Introducing BBC 500 “Black becomes Green”

PLASTTEKNIK Sverige/Danmark 10 April 2013

Black Bear Carbon offers a breakthrough in the recycling of waste tires!

Black Bear Carbon BV

o produces green carbon black from waste tires to be used in new tires and other rubber products

o solving an environmental waste disposal problem

o providing green energy

First batches have been produced and received remarkable positive assessments from potential buyers

Black Bear Carbon owns IP on breakthrough technology for this process

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products

carbon reinforcing filler

• BBC 500 ~ ASTM N550/N660

energy

• pyrolysis gas – supply direct

– condense to oil

– produce steam and/or electricity

• carbon credits

• CO2 certificates

green upsides

• worldwide, approximately one billion tyres are manufactured each year in around 450 tyre factories worldwide

• nearly an equal amount of tyres are removed from vehicles every year as waste (about 13 million tons)

• in the EU alone some 3.4 million tons of tyres become waste each year

tyres: global market

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Replace a substantial proportion of total EU demand for carbon black with green carbon black within the coming decade

Using 25% of EU feedstock could potentially generate 250 kilotons of

green carbon black - about 15% of the total EU carbon black demand of around 1.6 million tons

Current situation EU: estimated that more than 1.5 million tons per year of waste tyres are paid to be burnt as secondary fuels, thereby destroying more at least 450 kilotons per year of re-usable green carbon black in the process!

potential

tyre composition

30%

70%

carbon black andsilica

rubber, steel, fabric,other chemicals

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waste tyres can be ‘de-constructed’ into many of their original

parts (e.g. steel, fabric, rubber hydrocarbons, carbon black, silica)

approximate yields:

40% carbonaceous char 60% volatiles:

o condensable oil (~80%) o non-condensable gas (~20%)

pyrolysis

~ 600ºC

nitrogen

tyres: an excellent raw material!!

Chemical Percentage

Carbon Black 77.6

Volatiles 1,4

Sulphur 0,89

ZnO / ZnS 4,83

Silica (SiO₂) 13.9

Titanium dioxide (TiO₂) 0,02

Calcium oxide (CaO) 0,62

Aluminium oxide (Al₂O₃) 0,14

Iron oxide (Fe₂O₃) 0,34

Magnesium oxide (MgO) 0,04

Sodium 0,03

Phosphorus 0,04

Bromine 0,004

Chlorine 0,05

Potasssium 0,09

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example, chemical analysis of one feedstock type

BlackBear have performed detailed studies using all major feedstock types and have standardized the BBC 500 grade feedstock type according to optimal carbon and silica content. This is a trade secret.

total global demand for carbon black: around 12 million tons per year

carbon black

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makes tyres and other rubber products tough and durable

used as a pigment in plastics, inks, paints, mastics, etc

provides ultra-violet light resistance in plastics

silica

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in combination with carbon black and silane technology, silica provides an improved balance between rolling resistance, abrasion resistance and wet traction in passenger car tyres

product composition can vary significantly depending on feedstock type

Component Percentage Remark

carbon black content variable depending on feedstock type

silica (SiO₂) content variable depending on feedstock type

other ash (e.g. ZnO/ZnS)

6 - 8 fairly constant

BlackBear’s carbon black outperforms existing products!

13 illustrative

a few customer quotations

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Quotation from a leading Global Rubber Manufacturer:

“It can be seen that the compound containing BBC 500 has properties that compare very

well with the compound containing N550 and serves to demonstrate the opportunity for

more sustainable compound designs”

Quotation from a leading Global Rubber Compounder:

“Based on these trials the BBC 500 has shown to have merit in

extrusion compounds at high loadings and can be used in place of the regular

N550 for moulding applications”

Quotation from a Western European Tyre

Manufacturer: “According to these

results the BBC 500 is a good alternative for N660 in (this) tyre

compound and it is better for the tensile

strength, tear strength and elongation at break to fully replace N660”

Property BBC 500 N660 N550

Dispersion, SBR ASTM D3191, % 97.4 96.6 98.9

Average primary particle size, nm 31 49 - 60 40 - 48

Nitrogen surface area (BET), m²/g 86 33 - 39 40 - 49

STSA (statistical thickness) surface area, m²/g 69 34 39

Oil Absorption Number (OAN), m³/kg 82 90 121

Tensile Strength, SBR ASTM D3191, MPa 24.9 22.8 23.6

Pour density, kg/m³ 350 - 450 410 - 470 325 - 395

Volatile content, % < 2 0.12 – 0.25 0.12 – 0.25

PAH content, % below detection

limits ~0.07 ~ 0.06

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upgrading the product to produce BBC 500 to out-perform furnace ASTM

black grades such as N660 and N550

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product characterisation

Property Unit Proposal Test Method Reasoning Analytical properties

Specific Gravity g/cm³ 1.85 – 1.88 allow > 1.8 due to silica and zinc

Volatile content % < 2 ASTM D-1620 no smell, consistent surface chemistry, very low/zero PAH content at this level

Moisture content % < 1 ASTM D-1509 as per furnace black specification

Binder content % < 1 as per furnace black specification

Sieve residue % < 0,1 ASTM D-1514 as per furnace black specification

Silica (SiO₂) content % 2 - 25 ASTM D-1506 influence on crosslink density

Ash content excluding silica % < 8 ASTM D-1506 ensure only tires are used for feedstock

Pour density kg/m³ 360 +/- 35 ASTM D-1513 as per furnace black specification

Pellet hardness g, ave. < 55 ASTM D-5230 as per furnace black specification

Pellet hardness g, ind. < 85 ASTM D-5230 as per furnace black specification

PAH content mg/kg < 2 ASTM WK29806 can be automatic disqualifier

Performance properties

in ASTM D3191 test recipe

Rheometry, Delta S (MH-ML) Δ N660, % ≥ 90 ISO 6502 indicator for crosslink density (key!)

Tensile strength, MPa Δ N660, % ≥ 100 ISO 37 key reinforcement indicator

Elongation at break, % Δ N660, % ≥ 90 ISO 37 key reinforcement indicator

M300, MPa Δ N660, % ≥ 90 ISO 37 key reinforcement indicator

M300 / M100 Δ N660, % ≥ 108 ISO 37 key reinforcement indicator

Hardness, Shore A Δ N660, % 95 - 105 DIN 53505 key reinforcement indicator

Dispersion (dispergrador) % ≥ 95 - can be automatic disqualifier

test recipe: SBR

Ingredient PPHR

SBR 1500 100

Carbon black 50

Zinc oxide 3

Stearic acid 1

Sulphur-80 1,75

TBBS 1

Total 156,75

SBR 1500 Value

Polymerization cold, emulsion

ML (1+4) 100⁰C 52

Bound styrene, wt.% 23,5

BBC 500 compared with N550 in SBR rubber (ASTM D3191)

[using normalised data]

100 100 100 100 100 100 100 100 100 100 100

25

90 98

106 104

73

113

94 95

108 107 105

100

0

20

40

60

80

100

120

140

Re

lative

Pe

rce

nta

ge

N550

BBC 500

100 100 100 100 100 100 100 100 100 100 100 100

94 101

111

96 94

113

100

112

102

120 116

100

0

20

40

60

80

100

120

140

Rela

tive P

erc

enta

ge

N660

BBC 500

BBC 500 compared with N660 in SBR rubber ASTM D3191

[using normalised data]

100 100 100 100 100 100 100 100 100 100 100 100 100 94

101

93 100

84

120

102 111

96 94

123

97

116

0

20

40

60

80

100

120

140

Rela

tive P

erc

enta

ge

N660

BBC 500

normalized results for full replacement (i.e. same phr) of N660 with BBC 500 in a passenger tyre compound

BBC 500 compared with N660 and N550 in SBR rubber (ASTM D3191)

[tensile stress/strain curves]

BBC 500

N660

N550

SBR, Rheometry, MDR, 160⁰C (ASTM D3191)

Confidential

16.7 17.5

15.4

0

5

10

15

20

25

N550 N660 BBC500

T90

6.8

7.7

5.8

0

1

2

3

4

5

6

7

8

9

10

N550 N660 BBC500

ts2

SBR, Mooney scorch, 140⁰C (ASTM D3191)

21.7 22.7

18.2

0

5

10

15

20

25

30

N550 N660 BBC500

T5

Confidential

29.9 29.0

24.9

0

5

10

15

20

25

30

35

40

N550 N660 BBC500

T35

dispersion photos in ASTM D3191 compounds

N550 N660

BBC 500

Dispersion 98.9% Dispersion 96.6%

Dispersion 97.4%

electron microscope photos X 100 000

BBC 500

laboratory extrusion test: photo showing glossy surface and smooth edges of

a 390 phr EPDM sample using BBC 500

Trelleborg Wheel Systems (Rome): joint EU eco-innovation project/subsidy

European Commission Grant Agreement – “Carbon Black Green Tyre”

“Closing the carbon black cycle by recovering carbon black from

end-of-life tyres and reusing it in new tyres and technical rubber goods”

Goal:

“…to demonstrate

technical capability to

fully replace a grade of

furnace black with

BBC 500”

C2C

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environmental benefits

reduce environmental pollution save 2.000 to 2.500 liters of crude

oil for every ton of production

~ 80% lower emissions (e.g. dust, CO, SO₂, NO₂, VOCs)

save 5 – 6 tons CO₂ per ton of production

net energy producer (significant portion from natural rubber, a renewable resource)

In order to achieve industry standard quality BlackBear focused their IP on the following:

o ultra-low polycyclic aromatic hydrocarbon (PAH) content - below detection limits

o maximized mechanical/dynamic rubber reinforcing characteristics, at least comparable to ASTM N550 and N660

These inventions form the basis of an International Patent Application (PCT) filed in 2012

intellectual property

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our philosophy: excellent quality + price competitive + ‘green label’ = success

summary

technically defined and consistent quality BBC 500 can fully replace N660 and N550 in almost all applications comparable or better mechanical performance than N550 comparable or better dynamic performance than N660 PAH levels below detectable limits dispersion levels comparable to N550 and N660

key quality drivers

Beneficial to customers: high level of quality consistency within all of the recycled carbon black suppliers!