Supplementary Data

Recent progress on biomass co-pyrolysis conversion into high-quality bio-oil

H. Hassana,b, J.K. Lima, B.H. Hameeda,*

a School of Chemical Engineering, Engineering Campus,

Universiti Sains Malaysia, 14300 Nibong Tebal, Penang, Malaysia

b Faculty of Chemical Engineering ,Universiti Teknologi MARA (UiTM) Malaysia,

Permatang Pauh 13500 Penang, Malaysia

*Corresponding author. Tel.: +604-599 6422; Fax.: +604-594 1013

E-mail address: chbassim@usm.my (B.H. Hameed)

S1

Fig. S1: Reaction mechanism between biomass model compounds and PE at catalyst sites (1)

Diels–Alder reaction mechanism; (2) hydrocarbon pool mechanism; (3) hydrogen transfer

between PE and lignin. Reprinted from Xue et al. (2016), Copyright (2016), with permission

from Elsevier.

S2

Lignin

PE

HZSM-5

Depolymerization

PE derived alkanes and

olefins (aliphatics)

H+ transfer

PE PE derived olefins

Furans and furfurals

Xylan

Cellulose Acetic acid and non-furanic light oxygenates

Lignin-derived phenolic compound

Side-chain fragments

Fig. S2: Diagram of sample loading methods in the Py-GC/MS reactor: (a) without catalyst;

(b) with catalyst. Reprinted from Lin et al. (2015), Copyright (2015), with permission from

Elsevier

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Table S1: Several findings regarding synergetic effects between biomass and plastic and biomass and coal in co-pyrolysis.

Table S1 continue

Biomass Co-reactants Reactor types and operation conditions Remarks Reference

Pine wood

sawdust, bamboo

and empty fruit

bunch (EFB)

High density

polyethylene

(HDPE) and

polystyrene

(PS)

Co-pyrolysis experiments were carried out in a TGA.

10 mg of sample was subjected to a heating rate of 10

K/min from room temperature to 1073 K under

nitrogen flow rate of 50 mL/min. The pyrolysis

sample was held at an isothermal condition for 5 min

once the sample reached 383 K. Different blending

ratios were used for each of the biomass; 100%

biomass, 20% biomass and 80% plastic (20/80), 40%

biomass and 60% plastic (40/80), 60% biomass and

40% plastic (60/40), 80% biomass and 20% plastic

(80/20).

The maximum deviations occurred at

temperature range of 673-698 K for PS

blend and at 728-783 K for the HDPE

blend. The synergistic effect was

pronounced for lignin biomass

decomposition as the decomposition range

of plastics and lignin was overlapped.

There was an interaction between biomass

and plastics at higher temperature as the

deviation between the experimental and

calculated curves was wider.

Oyedun et al.,

(2014)

Corn stalk Fugu

subbituminous

coal

There are two parts of the pyrolyzer. In the upper part

the ash and the coal/biomass particles are mixed for a

few seconds and the coal/biomass particles were

pyrolyzed preliminary during the mixing process. The

The synergy effect was more dominant in

the liquid and gas product but not for the

char production. The experimental yield of

liquid and gas were different from the

Guo and Bi,

(2015)

S4

Table S1 continue

Biomass Co-reactants Reactor types and operation conditions Remarks Reference

mixed particles were further pyrolyzed at the bottom

part of the pyrolyzed. The blending weight of fugu

subbituminous coal (FSBC)/corn stalk (CS) are 10%,

30%, 50%, 70%, 90% and 100%.

calculated values over the whole blending

ratio and temperature.

Rice straw, saw

dust,

microcrystalline

cellulose and

lignin

Bituminous

coal

Co-pyrolysis experiments were carried out in a

TGA/DSC under nitrogen gas flow. The sample was

heated up to 900 °C with five different heating rates

(10, 15, 20, 25 and 30 °C/min).

The synergy effect was more pronounced

at temperature range of 500-900°C with

the experimental weight fractions of

blended samples were higher than

predicted ones. At temperature below 500

°C the weight loss of the blended samples

were due to the biomass decomposition.

Li et al.,

(2015c)

Energy grass Lignite 10 mg of feedstock was put into the TGA/DSC under

nitrogen gas flow. Before heating the reactor, the

apparatus was purged by using a nitrogen gas flow for

30 min to create an inert environment. Five different

heating rates (5, 10, 15, 20 and 30 °C/min) were

Experimental curves followed the

calculated curves at below 300 °C whilst

slight deviation occurred above 300 °C. A

simple additive behaviour with 3.5%

deviation from the theoretical in char

Guan et al.,

(2015).

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Table S1 continue

Biomass Co-reactants Reactor types and operation conditions Remarks Reference

studied at fixed temperature of 800 °C. yields was obtained during co-pyrolysis of

energy grass and lignite that indicated the

existence of synergistic effect.

Potato blend High density

polyethylene

(HDPE)

The experiment was performed using a TGA and

tubular furnace with 20 mg sample. The equipment

was purged with argon flow for 20 min before the

experiment was started. The samples was heated to

900 °C at three different heating rate of 10, 20 and 30

°C/min.

The product yield showed no difference

between the experimental and theoretical

values which indicated that there was no

interaction between potato blend and

HDPE during co-pyrolysis.

Xiong et al.,

(2015)

Table S2: Comparison of products obtained from co-pyrolysis and catalytic co-pyrolysis of biomass and plastics.

S6

Table S2 continue

Biomass Co-reactants Catalyst Reactor Temperature

°C

Mixture

ratio

(Catalyst:

Biomass:

Plastic)

Products of

co-pyrolysis

/catalytic

pyrolysis

Products of catalytic

co-pyrolysis

Reference

Corn

stover

Scum CaO and

HZSM-5

Microwave-

assisted

catalytic co-

pyrolysis

system

Temperature

range: 450 -

650

Optimum

temperature:

550

Corn

stover :

Scum :

CaO :

HZSM-5

1:1:1:1

- Biochar yield

decreased.

- Maximum yield

of aromatics

(83.68%).

- Contained

highly

oxygenated

aromatic due to

polymerization

process.

- Bio oil yield

increased with the

increased amounts of

HZSM-5.

- Yield of oxygen-

containing product

decreased.

- Production of

phenols was improved

with the addition of

catalyst.

Liu et al.,

(2016)

Switchgra

ss,

Polyethylene

terephthalate

H-ZSM5 Micro-

Pyrolyzer

650 H-ZSM5:

Plastic/Bio

- Under thermal

pyrolysis;

- The production of

total aromatic

Dorado et

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Table S2 continue

Biomass Co-reactants Catalyst Reactor Temperature

°C

Mixture

ratio

(Catalyst:

Biomass:

Plastic)

Products of

co-pyrolysis

/catalytic

pyrolysis

Products of catalytic

co-pyrolysis

Reference

cellulose,

xylan, and

lignin

(PET),

polypropylene

(PP), high

density

polyethylene

(HDPE), low

density

polyethylene

(LDPE),

polystyrene

(PS)

System (Fast

pyrolysis)

mass=

15: 1

Catalyst:

Biomass:

Plastic=

30:1:1

switchgrass was

decomposed into

a mixture of

oxygenated

hydrocarbons

while PP

decomposed into

a mixture of

saturated alkanes.

compounds was

increased when

mixtures of biomass

and plastic are

subjected to catalytic

fast pyrolysis (CFP).

- PE, PP and PET

generally showed the

biggest increment of

total aromatic yields.

al., (2014)

Seaweed

biomass,

Polypropylene Mesoporous

Al-SBA-15

Fixed-bed

reactor & Py-

500 1 : 5 : 5 -Water content in

bio-oil was

-The content of light

hydrocarbon and

Lee et al.,

(2014)

S8

Table S2 continue

Biomass Co-reactants Catalyst Reactor Temperature

°C

Mixture

ratio

(Catalyst:

Biomass:

Plastic)

Products of

co-pyrolysis

/catalytic

pyrolysis

Products of catalytic

co-pyrolysis

Reference

Laminaria

japonica

GC/MS reduced compared

to pyrolysis of L.

Japonica alone.

- Main

hydrocarbons

species

i) Gasoline range

(C5-C9),

ii) Diesel range

(C10-C17)

mono-aromatics were

increased.

- Main HC species

i) Gasoline range (C5-

C9)

ii) Diesel range (C10-

C17)

Corn stalk Food waste

(FW)

ZSM-5 Py–GC/MS 500 - 700 1:1:1 - Under thermal

pyrolysis, the

vapor product

contained various

oxygenated

- Significant

synergistic effect

between corn stalk

and FW, which

promoted the

Zhang et

al.,

(2015c)

S9

Table S2 continue

Biomass Co-reactants Catalyst Reactor Temperature

°C

Mixture

ratio

(Catalyst:

Biomass:

Plastic)

Products of

co-pyrolysis

/catalytic

pyrolysis

Products of catalytic

co-pyrolysis

Reference

compounds with

almost no

hydrocarbon and

aromatic species.

production of

aromatics and other

petrochemicals.

- The relative content

of aromatic increased

non-linearly with

increasing H/Ceff ratio.

Pine wood Low density

polyethylene

(LDPE)

Ga/ZSM-5,

Ga-Al-Si

and Ga-Si

MFI zeolite

Semi-batch

microreactor

Catalytic fast

pyrolysis

(CFD)

550 Pine wood

: LDPE=

2:1

catalyst:

reactant =

15:1

- - All Ga containing

zeolites decreased the

yield of alkanes and

polyaromatics

(PAHs).

- All Ga containing

Li et al.,

(2015b)

S10

Table S2 continue

Biomass Co-reactants Catalyst Reactor Temperature

°C

Mixture

ratio

(Catalyst:

Biomass:

Plastic)

Products of

co-pyrolysis

/catalytic

pyrolysis

Products of catalytic

co-pyrolysis

Reference

zeolites increased the

olefins and/or

monoaromatics

hydrocarbons.

Cellulose Low density

polyethylene

(LDPE)

ZSM-5 Curie-point

pyrolyzer

(JHP-

22, Japan

Analytic Ind.,

Japan),

Catalytic fast

pyrolysis

590 catalyst:

reactant

=10:1

- Co-feeding of

cellulose with

LDPE in CFP

significantly

increased the

yield of

monoaromatic

hydrocarbons and

decreased the

- When the boron-

modified ZSM-5 was

used as the catalyst in

co-feed CFP, it

produced higher

yields of desired

petrochemicals and

lower yields of

undesired PAHs than

Zhou et

al., (2014)

S11

Table S2 continue

Biomass Co-reactants Catalyst Reactor Temperature

°C

Mixture

ratio

(Catalyst:

Biomass:

Plastic)

Products of

co-pyrolysis

/catalytic

pyrolysis

Products of catalytic

co-pyrolysis

Reference

yield of undesired

PAHs.

the pristine ZSM-5.

Cellulose Low density

polyethylene

(LDPE)

ZSM-5 Pyroprobe

5200

analytical

pyrolyzer

(CDS

Analytical,

Inc.)

catalyst:

reactant

=10:1

(for non-

CFP) or

10:4-5 (for

CFP)

- Non-CFP of

cellulose

produced

predominantly

oxygenated

products such as

anhydrosugars,

furans, alcohols,

and ketones.

-Pyrolysis of the

cellulose and

- CFP of the mixture

produced a higher

aromatic selectivity

for more valuable

monoaromatics

- CFP of the mixture

produced much less

coke (11.94%) than

CFP of cellulose alone

(36.62%). -

Co-feeding of LDPE

Li et al.,

(2013b)

S12

Table S2 continue

Biomass Co-reactants Catalyst Reactor Temperature

°C

Mixture

ratio

(Catalyst:

Biomass:

Plastic)

Products of

co-pyrolysis

/catalytic

pyrolysis

Products of catalytic

co-pyrolysis

Reference

LDPE mixture

produced a

“combined”

pyrogram that

resembles the

superposition of

the two individual

components.

with cellulose

decrease the rate of

catalyst deactivation

by coke deposits that

occurred rapidly in

CFP of cellulose.

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