ogtemperaturprocess med tillsats att kol och klor. F¨orseparationen av zirko- nium fr˚anhafnium anv¨andsen av tv˚aolika metoder beroende p˚atillverkare den ena processen anv¨anderen kalium-aluminium-klorid saltsm¨alte-separation den andra processen anv¨ander l¨osningsmedletmetylisobutylketon samt saltsyra, svavelsyra och ammoniumhydroxid. Metallen reduceras med magnesium f¨or att rena bort kloridrester och vakuumdestilleras tills en por¨ossubstans kallad ”zirkoniumsvamp” ˚aterst˚ar. Den stora milj¨op˚averkan h¨ar¨arutsl¨appav b˚ade l¨osningsmedeloch syror samt de rester av uran och torium som f¨allsut i pro- cessen.

Den rena por¨osazirkoniumsvampen sm¨altsner till solida zirkonium stavar som sedan smids i en serie av processer f¨oratt producera de s¨oml¨osar¨orsom anv¨ands vid tillverkningen av k¨arnbr¨ansle. F¨orstkompakteras zirkoniumsvampen i en press till n˚agotsom kan liknas med gigantiska svetspinnar, som sedan sm¨alts ner i en vakuumugn som fungerar som en gigantisk pinnsvets. Sm¨altanstel- nar till en cylinder som sedan smids ut till l¨angre cylindrar som kapas upp min kortare bitar. Ett h˚alborras genom centrum av de kortare cylindrarna, sedan kl¨asde med ett sm¨orjandematerial innan de pressas ut till l˚angas¨oml¨osa r¨or. Det sm¨orjandematerialet tas bort med v¨atefluoridoch salpetersyra in- nan r¨orenr¨atasupp och kapas till sin slutliga l¨angd.Den st¨orstamilj¨op˚averkan fr˚andenna process ¨arenergi˚atg˚angenfr˚ansm¨altnings och smidnings processerna samt anv¨andandetav v¨atefluorid och salpetersyra.

Ett m˚almed rapporten ¨aratt genomf¨oraen analys f¨oratt se hur stor p˚averkan zirkonium legerings tillverkningen har p˚autsl¨appen fr˚an1kWh el producerad vid ett svenskt k¨arnkraftverk. M˚aletvar att genomf¨oraen livscykelanalys av tillverkningen av zircalloy-r¨or,detta kunde tyv¨arrinte genomf¨orasp˚agrund av brist p˚adata fr˚antillverkarna av zirkoniumsvamp och zircalloy-r¨or.Endast en analys av gruvbrytningen och dess p˚averkan p˚aen livscykelanalys av elen pro- ducerad i Forsmarks k¨arnkraftverk kunde genomf¨oras.

De unders¨oktaparametrarna ¨arutsl¨appav: v¨axthusgaser, f¨orsurande¨amnen, ozonskapande ¨amnen,¨overg¨odande¨amnenoch partiklar samt resursanv¨andandet av r˚avatten och energi. Resultatet av denna livscykelanalys var att om utsl¨appen fr˚antillverkningen av de zirkonium legeringar l¨aggstill Forsmarks nuvarande livscykelanalys s˚akommer utsl¨appen inte att ¨oka med mer ¨an0,1% f¨orn˚agon av de analyserade parametrarna.

4 Contents

0.1 Popul¨arvetenskaplig sammanfattning ...... 3

1 Introduction 11 1.1 Background ...... 11 1.2 Objectives ...... 11 1.3 Limitations ...... 12 1.4 Method ...... 12 1.4.1 Availability of data ...... 12 1.5 Structure of the report ...... 13

2 The Manufacturing of zirconium alloys 14 2.1 Introduction to zirconium ...... 14 2.2 Zircon mining ...... 19 2.2.1 Preparing for mining ...... 20 2.2.2 Mining ...... 21 2.2.3 Heavy minerals concentration ...... 23 2.2.4 Radiological concerns ...... 25 2.2.5 Mine rehabilitation ...... 26 2.2.6 Environmental impacts ...... 28 2.3 Mineral separation ...... 28 2.3.1 Radiological concerns ...... 31 2.3.2 Environmental impacts ...... 32 2.4 Zirconium sponge production ...... 32 2.4.1 Zirconium-hafnium separation process ...... 34 2.4.2 Zirconium sponge production process ...... 35 2.4.3 Environmental impacts ...... 36 2.5 Zircaloy ingot production ...... 37 2.5.1 Zirconium alloy ingot production processes ...... 37 2.5.2 Environmental impacts ...... 40 2.6 Zircaloy tube production ...... 41 2.6.1 Zircaloy tube production processes ...... 41 2.6.2 Environmental impacts ...... 43

3 LCA of zirconium production 45 3.0.3 Data sources ...... 46 3.1 LCA of zircon production ...... 47 3.1.1 Data sources ...... 47 3.1.2 Impact on the LCA for Forsmark NPP ...... 48

5 4 Discussion 50

5 Conclusions 52 5.1 Further work ...... 53

Appendices 57

A List of companies 58

B Production flowcharts 60

C LCA study 76

6 List of Figures

2.1 Generalized zirconium alloy tube production process ...... 15 2.2 Zirconium consumption by end use in 2008 [17] ...... 18 2.3 Overview of zirconium mining ...... 20 2.4 Bulldozer feeding mineral sand into a hopper. The hopper is slowly moving to the right, through the deposit. The feed water and slurry pipelines are shown in the bottom left. [20] ...... 22 2.5 Dredge barges and wet concentration plant in an artificial dredge pond. Dredge barge spraying water to erode shores of dredge pond [22] ...... 23 2.6 Left: Bank of spiral separators [3], Right: Spiral separator where heavy minerals concentrate towards the center of the spiral [3] . . 24 2.7 Heavy mineral mining on North Stradbroke Island [27] ...... 25 2.8 Mining with integrated rehabilitation [30] ...... 27 2.9 Overview of mineral separation ...... 29 2.10 Magnetic separation concept ...... 30 2.11 Electrostatic separation concept ...... 31 2.12 Overview of zirconium sponge production ...... 33 2.13 Left: Raw zirconium sponge [46]. Right: Crushed zirconium sponge [47] ...... 36 2.14 Overview of zircaloy ingot production ...... 38 2.15 Concept of zirconium alloy mixing, compacting and production of consumable electrode ...... 39 2.16 Vacuum arc remelting process ...... 39 2.17 Production of zirconium alloy materials ...... 40 2.18 Overview of zirconium tube production ...... 41 2.19 Left: Preheating of zirconium ingot in a furnace, Right: Reducing zirconium ingot diameter by forging ...... 42 2.20 Extrusion process ...... 43 2.21 Cold pilgering, pickling, annealing and straightening process . . . 43

3.1 Concept of environmental impact categories ...... 46

B.1 Zircon mining flow chart ...... 61 B.2 Wet concentration plant flow chart (1/2) ...... 62 B.3 Wet concentration plant flow chart (2/2) ...... 63 B.4 Mineral separation plant flow chart (1/2) ...... 64 B.5 Mineral separation plant flow chart (2/2) ...... 65 B.6 Zirconium-Hafnium separation flow chart (1/4) ...... 66 B.7 Zirconium-Hafnium separation flow chart (2/4) ...... 67

7 B.8 Zirconium-Hafnium separation flow chart (3/4) ...... 68 B.9 Zirconium-Hafnium separation flow chart (4/4) ...... 69 B.10 Zirconium sponge production flow chart (1/1) ...... 70 B.11 Zirconium ingot production flow chart (1/1) ...... 71 B.12 Zirconium tube production flow chart (1/4) ...... 72 B.13 Zirconium tube production flow chart (2/4) ...... 73 B.14 Zirconium tube production flow chart (3/4) ...... 74 B.15 Zirconium tube production flow chart (4/4) ...... 75

8 List of Tables

2.1 World production and reserves of zirconium minerals 2009 in kilo- tonnes, (two different sources.) ...... 17 2.2 World leading zircon producers 2008 ...... 19 2.3 Top five largest emissions by weight, reported by Australian zir- con mining companies [33] ...... 28 2.4 Properties of minerals commonly found in heavy mineral deposits 30 2.5 Example of substances reported from two Australian mineral sep- aration plants [33] ...... 32 2.6 Example of emissions reported from two American and one French zirconium sponge producer [48] [49] ...... 37 2.7 Chemical composition of the two most common zirconium alloys 38 2.8 Example of emissions reported from two American and one French zirconium alloy tube producer [48] [49] ...... 44

3.1 Zircon mining companies analyzed in the LCA study ...... 47 3.2 Emissions and resource consumption for the production of 1 kg zircon in Australia, based on 2009 year production ...... 48 3.3 Emissions and resource consumption for the production of 1 kWh electricity form Forsmark NPP excluded zircon production com- pared to emissions and resource consumption contribution from the zircon production ...... 49

A.1 List of zirconium mining companies ...... 58 A.2 List of zirconium sponge manufacturers ...... 59 A.3 List of zirconium alloy manufacturers ...... 59

C.1 Australian Zircon Emissions 2009 [33] ...... 76 C.2 Australian Zircon Production 2009 [56] ...... 76 C.3 Australian Zircon Facilities 2009 [33] ...... 76 C.4 Bemax Resources Limited Emissions 2009 [33] ...... 77 C.6 Bemax Resources Limited Facilities 2009 [33] ...... 77 C.7 Exxaro Production 2009 [57] ...... 77 C.8 Exxaro Emissions and Resource Consumption 2009 [57] . . . . . 77 C.9 Iluka Resources Limited Emissions 2009 [33] ...... 78 C.10 Iluka Resources Limited Production 2009 [58] ...... 78 C.11 Iluka Resources Limited Facilities 2009 [33] ...... 78 C.12 Iluka Resources Limited Emissions and Resource Consumption 2009 [58] ...... 79 C.13 Tiwest Emissions 2009 [33] ...... 79

9 C.14 Tiwest Production 2009 [57] ...... 79 C.15 Tiwest Facilities 2009 [33] ...... 79 C.16 Kenmare Resources Production 2009 [59] ...... 80 C.17 Kenmare Resources Emissions and Resource Consumption 2009 [59] ...... 80 C.18 USGS Mineral Prices 2009 [55] ...... 80

10 Chapter 1

Introduction

1.1 Background

In recent years, the public and the electricity custumers have started to show a growing interest in how the electricity is generated and how it affects the environment. As a response to this 99% of Vattenfall’s Swedish generation capacity produce Environmental Product Declarations (EPD) [1]. An EPD is a declaration of the environmental impact a product causes during its complete life-cycle and is based on the ISO 14025 standard for environmental lables and declarations. The EPD system provides the costumers and general public with a lifecycle based assessment of environmental impacts of the related product. In this case, the product is 1 kWh of electricity. The EPD is based on quantitative data on significant environmental aspects verified by a third party. The certified EPDs do not include any form of subjective judgement or valuation of the environmental performance. In addition to the EPDs, the electricity produced at the Swedish nuclear power plants in Forsmark and Ringhals are since 1999 certified according to the ISO 14001 standard for environmental management systems. In the continuous work of Vattenfall to improve the quality of the EPDs for the electricity from nuclear power plants, the production of zirconium alloy products are one of the few remaining potential significant environmental impacts to be analyzed in detail.

1.2 Objectives

This report aims to qualitatively describe the processes used in the production of nuclear grade zirconium alloy tubes and identify the potential environmental impacts of these processes. The objective is:

• to perfrom a lifecycle analysis to quantitatively determine the resource consumption and emissions associated with the production of 1 kilogram of nuclear grade zirconium alloy. • To identify if the zirconium alloy production has a significant impact on the environmental performance of the production of 1 kWh of electricity from Vattenfalls nuclear power plants.

11 1.3 Limitations

This report includes a qualitative analysis of the processes used from the min- ing of zircon to the production of nuclear grade zirconium alloy tube. The production of other zirconium alloy material such as spacer grids, channels etc. were not included. The assembly of zirconium; tubes, sheet and spacer grids to form nuclear fuel elements and the loading of uranium fuel into these are not included. The construction and decommissioning of the infrastructure required for the zirconium metal production processes have not been included due to lack of data, i.e. only the operational impacts are analyzed.

1.4 Method

The qualitative study was predominantly performed as literature a study with a visit to Sandvik’s zirconium tube production at Sandviken in Sweden. The literature study has focused on online sources, such as company and government environmental control agency web pages, academic research articles and patents. The quantitative study aimed to perform a life-cycle analysis of zirconium alloy production, to be able to calculate the emissions and resource consumption required to produce 1 kg of nuclear grade zirconium alloy tube. A survey with questions was sent to the companies involved, (see Appendix A). Unfortunately the number of companies willing to participate in this study was too low to avoid company proprietary data to be singled out in the low sample of responses, therefore the survey was abbandoned.

Instead, only publicly available sources were used, such as company environ- mental and annual reports and governmental agency databases. However the lack of direct responses from the industry made it the zirconium sponge and alloy producers were scarce.

1.4.1 Availability of data To perform a lifecycle study, data on resource consumption, emissions and pro- duction have to be obtained. This is not the kind of data companies willingly share, due to its proprietary nature. Emissions of substances with environmental impacts are something governments control by law and is therefore monitored by control agencies. How these governmental agencies manage and publish this data varies between countries.

The quantitative study was intended to be carried out as a survey sent out to all involved companies from the zircon mines to the zirconium alloy tube producers. However this was not possible due to the low response rate from the industry. Instead only official available information could be obtained. This meant that only data from transparent companies and environmental control agencies were available. Hence, only companies with an already strong environ- mental focus or operating in countries with transparent government agencies could be included in this study. The lack of direct response from the industry lead to a lack of data in how potential waste streams are treated, recycled/reused or discarded.

12 Of the major mining countries investigated, only Australia and USA were found to have controlling government agencies that openly publish environmen- tal reports online, for individual mining facilities. Some of the zircon mining companies publish detailed material on their production processes and waste treatment. For the zirconium metal producing countries only western countries were investigated in detail and Canada, France, Sweden and USA were found to pub- lish facility level environmental reports online. The zirconium metal producing companies are very secretive about their proprietary information and publish very little material on the production processes. However, since the zirconium metal producers do not publish production rates of production price levels, no allocation of emissions could be performed and no lifecycle analysis could be carried out.

1.5 Structure of the report

This report is divided into two main parts. Chapter 2 contains a qualitative study to analyze the production processes and determine the processes with the largest potential environmental impacts. The production process is divided into subchapters according to the majors subprocess which each end with a discus- sion on the environmental impacts. Chapter 3 contains a lifecycle analysis on the production of nuclear grade zirconium alloy and a discussion on the results. The overall results of the report will be discussed in chapter 4. Finally, the con- clusions and suggestions for further work will be presented in chapter 5. The Appendix includes an extensive flowchart representation of the manufacturing processes.

13 Chapter 2

The Manufacturing of zirconium alloys

This chapter will explain the basic production processes used for manufacturing nuclear grade zirconium alloy material and the environmental impacts associ- ated with these processes. The manufacturing of zirconium alloys can be roughly divided into five stages according to separation of production between different facilities, (see Figure 2.1).

• Mining and concentration of heavy minerals • Separation of the zirconium bearing-mineral zircon • Separation of zirconium from hafnium and the production of zirconium sponge

• Production of zirconium alloy ingots • Production of zirconium alloy tubes

2.1 Introduction to zirconium

Zirconium (Zr) is a metal with atomic number 40, it is located in the group IVb period in the periodical table in the same period as Titanium (Ti) and Hafnium (Hf). Zirconium occurs in nature in over 150 different minerals [2] but never in its metallic form. Zirconium is the 18th most abundant element in the Earths crust [3]. Pure zirconium metal oxidize at ambient temperature to form a potective oxide layer that gives it special corrosion resistance. Small fragments of zirconium metal (with high surface area to mass ratio) can spontaneously ignite at room temperature. Solid zirconium metal can not self-ignite at room temperature but will rapidly oxidize at temperatures above 900◦C. Zirconium has a melting point of 1852◦C and a boiling point of 4377◦C, at atmospheric pressure.

14 Figure 2.1: Generalized zirconium alloy tube production process

The primary source for economically recoverable zirconium is the zirconium silicate mineral zircon (ZrSiO4). Minor amounts of zirconium is also recovered from the mineral baddeleyite (ZrO2). Zircon occurs alongside titanium miner- als in so called heavy mineral sand deposits. Heavy mineral sands is the term used to describe minerals with a specific gravity greater than 2.9g/cm3, this can be compared to the most common mineral in sand, quartz (SiO2) with a spe- cific gravity of 2.7g/cm3. [4] The most notable titanium minerals usually found toghether with zircon is rutile (TiO2), ilmenite (Fe2O3 · 3 TiO2) and leucox- ene (Fe2O3 · TiO2 · mH2O) which are all commercially mined for their titanium content. Historically zircon was recovered as a byproduct from the titanium minerals but in recent years the higher demand and price for zircon have shifted the balance and new mining projects have zircon as their primary economical mineral.

Zircon occurance Heavy mineral sands are found in alluvial or aeolian placer deposits which are sedimentary deposits where the accumulation of mineral have occurred due to gravitational concentration over time. Alluvial deposits are formed through erosion and concentration by water and aeolian deposits are from erosion and concentration by wind. The concentration occurs due to the relative difference in specific gravity of heavy mineral sand and quartz.

15 Alluvial deposits are formed through erosion by water when waves wash in over ocean beaches and carry away the lighter materials leaving the heavier behind, or by running water in rivers where the denser materials are sedimented before the lighter. This lead to a concentration of heavy mineral on beaches or in riverbanks. Most of the historic accumulated deposits are from the Quaternary period i.e. the last 2.6 million years. [5] In this period, minerals deposits were accumulated during the cycle of glacial and interglacial periods when the sea levels rose and fell hundreds of meters. When the sea level rose old deposits were eroded, reshaped and concentrated. When the sea level fell, deposits were left behind as beaches. [5]

In the case of the historically accumulated deposits, these may now be located several hundred kilometers inland due to the marine regression since the last intergalacial period. The deposits may since then have been covered by later deposited material and may now be located a few to tens of meters under ground. A beach deposit may have a mineralization of up to 90% heavy minerals, but typical grades are 5-20% heavy minerals. [5] The Murray and Eucla Basins in Australia are examples of historic shoreline deposits, the Indian beaches in Orissa, Kerala and Tamil Nadu are examples of contemporary beach deposits. [6]

Aeolian deposits are formed by erosion by wind where the wind carry sand from beaches inland to form dunes. As the dunes migrate the lighter mate- rials are carried away further and the heavier minerals are left behind and are concentrated into heavy mineral deposits. Dunal deposits tend to have a lower mineralization than the beach deposits, typically 0.5-15% heavy minerals. What the dunal deposits lack in concentration they make up for in size. A typical dunal deposit is larger than a beach deposit, both in physical size and total mineralization. The South African Kwa-Zulu Natal and Australian North Stradbroke Island dunes are examples of historic, now vegetated, sand dunes while the Senegalese Grande Cˆotedunes are examples of contemporary moving sand dunes.

High heavy mineral concentration does not necessarily mean a high zircon grade. The zircon share of the total heavy minerals varies greatly between different deposits from 0-60% with a typical concentration of 10% [7]. The mineral zircon contains 0.4-4% [8] hafnium with a typical concentration of 2% [9], this is because zirconium and hafnium have very similar chemical properties which allow hafnium to replace the zirconium in the mineral and form hafnon (HfSiO4). Hafnon always coexistswith zircon and the term zircon used in the report will refer to zircon with hafnon impurities unless other stated. In fact, the similarites in chemical properties is a problem for the production of nuclear grade zirconium, as will be evident in the zirconium-hafnium separation described in Section 2.4.1.

Zirconium mining The majority of the mining of zirconium minerals today originate from zircon in beach or dunal deposits. River deposits are most often too small to be eco- nomically viable. There are a few exceptions though, the Kovdorsky mine [10]

16 on the Kola peninsula in north western Russia is the only commercial badde- leyite mine, that extracts baddeleyite as a co-product from its apatite and iron ore mining. Baddeleyite also coexist with zircon to form the mineral caldasite (ZrO2, ZrSiO4) wich is mined in the Minas Gerias region in Brazil [11]. For- merly baddeleyite was also mined in the Palabora [12] mine in South Africa which ceased production in 2002. Another exception is the extraction of zircon from oil sands tailings in the Athabasca basin in Canada [13]. These alternative production sources add together to less than 1% of the total world production of zirconium minerals and will not be discussed further.

The world production and reserves of zircon is concentrated to a few major producing countries, (as seen in Table 2.1). If production were to remain at the 2009 production levels the known resources would last over 40 years.

Table 2.1: World production and reserves of zirconium minerals 2009 in kilo- tonnes, (two different sources.) Country Production [kt] [14] Reserves(a) [kt] [15] Australia 474 23000 South Africa 392 14000 China 140 500 United States 100 3400 Indonesia 63 NA India 36 3400 Ukraine 35 4000 Mozambique 29 NA Brazil(b) 25 2200 Sri Lanka 10 NA Vietnam 8 NA Russia(b) 7 NA Malaysia 1 NA Other NA 5000 Total 1320 56000 (a) Reported as ZrO2 equivalents (b) Including baddeleyite and caldasite

The mineral zircon is used for a range of different applications, (as seen in Figure 2.2). The major end-use of zircon is the ceramics industry where zir- con is used as on opacifier in tiles and sanitary ware. Zircon is also used as moulding sand in foundry applications or as refractory material in bricks for high temperature furnaces. Other uses include the production of fused zirconia (syntetic Zr02) for refractory or ceramics applications, production CRT glass or production of zirconium chemicals which is the base of range of zirconium derivatives.

Finally a small fraction of the world production of zircon is used in the produc- tion of zirconium metal used in chemical process industries and nuclear power

17 plants. The nuclear grade zirconium metal market is a market with few ven- dors with a surplus capacity. The worldwide nuclear grade zirconium annual production capacity is about 8600 tonnes and the demand is about 5000 tonnes [16]. This indicates that the nuclear grade zirconium production only accounts for 0.5% of the total world zirconium mineral production.

Figure 2.2: Zirconium consumption by end use in 2008 [17]

Zirconium alloy value chain The value chain of zirconium strats with the mining of zircon by mining com- panies often specialized on just mining of heavy mineral sand, the companies involved are shown in Table A.1. The zircon is sold to the zirconium sponge producers, shown in Table A.2. All zirconium sponge producers also produce zirconium alloy tubes, sheet metal and other zirconium alloy products. How- ever, not all companies producing tubes and sheet metal produce zirconium sponge. The zirconium sponge producers sell some of the sponge to the other zirconium alloy producing companies, as shown in Table A.3.

The finished zirconium alloy tube, sheet metal etc. are used in fuel fabrication, where the zirconium and uranium are assembled into nuclear fuel elements. Most of the zirconium alloy producers also have their own fuel fabrication. The finished nuclear fuel elements are sold to the nuclear power plant operators which use the fuel in the reactor core for 4-5 years. When the fuel is burnt out the fuel elements are placed in temporarily cooling ponds at the nuclear power plant awainting disposal in a final repository. The zirconium tubes acts as one of the saftey barriers in the final repository. In the once through fuel cycle no zirconium are recycled from irradiated nuclear fuel elements.

18 Zirconium in the nuclear industry Zirconium alloys are a key material in modern light water nuclear power plants. A boiling water reactor (BWR) contain about 44 tonnes of zirconium and a pressure water reactor (PWR) contain about 29.5 tonnes of zirconium. [16] Zirconium alloys are used as construction material and fuel cladding i.e. the material which contain the uranium fuel pellets. The uranium pellets are placed in cladding tubes which are held together by spacers and assembled into fuel bundles and in surrounded by a fuel channel. Most of the materials in these components, except the fuel, are zirconium alloy materials.

Zirconium alloys are used as a construction material due to its high melting temperature, excellent corrosion resistance and low neutron cross section. The low thermal absorption cross section for neutrons (i.e. probability to absorb low energy neutrons), gives two major benefits in a reactor environment. The first benefit is increasing the ratio of neutrons per fission that are available to initiate a new fission. The second benefit is decreasing the neutron induced swelling which occurs when neutrons dislocate atoms in metal lattice structures. The dislocations lead to swelling and embrittelment of the metal making it prone to cracking.

2.2 Zircon mining

This chapter will explain the zircon mining process and analyze potential envi- ronmental impacts. For the full process flowchart refer to Appendix B.1. The mining processes can rougly be divided into four stages, (as seen in Figure 2.3): • Exploration and preparation for mining

• Mining of mineral sands • Concentration of heavy minerals • Rehabilitation of mined areas

Table 2.2: World leading zircon producers 2008 Company Operating Mining Market countries technique share Iluka Resources Ltd Australia, USA Dry 34% Exxaro South Africa Dry 15% Richards Bay Minerals South Africa Dredge 18% Bemax Resources Ltd Australia Dry 4% DuPont USA Dredge 3% Tiwest JV Australia Dry 2% Other N/A NA 24%

19 Figure 2.3: Overview of zirconium mining

2.2.1 Preparing for mining When a probable heavy mineral resource have been identified using various geographical and geological tools an exploration drilling program is carried out to indentify the resource. Small drilling rigs much like those used for water well or geothermal heat drilling are used to drill core samples in a grid covering the exploration area. The drilling pattern is typically asymmetric with a 100x200 m grid used. [18] When a resource is found, the grid size is subsequently decreased to better investigate the form and grade of the mineralization. During the drilling, core samples are taken from the surface down to the underlying clay or bedrock up to 250 m below surface for deep deposits. [18] The samples are sent to a laboratory to determine the precise heavy mineral grade and mineral composition. Once the drill samples and laboratory analysis is completed, a three dimensional structure of the mineralization is built which will be the base for the planning of the mining operations.

When the mineral explorations have found a new deposit rich enough to facil- itate mining a feasibility, an environmental impact report and a rehabilitation plan need to be established. These reports will include details on how the miner- als will be mined and processed, what environmental impacts that are expected, how the rehabilitation will be carried out and the economics of the project. To be able to perform the rehabilitation of the mine, a field study establishing the baseline conditions of the land is performed. This study is carried out in parallell with a mining feasibility study since it impacts the choice of mining technology and operations. The study aims to record the pre-mining conditions of geographical topology, groundwater, land use, flora and fauna, etc. The land topology is recorded and the groundwater levels and conditions are measured. The local species are recorded and seeds from vegetation may be collected to

20 ensure the local vegetation is re-established post rehabilitation. [5] In order to get a mining licence to start a new mine, the mining and rehabilitation plan and the environmental impact assesment have to sent to the respective author- ities. When all documments have been filed and the authorities granted all permissions the mining can commence.

Zircon mining is carried out as strip mining. The mining operations typically start with the clearing of vegetation and clearing of topsoil to establish the mining infrastructure such as roads and buildings. This is followed by the clearing of the deposit. If the deposit is covered by forest any lumber is first harvested and firewood is collected. [5] The remaining vegetation is cleared using bulldozers and the biomass is stored in stockpiles next to the mine pit awaiting rehabilitation. The bulldozers continue to clear the organic topsoil in the same manner once again to be stored in stockpiles next to the mine pit. If the deposit is located deep underground there will be a further need to remove the overburden which is performed using similar methods. All actions up till this point will have been similar for most mines but after the clearing of topsoil and overburden the difference between the two main mining techniques becomes evident.

2.2.2 Mining There are two main types of mining techniques; dredge mining and dry mining. The two techniques differ by the way they extract the minerals sand, but are similar in the way they concentrate the sand to form heavy mineral concentrate. The choice of mining technique depend on the deposits geological structure. Dredge mining involves floating dredges and concentration plant in an artificial pond which uses high pressure hose to erode the sandbanks. The base of the sandbanks are washed away and the sand fall into the pond where the floating dredge can scoop up the sand. Dredge mining requires a non permeable bottom of the deposit to enable the formation of water tables. It is required that the groundwater level lies above the bottom of the deposit to facilitate the formation of the artificial pond upon which the dredge and the concentration plant floats. The dredge mining technique is more suitable for mining larger continous deposits with low amounts of clay such as dunal deposits. If deposits are large enough, contain low amounts of clay and have the right groundwater properties dredge mining is often economically favourable over dry mining.

Dry mining is suitable for most other types of deposits. Dry mining methods involve the extraction of sand by conventional earth moving machinery such as front end loaders, self-elevating scrapers, excavators or bucket wheel excavators. The transportation of the mineral sand to the concentrator is performed either by pumping as a slurry or by conveyor belts. A combination of both dredge and dry mining is the hydraulic mining which uses high pressure water hoses to erode the deposit but no dredges or artificial pond. In this report only dredge and dry mining will be described though, since it includes the same methods used in hydraulic mining. For a flowchart description of the mining processes refer to Appendix B.1.

21 Dry mining Dry mining techniques consist of a wide range of mostly diesel powered machines such as bulldozers, scrapers, front end loaders, excavators or bucket wheel exca- vators, all depending of the properties and location of the deposit. Bucket wheel excavators are more suitable for large continuous deposits since their large size and cost, while front end loaders are more suitable for smaller deposits. Inde- pendent on how the sand is extracted, it is fed to a hopper for screening and removal of oversize materials. [19]

Figure 2.4: Bulldozer feeding mineral sand into a hopper. The hopper is slowly moving to the right, through the deposit. The feed water and slurry pipelines are shown in the bottom left. [20]

The sand is dug out by a excavator or a bucket wheel excavator, scraped of the surface of the deposit by a bulldozer or self-elevating scraper or scooped up by a front end loader. All techniques have the same aim, to keep a constant feed of sand to the hopper. The bucket wheel excavator use a conveyor belt to transport the sand to the hopper. The front end loader might load directly into the hopper or into a truck for transportation to the hopper. The scraper and bulldozer technique use a slightly different approach where the scraper moves the sand close to the hopper and the bulldozer feed it into the hopper. The hopper moves through the deposit as it slowly crawls forward, (as seen in Figure 2.4).

Inside the hopper the sand pass over a vibrating grizzle for separation of over- size materials such as stones and roots which are rejected and directly returned to the mining void. The sand are subsequently sprayed with a high pressure water jet to break up eventual chunks of clay. The slurry is and fed through a rotating trommel which separates the remaining small size rock. The remaining sand and clay slurry are pumped to the wet concentration plant. Where the

22 light worthless minerals, called gangue, like quartz are separated form the valu- able zircon and titanium minerals. To break up the clay and form the slurry requires large amounts of water. Almost any water source can be used to pro- vide the water and water recycling help reduce the withdrawal rates of these sources. In wet regions with an annual net rainfall, water recycling may be sufficient to maintain a water balance within the mining area. In arid regions with an annual net evaporation, a water source is a necessity. In Australia the use of saline groundwater puts special demands on the water management. [21] The saline water could damage vegetation and make the soil infertile, if released into previously non-saline areas.

Figure 2.5: Dredge barges and wet concentration plant in an artificial dredge pond. Dredge barge spraying water to erode shores of dredge pond [22]

Dredge mining The dredge mining technique use floating dredges to extract the sand, which can be compared to marine dredges used to build ports or deepen canals. Dredge mining basically consist one or more dredge barges and a floating concentration plant. The floating dredge barges use a high pressure water jet to undermine the shores of the dredge pond to make the sand collapse into the pond where the dredge barge use a suction dredge or bucket wheel to extract it, (see Figure 2.5). Since the sand is extracted from the pond it is already in slurry form when it pass trough a rotating trommel for separation of oversize materials. The remaining slurry is pumped to the floating concentration plant for further mineral concentration. The dredge barges and concentration plant are typically electric powered. As the dredge barge cuts into the deposit the dredge pond expands forwards, but as the concentration plant discards its rejects the pond is filled up behind. This means that the artificial pond migrates forward to follow the deposit.

2.2.3 Heavy minerals concentration Independent of which mining technique is used the heavy mineral concentration use basically the same techniques. The sand and clay slurry from the mine is fed

23 through fine screen to remove any remaining rock or roots before it is fed into a bank of hydro-cyclone separators where the heavier minerals are separated from the lighter clays and slits. A flocculant chemical might be used to speed ut the precipitation of clays. This is the only chemical used in the mining and separation processes. In dry mining the clays and slits are sent to a thickener which recovers the process water and thickens the clay. The thickened clay is pumped to an evaporations pond where the run off water is collected and reused. The remaining dry clay is then stored awaiting rehabilitation. The fact that the rejects are directly returned to the mining void in dredge mining removes the need of tailing ponds used in dry mining, and facilitates a quicker rehabilitation process.

Figure 2.6: Left: Bank of spiral separators [3], Right: Spiral separator where heavy minerals concentrate towards the center of the spiral [3]

The heavy minerals slurry is fed to a constant density tank to facilitate a smooth flow to the following bank of spiral separators. In the spiral separation the slurry pass multiple parallell and serial fiberglass spirals. The spiral is con- structed so the lighter materials are separated from the heavier by gravitational force where the heavier material are concentrated on inside of the spiral and the non valuable materials (gangue) on the outside, (see Figure 2.6). The spirals are placed in banks of parallell spirals to increse the total flow. These banks are placed in series to increase the heavy mineral concentration in steps. The heavy minerals from one spiral pass on to the next spiral and the light mate- rials are fed to a scavenger spiral to extract any remaining heavy minerals, (as seen in Appendix B.2). The wet concentration typically recovers 95% of the heavy minerals in the slurry and the composition of the formed Heavy Mineral Concentrate (HMC) is typically 90% heavy minerals and 10% quartz [23].

A wet high intensity magnetic separation (WHIMS) might be used to perform an initial separation in which the magnetic minerals are separated from the non- magnetic. The different minerals are dried in separate piles awaiting transport to the Mineral Separation Plant (MSP). The further refinement may take two routes. In a dry mining operation, the HMC is put in piles outside to dry naturally to achieve a low enough moisture level to allow easily handling. When

24 dry the minerals are transported to the MSP where the valuable minerals in the HMC are separated from each other and the gangue, (see Section 2.3. The MSP may either be located at the mine site or at a separate site. Larger deposits often have the MSP at the mine site while smaller deposits often share a common MSP to which the HMC are transported by truck or barge. In Australia it is common with long transports of HMC from mines located several hundred kilometers from the coast to the MSPs located close to major ports.

2.2.4 Radiological concerns Heavy mineral sand contain Naturally Occurring Radioactive Materials (NORM) such as the elements uranium, thorium and their decay-progenies. These NORM in the sand imposes special radiological considerations during mining, concentra- tion and transportation. In Australia, the uranium and thorium concentrations in heavy mineral concentrate typically have an activity concentration of 0.8- 8.5Bq/g [24] which is just below the 10Bq/g NORM trade restrictions proposed by the IAEA [25]. The Australian Radiation Protection and Nuclear Safety Agency (ARPANSA) performed a study investigating the radiations exposure in the transports of heavy mineral sand concentrate between mines and mineral separation plants and shipment to final costumers. The results showed that the highest annual exposure for a worker involved in the transports of heavy mineral sands in Australia were estimated to be 604 µSv/y [24]. Annual expo- sure to mining personel at an Australian mine were estimated to be 3 mSv/y [26], mostly due to external gamma radiation with a small part from internal exposure form dust inhalation and radon.

Figure 2.7: Heavy mineral mining on North Stradbroke Island [27]

25 2.2.5 Mine rehabilitation Mineral sand mining have been conducted in Australian in over 70 years and well establihed best rehabilitation principles have been established. Studies of rehabilitation progress are conducted by the Australian Centre for Minerals Extension and Research (ACMER) [28] for almost 20 years. Studies of rehabili- tations show that there exist methodes for sucessfully rehabilitating a mine site and reestablishing local species [29]. Since the heavy mineral grade of a deposit is typically 10 wt.% only a small fraction of the volume is extracted and over 90 % of the materials are returned into the mining void. This mean that the mining void can be almost completly backfilled and the former topology can be constructed.

Except for some radiological concerns, the tailings from heavy mineral sand mining are not hazardous. The tailings from heavy mineral sand mining are different than from most other metal mining in the sense that the tailings from sand mining are sand, which is already oxidized and unreactive. While tailings from mining of hard rock will crush the rock and expose the unextracted metals to oxygen and water which may lead to an increade release of metals into the environment. Further, ore from hard rock may contain sulphuric minerals which when exposed to oxygen and water will create suphuric acid and create acid mine drainage which will increase the release rate of metalls to water. Since the tailings from mineral sand mining are sand which already have been exposed to the elements and are already oxidized there are not the same problematic with heavy metal release.

In the case of dredge mining, the dredge pond continuously move forward following the deposit using the gangue separated from the HMC to backfill the void. Hence there is no need to store tailings in a special dedicated area. Topsoil and overburden will still have to be stored, although after the initial mine pit is established any further clearing of topsoil and overburden migh be used directly in the rehabilitation. Since the mine void is continuously backfilled the rehabilitation process can also be carried out continuously, (see Figure 2.8). There is however usually a gap (i.e. active open mining area) between mining and rehabilitation that is significantly larger than indicated by Figure 2.8.

In the case of dry mining, the tailings discarded by the concentration processes are fed back into the mining void via a tailings dam and transport by trucks. Since the tailing are in slurry form there is a need to let it dry before it is easy to handle. In dredge mining, the water is simply returned to the dredge pond and in dry mining the water are collected from the tailings dam and reused as process water. Once the material in the tailings dam is dry enough, it is transported back to the mining void by trucks and the rehabilitation can begin. Once back in the mining void bulldozers use the tailings to reconstruct the former topology of the deposit. When the desired shape has been acquired overburden and topsoil are replaced from their storages or if possible, taken directly from the clearing of new topsoil in the mine path. Clay is mixed with sand and spread on top of the dune to create a water absorbing layer to help revegetation.

26 Figure 2.8: Mining with integrated rehabilitation [30]

The seeds which were sampled in the preparation for mining, (described in Section 2.2.1), have now either been grown in a plant nursery or are planted directly. Saplings grown from the plant nursery are replanted to speed up the regrowth. If the mine is located in a windy region or experience heavy rainfall, extra measures to prevent erosion are needed. These might include the con- struction of wind fencing, spreading of biodegradable bitumen sand stabilizer or spreading of mulch from the cleared vegetation in the mine path. [31] Slow growing trees might have to be grown in a plant nurery and replanted as grown specimens. Dead trees and logs from the clearing might be placed to create cover and nesting possibilities for animals.

27 2.2.6 Environmental impacts The most notable environmental impacts in the zircon mining are the large areas of land required to be stripped of vegetation to uncover the mineral deposits. The destruction of habitats will affect threatened species although the impacts can be minimized if an ambitious rehabilitation program is conducted. The problems with the large areas cleared by mining is exacarbated by the fact that beach and dunal deposits in costal environments often are key habitats. Costal dunes provide a special environment which is sensitive to invading species such as weeds, this puts special demands on the rehabilitation.

The fact that most mineral sand deposits are located in costal environments is a source of some controversy for the sand mining industry. Sand mining on the heavy populated Australian east coast have lead to conflict where recreational, environmental and mining interests have opposed each other. Historically, as sand mining claimed larger and larger costal areas so did the population growth and environmental conservatists. This lead to the establishment of several pre- seves protecting against sand mining. One of the current controversies are the sand mining on North Stradbroke Island, 30 km from Brisbane [32].

Another notable impact is related to the large energy demand to operate a mine. Dredge mining activities typically use electricity as the primary energy source for the dredges and floating HMC-plant. For almost all other machines diesel is the primary energy source. Mining requires a diversity of diesel fu- eled machinery such as excavators, trucks and bulldozers. Mineral sands mines located far from existing infrastructure may have local diesel power plant to generate electricity while other mines have diesel powered back up generators. This corresponds to the reported emission shown in Table 2.3

Table 2.3: Top five largest emissions by weight, reported by Australian zircon mining companies [33] Emission % of facilities reporting Particulate matter 79.3 Carbon monoxide 79.3 Oxides of nitrogen 79.3 Sulphur dioxide 79.3 Volatile organic compounds 79.3

2.3 Mineral separation

The mineral separation is where the valuable minerals in the heavy mineral con- centrate are separated from each other, where the zirconium bearing zircon is separated from the titanium minerals and gangue. The process is unlike most other metal mining due to the almost complete lack of chemicals in the separa- tion. The processes only rely on the minerals different physical characteristics. For a full process flowchart of the separation refer to Appendix B.4. The mineral separation can be divided into roughly three stages: (see Figure 2.9).

28 • Magnetic separation • Electrostatic separation

• Gravitational separation

Figure 2.9: Overview of mineral separation

An initial magnetic separation may be performed by the WHIMS in the wet concentration, (see Section 2.2.3). Other than that the separation of heavy mineral sands occur in special Mineral Separation Plants (MSP) either at the mine site or at a separate location. Larger deposits which have a long mine life typically have their own MSP. For smaller deposits which are typically mined out in a few years the extensive infrastructure of the MSP are shared between several deposits. The HMC is typically transported by truck and barge from the mine site to the MSP. The properties used to separate the minerals are magnetic suseptability , electrical conductivity and specific gravity. The properties of the minerals most commonly found in heavy mineral deposits are shown in Table 2.4.

In the first stage of separation the HMC is passed through a rare earth magnetic roll separator where magnetic minerals are separated from the non- magnetic minerals, see Figure 2.10. The HMC feed enters the magnetic sepa- ration on a conveyour belt. The magnetic ilmenite and leucoxence are pinned to the belt by the magnet while the non-magnetic minerals such as zircon are unaffected and are thrown clear of the belt.

29 Table 2.4: Properties of minerals commonly found in heavy mineral deposits Mineral Magnetic Electrical Specific Chemical Formula Susceptibility Conductivity Gravity Ilmenite -sulphate High High 4.5-5.0 F eO.T iO2 -chloride High High 4.5-5.0 F e2O3.3T iO2 Rutile Low High 4.2-4.3 T iO2 Leucoxene Medium Low 3.5-4.1 F e2O3.T iO2.mH2O Zircon Low Low 4.7 ZrSiO4 Monazite Medium Low 4.9-5.3 (Ce, La, T h, Nd, Y )PO4 Staurolite Medium Low 3.6-3.8 F e2Al9O6(SiO4)4(O,OH)2 Kyanite Low Low 3.6-3.8 AlSiO5 Garnet Medium Low 3.4-4.2 (Mg, Ca, Mn, F e)3(Al, Cr, F e)2(SiO4)3 Quartz Low Low 2.7 SiO2 Cassiterite Low High 7.0 SnO2

Figure 2.10: Magnetic separation concept

In the second stage the non-magnetic minerals are fed through a high tension roll separator, (see Figure 2.11). The mineral feed pass an ionizing electrode where the mineral grains are ionized. The conductive minerals like rutile easily transfer their charge to the earthed metal roll and lose the ionization. The non-conducting minerals like zircon acquire an opposite electrical charge to the metal roll. This leads to an electrostatic pinning effect where the opposite charge non-conductors and roll are attracted to each other. The non-conductors pin to the roll surface until they reach the AC wiper electrode where the grains lose their charge. A plate electrode is used to widen the separation gap by giving a strong lifting effect on the uncharged conductors. The minerals are separated into different bins depending on level of electrical conductivity (EC). The zircon recovery efficiency of this process is typically 90% [23].

In the third stage the non-conductive zirconium bearing mineral is fed through a wet spiral separation for gravitational separations, (described earlier in Section 2.2.3). At this point the first crude zircon concentrate is formed. The follow- ing refinement processes intend to increase the grade of the zircon product by removing additional impurities. A second electrostatic separation removes the

30 Figure 2.11: Electrostatic separation concept remaining rutile or ilmenite and a second magnetic separation remove the re- maining monazite and garnet. Finally a gravitational separation using air or water tables remove any quartz, kyanite or staurolite to form premium grade zircon.

2.3.1 Radiological concerns Heavy mineral concentrate is rich in radioactive elements. The main source of the radioactive elements are the mineral monazite (Ce, La, T h, Nd, Y )PO4 which in Australia typically contain 5-7% thorium and 0.1-0.3% uranium [26]. The concentration of monazite in heavy mineral deposits is typically less than 1% although the concentrations may vary significantly between different loca- tions and concentrations of 2-5% are common in Indian beach deposits [34]. Monazite is usually considered a problem due to its high content of radioac- tive thorium although monazite is coextracted with zircon in India, where the monazite is used as a source of thorium. Other heavy minerals like zircon also contain uranium and thorium trapped within the lattice sturucure of the min- eral.

Raw zircon may contain 200-700 ppm uranium and 200-700 ppm thorium [35]. To meet the quality of premium grade zircon the uranium and thorium (U+Th) contents must be kept below 500 ppm. Commercial zircon typically contain 350-450 ppm (U+Th) [36]. This is ensured largly by removing monazite in the mineral separation process. The separation and concentration of monazite introduces a waste stream with increased radioactivity. The concetrated waste stream may contain over 30% monazite. This waste is returned to the mine void and are covered with several meters of overburden in the rehabilitation process. The uranium concentrations in the zircon can be compared to the

31 R¨ossinguranium mine in Namibia, one of the worlds largest uranium mines which mine a low grade deposit of 300 ppm uranium [37].

Dust containing Natural Occuring Radioactive Materials (NORM) particles is a health problem for workers in the mineral sands industry. However, focus on dust reduction such as increased use of wet processes have decreased the dose to workers in the Australian mineral sand industry from 16 mSv/y in the early 1990’s [38] to less than 1 mSv/y in the early 2000’s [3].

2.3.2 Environmental impacts Emissions reported by two Australian mineral separation plants are shown in Table 2.5. The emissions include carbon monoxide, oxides of nitrogen, partic- ulate matter, sulphur dioxide and volatile organic compounds which probably originate from the burning of fossile fuels. Some of the particulate matter and the heavy metals probably occur through dust spreading from the handling of the mineral sands. The overall direct emissions from the mineral separation plant are low. When compared to the mines, the mineral separation plant emis- sions are less than the rounding error of the mine emissions, for most substances reported.

Table 2.5: Example of substances reported from two Australian mineral sepa- ration plants [33] Substance emitted Recipient Carbon monoxide Air Chromium compounds Air Flouride compounds Air Oxides of nitrogen Air Particulate matter Air Sulphur dioxide Air Volatile organic compounds Air

The major environmental impact from the mineral separation processes is related to use of electricity. Other important impacts are the dust from the handling of the sand and the health effects of dust and radioactive particles.

2.4 Zirconium sponge production

In order to produce zirconium metal from zircon sand the strong zirconium oxide bindings have to be broken by chlorination. The zirconium have to be separated from hafnium because of their almost opposite characteristics in a nuclear re- actor environment. Subsequently, the zirconium have to be reduced into metal form and be distilled to remove impurities to form an almost pure zirconium spongelike material called zirconium sponge. The zirconium sponge production can roughly be divided into; chlorination, zirconium-hafnium separation and reduction, (see Figure 2.12).

32 Figure 2.12: Overview of zirconium sponge production

Raw natural zircon typically contain 2 wt.% [9] hafnium which need to be removed for nuclear zirconium applications. To meet the industry standards of zirconium sponge the hafnium content have to be below 100ppm [39]. The fundamental difference between ordinary zirconium metals and nuclear grade zirconium metals are the hafnium content of the metal. Since zirconiums and hafniums extremly similar chemical properties, there is no need to remove the hafnium for appllications in the chemical process industry. However, because of the almost opposite physical properties hafnium need to be removed for nuclear applications.

Natural occurring zirconium is a mixture of 5 stable isotopes with a total thermal absorption cross section of 0.19 barn. Natural occuring hafnium is a mixture of 5 stable isotopes with a thermal absorption neutron cross sec- tion of 104 barn. This means that hafnium have an almost 600 times greater probability of absorbing a thermal neutron than zirconium. In a nuclear re- actor environment hafnium is considered a reactor poison because of the large cross-section. Hafnium is actually used in control rods to absorb neutrons. To improve the neutron economics in the nuclear reactor, i.e. losing fewer neutrons, the naturally occurring hafnium have to be removed. This is performed in the zirconium-hafnium separation process, (see Section 2.4.1).

Zirconium and hafnium have very similar chemical properties. They have the same valences and their ionic radii differ by only 2% due to the lanthanide contraction [40]. This make the separation of the two metals very difficult.

33 There exist several more or less commercial techniques for the separation of zirconium from hafnium. The major techniques can be divided into liquid- liquid solvent extraction, extractive distillation and ion-exchange separation. However, only the liquid-liquid extraction and the extractive distillation will be described in detail in this report since they are the techniques used by the major western zirconium producers.

2.4.1 Zirconium-hafnium separation process Both the liquid-liquid extraction and the extractive distillation require the zir- conium and hafnium to be chlorinated to form zirconium and hafnium chloride (ZrCl4, HfCl4). The raw zircon sand is fed to a fluidized bed carbo-chlorinator where the zircon reacts with coke and chlorine at temperatures of 1200◦C to from the Zr,Hf,Si-tetrachlorides and carbon monoxide, according to 2.1.

ZrSiO4, (HfSiO4) + 4 Cl2 + 4 C −−→ ZrCl4 + SiCl4, (HfCl4) + 4 CO (2.1)

The Zr,Si,Hf-tetrachloride fumes are condensed to remove the silicon tetra- chloride which condense at higher temperatures than the zirconium and hafnium chlorides [41]. The silicon tetrachloride can be used in the production of pure silicon for the semiconductor industry. The Zr,Hf-tetrachlorides are condensed and are ready for zirconium-hafnium separation.

Extractive distillation Extractive distillation uses a counter flow technique with a column of molten salt with for the separation. This technique is currently only used in France [42]. The process use a column of molten potassium chloroaluminate (KAlCl4) salt which is heated from below. The zirconium and hafnium chlorides are ◦ dissolved by the KAlCl4 solvent at 350 C [43]. The solvent are circulated from top to bottom in a column while the zirconium-hafnium chloride fumes rise from bottom to top. The rising vapor is progressivly enriched in hafnium chlorides and the flow going down are enriched in zirconium chlorides. The enriched zirconium chlorides are condensed and extracted. The hafnium chlorides are also extracted and are further processed in similar ways to the zirconium to produce hafnium metal. The zirconium separation efficiency of this process is 98% [43].

Liquid-liquid extraction The liquid-liquid extraction exists in several forms using different solving agents. The major techniques today are the tributyl phosphate nitric acid (TBE-nitrate) process, currently used in India [44] and the methyl isobutyl ketone (MIBK) process used in USA [45]. The MIBK process allows for extraction of both zirconium and hafnium but the TBP-nitrate process only allows extraction of zirconium. In this report only the MIBK process will be decribed in detail. For a full flowchart representation of the MIBK process refer to Appendix B.8 and B.9

34 The methyl isobutyl ketone ((CH3C(O)CH2CH(CH3)2) liquid-liquid extrac- tion is a complex process with a lot of chemicals and process stages. Only the most significant steges will be described here. The process starts with the hydrolization of the zirconium and hafnium chlorides, according to 2.2).

(Zr Hf)Cl2 + H2O −−→ (Zr Hf)OCl2 + H2 (2.2)

The zirconium and hafnium oxychlorides ((Zr, Hf)OCl2) are mixed with am- monium thiocyanate (NH4SCN) and MIBK (CH3C(O)CH2CH(CH3)2). The oxychlorides complexes with ammonium thiocyanate to form (Zr, Hf)O(SCN)2. The Zr and Hf complexes have different solubility in the MIBK and are sep- arated using a column with counter flow liquid-liquid extration. The hafnium complexes end up in the organic phase which floats to the top and the zirconium in the aqueous phase in the bottom. The hafnium is from this point extracted using the same processes as for the zirconium and will not be described ex- plicitly. The extracted zirconium complexes are sent to a second column for further separation. The zirconium complexes are extracted and re-chlorinated to zirconium oxychloride (ZrOCl2), using hydrochloric acid (HCl) to remove the ammonium thiocyante.

The ammonium thiocyanate is scavenged and reused in the process. At this point the zirconium typically contain less than 50 ppm hafnium [43]. The zirconium oxychloride is precipitated using sulphuric acid (H2SO4) to form a zirconium sulphate complex (Zr5O8(SO4)2 · mH2O). Ammonium hydroxide (NH4OH) is added to the complex to form zirconium hydroxide (Zr(OH)2) ◦ which are calcined at 1000 C to form dry zirconia (ZrO2). The zirconia is carbo-chlorinated to form zirconium chloride using the same process as above, (see 2.1). The final zirconium chloride is sent on to the zirconium sponge pro- duction process. The zirconium separation efficiency of this process is 89% [43].

2.4.2 Zirconium sponge production process In the production of zirconium alloys the production of zirconium sponge is the first stage where the zirconium exist in metal form. The hafnium free zirconium tetrachloride is reduced into a porous spongelike metal, hence the name zirconium sponge. The zirconium sponge production use either zirconium chloride (ZrCl4) or zirconium oxychloride (ZrOCl2 · 8 H2O) as zirconium source. However, only the use of ZrCl4 will be described in detail. The zirconium chloride is reduced by magnesium in a furnace at 800-850◦C in the so called Kroll process, according to 2.3.

ZrCl4 + 2 Mg −−→ Zr + 2 MgCl2 (2.3)

The resulting spongelike material, called zirconium sponge, is purified by heated vacuum distillation where the magnesium chloride is removed. The magnesium chloride is evaporated, extracted and recycled by dissassociating the magnesium from the chlorine by electrolysis, according to reaction 2.4.

MgCl2 −−→ Mg + Cl2 (2.4)

35 Figure 2.13: Left: Raw zirconium sponge [46]. Right: Crushed zirconium sponge [47]

The magnesium is reused in the Kroll process and the chlorine are reused in the carbo-chlorination processes. The raw zirconium sponge is mechanically crushed into small pieces for easier handling, (see in Figure 2.13). The small pieces are packed in drums and transported to zirconium alloy producing facil- ities. The few companies which produce zirconium sponge also produce zirco- nium alloy materials but not all companies producing zirconium alloy materials produce their own zirconium sponge, (see Appendix A.2).

2.4.3 Environmental impacts When analysing the environmental impacts from the zirconium sponge produc- tion it have become evident that sponge production is an industry with few actors who are very protective of their proprietary processes. No detailed infor- mation could be aquired on which chemicals that are recovered and reused in the processes. It is hard to estimate the environmental impacts only based on the chemicals and processes used. However, when looking at two American sponge producing facilities, many of the chemicals described in this section appear in their emission reports sent to the US Environmetal Protection Agency (EPA). The reports are published in the Toxic Release Inventory database run by the EPA [48]. However since facilities with sponge production also may contain later stages in the manufacturing of zirconium alloys it difficult to be certain the emisions originate from the zirconium sponge production, since no data on production levels or production mix were available. The MIBK emissions how- ever most probably originate from the Zr-Hf separation. Examples of typical emissions from two American zirconium sponge producers are shown in Table 2.6. The ammonia in Table 2.6 may originate from the ammoinum thiocyanate

(NH4SCN), the chlorine and hydrochloric acid may originate from the clorina- tion, the MIBK is certainly from the MIBK-extraction and the nitrates may originates from the ammonium thiocyanates.

36 Table 2.6: Example of emissions reported from two American and one French zirconium sponge producer [48] [49] Substance emitted Recipient Ammonia Air & Water Chlorine Air Hydrochloric acid Air Methyl isobutyl ketone Air & Water Nitrate compounds Water

There are potentially large differences in environmental impacts from the two different zirconium-hafnium separation techniques. The extractive distillation only use one major chemical where the liquid-liquid extration uses several. The chemicals in the MIBK process are known to have its disadvantages. The cre- ation of toxic gases like hydrogen sulphide (H2S) and hydrogen cyanide (HCN) in contact with ammonium thiocyanate [50]. The MIBK solubility in water and the MIBK vapour to air and high concentrations of ammonium and cyanides in waste [45].

Perhaps the most serious environmental concern is the radioactive residue that are concentrated in the waste streams in the zirconium-hafnium separation. The radioactive waste treatment process still remain a question mark since there were no material available describing the treatment and handeling of this waste. There exist methodes for extracting the uranium into a saleable uranium product [51]. This would however introduce new demands and legislation on the producers. No references to uranium being produced by this method were found. As previously mentioned (in Section 2.2.4) the zircon may have the same uranium conentration as the low grade uranium ore. The final sponge typically contain less than 3 ppm uranium [43]. The radioactive waste stream containing the uranium and thorium may have a severe environmental impact if not treated and disposed correctly. Unfortunately no information on treatment and disposal could be obtained.

The magnesium reduction of zirconium chloride (Kroll process) and the fol- lowing heated vaccum distillation requires high temperatures and vaccum cham- bers which are energy intensive.

2.5 Zircaloy ingot production

The manufacturing of zirconium alloy products use zirconium sponge as the raw material. The first stages in the production of all zircaloy materials require the mixing of the metals to attain the right composition of metals in the alloy.

2.5.1 Zirconium alloy ingot production processes The production of zircaloy ingots starts from the mixing of zirconium sponge with the alloying metals. This is where the final composition of the alloy is de- cided, the subsequent stages may only slightly alter the chemical composition of

37 Figure 2.14: Overview of zircaloy ingot production the alloy by introducing impurities, mainly oxygen and nitrogen. The chemical composition of two of the most common zirconium alloy materials are shown in Table 2.7. Because zirconiums high melting temperature of 1852◦C and high oxidization at these temperatures zirconium is melted in vacuum arc furnaces.

Table 2.7: Chemical composition of the two most common zirconium alloys Element Zircaloy-2 Zircaloy-4 % % Zirconium 97.7-98.5 97.9-98.4 Tin 1.2-1.7 1.2-1.7 Iron 0.07-0.2 0.18-0.24 Chromium 0.05-0.15 0.07-0.13 Nickel 0.03-0.08 - Oxygen 0.1-0.14 0.1-0.14 Hafnium 0.01 0.01

The alloy and sponge mix is pressed into a semi cylindrical briquette using a hydraulic compacting press. The briquettes in their semi cylindrical form are welded together two and two to form a full cylinder using electron beam welding (EBW). The welding use a electron beam in a vacuum chamber to weld the cylinders together. The cylinders are subsequently welded together to form

38 Figure 2.15: Concept of zirconium alloy mixing, compacting and production of consumable electrode a longer rod. Recycled scrap from later stages of the production are also pressed into briquettes and comprise of up to half of the cylinders at this stage. The cylinders are welded together with approximately every second cylinder being fresh material and every second being recycled material to facilitate a uniform distribution of the alloying ingredients. The final cylinder is called a consumable electrode and is basically a gigantic welding rod, a few meters long and weighing several tonnes.

Figure 2.16: Vacuum arc remelting process

The consumable electrode is melted in a vacuum arc remelting (VAR) furnace which is basically a gigantic welding machine. The consumable electrode is fastened in the top of the furnace and the electrode is put close enough to the bottom of the water cooled copper mold to enable a spark gap, (see Figure

39 2.16). The copper mold is filled with recycled zirconium scrap in the bottom to avoid spark from the electrode to the copper which would introduce copper contaminants. Several kilo ampere of DC-current is fed through the electrode which is continuously fed downwards to keep a static spark gap between the electrode and the molten zirconium forming at the bottom. To prevent sparks from the electrode directly to the copper the distance from the electrod to the mold is larger in diameter than the spark gap. This is important since the large currents used are sufficient to burn a hole in the copper mold in just a few seconds. Since the copper mold is water cooled this would lead to injection of water into the over 2000◦C molten zircaloy where the water would turn into steam. This would lead to an initial steam explosion followed by a hydrogen explosion since the zirconium oxidization occurring at these temperatures would release large amounts of hydrogen. During normal operation the vacuum in the furnace is kept below 1 Pa and the fumes releases in the melting process are fed through a water scrubber before releasing to air.

When the hot ingot have cooled down to handling temperatures it is cut up into cylindrical briquettes and once again welded together using a EBW machine. This is to mix the different sections of the ingot and get a more uniform melt in the next round of VAR. This process of melting, cutting and welding is repeated three times or more until final alloy uniformity is reached. When the ingot alloy composition is sufficiently uniform the ingot is cut and machined into its final dimensions, removing sharp edges at the top en bottom of the ingot and removing any surface copper contaminants from the mold. After this the ingot is ready to be forged into whatever form is required. The ingot may be forged into billets for bar and tube production, sheet for spacer and channel production, wire for spacer production etc., (as seen in Figure 2.17). However, only the tube production will be described in this report.

Figure 2.17: Production of zirconium alloy materials

2.5.2 Environmental impacts The major impacts from the ingot production process is related to the electricity required to operate vacuum arc remelting furnace, the electron beam welding machine and related vacuum pumps. The vacuum arc melting produces minor

40 ammounts of metal fumes which are evacuated through the vacuum pumps and passed through a scrubber before release into atmosphere. The direct emissions related to these processes appear to be low.

2.6 Zircaloy tube production

Zircaloy tube production can roughly be divided into forging of the ingot, extru- sion and pilgering as described in Figure 2.18. Through all these stages there is high requirements on the molecular structure of the zirconium, since the struc- ture is the base for the corrosion resistance. Hence the production of nuclear grade ziraloy tube require additional processing than conventional zirconium alloys.

Figure 2.18: Overview of zirconium tube production

2.6.1 Zircaloy tube production processes The first step in zircaloy tube production is the forging of the ingot. The forging require the heating of the zircaloy material into the α and β phases. In the α- phase the metal recrystalize and the metal lattice is hexagonal. In the β-phase the lattice structure change into body centered cubic. In general the plasticity and workability of the material increase with temeperature but so does the oxidation. To minimize the oxidation and keeping the oxygen levels of the final product low the temperature is kept as low as possible while still maintaning

41 sufficient workability of the material. To begin the forging the ingot is heated in a furnace to about 1050◦C to reach the β-phase in which the ingot is forged to a round log with a diameter of approximately 350 mm [43]. For the forging down to the final dimension the log is reheated in the furnace to about 750◦C to reach the α-phase. In this phase the fusion structure can be broken down to homogenize structure of the log. The log is subsequently forged down to its final diameter of approximately 180 mm [43]. After cooling the log is cut up into smaller cylinders called billets which are approximately 400 mm long. The billets are subsequently pierced using a drill to form hollow billets.

Figure 2.19: Left: Preheating of zirconium ingot in a furnace, Right: Reducing zirconium ingot diameter by forging

To achieve the proper corrosion resistance the hollow billets are beta-quenched. Beta-quenching is a process where the metal is heated to its β-phase and then rapidly cooled down. The beta-quenched billet is machined to its final dimen- sions using lathes. The final hollow zircaloy billet is extruded to tube shells. The extrusion requires special lubricants or coatings on the billets. The coating need to be ductile, reduce friction and prevent oxidization of the zirconium. Commonly used coatings are glass or copper which are applied to the hollow billets [52]. In the extrusion process the hollow billet is pressed through a die to reduce the diameter and elongate the billet into a seamless tube called tube reduced extrusion (TREX), (see Figure 2.20).

The crude extruded tube shells (TREX) are straightened by roll straightening. The ends are cut off and the cuts are smothened to remove burrs. The cut off end pieces are recycled and used either in the VAR furnace or compacted into briquettes. The TREX have to be cleaned in acid baths to dissolve the coatings, this acid bath process is called pickling. For copper coatings nitric acid is used [52].

The tube shells diameter is reduced in an inintial cold pilgering where a grease lubricant is used. The reduced tube which is elongated is cut into lenght and the discarded end pieces are recycled. The cut tubes are pickled in acid baths of hydrogen flouride and nitric acid to remove pilgering grease. The cold pilgering adds strain to material which need to be removed by a heat treatment called annealing. The annealing requires the zirconium to be heated up to 750◦C to

42 Figure 2.20: Extrusion process reach the α-phase where the material recrystalize and built up strain is released. The tubes are annealed in a vacuum furnace to avoid oxidization. Subsequent to annealing the tubes are straightened using roll straightening in which the tubes are rolled on large metal cylinders. These steps of cold pilgering, pickling, annealing and roll straightening are performed three or more times until the final dimensions of the tube is reached.

When the tubes have been reduced to their final diameter they are sand- blasted to smoothen the surface. A final pickling is performed to remove any contamninats before the tubes are cut into final lenghts and shipped to the nuclear fuel manufacturing plant.

Figure 2.21: Cold pilgering, pickling, annealing and straightening process

2.6.2 Environmental impacts The major impacts from the zirconium tube production is related to use of acids in the pickling. Unfortunately this study were unable to analyze waste handel-

43 ing and only reported emission could be obtained. Some of the most notable emissions are shown in 2.8. However, since some of the facilities producing zir- conium alloy tube also may produce other products it is difficult to be certain that all emissions are related to the zirconium alloy tube production.

Table 2.8: Example of emissions reported from two American and one French zirconium alloy tube producer [48] [49] Substance emitted Recipient Chlorine Air Hydrogen flouride Air Hydrochloric acid Air Nitrate compounds Water Nitric acid Air

The releases of hydrogen flouride, nitric acid in Table 2.8 are most probably from the pickling processes. The releases of chlorine, hydrochloric acid and nitrate compounds are probably also related to the pickling processes. The production of zirconium alloy tubes require several heating stages which are energy consuming. Depending on the energy source used for the different heating stages the environmental impact may vary significantly depending on if it is electicity from water power or directly burned fossile fuels used.

44 Chapter 3

LCA of zirconium production

To be able to quantitatively describe the environmental impacts of the produc- tion of nuclear grade zirconium alloy materials, a life cycle analysis (LCA) was carried out. The goals of this LCA study were to determine the emissions and resource consumption for the production of 1kg of zirconium alloy tube. The aim was to be able to compare the results with the current LCA from Vatten- fall’s Forsmark nuclear power plant (NPP) found in the Forsmark EPD [53]. To analyze the impact zirconium alloy production have on the environmental impacts of the production of 1 kWh of electricty. Unfortunately only the zircon production could be analyzed in detail, due to lack of data form the zirconium metall producing industries.

The emissions include lots of different substances with different environmen- tal effects. To be able to compare and communicate the the effects of a large number of substances their effects are classified into a few environmental impact categories (EIC) such as greenhouse gases, acidifying substances etc. The EIC provides a plattform for easy comparison of different activities. The general concept of how environmental impact categories are explained in Figure 3.1. Substances may affect several different EIC and have different impacts on dif- ferent EICs. I.e. Sulphur dioxide is both an ozone creating substance and an acidifying substance. All substances affecting an EIC are muliplied by a cor- responding weight factor and are summed to calculate the total environmental impact.

The data needed to quantitatively determine the impacts from the production of any product are the emissions from the production, the resource consumption and the production levels. However, since companies produce multiple products the emissions have to be allocated amongst the products. This allocation can be performed in several different ways, the method chosen by Vattenfall and used in this study is the allocation by market price. To be able to perform this allocation the total production of different products and their respective prices have to be known.

45 Figure 3.1: Concept of environmental impact categories

3.0.3 Data sources To gather data on the production, emissions, resource consumption, production mix and product prices the idea came to contact companies involved and send out a survey where they were to answer questions about their environmental performance. Regrettably there was a very low interest for this kind of study in the industry when first approached. After repeated contact attempts and rejections only a few zircon mining companies showed any interest in joining such a survey. All with the concern only to join if the number of participants were large enough to allow them not be singled out to avoid disclosing prorietary data. There were no replies from the zirconium sponge and alloy industries. Unfortunately the number of responses were to low to statistically guarantee that no single company could be identified and the survey were discontinued.

Fortunately there are a lot of statistics available online through company annual and environmental reports and governmental agencies around the world, at least in the countries which have more transparent policies. The types of sources available are; environmental protection agencies to which companies have to report emissions, geological surveys which keep track on production of minerals and mineral prices, company annual and environmental reports which may include emissions, resource consumption and production. This study is based entirely on this kind of publicly available sources. However the study is

46 limited to include only the mining and production of zircon, since there were no available data on production levels or product prices from the zirconium sponge and alloy producers.

3.1 LCA of zircon production

To perform a LCA of zircon production six companies were analyzed, four in Australia, one in Mozambique and one in South Africa, (as shown in Table 3.1). For the Australian companies there exsit facility level emission reports as well as company annual reports with company total production levels for different minerals. Since no facility level production figures could be obtained the emissions on the facility level emissions were summed to form company total emissions to enable comparison with company total production levels. For the Mozambiqan and South African companies their annual report contain some emissions and resource consumption along production levels, as seen in Appendix C. The company total emissions, production and product prices were used to calculate the emissions allocated to the production of 1 kg of zircon.

Table 3.1: Zircon mining companies analyzed in the LCA study Company Country Australian Zircon Australia Bemax Resources Limited Australia Exxaro South Africa Iluka Resources Australia Kenmare Resources Mozambique Tiwest Australia

3.1.1 Data sources The National Pollutant Inventory (NPI) [33] is database on emissions from Australian facilities. The database is run by the Australian government De- partment of Sustainabiity, Environment, Water, Population and Comminuties (DSEWPaC) [54]. Australian industrial facilities which have emissions over certain thresholds or handle hazardous substances over certain volumes are re- quired by Australian law to annually report their emission to the NPI database. The emission reports contain facility esitmates on the substances tripping the reporting thresholds, for any of the 93 substances being monitored. The sub- stances being monitored are selected based on environmental effects, human health effects and exposure. However, greenhouse gases such as carbon dioxide and ozone depleting substances are not included in the NPI data.

The data on resource consumption and greenhouse gas emissions are from the three companies Iluka Resources, Exxaro and Kenmare Resources annual reports. These three companies were the only who are publishing quantitative data on their environmental performance in their annual reports. The data published include energy consumption by fuel, CO2 emissions and water con- sumption. Data on mineral prices are from the United States Geological Survey

47 (USGS). The USGS collect data on the import and export prices of mineral commodities in the US. The pricing data are obtained from the Mineral Year Book [55] published by the USGS.

The comodity prices and the production levels are used to calculate the share of zircon production by market value according to 3.1. The share of zirconium production are used to allocate the emissions and resouce consumption between the different minerals produced. Company by company raw and intermediated calculated data are shown in Appendix C. P rod · P rice Zircon share = Zr Zr (3.1) P rodZr · P riceZr + P rodother · P riceother The formula used to calculate the emissions or resource consumption of 1 kg of zircon produced i.e. the amount of substance (emissions or resource) per kilogram of zircon produced are given in 3.2.

Substance · Zircon share Substance per 1 kg zircon produced = tot (3.2) P roductionZr The different companies substance utilization (emissions and resource con- sumption), shown in Appendix C, were combined using a weighted average to calculate the average industry emissions and resource consumption shown in Table 3.2. For each parameter in Table 3.2 the share of world production of zircon included in the sample data is displayed.

Table 3.2: Emissions and resource consumption for the production of 1 kg zircon in Australia, based on 2009 year production Impact category Unit Impact per Sample data kg zircon % of world produced production Greenhouse gases [kg] CO2-eq 9.22 E-01 37% Acidification potential [kg] SO2-eq 1.00 E-03 34% Photochem. ozone- creation potential [kg] Ethene-eq 2.56 E-04 34% Eutrophication potential [kg] Phosphate-eq 2.05 E-04 34% Particulate matter to air [kg] 1.52 E-02 34% Water usage [kg] 2.29 E+01 37% Energy usage [kWh] 2.06 E-03 35%

3.1.2 Impact on the LCA for Forsmark NPP To analyze the impact of zircon production on the life-cycle of a nuclear power plant (NPP). The results in Table 3.2 were used in the calculations of LCA from the EPD for Forsmark NPP [53]. The emissions and resource consumption for the production of 1 kg zircon were multiplied by the kilograms zircon required in the production of 1 kWh electricity from the EPD, the results are shown in Table 3.3.

48 Table 3.3: Emissions and resource consumption for the production of 1 kWh electricity form Forsmark NPP excluded zircon production compared to emis- sions and resource consumption contribution from the zircon production Impact category Forsmark emissions Forsmark emissions % Increase zircon excluded from zircon production Greenhouse gases [kg] CO2-eq 6.43 E+00 2.85 E-03 0.0443% Acidification potential [kg] SO2-eq 4.75 E-02 3.09 E-06 0.0065% Photochem. ozone creation potential [kg] Ethene-eq 5.63 E-03 7.91 E-07 0.0141% Eutrophication potential [kg] Phosphate-eq 4.90 E-03 6.32 E-07 0.0129% Particulate matter to air [kg] 1.52 E-02 1.11 E-05 0.0729% Water usage [kg] 9.77 E+03 7.07 E-02 0.0007% Energy usage [kWh] 2.50 E-02 6.43 E-06 0.0257%

None of the parameters investigated in the zircon production contributes by more than 0.1%, (as seen in Table 3.3). This implies that the zircon production as a part of the zirconium alloy production have an insignificant impact on EPD for Forsmark NPP.

49 Chapter 4

Discussion

During the work with this report the most suprising findings are not the infor- mation actually found but rather the complete lack of information in certain areas. For example, China have approximatley 10% of the world production of zircon, yet almost information no zircon production in China could be found. Overall, it is easy to find information on the mining processes but almost all information found are from a small set of companies, most of them located in Australia. When it comes to the zirconium metal manufacturing companies the case is the opposite.

The zirconium metal manufacturing industry is characterized by a situation with production overcapacity and new companies emerging and trying to es- tablish. The zirconium metal industry are very concerned about proprietary data leaking to competitors and hence gathering information on the industry processes have been very difficult. There are currently two major techniques of separating zirconium from hafnium used in the western world where the newer extractive distillation technique seem to have lower emission of chemicals than the older liquid-liquid extraction. The direct emissions of the zirconium sponge production are related to the solvents and acids used in the zirconium-hafnium separation.

The production of zirconium sponge, ingots and tubes are probably more energy intensive than the zircon mining due to all the heating stages in the melting, forging and annealing stages. Since most energy used in these stages are from electrcity the environmental impacts differ from country to country. France with a high percentage of nuclear electricity will have different emissions than the USA with a high percentage of fossile fuels. This would also imply that the zirconium alloy production might have higher emissions related to the burning of fossile fuels than the zircon mining. Unfortunately this could not be analyzed in detail.

LCA data sources The National Pollutant Inventory (NPI) data contain fa- cility level emissions but production levels found are given on company level. This means that in order to calculate company emissions the facility level emis- sion have to be summed. This however introduce a problem since it might be

50 difficult to know if a certain facility is involved in the zircon production chain. The list of facilities found in Appendix C are the facilities which have been identified or assumed to be involved in the zircon production at one or another stage. The list involves mines not yet in production or in rehabilitation as well as ports facilities for shipping and storing zircon products.

Uncertainties in LCA calculations The emissions reported to the NPI database are best estimates from the companies and are considered accurate. The reported production levels are either directly from company annual reports or governmental agencies and are therefore considered accurate. The allocation of emissions by market price introduce the uncertaities of not knowing the actual prices paid for the minerals, the matching of production reported by companies to prices monitored by the USGS are not straight forward. There are a few assumptions on the prices of different minerals as shown in the footnotes in Appendix C. These assumptions are best guesses on price levels for the chloride and sulphate slag, pig iron, scrap iron and secondary ilmeninte. Comparing leucoxene to ilmenite is conservative since leucoxene usually is considered a higher value mineral.

Further, only the average price levels for production in Australia and imports to the USA were available which further might reduce the accuracy of the prices. Overall the allocation of emissions by marketprice is not that sensitive to errors in prices since the high price of zircon. For most companies the economic im- portance of zircon over the other minerals are evident, and for most companies have a zircon share of sales of over 50%, as seen in C. Since the zircon share of sales is so high an relative high error in the price of the other minerals would have a relative low impact on the emissions allocated to the zircon production.

51 Chapter 5

Conclusions

There is almost no use of chemicals in the mining and mineral separation pro- cesses. The minerals sand are almost entirely separated using physical rather than chemical methods. The direct emissions from mining are mainly related to the use of fossile fueled machinery and disel generators as well as some spread of heavy minerals through spread of dust. The major resource consumptions for the mining operations are the large amounts of energy and water required.

Zircon mining differs from other types of metal mining as there are no prob- lems with acid mine drainage from tailings, and mined areas can often be re- shaped back into their old topology. The large environmental impacts are the vast areas cleared for mining which inevitably leads to large destruction of nat- ural habitats, often in exposed costal areas. One concern though is that dunal deposits in costal areas are often habitats with a special biodiversity. This re- quires special consideration on the operation and rehabilitation meassures to protect local, maybe endangered species. On the other hand the rehabilitation processes are well developed and used through out the industry. After the initial regrowth phase the lasting impacts to the landscape is relatively small.

Heavy mineral concentrates contain naturally occuring radioactive materials (NORM) which imposes radioactive protection meassures and the overall doses to personel and public are well within regulatory boundaries. Mineral separation produce concentrated NORM which are backfilled into the mining void and covered by several meters of overburden. Concentrated zircon contain as much uranium as low grade uranium ore. The uranium and thorium in zircon is extracted in the zirconium-hafnium separation and the final zirocnium sponge contain almost no uranium or thorium. This means that somewhere in the separation stages there must occur a waste stream enriched in uranium and thorium with concentrations similar to those in an uranium mine. The waste could be used as a source of uranium and thorium [51] but there are no sources found if this is performed or if the waste stream is just disposed of.

The major direct emissions from the zirconium metal manufacturing industry are related to the use of acids in the pickling processes. Other major emission might occur due to the large energy demand of the different heating proceses.

52 The production of zirconium sponge, ingots and tubes are potentially more energy intensive than the zircon mining and might have higher emissions of greenhouse gases.

A licecycle analysis for the zircon mining was carried out. The result from the zircon mining were compared to Environmental Product Declaration for Forsmark NPP which showed that zircon mining have a less than 0.1% impact on all analyzed parameters in a lifecycle analysis for electricity from nuclear power.

5.1 Further work

This study was unable to get data on resource consumption other than a few parameters from a few zircon mining companies. Any further study should try to obtain first hand data on resource consumption from the companies involved in the whole production chain from zircon mining to zircaloy tube production. Emission reports were only found for a few contries with transparent government agencies. Any further study should try to obtain first hand data on emissions from a more diversified set of countries and companies.

This study was unable to obtain information on production, waste treat- ment and emission mitigation measures from the zirconium sponge and metal manufacturing industry. Any further study should try establish good lasting relations with zirconium metal producing companies and have the time and patience needed to allow for the long process of getting their attention and re- cieving an answer.

Questions that remain to be answered: • How is the radioactive waste from the Zr-Hf separation treated and dis- posed of?

• How are the acids in the pickling processes treated and disposed of? • What are the production and price levels of the zirconium metal manu- facturers? • What is the resource consumption of the different production stages?

• How does the environmental performance differ between countries with diffrent environmental regulations?

53 References

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57 Appendix A

List of companies

Table A.1: List of zirconium mining companies Company Operating country Website Alkane Resources Australia www.alkane.com.au Australian Zircon Australia www.australianzircon.com.au Millenium Inorganic Brazil www.cristalarabia.com Donald Mineral Sand Australia www.donalmineralsands.com.au DuPont USA www2.dupont.com Gunson Resources Australia www.gunson.com.au Matilda Zircon Australia www.matildazircon.com.au Mineral Deposits Australia www.mineraldeposits.com.au Sibelco Australia www.sibelco.com.au Doral Mineral Sands Australia www.afm.com.au Bemax Resources Limited Australia www.bemax.com.au Kenmare Resources Mozambique www.kenmareresources.com Iluka Resources Limited Australia, USA www.iluka.com Industrias Nucleares do Brasil Brazil www.inb.gov.br Richards Bay Minerals South Africa www.rbm.co.za Titanium Corporation Canada www.titaniumcorporation.com Tiwest Australia www.tiwest.com.au Exxaro South Africa www.exxaro.com Kerala Minerals and Metals Ltd India www.kmml.com Beach Mineral Company India www.bmcindia.net Indian Rare Earths Limited India www.irel.gov.in V.V. Mineral India www.vvmineral.com Kemdel India www.kemdel.org Eurochem Russia www.eurochem.ru Titanium Resources Sierra Leone www.sierra-rutile.com

58 Table A.2: List of zirconium sponge manufacturers Zirconium sponge producers Operating country Website ATI Wah Chang USA www.wahchang.com Areva/Cezus France www.areva.com Chepetsky Mechanical Plant Russia www.chemz.net Jingan Hi-Tech China www.chinazrchem.com Nuclear Fuel Complex India www.nfc.gov.in Westinghouse Electric Company USA www.westinghousenuclear.com

Table A.3: List of zirconium alloy manufacturers Zirconium alloy producers Operating country Website ATI Wah Chang USA www.wahchang.com Areva/Cezus France www.areva.com Chepetsky Mechanical Plant Russia www.chemz.net Fine Tubes Limited UK www.finetubes.co.uk Global Nuclear Fuel USA www.gepower.com Jingan Hi-Tech China www.chinazrchem.com Korea Nuclear Fuel Company Korea www.knfc.co.kr Nuclear Fuel Complex India www.nfc.gov.in Posco Korea www.posco.co.kr Sandvik Sweden www.sandvik.com Westinghouse Electric Company USA www.westinghousenuclear.com

59 Appendix B

Production flowcharts

60 Figure B.1: Zircon mining flow chart

61 Figure B.2: Wet concentration plant flow chart (1/2)

62 Figure B.3: Wet concentration plant flow chart (2/2)

63 Figure B.4: Mineral separation plant flow chart (1/2)

64 Figure B.5: Mineral separation plant flow chart (2/2)

65 Figure B.6: Zirconium-Hafnium separation flow chart (1/4)

66 Figure B.7: Zirconium-Hafnium separation flow chart (2/4)

67 Figure B.8: Zirconium-Hafnium separation flow chart (3/4)

68 Figure B.9: Zirconium-Hafnium separation flow chart (4/4)

69 Figure B.10: Zirconium sponge production flow chart (1/1)

70 Figure B.11: Zirconium ingot production flow chart (1/1)

71 Figure B.12: Zirconium tube production flow chart (1/4)

72 Figure B.13: Zirconium tube production flow chart (2/4)

73 Figure B.14: Zirconium tube production flow chart (3/4)

74 Figure B.15: Zirconium tube production flow chart (4/4)

75 Appendix C

LCA study

Table C.1: Australian Zircon Emissions 2009 [33] Substance Emissions [kg] Particulate matter 6.77 E+05 Sulphur dioxide 2.16 E+01 Nitrogen oxides 5.37 E+04 NMVOC (unspecified) 5.07 E+03 Acidifcation Potential(a) 2.69 E+04 Eutrophication Potential(b) 6.98 E+03 Photochem. Ozone Creation Potential(c) 5.40 E+04 (a) (Nitrous oxides * 0.5) + (Sulphur dioxide * 1) (b) (Nitrous oxides * 0.13) (c) (Nitrous oxides * 1) + (NMVOC * 0.048) + (Sulphur dioxide * 0.028)

Table C.2: Australian Zircon Production 2009 [56] Substance Production [tonnes] Ilmenite 798 Rutile 2380 Zircon 9553 Zircon share(a) 86.5% (a) Zircon value of total production, calcu- lated using prices from Table C.18

Table C.3: Australian Zircon Facilities 2009 [33] Facility Location Australian Zircon Mindarie, SA

76 Table C.4: Bemax Resources Limited Emissions 2009 [33] Substance Emissions [kg] Particulate matter 1.88 E+06 Sulphur dioxide 7.40 E+02 Nitrogen oxides 2.96 E+05 NMVOC (unspecified) 2.65 E+04 Acidifcation Potential(a) 1.49 E+05 Eutrophication Potential(b) 3.84 E+04 Photochem. Ozone Creation Potential(c) 2.97 E+05 (a) (Nitrous oxides * 0.5) + (Sulphur dioxide * 1) (b) (Nitrous oxides * 0.13) (c) (Nitrous oxides * 1) + (NMVOC * 0.048) + (Sulphur dioxide * 0.028)

Table C.6: Bemax Resources Limited Facilities 2009 [33] Facility Location Broken Hills Mineral Separation Plant Broken Hills, NSW Ginko Mineral Sands Operations Pooncarie, NSW Gwindinup Operations Gwindinup, WA North Shore Operations Bunbury, WA Sandlewood Mine Benger, WA Snapper Mine Pooncarie, NSW Tutunup Operations Tutunup, WA

Table C.7: Exxaro Production 2009 [57] Substance Production [tonnes] Chloride slag 201000 Ilmenite 612000 Pig iron 181000 Rutile 46000 Scrap iron 15000 Sulphate slag 44000 Zircon 164000 Zircon share(a) 39.5% (a) Zircon value of total production, calcu- lated using prices from Table C.18, assum- ing scrap iron is priced as ferrous scrap and assuming chloride and sulphate slag is priced as titaniferrous slag

Table C.8: Exxaro Emissions and Resource Consumption 2009 [57] Substance Amount Unit CO2 1206.5 Kt Energy 5007.3 TJ Water 13029937 M 3

77 Table C.9: Iluka Resources Limited Emissions 2009 [33] Substance Emissions [kg] Ammonia 1.51 E+04 Nitrogen oxides 2.50 E+06 NMVOC (unspecified) 2.02 E+05 Particulate matter 5.12 E+06 Sulphur dioxide 7.78 E+04 Acidifcation Potential(a) 1.35 E+06 Eutrophication Potential(b) 3.30 E+05 Photochem. Ozone Creation Potential(c) 2.76 E+05 (a) (Ammonia * 1.6) + (Nitrous oxides * 0.5) + (Sulphur dioxide * 1) (b) (Ammonia * 0.33) + (Nitrous oxides * 0.13) (c) (Nitrous oxides * 1) + (NMVOC * 0.048) + (Sulphur dioxide * 0.028)

Table C.10: Iluka Resources Limited Production 2009 [58] Substance Production [tonnes] Ilmenite (saleable) 342100 Ilmeinte (upgradable) 496700 Rutile 141400 Zircon 263100 Zircon share(a) 63.1% (a) Zircon value of total production, calculated using prices from Table C.18, assuming same price for sal- able and upgradable ilmenite

Table C.11: Iluka Resources Limited Facilities 2009 [33] Facility Location Bunbury Wharf Bunbury, WA Capel Capel, WA Douglas Mineral Sands Mine Douglas, VIC Eneabba East Eneabba, WA Geraldton Wharf Geraldton, WA Gingin Mine Site Gingin, WA Hamilton Mineral Separation Plant Hamilton, VIC Jacinth Ambrosia Mine Site Nullarbor, SA Kulwin Mineral Sands Mine Ouyen, VIC Nargulu Narngulu, WA Wagerup Mine Waroona, WA Waroona Mine Site Waroona, WA Yoganup West Capel, WA

78 Table C.12: Iluka Resources Limited Emissions and Resource Consumption 2009 [58] Substance Amount Unit CO2 1078 Kt Energy 10945 TJ Water 36478 M liters

Table C.13: Tiwest Emissions 2009 [33] Substance Emissions [kg] Ammonia 1.18 E+05 Nitrogen oxides 3.83 E+05 NMVOC (unspecified) 3.23 E+04 Particulate matter 3.00 E+06 Sulphur dioxide 1.14 E+06 Acidifcation Potential(a) 1.52 E+06 Eutrophication Potential(b) 8.87 E+04 Photochem. Ozone Creation Potential(c) 4.16 E+05 (a) (Ammonia * 1.6) + (Nitrous oxides * 0.5) + (Sulphur dioxide * 1) (b) (Ammonia * 0.33) + (Nitrous oxides * 0.13) (c) (Nitrous oxides * 1) + (NMVOC * 0.048) + (Sulphur dioxide * 0.028)

Table C.14: Tiwest Production 2009 [57] Substance Production [tonnes] Ilmenite 414000 Leucoxene 28000 Rutile 32000 Zircon 66000 Zircon share(a) 54.3% (a) Zircon value of total production, calcu- lated using prices from Table C.18, assum- ing leucoxene is priced as ilmenite

Table C.15: Tiwest Facilities 2009 [33] Facility Location Bunbury Port Authority Vittoria, WA Chandala Muchea, WA Cooljarloo Cataby, WA

79 Table C.16: Kenmare Resources Production 2009 [59] Substance Production [tonnes] Ilmenite 471500 Rutile 1800 Zircon 21100 Zircon share(a) 34.7% (a) Zircon value of total production, calcu- lated using prices from Table C.18

Table C.17: Kenmare Resources Emissions and Resource Consumption 2009 [59] Substance Amount Unit CO2 76228 tonnes Electricity 82724 kWh Water 3840 M liters

Table C.18: USGS Mineral Prices 2009 [55] Substance Price [USD/tonne] Ilmenite, F.O.B. Australian port 73 Ferrous scrap, import 237 Pig iron, all grades import 262 Rutile, bulk F.O.B. Australian port 533 Titaniferrous slag, import, 80% to 95% T iO2 420 Synthetic Rutile, US Import 318 Zircon, Australia 890

80