15
Best Available Technologies and Environmental Practices for the Recycling of ULAB Slide Slide Notes 3 Best Available Technologies and Environmental Practices for the Recycling of ULAB 4 The last meeting of the Basel Convention Open Ended Working Group in 2020 voted unanimously to update the Technical Guidelines and an updated version has been submitted to the Basel Secretariat, but it will be up to the next Conference of the Parties to decide whether to adopt it or not. In addition, the Training Manual is also being updated as part of a UNEP ULAB project in Africa and a Basel Secretariat project in Central and South America. The content of this presentation is based on the revised versions of both documents 5 One of the new sections in the Technical Guidelines is smelter location. Necessary, because so many ULAB recycling plants are in locations that are totally unsuitable. So do not locate a recycling plant: × In a valley or a flood plane × On top of a mine site or rubbish dump × In an area known for seismic or volcanic activity × At a site without reliable utilities – such as electricity × At a site without good road or rail access × Close to a hospital, food outlet, farmland, school, community housing or a water source 6 So where might you locate a ULAB recycling plant: In a designated Industrial Zone that has – Reliable utilities, water, fuel, electricity Is close to and links with a good road network Stable topography and no history of flooding No farmland in the immediate vicinity No sensitive flora or fauna in the area Adequate space to expand operations 3 Best Available Technologies and Environmental Prac�ces for the Recycling of Used Lead Acid Ba�eries 4 Best Available Technologies and Prac�ces 4 5 Best Available Technologies and Prac�ces 5 6 Best Available Technologies and Prac�ces 6

Best Available Technologies and Environmental Practices

  • Upload
    others

  • View
    2

  • Download
    0

Embed Size (px)

Citation preview

Best Available Technologies and Environmental Practices for the Recycling of ULAB

Slide Slide Notes

3

Best Available Technologies and Environmental Practices for the Recycling of ULAB

4

The last meeting of the Basel Convention Open Ended Working Group in 2020 voted unanimously to update the Technical Guidelines and an updated version has been submitted to the Basel Secretariat, but it will be up to the next Conference of the Parties to decide whether to adopt it or not. In addition, the Training Manual is also being updated as part of a UNEP ULAB project in Africa and a Basel Secretariat project in Central and South America. The content of this presentation is based on the revised versions of both documents

5

One of the new sections in the Technical Guidelines is smelter location. Necessary, because so many ULAB recycling plants are in locations that are totally unsuitable. So do not locate a recycling plant:

× In a valley or a flood plane × On top of a mine site or rubbish dump × In an area known for seismic or volcanic activity × At a site without reliable utilities – such as

electricity × At a site without good road or rail access × Close to a hospital, food outlet, farmland,

school, community housing or a water source 6

So where might you locate a ULAB recycling plant: In a designated Industrial Zone that has – Reliable utilities, water, fuel, electricity Is close to and links with a good road network Stable topography and no history of flooding No farmland in the immediate vicinity No sensitive flora or fauna in the area Adequate space to expand operations

3

Best Available Technologies and Environmental Prac�ces for the Recycling of Used Lead Acid Ba�eries

4

Best Available Technologies and Prac�ces

4

5

Best Available Technologies and Prac�ces

5

6

Best Available Technologies and Prac�ces

6

7

Part 1: ULAB Collection, Storage and Transportation

8

If we just remind ourselves that the HSE matrix requires ULAB to be collected whole and complete with acid electrolyte and transported in such a manner that the electrolyte will not leak into the environment. Breaking must not be manual and effluent should not be discharged. Emissions must be controlled and ideally there should be no hazardous waste.

9-10

The key processes involved in the recycling of ULAB are collection, transportation, reception, breaking, where the plastic case material and the electrolyte are separated from the Lead components, smelting where most of the impurities are removed and referred to the slag and also where fume and dust are generated, and finally refining where the last traces of impurities are removed and returned to the process. The focus in this section is collection and transportation

11-13

The most effective way to collect ULAB and ensure that they are recycled in an environmentally sound manner is by introducing Extended Producer Responsibility or EPR. EPR places the responsibility for the environmentally sound management of LAB and ULAB on the manufacturer and it operates as a closed loop system that is a model for the circular economy. EPR uses reverse logistics to collect ULAB from retailers when deliveries of new LAB are made. In the case of imported LAB, the importer is responsible for ensuring that all the imported LAB are collected and delivered to a licensed smelter.

14

Apart from making the LAB Manufacturer or the Importer responsible for the ESM of ULAB, EPR also requires that manufacturers: Source raw materials from legitimate and ESM

suppliers Never purchase Lead from an informal recycler

or a dealer linked to informal recycling.

7

Best Available Technologies and Prac�ces

7

8

Best Available Technologies and Prac�ces

ULAB Collec�on Closed Loop ULAB Undrained Transporta�on Plas�c Container Leak Proof

Temporary Storage Under Cover No LeakageULAB Breaking Saw/Hammer Mill Not Manual

Electrolyte Neutralisa�on No DischargeRecycling Ven�lated Smel�ng Emission Control

By- Products Inert Products No Hazardous Waste

8

10

Best Available Technologies and Prac�ces

ULABCOLLECTION

ULABTRANSPORTATION

ULABRECEPTION

ULABBREAKING/SAWSMELTINGREFINING

ACIDPLASTICFUMESLAGLEAD DROSS

10

13

Best Available Technologies and Prac�cesPb Ingots

ULAB

ULAB

ULABLAB

Domse�c LAB Manufacturers

LAB Distribu�on

Network

LAB Sales Outlets

LAB Users

Domes�c ULAB Recycler

LAB

Scrap Dealers

Importers’ LAB Distributors

Importers’ & Independent LAB Retailers ULAB

LAB

LAB

ULAB

ULAB

IndependentULAB

Collectors

ULAB

ULAB

LAB Importers

LAB

LAB

Closed LoopEPR

Reverse Logistics

14

Best Available Technologies and Prac�ces

Extended Producer Responsibility - EPR 14

15

Certain automotive and energy storage ULAB can weigh 50 kilos or more, and so, it is essential to adopt the correct packing techniques when the ULAB are prepared for transport.

16

The electrolyte should not be drained from the ULAB. When ULAB are prepared for transportation whether in a container or on a pallet, they should be arranged in layers of equal height to minimize movement during transit. If the ULAB are stacked on a pallet, then the corrugated cardboard layered between new LAB when they are delivered to retailers, should be placed between each layer of ULAB to minimize movement and absorb any electrolyte that might leak during transportation.

17

Ideally, all LAB should have the terminals or posts recessed into the top of the battery such that the terminals do not protrude. This prevents the terminals puncturing the case of a ULAB placed on top of it during transportation.

17

In summary, the HSE risks associated with the illicit dumping of the Battery electrolyte are:

× It is classified as a Hazardous Waste under the Basle Convention

× It is an irritant to the skin and internal organs. × It can cause blindness if splashed into the eyes. × It is a carcinogen. × It is so corrosive – it will dissolve concrete.

19

If all the procedures so far described are followed, ULAB ready for transportation on a pallet should be shrink wrapped and strapped - And look like this…

20

ULAB that are either leaking or damaged such that they might leak in transit must be placed securely into a leak proof container.

15

Best Available Technologies and Prac�ces

15

16

Best Available Technologies and Prac�ces

16

18

Best Available Technologies and Prac�ces

18

19

Best Available Technologies and Prac�ces

19

20

Best Available Technologies and Prac�ces

20

21-23

Increasingly, ULAB are being collected and transported in UN Certified leakproof containers and the benefits are: UN Certified as a leakproof design It can be used in any vehicle, not only one

licensed to carry hazardous waste It is Lightweight It is Fork truck friendly The containers are stackable They are reusable and recyclable

24-25

A collapsible version from Australia that can be stacked four high when empty, making distribution easier and cheaper is also UN Certified and comes: Regulation compliant Has UV, acid and rain resistant panels. Ergonomically designed to load from the front. With a 25 litre bund in the base to contain any

electrolyte leakage Has six lockable latches

26

Ideally, ULAB should be stored undercover as shown here in Tanzania.

27

Internal floors should be resin coated and sealed to ensure they are impermeable to acid as we see here in this example in China.

28

Plastic containers can be stacked, but if the ULAB are packaged on pallets, they can be stacked in racks as seen here in Central America.

29

Wherever ULAB are stored provision must be made for a sump where any spillage of battery electrolyte can drain. In the example shown the sump pump used to remove any spillage is powered by a ULAB that still has some useful life.

30

ULAB are classified as a hazardous waste and so any vehicle transporting ULAB must display the appropriate Hazchem decals and an emergency contact number.

25

Best Available Technologies and Prac�ces

25

Regula�on compliant

UV, Acid & Rain Resistant Panels

Ergonomic front loading of ULAB

25 litre bund for any spillage

6 lockable latches

Collapsible and can be stacked 4 high for

distribu�on

26

Best Available Technologies and Prac�ces

26

Best Available Technologies and Prac�ces

27

Best Available Technologies and Prac�ces

27

Best Available Technologies and Prac�ces

28

Best Available Technologies and Prac�ces

28

Best Available Technologies and Prac�ces

29

Best Available Technologies and Prac�ces

29

Best Available Technologies and Prac�ces

30

Best Available Technologies and Prac�ces

30

31

ULAB must never be stacked loose into the back of a truck. The pallets or plastic containers should be chocked and secured to minimize movement during transit.

32

UN Certified ULAB containers can be transported in any truck, but the Hazchem decals must be displayed, and the containers secured as shown.

33

Part 2: ULAB Breaking

34

In this section the focus is ULAB reception and breaking.

35

Lithium-Ion batteries must be removed from the breaking process, and for good reason, but this is not an easy matter because so many Lithium-Ion batteries are similar in shape and size to LAB.

36

If a Lithium-Ion battery enters the breaker’s hammer mill or saw, it will explode as we see here in this video from a recycling plant in the USA.

37

All too often when I visit small and medium sized ULAB recycling plants, I find the ULAB are broken manually with either axes, machetes, or hammers. Manual breaking is unsafe, unsound and unnecessary and should be avoided completely.

38

More efficient and safer is a ventilated Battery Saw. The electrolyte has to be drained into the ETP prior to dismantling and blades need to be adjusted to the height of the ULAB. The top cover is removed by the saw and the Lead bearing components are released from the battery case. However, the battery saw cannot separate the battery grids from the paste.

31

Best Available Technologies and Prac�ces

31

32

Best Available Technologies and Prac�ces

32

33

Best Available Technologies and Prac�ces

SOMALIA

33

34

Best Available Technologies and Prac�ces

ULABCOLLECTION

ULABTRANSPORTATION

ULABRECEPTION

ULABBREAKING/SAWSMELTINGREFINING

ACIDPLASTICFUMESLAGLEAD DROSS

34

35

Best Available Technologies and Prac�ces

35

36

Best Available Technologies and Prac�ces

36

Separate and

remove used Li-

ion ba�eries

from ULAB

Li-ion ba�eries

can explode if they pass through a breaker

37

Best Available Technologies and Prac�ces

Unsafe

Unsound

Unwise

No

Manual

Breaking

37

38

Best Available Technologies and Prac�ces

Electrolytemust

be drainedto the

ETPprior to entering the saw

SawBladesmustbe

adjustedto the

height ofthe ULAB

38

39

Ideally, the ULAB should be broken using an automated mechanical hammer mill. Unlike the battery saw, the ULAB are fed onto the conveyor and into the beaker whole and complete with electrolyte. A manual feed to the conveyor is recommended to ensure that Lithium-Ion batteries are not charged to the breaker.

40

The breaker will then separate the plastics, the paste, and the grids through a hydro-gravitational process.

41

The plastic cases, normally polypropylene, are broken into small chips and before they are ejected from the breaker, they are washed and rinsed to remove any Lead Oxides.

42

Whilst the industry has welcomed the growth in Energy Storage over the past 20 years, the fact that so many of the solar and invertor batteries weigh 50, 60 or even 70 kilos means the standard 14 kilo automated breaker is not going to cope with these huge LAB.

43

So, a new generation of hammer mill automated breakers is required to deal with the new generation of energy storage batteries.

44

Here we can see one of the new breakers capable of crushing 70 kilo ULAB.

45

As you now know, 18% or more of the weight of a LAB is dilute sulfuric acid and if dumped into the environment or released without treatment from a ULAB recycling plant, rivers, lakes and water sources will be contaminated.

39

Best Available Technologies and Prac�ces

Electrolytemust not

be drainedfrom the

ULABprior to entering the mill

39

Manual charging to

Ensure Li Ion

Ba�eries are not

processed

40

Best Available Technologies and Prac�ces

40

GridMetallics

Best Available Technologies and Prac�ces

41

Best Available Technologies and Prac�ces

41

Plas�cSepara�on

42

Best Available Technologies and Prac�ces

42

43

Best Available Technologies and Prac�ces

43

44

Best Available Technologies and Prac�ces

44

45

Best Available Technologies and Prac�ces

ULAB Electrolyteis dilute Sulfuric

Acid. It is corrosive and

Destroys Eco -Systems

45

44

Ideally, the best solution is to have a closed loop, such that any process effluent is contained in an ETP, and not discharged from the site.

47

But you cannot store effluent forever, so the solution is to treat the effluent such that a Lead-free saleable product is produced……

48

…..and there are three products that can be considered, sodium sulfate, Calcium sulfate or Gypsum, or Ammonium sulfate fertilizer.

49

In Kenya, the ABM plant’s ETP is producing Gypsum for the cement industry.

50

IN Brazil, Antares produce Gypsum for the agricultural industry, because in a granular form it is: A soil improver and conditioner That promotes root growth. And increases productivity.

51

It is most important before deciding which effluent treatment process to install, that market research is conducted thoroughly to determine which effluent product option is applicable to the country and the location.

52

When designing and constructing an ETP consideration must be given to climate and the prevailing weather conditions, particularly if there is a rainy season. The last thing we want is for flood water to overwhelm the ETP such that effluent is discharged into the flood water.

53

So, it is necessary to elevate the ETP process tanks so that they are above the highest recorded flood levels.

46

Best Available Technologies and Prac�ces

46

47

Best Available Technologies and Prac�ces

Electrolytemust

be treatedin an

ETP toproduce asaleable

by-product

Eco -friendlyprocesswithout

any discharges

47

50

Best Available Technologies and Prac�ces

• Glass Making • Paper Making

• Building Industry - Cement• Agriculture – Soil improver

• Fertilizer

50

50

Best Available Technologies and Prac�ces

50

53

Best Available Technologies and Prac�ces

53

51

Best Available Technologies and Prac�ces

• Glass Making • Paper Making

• Building Industry - Cement• Agriculture – Soil improver

• Fertilizer

51

52

Best Available Technologies and Prac�ces

52

Monsoon Rains and

Floods can overwhelm

an ETP and result in

widespread pollu�on

49

Best Available Technologies and Prac�ces

49

Mi�ga�ng the effects

of flooding and

monsoon rains

Best Available Technologies and Prac�ces

54

Any acid free and neutral effluent left over from the ETP process can be used as a coolant for the ingots during casting of the refined Lead or alloys. It can also be used to damp down any dusty areas of the plant.

55

In this section the focus is Smelting.

56

If the ULAB are broken using a Battery Saw the furnace charge will be a mixed feed of metallic plates or grids and battery paste. A mixed feed operation is energy inefficient because the Grids only need a melting operation and do not required 3 hours or so of smelting. The furnace bullion contains alloying metals and so refining to 99.97 or 99.99% purity takes longer and requires more energy and reagents.

57

ULAB breaking using an automated Hammer Mill separates the Grids and the Paste. This means the grids can be processed through a melting furnace operation and the paste can be processed through a smelting operation.

58-59

If ULAB throughput is sufficient to justify a twin furnace operation, then one furnace can be dedicated to smelting paste and should therefore always produce bullion that is close to pure Lead and requires the minimum of refining. The second furnace should be used to melt the grids, but because melting the grids takes a lot less time than smelting, the second furnace will have spare capacity and so when it is not melting grids, it can be used to process the baghouse dust, refining drosses and any other Lead bearing process by-products.

60

Processing the grids through a melting furnace and the paste through a smelting operation will result in a grid bullion that contains alloying metals and paste bullion that is almost 99% pure. Ideally the grid bullion should be refined to produce grid alloys and the paste to produce pure Lead to 99.97 or 99.99% purity. Segregated furnace processing and refining uses approximately 70% less fuel to process the grids and consequently results in a similar reduction in Green House Gasses.

54

Best Available Technologies and Prac�ces

54

55

Best Available Technologies and Prac�ces

SOMALIA

55

56

Best Available Technologies and Prac�ces

No Segrega�on of Ba�ery Components:

Grid Metallics and Ba�ery Paste mixed feed

Smel�ng: Single Furnace opera�on – Energy Inefficient

Because - The Grids only require mel�ngAnd - Furnace bullion requires more energy to refine

56

57

Best Available Technologies and Prac�cesSegrega�on of Ba�ery Components:

Grid Metallics Ba�ery Paste

Processing:

Grid Metallics – Mel�ng furnace Paste – Smel�ng furnace

57

59

Best Available Technologies and Prac�ces

ULABCOLLECTION

ULABTRANSPORTATION

ULABRECEPTION

ULABBREAKER

FURNACE 2GRID MELTING

ACIDPLASTICFUMESLAG

FURNACE 1 PASTE SMELTING

GRID ALLOYS

PURE LEAD

DROSS

PURE LEAD INGOTS

LEAD ALLOY INGOTS

59

60

Best Available Technologies and Prac�ces

Segrega�on of Ba�ery Components:

Processing:

Approximately 70% less fuel Lower Green House Gas Emissions

A One or Two Furnace Opera�on?

60

61

There are three basic configurations for a Rotary furnace. This one has the burner and the tap holes in the front.

62

This furnace has the burner mounted at the rear of the drum.

63

This configuration has the tap holes in the centre of the drum.

64

For those smelters with a centre tapping port, the only way to effectively contain the fume emissions during tapping is to encapsulate the whole furnace and keep it completely enclosed during tapping.

65

In this video clip from a smelting operation in the Philippines, the fume and dust are contained when the access doors to the metal pot are closed.

66

For rotary furnaces with tapping ports at the front of the drum, ventilation hoods should be mounted at the rear to contain any rouge combustion emissions and the front to capture dust emissions during charging and tapping.

67

In this clip from a recycling plant in the Dominican Republic, the molten Lead is being tapped from one of the front tapping ports through an insulated and enclosed ventilated launder into a crucible located to the right of the furnace. Normally the doors would be closed during tapping and are only open to allow filming of the fume and dust containment.

61

Best Available Technologies and Prac�ces

Tap hole

Tap holeDoor

Burner

61

62

Best Available Technologies and Prac�ces

Door

BurnerTap hole

Tap hole

62

63

Best Available Technologies and Prac�ces

Tap hole

Tap holeDoor

Burner

63

65

Best Available Technologies and Prac�ces

65

Dust and fume is captured by the

extrac�on system and the doors are

closed during tapping

66

Best Available Technologies and Prac�ces

Front ven�la�onfume and

dust capture

Rear ven�la�onfume and

dust capture

66

67

Best Available Technologies and Prac�ces

Front Tap Hole 67

Molten metal is tapped

to a holding ke�le

Front ven�la�onfume and

dust capture

68-69

Whilst the Rotary furnace technology is the most versatile, there are many alternatives. One such alternative is the Ausmelt / IsaSmelt furnace. This is an upright furnace: With a submerged fuel and oxygen lance. It is a two-stage process for metal and slag. It operates at 1,250o Celsius. Best suited to processing battery paste. Produces pure Lead bullion. Slag is removed at 1,500 o Celsius. High throughput is required to be viable.

70-72

This is the bottom blown SKS furnace that was developed in China. This is a two-stage oxygen blown process. Produces Lead bullion and a high Lead slag. Can process primary and secondary feedstock.

73

What is not always understood is the difference between Lead Dust and Lead Fume. Lead fume particles range between 0.1 and 0.7 microns, and Lead Dust ranges from 0.8 to 500 microns. When workers require respirators to provide additional protection against dust or fume, the standard is an N95 mask or equivalent that can capture 95% or more of all particles over 0.3 microns.

74

Lead fume is generated when the temperature of Lead is over 500o Celsius and the problem is that fume is invisible to the naked eye and so operators sometimes believe a working environment to be Lead free, when in fact it is at its most unhygienic and harmful.

75

Uncontrolled furnace emissions will contaminate the environment and lead to widespread population exposure.

76

The tried and tested process of dust capture is to use a filter plant or Baghouse. The filtration processes can vary between ceramic filters, fabric filter bags and electrostatic precipitators, but the principles are the same.

69

Best Available Technologies and Prac�ces

69

Submerged lance – Fuel + O2

One stage processOperates at 1,250o Celsius Best suited for ba�ery paste Produces Pure Lead bullion Slag is removed at 1,500 o

High throughput required

72

Best Available Technologies and Prac�ces

Bo�om Blown - SKS 72

73

Best Available Technologies and Prac�ces

Particle Size for Lead Dusts and Fume

Lead Fume: 0.1 to 0.7 microns

Smelter dust: up to 500 microns

Respiratory Protection: N95/FFP2 Dust Mask filters -

95% of all particulates over 0.3 microns

N100/FFP3 Dust Mask filters -

100% of all particulates over 0.3 microns

73

74

Best Available Technologies and Prac�ces

VISIBLE TO THE EYEINVISIBLE TO THE EYE

0.001 0.005 0.01 0.05 0.1 0.5 1 5 10 50 500 1,000 5,000

PARTICLE SIZE IN MICRONS

Lead Fume: 0.1 to 0.7 micronsSmelter dust: up to 500 microns

74

75

Best Available Technologies and Prac�ces

75

76

Best Available Technologies and Prac�ces

FilterPlant or Baghouse 76

77-78

Essentially, a fan with a high extraction rate will draw the off gasses from the furnace through a combustion flue and into a drop out chamber that slows down the particles giving the fume time to condense into dust. Then the gasses and dust pass through a filter medium that will remove the dust particles. The gases that pass through the filter medium should be dust free and will then be ejected to atmosphere through a chimney stack. Traditionally, two filter banks are installed so that one is in operation and the other is being cleaned.

79

Typically, fabric filter bags will capture dust at 25 microns, but recent development in filter media have lead to the introduction of bags that can filter particulates down to 5 microns.

80

If fabric filter media are used, cooling the off gasses to promote condensation of the fume to dust and then promoting growth of the dust particles to a size that can be captured is critical and local climatic conditions must be considered when designing the baghouse dust extraction collection system.

81

Baghouse dust is ejected from the baghouse though non-return valves and is collected in sealed drums or containers and then charged directly to the furnace to recover the Lead in the dust.

82

Wet and dry electrostatic precipitators can capture particulates down to 0.1 microns and require little maintenance.

83

The battery paste is a mix of Lead Oxides and Sulfates and during the smelting process reduction of the Lead Sulfates to release the Lead will result in the formation of Sulfur Dioxide gas. Sulfur dioxide gas will rapidly combine with moisture and form dilute sulfuric acid – or acid rain. So. it is critical to prevent sulfur dioxide being released into the atmosphere.

84-85

The most effective method to prevent the release of sulfur dioxide it to remove the sulfur from the recycling process, and there are three options.

• Before Smelting • During smelting • After smelting

So, selecting the first option, before smelting.

78

Best Available Technologies and Prac�ces

78

79

Best Available Technologies and Prac�ces

79

Typically Filter Bags

Capture Dust from 25

microns upwards

80

Best Available Technologies and Prac�cesLong ven�la�on

ducts are required to cool and

condense the fume to form dust

@ 25 microns

80

81

Best Available Technologies and Prac�ces

Capture the dust

in a Steel Drum

and charge the

drum directly to

a furnace

81

82

Best Available Technologies and Prac�ces

Captures fume

and dust down to

0.1 microns and

requires li�le

maintenance

82

83

Best Available Technologies and Prac�ces

83

85

Best Available Technologies and Prac�ces

Three Op�ons:Before Smel�ngDuring Smel�ngA�er Smel�ng

85

86

Converting the Lead sulfate to Sodium sulfate produces a saleable commercial product.

87

Alternatively, under the right conditions, Ammonium Sulfate fertilizer can be produced.

88

Now let us examine desulfurization during smelting.

89

This is how sulfur dioxide is formed during the smelting process.

90

Iron and Sulfur have a great affinity and adding scrap iron to the furnace charge will remove 95%+ of the sulfur.

91

Now let us consider removing the sulfur after smelting.

92

There are several options, but consideration will be given to the two most common. Both options require the use of a Scrubbing Tower, which is essentially a tall steel vessel that has a solution of either Sodium Carbonate or Calcium Carbonate sprayed into the chamber from the top of the vessel. The alkaline solution passes over thousands of plastic fillers or spacers that effectively increase the surface area of the liquid, thereby enabling more opportunities for contact between the furnace off-gas entering the tower at the base and the alkaline solution.

86

Best Available Technologies and Prac�ces

Two Op�ons: 1

PbSO4 + Na 2CO3 = PbCO 3 + Na 2SO4

Lead + Sodium = Lead + Sodium Sulfate Carbonate Carbonate Sulfate

Paper making: 1883 – Carl Dahl – invented the Kra� Process

86

87

Best Available Technologies and Prac�ces

87

Two Op�ons: 2

PbSO4 + (NH4)2CO3 = PbCO 3 + (NH 4)2SO4

Lead + Ammonium = Lead + Ammonium Sulfate Carbonate Carbonate Sulfate

88

Best Available Technologies and Prac�ces

88

Three Op�ons:Before Smel�ngDuring Smel�ngA�er Smel�ng

89

Best Available Technologies and Prac�ces

PbSO4 + Heat + C → PbO + CO + SO2

PbO + CO → Pb + CO2

2PbO + C → Pb + CO

Paste De-Sulfurization 89

90

Best Available Technologies and Prac�cesAdding Scrap Iron

to the Furnace Charge can remove

up to 95% of the Sulfur in the ba�ery paste

90

91

Best Available Technologies and Prac�ces

Three Op�ons:Before Smel�ngDuring Smel�ngA�er Smel�ng

91

92

Best Available Technologies and Prac�ces

Furnace Off-Gaswith SO2

To Atmosphere

Sodium/Calcium Carbonate feed

Spray Nozzles

Packing

92

93-95

Increasingly over the past decade recycling operations are choosing two of the three options to ensure that the stack emissions are free of sulfur dioxide. Lime is normally chosen to make the alkaline wash and the Gypsum produced can be sold as a saleable product. It is also more common to find that modern smelters choose one of the first two options, that is, before and during smelting, and use the scrubbing tower option to remove any residual traces of sulfur dioxide. One last comment and that is a new generation of baghouses that have only one chamber, but comes with individual real time bag cleaning cycles. This innovation reduces the size of the baghouse and the cost.

96

The other issue that must be addressed is the furnace residue or slag. Competent recycling operations will achieve very low lead contents in the furnace slag, down to 1% or less, but in many countries the slag is still classified as a hazardous substance and consideration must be given as to which disposal or reuse option to select as there may be implications relating to hazardous waste regulations.

97

The problem is that the slag can pose environmental and health threats because: × It can contain Lead prills and Lead compounds. × It is hydroscopic and will break down on exposure

to air and moisture. × Broken down it is an irritant to the eyes, skin and

lungs. × Certain compounds in the slag are water soluble. × It is toxic.

98

One solution is to dispose of the slag in a licensed purpose-built hazardous waste dump and the example here is a well-managed site in the Philippines. But landfill disposal sites for hazardous waste are not a long-term sustainable solution.

99

Ideally what is required is an end product that is inert and will not leach Lead into the environment. In Indonesia, one company is already experimenting with stabilizing the slag in cement to produce a paving Slab from a formulation that includes approximately 15% of Lead Slag in the mix.

95

Best Available Technologies and Prac�ces

95

96

Best Available Technologies and Prac�ces

96

Best Available Technologies and Prac�ces

97

Best Available Technologies and Prac�ces

Can contain Lead Prills and Lead compounds

Hydroscopic and will break down on exposure to air

Broken down – irritant – eyes, skin and lungs

Broken down – certain toxic compounds are soluble

Toxic

97

98

Best Available Technologies and Prac�ces

Dispose of the Slag at a licensed

Hazardous waste Landfill Site

Problem is that Landfill Sites come

at a cost

98

Best Available Technologies and Prac�ces

99

Best Available Technologies and Prac�ces

One Company in Indonesia is

experimen�ng with paving slab

produc�on using a percentage of Slag in the cement mix

99

100

The paving slabs must comply with building regulations, be stable and not leach.

101

In Brazil, Antares have patented a slag stabilization process called Eco Escoria that enables the company to produce a building material using a percentage of the slag.

102

The alternative technology to pyro-metallurgical recycling is hydro-metallurgical processing. The benefits would be: No atmospheric emissions. No fume or dust generated. The recycled Lead would be 99.99% pure But there are challenges: • To be economically viable • To produce a non-toxic waste • To eliminate completely the need for a furnace

103

Currently engaged on possible hydro-metallurgical recycling processes are: Imperial College London Oxford University VerdeEn Chemicals – Houston and India

104-106

Hydro-metallurgical recycling of ULAB will require battery breaking to separate the grid metallics and the paste. The grid metallics will go straight to electrochemical deposition for processing to pure Lead ingots. The paste will likely require de-sulfurization before electrochemical treatment to produce Lead oxide directly and not pure Lead.

107

However, there is hybrid option that would see the grid metallics going to a low temperature melting furnace to produce grid alloys and the paste going to the electrochemical processing to produce Lead oxide.

108

Aurelius Technologies have pilot hydro-metallurgical recycling plants in Wolverhampton in the UK and a second in Brazil in partnership with Antares Reciclagem.

100

Best Available Technologies and Prac�ces

The Company is manufacturing non-leachable

hexagonal paving slabs for outdoor

use

100

Best Available Technologies and Prac�ces

101

Best Available Technologies and Prac�ces

The Company has patented a

building material product that is stable and does not leach Lead –available 2021

101

102

Best Available Technologies and Prac�ces

102

Benefits: No atmospheric emissions No fume or dust generated Can produce Lead bullion at 99.99% purity

Challenges To be economically viable To produce a non toxic waste To eliminate completely the need for a furnace

103

Best Available Technologies and Prac�ces

103

David Payne, Ola Hekselman –

Imperial College, London.

Promila Sharma –Pure Earth.

Brian Wilson - ILA

106

Best Available Technologies and Prac�ces

106

Electrochemical Deposi�on Lead Oxide

ULAB ULAB Breaking

Lead Paste

Smel�ng/Mel�ng Refining Pure

Lead

Grid Metallics

Grid Metallics

Lead Paste

SulfurRemoval

107

Best Available Technologies and Prac�ces

107

Electrochemical Deposi�on Lead Oxide

ULAB ULAB Breaking Mel�ng Refining Lead

Alloys

Grid Metallics

Lead Paste

SulfurRemoval

108

Best Available Technologies and Prac�ces

108

Aurelius Technologies

Pilot Plants:Wolverhampton

andBrazil

109

This is the VerdeEn Chemicals pilot plant in India. You can see the mini-breaker in the foreground and the electrochemical processing plant at the rear of the plant.

110

This is the Compression Casting machine that takes the Lead detritus and compresses it into 25 kilo discs.

111

So, what else is improving the industry’s environmental performance?

112

We can completely enclose the recycling plant and attach the building to a baghouse, such the building is under negative pressure. This means that as and when doors are open for access or exit, any dust inside the building will stay inside the building.

113

What other improvements are on the horizon?

114

The installation of solar panels on the building will generate 300 kw or more of electrical energy and help to reduce GHC emissions.

115

Thank you

109

Best Available Technologies and Prac�ces

109

VerdeEn Chemicals

Pilot Plant:

110

Best Available Technologies and Prac�ces

110

VerdeEn Chemicals

Pure Lead

111

Best Available Technologies and Prac�ces

111

112

Best Available Technologies and Prac�ces

112

113

Best Available Technologies and Prac�ces

113

114

Best Available Technologies and Prac�ces

114

115

Best Available Technologies and Prac�ces

SOMALIA

Thank You