s10_bio binders and bio polymers_ltc2013

7/29/2019 S10_Bio Binders and Bio Polymers_LTC2013

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Development of Rubber-Modified Fractionated

Bio-oil for Use as Noncrude Petroleum Binder

in Flexible Pavements

Joana Peralta

R. Christopher Williams

Marjorie Rover


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Outline

Introduction

State of the art

Objective

Experimental Method and Plan Rheological Testing

Conclusions


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Bio-based Economy and Biomass

Bio-based economy - Generating energy from renewableorganic matter

Increase in asphalt priceIncrease of demand and installation

of coking facilities in refineries

Biomass is the largest renewable energy resource

Fossil fuels Bio-oils from bio-renewable resources

Bio-Fuels:Biomass Bio-fuels + Biomass co-products

SolidBio-oils

Gas


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Bio-based Economy and Biomass

Bio-binders:

Testing and grading of bio-binders

Maximum temperature treatment120oC due to the volatilization of bio-oil

compounds

RTFOT temperaturebetween 110 and 120oC consistent with production

temperature

PAV aging time2.5 hours

Bio-oils Bio-BindersBitumen Modifiers

(


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Fast Pyrolysis

16.2 cm diameter

fluidized bed reactor

25kWt fast pyrolysis system developed at Iowa State University by CSET(6-10 kg/h of solid feed)

Two Cyclone augerTwo-stage

auger

An external burner Vapor condenser system

(four condensers and

electrostatic precipitator)


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History and Current State-of-the-art

The utilization of bio-oil as a bitumen modifier or extender In 2008, different lignin fractions (antioxidant)

The addition of lignin fractions led to a stiffening effect

High temperature properties have been positively affected

Overall performance grade has been improved and widened

In 2009, different types of bio-oils

Up to 9% can be used

The performance grade increased by six degrees Celsius

The utilization of bio-oil as a bitumen replacement

Rheological and chemical properties are promising


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DEVELOPMENTOFABIO-BINDERCAPABLE

TO

FULLYREPLACECONVENTIONALASPHALT

IN

FLEXIBLEPAVEMENTS


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Experimental Materials

Bio-oilsFast pyrolysis system,

developed at Iowa State

University

Crumb rubber from used tiresCryogenic milling

Environmental shredding

Separation of the bio-binder

by the`binder accelerated separation

method BAS

Filter

Residual bio-oil

receptacle

Centrifuge


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Experimental Methods

Bio-oil and crumb rubber blendingControlled velocity - 1000 rpm

Controlled interaction temperature -125C

Different rubber concentrations10 and 15%

Different interaction times, 30min, 1h, 1h30, 2h, 2h30 and 3h

Binder visual observation determined that 1h30min should be the

adequate interaction time

Sample designation

Crumb rubber 10% 15%

Cryogenic A B

Environmental D E


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Experimental Procedure and Plan

Characterization of the original bio-oil (DSR, FT-IR) Simulation of the bio-oil aging in the bio-binder production

Characterization of the aged bio-oil (DSR, FT-IR)

Laboratory production of the different bio-binders

Collection of a sample of the bio-binder

BBR testing

FT-IR

Separation of the bio-binder by the binder accelerated separation

method BAS

Collection of samples of residual bio-binder

RTFOT DSR and FT-IR

PAV DSR, FT-IR


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Bio-Binderrubber swelling and BBR testing

Rubber swelling

A3.51x

B2.70x

D3.25x

E2.28x

Superpave requirements and

specifications, a pavementbinder fails at a given

temperature by either

stiffness value < 300 MPa

or an m-value > 0.300

y = -21.945x - 53.9R = 0.9931

y = -10.178x - 11.4R = 0.9989

y = -21.558x + 62.75

R = 0.9149

y = -14.513x - 6.1R = 0.9912

0

100

200

300

400

500

600

700

-30 -25 -20 -15 -10 -5 0

Stiffness(MPa)

Test Temperature (C)

A B D E

y = 0.9546e0.0935x

R = 1

y = 1.0336e0.0905x

R = 0.9995y = 0.8613e0.0987x

R = 0.9965

y = 0.6376e0.075xR = 0.976

0

0.1

0.2

0.3

0.40.5

0.6

0.7

-30 -25 -20 -15 -10 -5 0

M-Value

Test Temperature (C)

A B D E


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Residual bio-binder grading

RTFOT Mass loss, %A B C D

2.418 1.947 3.211 2.073

RTFOT temperature120 C

time20 min

PAV

temperature100C

time2h30

Degassing

Temperature120C

time30 min

Bio-oilsControl Bio-Binder

AAM-1 A B D E

base 67.77 47.87 47.87 47.87 47.87

aged 49.20 49.20 49.20 49.20

res 60.51 67.50 62.58 68.12

RTFOTres 66.68 67.76 70.66 68.06 71.57

PAVres 20.26 22.43 30.35 26.71 32.60


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Master Curves

1E+00

1E+02

1E+04

1E+06

1E+08

1E+10

1E-07 1E-05 1E-03 1E-01 1E+01 1E+03

G*(Pa)

Freq*aT (Hz)

Tref

= 20oC

Bio-Oil

Ares

Bres

1E+00

1E+02

1E+04

1E+06

1E+08

1E+10

1E-07 1E-05 1E-03 1E-01 1E+01 1E+03

G*(Pa)

Freq*aT (Hz)

Tref

= 20oC

Bio-Oil

Dres

Eres

Testing temperatures

ranges from 20C70C

intervals10 C


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Conclusions A bio binder consisting of fractionated bio-oil reacted with crumb rubber can produce

a binder that is comparable to asphalt binders derived from crude petroleum. The bio-oil can be successfully reacted with crumb rubber at 125oC and is

substantially lower than the temperature that it is reacted with normal asphalt binders

The rubber swells approximately three times its weight

The cryogenic rubber is more effective than the environmental rubber at producing

lower temperature gradesthe stiffness of the cryogenic rubber is lower than theenvironmental rubber at low temperatures.

The FT-IR indicates that the styrene butadiene rubber from the tire rubber is likely

chemically combining with the fractionated bio-oil.

Additional work needs to be done understanding the oxidative aging that is occurring

in the field..so field paving projects need to be done!

Next- development of biopolymers


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Development of Biopolymers

from Soybean Oil

Andrew Cascione & Nac Hernndez

Dr. Christopher Williams and Dr. Eric Cochran

18


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Introduction

Asphalt cement commonly modified withan SBS tri-block copolymer

Kratons formula for asphalt modifiers

19

0.2 mm


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Butadiene

Byproduct of steam cracking process

(ethylene production from crude)

(ethylene is also produced from natural

gas which yields no butadiene)

Gas Phase (explosion hazard)

Polymerization of SBS

Anionic Polymerization

Costly/Oxygen sensitive

Organo metalic initiators

20


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Soybean Oil

Substitute of the rubbery block

Triglycerides

4.6 double bonds

Chemical modification

Different polymerization techniques

21


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$/

metricton

Butadiene and Soybean Oil

Commodity Trends

22

http://www.indexmundi.com
http://www.indexmundi.com/http://www.indexmundi.com/


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Radical Polymerization-Mechanism

RP consists of 4 main events:1. Decomposition

This step requires an Initiator capable of forming free radicals.

2. Initiation

The decomposed free radical fragment of the initiator attacks amonomer, yielding a monomer-free radical.

3. Propagation

Monomer-free radical or polymer-free radicals can attack othermonomers to increase the chain length by 1.

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Radical Polymerization-Mechanism

4. Termination

(a) Combination

Two polymer free radicals of different lengths combine to form a

single dormant polymer.

(a)Disproportionation

Two polymer free radicals of different lengths combine to form

two distinct dormant polymers.

24


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Polymers via Free Radical

Polymerization

Multifunctional nature Potential to crosslink with at least

one other polytriglyceride

When a fraction of 1/N havecrosslinked (N=# of repeat units)

Polymers reach their gel point

Thermosets

(Courtesy of Richard LaRock)

Linear polymer chains

Ability to flow Will not flowSoybean Oil

25


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Atom Transfer Radical Polymerization

(ATRP)

26


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Atom Transfer Radical Polymerization

(ATRP)

27

SB Biopolymer

SBS Biopolymer

Soybean Oil


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Asphalt Polymer Blends

Virgin PG XX-34 blended with

3% Kraton SBS D1101

3% Kraton SBS D1118

3% SB Diblock Biopolymer

3% SBS Triblock Biopolymer

Blended polymer and asphalt in shear mixer at180C for 2 hours

28


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0

12

3

4

5

6

7

8

9

10

46 52 58 64

SBS*

Biopolymer

0

12

3

4

5

6

7

8

9

10

46 52 58 64

SBSBiopolymer

0

12

3

4

5

6

7

8

9

10

46 52 58 64

SB

Biopolymer

0

12

3

4

5

6

7

8

9

10

46 52 58 64

Kraton

1118

0

12

3

4

5

6

7

8

9

10

46 52 58 64

Kraton

1101

0

12

3

4

5

6

7

8

9

10

46 52 58 64

XX-34

0

12

3

4

5

6

7

8

9

10

46 52 58 64

G*(KPa)

Temperature C

Unaged Binder G* (KPa)

29


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70

75

80

85

90

46 52 58 64

Phasean

gle

Temperature C

XX-34

70

75

80

85

90

46 52 58 64

Phasean

gle

Temperature C

SBS*

Biopolymer

70

75

80

85

90

46 52 58 64

Phasean

gle

Temperature C

SBSBiopolymer

70

75

80

85

90

46 52 58 64

Phasean

gle

Temperature C

SB

Biopolymer

70

75

80

85

90

46 52 58 64

Phasean

gle

Temperature C

Kraton

1118

70

75

80

85

90

46 52 58 64

Phasean

gle

Temperature C

Kraton

1101

70

75

80

85

90

46 52 58 64

Phasean

gle

Temperature C

Unaged Binder Phase Angle

30


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High Temperature Performance Grade

46

52

58

64

70

XX-34 Kraton

1101

Kraton

1118

SB

Biopolymer

SBS

Biopolymer

SBS*

Biopolymer

PerforamnceGrade

Unaged RTFO

Similar Aging

31


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Asphalt-Polymer

Blend

Mass Loss

XX-34 0.43 %

Kraton D1101 0.77 %

Kraton D1118 0.89 %

SB Biopolymer 2.79 %

SBS Biopolymer 2.48 %

SBS* Biopolymer 0.93 %

Not So Good

BigImprovement!

32


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Low Critical Temperatures

XX-34Kraton

D1101

Kraton

D1118

SB

Biopolymer

-35.3 -34.7 -34.7 -34.5

PG -34 PG -28

SBS

Biopolymer

SBS*

Biopolymer

-33.8 -33.1

33


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Continuous Grade Range

XX-34 Kraton

1101

Kraton

1118

SB

Biopolymer

SBS

Biopolymer

SBS*

Biopolymer

86.7

94.2

89.589.2

95.2

93.4

34


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Multiple Stress Creep and Recovery

(MSCR) Test Simulated Data

0%

2%

4%

6%

8%

10%

12%

14%

16%

18%

0 2 4 6 8 10 12

Strain

Time, S

p = peak strain

r = recovered strain

p = unrecovered Strain

35


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Asphalt-Polymer

BlendTemp C

Jnr3.2kPa-1

Traffic LevelTraffic Level

Criteria

XX-34 46 1.55H

Heavy(1.01 2.00)

SBS Biopolymer 46 0.90V

Very Heavy(0.51 1.00)

Asphalt-Polymer

BlendTemp C

Jnr3.2kPa-1


Criteria

XX-34 46 1.55H

Heavy(1.01 2.00)

Asphalt-Polymer

BlendTemp C

Jnr3.2kPa-1


Criteria

Multiple Stress Creep and Recovery

(MSCR) Test

36

Asphalt-Polymer

BlendTemp C

Jnr3.2kPa-1


Criteria

XX-34 46 1.55H

Heavy(1.01 2.00)

SBS Biopolymer 46 0.90V

Very Heavy(0.51 1.00)

Kraton D1101 46 0.50E

Extremely Heavy(0.00 0.50)

SBS* Biopolymer 46 0.33E

Extremely Heavy(0.00 0.50)

100


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0

10

20

30

40

50

60

70

80

90

0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.8 2

Percen

tRecovery

Non-recoverable creep compliance (Jnr3.2) kPa-1

SBS*Biopolymer

20.2%

Kraton 1101

25.0%

XX-34

4.1%

SBS

Biopolymer

6.6%

Passing % Recovery

Failing % Recovery

37


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Master Curves

Frequency Sweep in DSR from 16 C - 70 C

Fit G* data to CAM Model

Estimated Shift Factors using WLF

Used Shift Factors to shift data

log () =( )

(2 + )

= 1 +

38

XX 34


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0

10

20

30

40

50

60

70

80

90

100

0.0

1.0

2.0

3.0

4.0

5.0

6.0

7.0

8.0

-2.0 -1.0 0.0 1.0 2.0 3.0 4.0 5.0 6.0

Phasea

ngle

Log[G

*(Pa)]

Log [Reduced Frequency ()]

XX-34

CAM Model Fit G*

Phase Angle

39

Kraton D1101


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0

10

20

30

40

50

60

70

80

90

100

0.0

1.0

2.0

3.0

4.0

5.0

6.0

7.0

8.0

-2.0 -1.0 0.0 1.0 2.0 3.0 4.0 5.0 6.0

Phase

angle

Log[G*

(Pa)]


Kraton D1101

CAM Model Fit G*

Phase Angle

40

SBS Biopolymer


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0

10

20

30

40

50

60

70

80

90

100

0.0

1.0

2.0

3.0

4.0

5.0

6.0

7.0

8.0

-2.0 -1.0 0.0 1.0 2.0 3.0 4.0 5.0 6.0

Phasea

ngle

Log[G*

(Pa)]


SBS Biopolymer

CAM Model Fit G*

Phase Angle

41

SBS* Biopolymer


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0

10

20

30

40

50

60

70

80

90

100

0.0

1.0

2.0

3.0

4.0

5.0

6.0

7.0

8.0

-2.0 -1.0 0.0 1.0 2.0 3.0 4.0 5.0 6.0

Phasea

ngle

Log[G*(Pa)]


SBS Biopolymer

CAM Model Fit G*

Phase Angle

42

KXX-34 vs Kraton 1101 vs SBS* Biopolymer X


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0

10

20

30

40

50

60

70

80

90

100

0.0

1.0

2.0

3.0

4.0

5.0

6.0

7.0

8.0

-2.0 -1.0 0.0 1.0 2.0 3.0 4.0 5.0 6.0

Phasea

ngle

Log[G*(Pa)]


K

0

10

20

30

40

50

60

70

80

90

100

0.0

1.0

2.0

3.0

4.0

5.0

6.0

7.0

8.0

-2.0 -1.0 0.0 1.0 2.0 3.0 4.0 5.0 6.0

Phasea

ngle

Log[G*(Pa)]


XX-34 vs Kraton 1101 vs SBS Biopolymer

0

10

20

30

40

50

60

70

80

90

100

0.0

1.0

2.0

3.0

4.0

5.0

6.0

7.0

8.0

-2.0 -1.0 0.0 1.0 2.0 3.0 4.0 5.0 6.0

Phasea

ngle

Log[G*(Pa)]


X

CAM Model Fit G*

Phase Angle

43

KXX-34 vs Kraton 1101 vs SBS* Biopolymer X


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0

10

20

30

40

50

60

70

80

90

100

0.0

1.0

2.0

3.0

4.0

5.0

6.0

7.0

8.0

-2.0 -1.0 0.0 1.0 2.0 3.0 4.0 5.0 6.0

Phasea

ngle

Log[G*(Pa)]


K

0

10

20

30

40

50

60

70

80

90

100

0.0

1.0

2.0

3.0

4.0

5.0

6.0

7.0

8.0

-2.0 -1.0 0.0 1.0 2.0 3.0 4.0 5.0 6.0

Phasea

ngle

Log[G*(Pa)]


XX-34 vs Kraton 1101 vs SBS Biopolymer

0

10

20

30

40

50

60

70

80

90

100

0.0

1.0

2.0

3.0

4.0

5.0

6.0

7.0

8.0

-2.0 -1.0 0.0 1.0 2.0 3.0 4.0 5.0 6.0

Phasea

ngle

Log[G*(Pa)]


X

CAM Model Fit Phase Angle

44


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Next Steps

Optimization of block copolymer

Comprehensive experimental plan on the

blending method

Micrographs with supporting FTIR Analysis

HMA performance testing

Build Pilot Plant

45


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Acknowledgements

Center for Sustainable Environmental Technologies RobertBrown

Bioeconomy InstituteJohn Corwin

InTransJudy Thomas

Iowa DOTScott Schram

APAI and its members

Our colleagues in the Asphalt Lab
http://localhost/upload.wikimedia.org/wikipedia/commons/1/1a/Soybean_fields_at_Applethorpe_Farm.jpg


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Thank You!

Any Comments or Questions?
http://localhost/upload.wikimedia.org/wikipedia/commons/1/1a/Soybean_fields_at_Applethorpe_Farm.jpghttp://localhost/upload.wikimedia.org/wikipedia/commons/1/1a/Soybean_fields_at_Applethorpe_Farm.jpghttp://localhost/upload.wikimedia.org/wikipedia/commons/1/1a/Soybean_fields_at_Applethorpe_Farm.jpg

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