1 of 30

Topic 4: Zeolite-Based Catalysts for Upgrading Post-Consumer Recycled Plastic Pyrolysis Oils

​

​

​

​

​

​

​

Dr. Ive Hermans

​

Department of Chemistry

​

Department of Chemical and

Biological Engineering

​

Wisconsin Energy Institute

2 of 30

2

connections

thermal

depolymerization

post consumer

plastic wastes

catalytic

upgrading

topic 4

topic 3

topic 1 & 2

Confidential

3 of 30

3

Team

Confidential

Dr. Matias Alvear

Collin Oi

UW-Madison

Jiayang Wu

UW-Madison

Zahra Alikhani

Jacob Jansen

UW-Madison

Dr. Tannon Daugaard

ISU

Jessica Brown

ISU

Prof. Robert Brown

ISU

Prof. George Huber

UW-Madison

Prof. Xianglan Bai

ISU

4 of 30

4

Milestones since last CUWP meeting

Confidential

4

5 of 30

5

from model compound to plastic oil

Dr. Taekyung Ryu

UW-Madison

Collin Oi

UW-Madison

6 of 30

6

ZSM-5 (structure type MFI): a promising catalyst

along [010]

ZSM-5 (MFI)

a pentasil zeolite

3D, 10-ring material

[100] 5.1 x 5.5 Å ↔ [010] 5.3 x 5.6 Å

pore architecture of ZSM-5 favors BTX

​

pentasil chains

secondary building unit�(SBU)

Confidential

7 of 30

7

Setup

catalyst packing

Reaction startup and condition setup

  • Reactor 500 °C
  • Evaporating tube 250 °C
  • Residence time ~0.1 second
  • Cooling condensers in dry ice/isopropanol baths

Regeneration

  • Nitrogen flow is stopped
  • Extra dry air is started at 200 sccm
  • 2 hours at 500 °C

​

​

(catalyst sieved 425-600 μm)

Confidential

8 of 30

8

1-octene: model compound for PE plastic oil

model compounds

350-500 °C

zeolite

Cracking model compound using zeolites

Confidential

9 of 30

9

Aromatics-rich

Olefin-rich

reaction conditions: mZSM-5 = 10-20000 mg, 500 °C, 4 kPa of octene, N2 = 140 mL/min

Appl. Catal. B, 2023 324, 122219.

1-octene (model compounds): contact time vs selectivity

Confidential

10 of 30

10

olefins & paraffins transform into aromatics over ZSM-5

Appl. Catal. B, 2023 324, 122219.

ZSM-5 (MFI)

SAR (SiO2/Al2O3) = 30

​

Confidential

11 of 30

11

Influence of oxygenates

Oxygenates up to at least 1 wt% do not cause significant deactivation

(full 1-octene conversion)

1-octene cofed with 0.0%, 0.5%, and 1.0% hexanoic acid over ZSM-5 (Si/Al = 15). Each feedstock was tested for 6 hours at 500 oC at a flow rate of 2.4 mL h-1 with 120 mL h-1 N2 gas.

Confidential

Jacob Jansen

UW-Madison

12 of 30

12

influence of site-cooperation & kinetic coupling

changing the product distribution by tuning acidity & site cooperation

Confidential

13 of 30

13

starting HDPE waste

Confidential

Prof. Keith Vorst

(lead Topic 2, ISU)

Jiayang Wu

(Topic 3, UW)

14 of 30

14

hydrocarbon composition HDPE plastic oil

Confidential

*

*

*phthalates

Jiayang Wu

UW-Madison

15 of 30

15

hydrocarbon composition HDPE plastic oil

Confidential

Jiayang Wu

UW-Madison

16 of 30

16

upgrading the heavy fraction

Confidential

Dr. Houqian Li

UW-Madison

Science, 2023 381, 6658

17 of 30

17

sample

Al

Sb

Cd

Ca

Co

Cr

Cu

Fe

Pb

Mg

Ni

Sn

Ti

Zn

(ppm)

plastic

HDPE color

285.00

*b

124.6

2205.49

905.70

84.17

*b

252.10

251.30

65.88

*a

*b

97.38

37.44

oil

HDPE color heavy

93.79

*a

17.00

25.22

*b

*b

*b

17.75

*a

*b

*b

*b

*b

*a

​

HDPE color light

63.36

*b

*b

16.92

*b

*b

*b

*b

*a

*b

*b

*b

*b

*a

MLOD (ppm)

6.43

10.03

0.10

0.13

0.93

1.40

1.17

0.37

3.97

1.03

1.23

16.40

0.47

0.53

MLOQ (ppm)

21.44

33.44

0.33

0.44

3.11

4.67

3.89

1.22

13.22

3.44

4.11

54.67

1.56

1.78

*a: value between method limit of detection (MLOD) and method limit of quantitation (MLOQ).

*b: value below method limit of detection (MLOD).

​

Milestone 3.4.1: contaminant content HDPE plastic oil

ICP

(naphtha-range)

Dr. Son Dong

Confidential

Abulrahman Moosa Alzailaie

18 of 30

18

HDPE

model compounds

350-500 °C

zeolite

Cracking HDPE oil using zeolites

Confidential

19 of 30

19

taking on real colored HDPE plastic oil

reaction conditions: m ZSM-5 = 5g, 500 °C, 2.4 cc oil/h, N2 = 140 mL/min

2%

36%

benzene

toluene

xylene

ethylene

propylene

butene

others

44% BTX yield

63% monomer yield

Confidential

20 of 30

20

Zn impregnation to ZSM-5 increases the yields of aromatics,

while modified Zn-ZSM-5 favors the yields of olefins

reaction conditions: mZSM-5 = 500 mg, 500 °C, 2.4 cc HDPE oil/h, N2 = 140 mL/min

ZSM-5

Zn/ZSM-5

Zn meso/ZSM-5

steamed Zn-meso/ZSM-5

yield (% wt)

C1-C5 Alkanes

C2-C5 Olefins

BTX

Styrene

C9+Aromatics

Coke

ZSM-5

15.1

26.8

28.3

7.3

4.4

0.6

Zn/ZSM-5

11.9

21.2

40.9

8.9

4.8

0.7

Zn meso/ZSM-5

11.0

29.9

32.9

8.0

6.2

0.9

steamed Zn meso/ZSM-5

3.4

44.8

24.8

5.2

5.9

0.8

product distribution from cracking HDPE oil

Chem Eng J 2024, online

Confidential

21 of 30

21

Yields of useful monomers vs. time-on-steam

​

Time on stream with intermediate regeneration

Confidential

Go / No-go

​

22 of 30

22

From offline analytics to online analytics

Confidential

23 of 30

23

Moving forward: New postconsumer oils

Confidential

HDPE oil

Polypropylene oil

24 of 30

24

Moving forward: online analytics

Confidential

HDPE oil

25 of 30

25

Moving forward: online analytics

Confidential

Polypropylene oil

26 of 30

Next Milestones

Confidential

26

Milestone 4.4.1: Test performance of catalysts from Task 3.4 for the cracking, dehydrogenation, and aromatization of heteroatom-free product stream from Task 3.3.2. 

Milestone 4.4.2: Obtain >70% yields of monomers from thermal depolymerization of actual plastic waste using optimized zeolites in continuous flow reactor for 100 hours on stream with intermediate regeneration in a reactor that process 5 mL/day. 

Milestone 4.4.3: Demonstrate catalyst regeneration to regain >90% of the original catalyst activity (Q19). 

Milestone 4.4.4 (End of Project Goal): Produce >80 wt% of the plastic monomers from plastics-derived wastes and oils (Q19). 

 

Task 4.4

Catalytic upgrading process of plastics-derived wastes and oils

27 of 30

27

Moving forward: Fluidized bed cracking

Confidential

28 of 30

28

further steps

Confidential

  • TEA (in progress)

​

​

  • Influence of oxygenates and impurities (alcohols & aldehydes ; metals)

​

​

  • Regeneration (influence of contact time / steam)

​

​

  • Fluidized bed (can we improve the selectivity at a given contact time?)

​

​

  • Feeding entire oil vs light fraction (add additional pre-cracking cat?)

29 of 30

Topic 4: Zeolite-Based Catalysts for Upgrading Post-Consumer Recycled Plastic Pyrolysis Oils

​

​

​

​

​

​

​

Dr. Ive Hermans

​

Department of Chemistry

​

Department of Chemical and

Biological Engineering

​

Wisconsin Energy Institute

30 of 30

30

25.8% (GC area)

two intersecting 3D channels with one straight parallel channel and the other running parallel defined by sinusoidal 10-membered ring

​

openings of [100] 5.1 x 5.5 Å & [010] 5.3 x 5.6 Å

​

ZSM-5

SAR (SiO2/Al2O3)=30

effect of pore architecture of ZSM-5

inside pores (extraction with HF+ DCM)

74.2% (GC area)

outside pores (extraction with DCM)

74.2% Carbon (GC area)

straight alkene: C6 and C10 (4%)

branched alkene: C9-C12 (96%)

more Branched alkenes!

​

kinetics diameter = 6-10 Å

25.8% Carbon (GC area)

straight alkene: C10-C20 (72.9%)

branched alkenes: C9-C12 (18.1%)

aromatics: C11-C15 (9%)

more straight alkenes!

​

kinetics diameter = 6-9 Å

​

monoaromatics can diffuse out of

ZSM-5 pores with openings of ~ 5.6 Å

Confidential

30