HTL OF COMMON POLYMERS IN PRESENCE OF ......TCBIOMASSPLUS2019 JULIANO SOUZA DOS PASSOS 9 OCTOBER 2019 PHD STUDENT DEPARTMENT OF ENGINEERING AARHUS UNIVERSITY HTL OF COMMON …

TCBIOMASSPLUS2019 JULIANO SOUZA DOS PASSOS

9 OCTOBER 2019 PHD STUDENTDEPARTMENT OF ENGINEERING

AARHUSUNIVERSITY

HTL OF COMMON POLYMERS IN PRESENCE OF ALKALINE CATALYST AND LIGNOCELLULOSIC MATERIALS

@AUBiorefining@JdosPassos@HyFlexFuel

Juliano Souza dos Passos; Patrick [email protected] ; [email protected]

mailto:[email protected]




AARHUSUNIVERSITY

PLASTIC WASTE

60%

10%

30%

Plastics – the Facts 2017. PlasticsEuropeGeyer, Jambeck, Law Sci. Adv. 2017; 3: e1700782



AARHUSUNIVERSITY

PLASTIC WASTE

60%

10%

30%

Plastics – the Facts 2017. PlasticsEuropeGeyer, Jambeck, Law Sci. Adv. 2017; 3: e1700782

Primary production Primary waste0

50

100

150

200

250

300

350

400

Poly

mer

s w

eigh

t [M

ton/

year

]

Others PVC PUR PS PET HDPE PP & A fibers PP LLD, LDPE



AARHUSUNIVERSITY

HYDROTHERMAL LIQUEFACTION (HTL)

Synthetic- and bio-polymers

20 min @ 350 ºC (180 bar)

+ H2Ow/ wo/ KOH



AARHUSUNIVERSITY

HYDROTHERMAL LIQUEFACTION (HTL)

Synthetic- and bio-polymers

20 min @ 350 ºC (180 bar)

+ H2O

• Aqueous Phase

• Oil

• Solids

• Gas

w/ wo/ KOH

Batch HTL



AARHUSUNIVERSITY

POLYOLEFINS AND PS

LDPE LDPEcat HDPE HDPEcat PP PPcat PS PScat0

20

40

60

80

100

Mas

s ba

lanc

e [%

]

AP (diff) Gas Oil Solids



AARHUSUNIVERSITY

POLYOLEFINS AND PS

LDPE LDPEcat HDPE HDPEcat PP PPcat PS PScat0

20

40

60

80

100

Mas

s ba

lanc

e [%

]


PE PP PS

• No reactive sites• Depends on thermal cracking• Onset decomposition > 350 ºC for all

PE ≈ 525 ºCPP ≈ 400 ºCPS ≈ 390 ºC



AARHUSUNIVERSITY

POLYOLEFINS

LDPE PPHDPE



AARHUSUNIVERSITY

OTHER POLYMERS

ABS ABScat PET PETcat PA6 PA6cat PA66 PA66cat PUR PURcat Epoxi Epoxicat PC PCcat PVC PVCcat0

20

40

60

80

100

Mas

s ba

lanc

e [%

]




AARHUSUNIVERSITY

ABS

ABS ABScat0

20

40

60

80

100

Mas

s ba

lanc

e [%

]


5001000150020002500300035004000

Wave number [cm- 1

]

Abso

rban

ce

ABS

ABS HTL residue

ABS HTLcat residue

Suggestion:



AARHUSUNIVERSITY

Acquisition Time (min

6.00 8.00 10.00 12.00 14.00 16.00 18.00 20.00 22.00 24.00 26.00 28.00 30.00 32.00 34.00 36.00 38.00 40.00

ABS1 (ABS1.D)

Cou

nts

7x10

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1

1.1

1.2CH3

O O

O

CH3

ABS

ABS ABScat0

20

40

60

80

100

Mas

s ba

lanc

e [%

]


Acquisition Time (mi

6.00 8.00 10.00 12.00 14.00 16.00 18.00 20.00 22.00 24.00 26.00 28.00 30.00 32.00 34.00 36.00 38.00 40.00

ABScat1 (ABScat1.D)

Cou

nts

7x10

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1

1.1

1.2

H3C

O

O

O

O

CH3

O

O

NH

H3C CH3

without catalyst

with catalyst



AARHUSUNIVERSITY

EPOXY AND PC

0

20

40

60

80

100

Mas

s ba

lanc

e [%

]


Epoxi Epoxicat PC PCcat

C H N S O*

PCPolymer 75.7% 5.5% 0.0% 0.0% 18.8%

Oil 77.5% 6.9% 0.0% 0.0% 15.6%

EpoxiPolymer 68.5% 8.2% 3.2% 0.0% 20.1%

Oil 72.6% 8.0% 2.6% 0.1% 16.7%*Oxygen by difference



AARHUSUNIVERSITY

EPOXY AND PC

0

20

40

60

80

100

Mas

s ba

lanc

e [%

]


Epoxi Epoxicat PC PCcat

PC PCcat0

20

40

60

80

100

0

20

40

60

80

100

Epoxi Epoxicat

% in Oil

Non-quantified, including:Dimers, trimers andoligomers of BPA;Variations ofo,m,p ethyl phenols and cumenols;Non-identified compounds.



AARHUSUNIVERSITY

PET

0

20

40

60

80

100

Mas

s ba

lanc

e [%

]


PET PETcat

5001000150020002500300035004000

Wave number [cm- 1

]

Abso

rban

ce

PET

PET HTL residue

PET HTLcat residue

TA reference

Solids FTIR

CO2

Catalytic

Soluble salts



AARHUSUNIVERSITY

PA6 AND PA66

0

20

40

60

80

100

Mas

s ba

lanc

e [%

]


PA6 PA6cat PA66 PA66cat

5001000150020002500300035004000

Wave number [cm- 1

]

Abso

rban

ce

PA66

PA66 HTL residue

Amorphous phase

γ depolymerizes more than α



AARHUSUNIVERSITY

PUR

0

20

40

60

80

100

Mas

s ba

lanc

e [%

]


PUR PURcat

PUR PURcat

0

20

40

60

80

100

% in Oil

Non-quantified, including:Aromatic compounds with 3or more rings;Non-identified heavy compounds (oligomers)



AARHUSUNIVERSITY

LIGNOCELLULOSIC WASTE FOR CO-LIQUEFACTION

3 - DBFZ - German Biomass Resarch Centre



AARHUSUNIVERSITY

LIGNOCELLULOSIC WASTE FOR CO-LIQUEFACTION

3 - DBFZ - German Biomass Resarch Centre

Feedstock Potential (MtD/y)3

Cereal (wheat) straw 241Sugarbeet leaves 128

Final fellings from conifer trees 129Final fellings from nonconifer trees 93

Switchgrass 66Thinnings from conifer trees 64

Maize stover 63Miscanthus* 62

Unused grassland cuttings 58Stumps from final fellings from conifer trees 51

Thinnings from nonconifer trees 47Logging residues from final fellings from conifer trees 40

Sunflower straw 34Cereal bran 34

Stumps from final fellings from nonconifer trees 30Logging residues from thinnings from conifer trees 26

Non hazardous post consumer wood 25Logging residues from final fellings from nonconifer trees 25

Other residues (conifers) 22Oil seed rape straw 21

* - Potential according to area available



AARHUSUNIVERSITY

MISCANTHUS + POLYMERS

PC PP LDPE PVC HDPE PS Epoxi PET ABS PA6 PUR PA660.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4

1.6

1.8

2.0

Syne

rgy

Effe

ct

Oil

PA6 PA66 PC Epoxi PET ABS LDPE HDPE PP PVC PS PUR0.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4

1.6

1.8

2.0

Syne

rgy

Effe

ct

Solids

PA6 PS PET PVC PUR LDPE PP PC HDPE ABS PA66 Epoxi0.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4

1.6

1.8

2.0

Syne

rgy

Effe

ct

Gas

𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆 𝑆𝑆𝑒𝑒𝑒𝑒𝑆𝑆𝑒𝑒𝑒𝑒 =𝑆𝑆𝑦𝑦𝑆𝑆𝑦𝑦𝑦𝑦𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑆𝑆𝑦𝑦𝑆𝑆𝑦𝑦𝑦𝑦𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒

PUR PS ABS PA66 HDPE PP Epoxi PVC LDPE PET PA6 PC0.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4

1.6

1.8

2.0

Syne

rgy

Effe

ct

AP

𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆 𝑆𝑆𝑒𝑒𝑒𝑒𝑆𝑆𝑒𝑒𝑒𝑒 > 1 → 𝑃𝑃𝑃𝑃𝑃𝑃𝑦𝑦𝑒𝑒𝑦𝑦𝑃𝑃𝑆𝑆

𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆 𝑆𝑆𝑒𝑒𝑒𝑒𝑆𝑆𝑒𝑒𝑒𝑒 < 1 → 𝑁𝑁𝑆𝑆𝑆𝑆𝑁𝑁𝑒𝑒𝑦𝑦𝑃𝑃𝑆𝑆

𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆 𝑆𝑆𝑒𝑒𝑒𝑒𝑆𝑆𝑒𝑒𝑒𝑒 ≈ 1 → 𝑁𝑁𝑆𝑆𝑁𝑁𝑒𝑒𝑆𝑆𝑁𝑁𝑦𝑦



AARHUSUNIVERSITY



0.2

0.4

0.6

0.8

1.0

1.2

1.4

1.6

1.8

2.0

Syne

rgy

Effe

ct

Oil

PA6 PA66 PC Epoxi PET ABS LDPE HDPE PP PVC PS PUR0.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4

1.6

1.8

2.0

Syne

rgy

Effe

ct

Solids

PA6 PS PET PVC PUR LDPE PP PC HDPE ABS PA66 Epoxi0.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4

1.6

1.8

2.0

Syne

rgy

Effe

ct

Gas

𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆 𝑆𝑆𝑒𝑒𝑒𝑒𝑆𝑆𝑒𝑒𝑒𝑒 =𝑆𝑆𝑦𝑦𝑆𝑆𝑦𝑦𝑦𝑦𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑆𝑆𝑦𝑦𝑆𝑆𝑦𝑦𝑦𝑦𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒

PUR PS ABS PA66 HDPE PP Epoxi PVC LDPE PET PA6 PC0.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4

1.6

1.8

2.0

Syne

rgy

Effe

ct

AP

𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆 𝑆𝑆𝑒𝑒𝑒𝑒𝑆𝑆𝑒𝑒𝑒𝑒 > 1 → 𝑃𝑃𝑃𝑃𝑃𝑃𝑦𝑦𝑒𝑒𝑦𝑦𝑃𝑃𝑆𝑆

𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆 𝑆𝑆𝑒𝑒𝑒𝑒𝑆𝑆𝑒𝑒𝑒𝑒 < 1 → 𝑁𝑁𝑆𝑆𝑆𝑆𝑁𝑁𝑒𝑒𝑦𝑦𝑃𝑃𝑆𝑆

𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆 𝑆𝑆𝑒𝑒𝑒𝑒𝑆𝑆𝑒𝑒𝑒𝑒 ≈ 1 → 𝑁𝑁𝑆𝑆𝑁𝑁𝑒𝑒𝑆𝑆𝑁𝑁𝑦𝑦



AARHUSUNIVERSITY



0.2

0.4

0.6

0.8

1.0

1.2

1.4

1.6

1.8

2.0

Oil N [%]

Syne

rgy

Effe

ct

0

2

4

6

8

10

12

14

N [%

]

25/75 50/50 75/250.0

0.5

1.0

1.5

2.0

2.5

3.0

Syne

rgy

Effe

ct

PUR/Miscanthus

Solids Oil Gas AP



AARHUSUNIVERSITY

NEXT STEPS

Polyolefins solutions?

Upscaling and its consequences



AARHUSUNIVERSITY

Find more info here: eng.au.dk/biorefining

Konstantinos AnastasakisProcess Modelling and Technoeconomics

[email protected]

Juliano Souza dos [email protected]

@JdosPassos

Patrick [email protected]

@AUBiorefining

Marianne GlasiusAnalytical Chemistry

[email protected]





Documents

HTL OF COMMON POLYMERS IN PRESENCE OF ......TCBIOMASSPLUS2019 JULIANO SOUZA DOS PASSOS 9 OCTOBER 2019 PHD STUDENT DEPARTMENT OF ENGINEERING AARHUS UNIVERSITY HTL OF COMMON …