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Supporting Information

Efficient Renewable Fuel Production from Sewage Sludge

Using a Supercritical Fluid Route

Hermawan Prajitno, Hassan Zeb, Jongkeun Park, Changkook Ryu, Jaehoon Kim

1

Table S1. Comparison of bio-oil yield and properties from different sewage sludge liquefaction approaches.

No.

Sewage sludge propertiesOrganic matters (wt%); Ash (wt%); O (wt%);

HHV (MJ kg−1)

Reaction conditionsT (°C); P (MPa); t (min); solvents/fluids; biomass to solvent ratio (w/w)

H2

Catalyst

AchievementsBio-oil yield* (wt%); O (wt%); HHV (MJ kg−1); TAN (mg KOH g oil−1)

Ref.

1

Type:

OM:Ash:O:HHV:

Secondary pulp85.015.025.318.3

T:P:t:Solvents:Ratio:

280N/A60Water1:10

H2: NoCatalysts: K2CO3, Ca(OH)2, Ba(OH)2

Oil yield:O:HHV:TAN:

26.010.936.7N/A

Xu and Lancaster [1]

2

Type:OM:Ash:O:HHV:

Primary sludge78.521.529.815.7


5003760Water1:49

H2: NoCatalysts: No


19.110.436.8N/A

Zhang et al. [2]

3

Type:

OM:Ash:O:HHV:

Secondary pulp75.624.425.715.8


5003760Water1:49

H2: NoCatalysts: No


22.57.438.2N/A Zhang et al. [2]

4

Type:OM:Ash:O:HHV:

N/AN/AN/A47.5a

14.6


400N/A10Ethanol1:40

H2: N/ACatalysts: Na2CO3, NaOH, FeSO4, FeS


48.06.9a

41.0N/A

Li et al. [3]

5 Type:OM:

Primary sludge60.0

T:P:

380N/A

H2: Yes, 1.6 MPaCatalysts: Raney Ni

Oil yield:O:

73.08.5

Lemoine et al. [4]

2

Ash:O:HHV:

40.047.516.6

t:Solvents:

Ratio:

15MeTHF, tetralin1:14

HHV:TAN:

39.8N/A

6

Type:OM:Ash:O:HHV:

N/A62.437.648.5a

13.6


375280Water1:4

H2: NoCatalysts: No


62.314.6a

31.14.0

Wang et al. [5]

7

Type:OM:Ash:O:HHV:

N/A60.839.247.514.6


35010.120Ethanol1:10

H2: N/ACatalysts: No


65.011.136.1N/A

Huang et al. [6]

8

Type:OM:Ash:O:HHV:

N/AN/AN/A13.92N/A


350N/A30Water1:9

H2: N/ACatalysts: Sewage sludge-based activated carbon


30.0N/A39.1N/A

Zhai et al. [7]

9

Type:

OM:Ash:O:HHV:

Secondary sludge60.839.217.414.6

T:P:t:Solvents:

Ratio:

3805–1320Methanol, ethanol, acetoneN/A



75.06.738.4N/A Huang et al. [8]

10

Type:OM:Ash:O:HHV:

N/A63.3236.6830.35a

15.3


300N/A40Water1:5

H2: Yes, 2.0 MPaCatalysts: Na2CO3, Raney Ni, FeSO4, MoS2


45.613.035.8N/A

Malins et al. [9]

3

11

Type:OM:Ash:O:HHV:

N/A45.3254.6810.74a

N/A


280N/A20Ethanol1:10



31.05.93a

N/AN/A

Leng et al. [10]

aBy difference

*Estimated based on literature data using Bio−oil yield=Weight of bio−oil(dafb)

Weight of sewage sludge (dafb)x 100

4

Table S2. Properties of the dried sewage sludge used in this study.

Ultimate analysis (wt%)a Proximate analysis (wt%) Lipid content(wt%)

HHV(MJ kg−1)

C H O N S Moisture OMa,b Inorganicsa

15.0 16.3a

38.1 3.6 23.2 6.4 1.1 5.7 71.7 28.3

Inorganic (ppm)

Ca Fe Si K Al P S Mg Cl Zn Na Cu Pb Cr Ni

47570 43100 40000 20590 18500 17710 12930 9360 7860 4455 3230 1170 440 180 110aOn a dry basisbOM: organic matter

As listed in Table S2, the dried sewage sludge consisted of 71.7 wt% organic matter and 28.3 wt%

inorganic species. This material also contained 15.0 wt% lipids on a dry ash-free basis, which is in

the range of values reported previously [4,6,11]. The lipid content in the dried sewage sludge was

determined by Soxhlet extraction using hexane as a solvent (Method SM 5520E). After extraction,

the lipids were recovered by evaporating hexane at 40 °C under vacuum. The major metal species

present in the ash of sewage sludge were calcium, iron, silicon, potassium, and aluminum; low

concentrations of several hazardous metals such as zinc, copper, lead, chromium, and nickel were

also detected. The calorific value of the dried sewage sludge was very low (16 MJ kg−1) because it

contained approximately 70 wt% combustible organic matter and 23.2 wt% of the oxygen content

in organic matter.

5

Fig. S1. Thermogravimetric analysis of the dried sludge under air flow.

The combustion behavior of the organic matter present in sewage sludge was observed by TGA

(Fig. S1). Two exothermic peaks were observed at around 342 and 511 °C; the first weak peak

corresponded to the light fraction (e.g., aliphatics, fatty acids, and carbohydrates), while the second

strong peak at a higher temperature corresponded to complex aromatic species [4]. From the weight

loss, the light fraction content was estimated to be 42 wt%, while the aromatic species content was

around 58 wt% on an organic matter basis.

6

(a)

(b)

Fig. S2. Reaction and separation protocol using (a) methanol or ethanol as the solvent and (b) water or water–alcohol mixtures as the solvent.

The gas produced by reaction of the sewage sludge with the solvent (Figs. S2a and b) was purged

through a wet gas meter (W-NK-2 type, Shinagawa Corporation, Japan) to estimate the volume of

gas produced; the gas was collected using a Tedlar® gas sampling bag (1 L) for composition

7

analysis. For liquefaction in scMeOH and scEtOH (Fig. S2a), the liquid and solid products inside

the reactor were transferred into a beaker, and the reactor was then rinsed with acetone to collect the

solid residue. Next, the liquid was separated from the solid products by vacuum filtration. The solid

residue retained on the filter paper was dried at 70 °C for 24 h. Before analyzing the weight of the

solid residue, the remnant bio-oil contained in the residue was further extracted by Soxhlet

extraction using acetone as the solvent. Typically, 0.5–1.5 wt% residual bio-oil was extracted by

Soxhlet extraction. The filtrate was evaporated at 50 °C under reduced pressure for 45 min using a

rotary evaporator. The liquid product was then further dried in a vacuum oven at 70 °C for 24 h and

designated as bio-oil. For the scH2O, scH2O–scMeOH mixture, and scH2O–scEtOH mixture cases,

ethyl acetate was used as the rinsing solvent (instead of acetone) to separate the water and organic

phase and extract bio-oil from the water phase into the organic phase (see Fig. S2b).

8

Fig. S3. Thermogravimetric analysis of the dried sewage sludge, solid reside, and bio-oil under air flow. In the case of the solid residue, the weight loss was caused by coke formation during the liquefaction reaction.

9

Table S3. Reaction operating conditions, yield of products, and bio-oil properties

Case Solvent T(°C)

Time(min)

Dried sludge concentration

(wt%)

P(MPa)

Ash in oil

Solid residueb,c H2Od

(wt%)

TAN(mg KOH

g−1)

C H N S O HHV(MJ kg−1)

(wt%) (wt%)

1 scMeOH 300 30 9.1 16.5–18.6 0.1 40.2 0.7 14.4 58.8 7.8 7.7 0.7 19.4 28.5

2 scMeOH 350 30 9.1 26.5–29.0 0.3 36.0 1.2 19.9 66.5 8.1 7.1 0.9 15.8 31.8

3 scMeOH 400 30 9.1 36.5–39.7 0.3 32.7 3.6 20.7 72.3 8.3 5.8 0.4 12.4 34.1

4 scMeOH 400 10 9.1 33.6–36.5 0.0 33.4 3.2 27.9 69.1 8.0 6.8 0.5 13.0 32.7

3 scMeOH 400 30 9.1 36.5–39.7 0.3 32.7 3.6 20.7 72.3 8.3 5.8 0.4 12.4 34.1

5 scMeOH 400 60 9.1 37.0–41.2 0.0 33.8 5.7 16.5 70.8 7.4 6.4 1.2 9.5 33.0

6 scMeOH 400 120 9.1 33.7–40.6 0.1 34.0 5.4 33.7 73.3 8.2 5.2 0.4 9.6 34.6

3 scMeOH 400 30 9.1 36.5–39.7 0.3 32.7 3.6 20.7 72.3 8.3 5.8 0.4 12.4 34.1

7 scMeOH 400 30 16.7 37.1–41.0 0.0 42.1 9.6 26.4 74.6 8.4 5.4 0.2 10.6 35.2

8 scMeOH 400 30 25.0 40.3–44.0 0.4 41.1 11.2 36.6 74.3 8.3 5.0 0.1 9.4 35.0

9 scEtOH 400 30 9.1 28.5–32.2 0.4 32.0 2.5 24.0 71.5 8.5 5.0 1.2 8.2 34.6

10 scH2O 400 30 9.1 36.5–39.7 0.0 42.6 - 35.5 75.6 8.6 5.5 3.2 8.0 36.5aBy differencebOn a dry basiscEstimated by TGA under air dMeasured after reaction

10

300 350 4000

10

20

30

40

50

60

70

80

90

100

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.00.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4

1.6

1.8

2.0

Gas productsCoke

LHCs

(a)

Bio-oil

Yie

ld (w

t%) a

nd C

onve

rsio

n (%

)

Temperature (C)

Conversion

3

12

R

(b)

H/C

O/C

R Dried Sewage Sludge1 300 C, 30 min, 9.1 wt% sludge2 350 C, 30 min, 9.1 wt% sludge3 400 C, 30 min, 9.1 wt% sludge

Oil

Coal

Lignite

Anthracite

Peat

Biomass

300 350 4000

10

20

30

40

50

60

70

80

90

100(c)

C4+ C

3H

6 + C

3H

8

C2H4 + C2H6

CH4

CO2

CO H

2

Gas

com

posi

tion

(mol

%)

Temperature (C)

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

Tota

l am

ount

of g

as (L

)

300 350 4000

10

20

30

40

50

60

70

80

90

100(d)

Others Nitrogenated Hydrocarbon Aromatic Oxygenated Phenol Ester Acid Ketone Aldehyde Alcohol

GC

-MS

rela

tive

peak

are

a (%

)

Temperature (C)

Fig. S4. Effects of reaction temperature on (a) product yields, (b) H/C and O/C ratios (on a van Krevelen diagram), (c) gas composition, and (d) bio-oil composition.

11

Fig. S5. Gas chromatogram of the gases produced from the blank experiment of scMeOH at 350 °C.

Fig. S4 shows the effect of temperature on the yields of the products in scMeOH and Table S3

summarizes the obtained results. On increasing the temperature from 300 to 400 °C, the conversion

increased from 82.4% to 91.4%, while the yield of bio-oil decreased from 62.9 to 51.0 wt% and the

yield of coke decreased from 16.5 to 8.3 wt%. During the liquefaction of sewage sludge,

gasification was not significant. Even at a high reaction temperature of 400 °C, the gas yield was

less than 5 wt%. Analysis of the product yield indicates that more effective conversion of the

organic species to the liquid phase occurred at higher temperatures, but the amount of recoverable

bio-oil decreased because the amount of light fractions, which evaporated during drying under

vacuum, increased with temperature. In fact, as shown in Fig. S4a, the yield of light hydrocarbon

species (LHCs), which could not be recovered during product separation, increased with increasing

temperature. Under the assumption of complete recovery of the LHCs (e.g., by distillation), the

total oil yield (bio-oil + LHCs) increased slightly from 83.1 to 87.4 wt% on increasing the

12

temperature from 300 to 400 °C. Enhanced oil production and decreased coke formation at high

temperatures clearly indicated that cracking is more activate and that the formation of coke

decreases at increasing temperatures because hydrogen is generated in situ from the decomposition

of scMeOH [12], which can suppress coke formation. As shown in Fig. S5, methanol in its

supercritical state produced a substantial amount of hydrogen (0.44 mmol g methanol−1 at 350 °C).

In addition, the unique reactivity associated with scMeOH (e.g., alkylation [13,14],

hydroxylalkylation [15,16], and esterification [17]) resulted in effective quenching of radicals

and/or other intermediates with reactive functional groups (e.g., double bonds and carboxylic

acids); thus, condensation or repolymerization between the reaction intermediates is retarded.

Table S3 lists the content of ash in the bio-oil, as determined using TGA under air flow. Fig. S3

shows a representative TGA profile of the bio-oil produced at 400 °C. The amount of ash contained

in the bio-oils after combustion at temperatures up to 600 °C was negligibly small (less than 0.4 wt

%), suggesting that most of the inorganic matter in sewage sludge is partitioned into the solid

residue phase during liquefaction. The low ash content in the bio-oil is particularly beneficial for

practical applications, such as combustion and transportation fuels, as ash can be deposited,

resulting in the corrosion of boilers and engine parts.

Table S3 summarizes the content of C/H/N/S/O in the bio-oils obtained at different reaction

temperatures and Fig. S4b shows the corresponding van Krevelen diagram. On increasing the

temperature from 300 to 400 °C, a notable increase in the C and H contents and decrease in the O

content were observed, indicating that the deoxygenation ability associated with scMeOH is

enhanced at high reaction temperatures. As a result, on increasing the temperature from 300 to 400

°C, the HHV increased considerably from 28.5 to 34.1 MJ kg−1. Compared with the HHV of dried

sewage sludge, the energy content of the bio-oil produced at 400 °C increased approximately two

fold. In addition, as observed in the van Krevelen diagram, all of the produced oil was located

between the coal and oil regions, suggesting that the produced bio-oil can be potentially used as a

13

combustion or transportation fuel.

Fig. S4c shows the composition of the gases produced at various liquefaction temperatures. At a

low temperature of 300 °C, a substantial amount of CO2 was produced, indicating that

decarboxylation is the main pathway for reducing the content of oxygen in the dried sewage sludge.

On the other hand, on increasing the temperature to 400 °C, the formation of a substantial amount

of H2 (23.6 mol%) was observed, indicating that the production of hydrogen from scMeOH

increases with temperature. The presence of hydrogen helped retard coke formation, as discussed

previously.

Table S5 shows the detailed chemical composition of the bio-oil, as determined by

GC-TOF/MS, and Fig. S6a shows a representative chromatogram. The bio-oils were composed of

hundreds of different chemical species, which were categorized as alcohols, ketones, acids, esters,

phenols, and aromatics, as well as oxygenated and nitrogenated compounds (Fig. S4d). The

production of ester compounds was predominant, which can be derived from the enhanced

esterification of lipids or other reaction intermediates containing carboxylic acids by scMeOH

[17,18]. The area% corresponding to acids was extremely small, ranging from 0% to 1.2%.

Compared with bio-oil produced by rapid pyrolysis, the abundance of ester compounds and the low

amount of acids indicated that a bio-oil with highly desirable properties, such as long shelf life, high

thermal stability, and negligible corrosiveness, can be produced via this promising scMeOH-based

liquefaction approach [19,20]. As shown in Fig. S4d, the reduction of oxygenated compounds with

increasing temperature was in good agreement with the results obtained from elemental analysis

(EA). Despite the extremely small amount of acidic compounds, the presence of phenolic species

contributed to low TAN values (14.4–20.7 mg KOH g−1, Table S3). The relatively high content of N

in the produced bio-oil (6–8 wt%, EA) and nitrogenated compounds (25–31 area%, GC-TOF/MS)

as heterocycles, amines, and amides is attributed to the decomposition and rearrangement of the

proteins present in sewage sludge [21].

14

Table S4. Product yields, conversion, and bio-oil properties in subH2O (310 °C).

15

Yields and conversionBio-oil (wt%) 41.6Gas (wt%) 1.0Coke (wt%) 20.9Conversion (%) 89.6

Bio-oil propertiesC (wt%) 66.9H (wt%) 7.6N (wt%) 6.3S (wt%) 1.2O (wt%) 14.2O/C (mol mol−1) 0.21HHV (MJ kg−1) 31.5TAN (mg KOH g oil−1) 83.1

Gas compositionC1 (mol%) 17.4C2 (mol%) 32.7C3 (mol%) 3.4C4 (mol%) 1.8C6+ (mol%) 0.3H2 (mol%) 0.3CO (mol%) 10.5CO2 (mol%) 33.6

(a)

(b)

(c)

Fig. S6. GC-TOF/MS chromatograms of the bio-oils produced at 400 °C for 30 min in (a) scMeOH, (b) scEtOH, and (c) scH2O with a S/N (signal/noise) ratio of 400.

16

Table S5. Chemical compounds in the bio-oil produced in different solvents.

Sample Case 3scMeOH400 °C30 min

9.1 wt%

Case 9scEtOH400 °C30 min

9.1 wt%

Case 10scH2O400 °C30 min

9.1 wt%Name of compound Retention

time (min)

Area%

Alcohols 2.599 17.704 5.2951-Butanol 02:48.8 - 2.228 -2-Hexanol 05:15.6 - 1.654 -1-Butanol, 2-ethyl- 06:05.9 - 1.265 -1-Hexanol 06:40.6 - 8.942 -2-Heptanol 07:18.2 - 0.740 -1-Hexanol, 2-ethyl- 09:41.5 - 1.374 -Benzyl alcohol 09:49.0 0.231 - -1-Octanol 10:24.0 - 0.457 -Phenylethyl alcohol

11:08.9 0.352 1.045 1.246Benzeneethanol, á-methyl- 12:05.0 1.037 - -Benzenemethanol, à-ethyl- 12:47.2 - - 0.1383-Phenylpropanol 12:57.5 0.589 - -p-Cymene-2,5-diol

14:32.0 0.167 - -Benzeneethanol, 4-hydroxy- 15:36.7 - - 3.552à-Isopropylbenzyl alcohol 15:55.3 - - 0.3591-Dodecanol 19:16.6 - - -1-Dodecanol, 3,7,11-trimethyl- 19:16.9 0.223 - -

Ketones 2.276 0.567 1.120Butyrolactone 07:32.8 0.531 - -2-Cyclopenten-1-one, 2,3-dimethyl- 09:52.5 - - 0.368Ethanone, 1-(1-cyclohexen-1-yl)- 10:17.1 - - -2-Cyclopenten-1-one, 3,4,4-trimethyl- 10:17.2 - - 0.1513,5-Heptadien-2-one, 6-methyl-(E)- 10:17.7 0.200 - -Pulegone 10:55.4 0.237 - -3-Hexen-2-one, 3,4-dimethyl- 11:36.0 - - 0.2683-Penten-2-one, 3-ethyl-4-methyl- 11:36.2 0.493 - -1,4-cyclohexanedione, 2-octyl- 11:40.7 - 0.332 -1-Propanone, 1-cyclohexyl- 12:50.4 0.352 - -2-Cyclopenten-1-one, 3,4,5-trimethyl- 13:04.4 - 0.235 -2-Cyclopenten-1-one, 3,4-dimethyl- 13:09.7 0.280 - -1,3-Cyclopentanedione, 2-butyl- 13:31.1 - - -2-Cyclopenten-1-one, 2-hydroxy-3-methyl- 13:31.1 0.183 - -1H-Inden-1-one, 2,3-dihydro- 13:43.3 - - 0.1331H-Inden-1-one, 2,3-dihydro-2-methyl- 14:14.5 - - 0.200

Acids 0.399 4.493 1.511Propanoic acid 03:17.5 - 1.111 -Butanoic acid 05:01.3 - 1.385 -Butanoic acid, 3-methyl- 06:10.3 0.399 1.426 -Butanoic acid, 2-methyl- 06:22.1 - 0.571 -Octanoic acid 12:00.7 - - 0.374Decanoic acid, 2-methyl- 12:46.8 - - -Nonanoic acid 13:24.6 - - 0.254Undecanoic acid 17:12.7 - - 0.297Tetradecanoic acid 19:27.0 - - 0.176n-Hexadecanoic acid 21:30.2 - - 0.411

17

Esters 33.179 16.966 0.964Butanedioic acid, dimethyl ester 09:44.5 0.735 - -2-Hexenoic acid, ethyl ester 09:56.5 - 0.828 -Butanedioic acid, methyl-, dimethyl ester 10:19.3 0.808 - -Butanedioic acid, 2,3-dimethyl-, dimethyl ester 11:15.9 0.187 - -Pentanedioic acid, dimethyl ester 11:26.9 0.382 - -Butanedioic acid, ethyl-, dimethyl ester 11:40.4 0.101 - -Butanedioic acid, diethyl ester 12:07.1 - 2.139 -Benzeneacetic acid, methyl ester 12:08.2 1.505 - -Octanoic acid, ethyl ester 12:22.8 - 0.372 -Benzeneacetic acid, à-methyl-, methyl ester 12:40.4 0.150 - -Cyclopentaneundecanoic acid, methyl ester 12:47.5 0.271 - -Benzeneacetic acid, ethyl ester 13:08.1 - 3.696 -Pentanedioic acid, diethyl ester 13:35.1 - 0.309 -Benzenepropanoic acid, methyl ester 13:35.3 1.386 - -Decanoic acid, methyl ester 14:11.9 0.551 - -Benzenepropanoic acid, ethyl ester 14:36.5 - 1.248 -Undecanoic acid, methyl ester 15:31.5 0.308 1.270 -Dimethyl phthalate 16:00.1 - - 0.4371,4-Benzenedicarboxylic acid, dimethyl ester 16:34.7 0.663 - -Dodecanoic acid, methyl ester 16:46.5 1.761 - -Tridecanoic acid, methyl ester 17:32.8 0.437 - -Dodecanoic acid, ethyl ester 17:36.7 - 0.649 -1,4-Benzenedicarboxylic acid, diethyl ester 18:22.9 - 0.232 -Methyl tetradecanoate 19:04.9 2.145 - -Pentadecanoic acid, methyl ester 19:45.8 2.856 - -Ethyl tridecanoate 19:49.4 - 0.768 -Tridecanoic acid, 12-methyl-, methyl ester 19:51.2 1.242 - -Hexadecanoic acid, methyl ester 20:47.8 11.924 - -Hexadecanoic acid, 15-methyl-, methyl ester 21:47.1 1.459 - -Hexadecanoic acid, ethyl ester 21:50.1 - 4.058 -Methyl stearate 23:04.0 3.489 - -Pentadecanoic acid, ethyl ester 23:40.1 - 1.398 -Eicosanoic acid, methyl ester 24:49.2 0.244 - -Docosanoic acid, methyl ester 26:25.2 0.428 - -Diisooctyl phthalate 26:37.5 0.147 - 0.528

Phenols 7.781 6.154 27.202Phenol 08:52.8 0.225 0.693 4.517Phenol, 2-methyl- 10:09.6 - - 0.435p-Cresol 10:30.3 - 2.554 10.996Phenol, 2,3-dimethyl- 11:01.6 0.724 - -Phenol, 2-ethyl- 11:31.0 - - 0.332Phenol, 3,4-dimethyl- 11:40.6 - - 0.759Phenol, 4-ethyl- 11:57.3 - 1.055 8.113Phenol, 2-ethyl-5-methyl- 12:15.5 - - 0.448Phenol, 2,4,6-trimethyl- 12:33.0 3.758 - -Phenol, 2-(1-methylethyl)- 12:52.5 - - 0.552Phenol, 2-ethyl-6-methyl- 12:53.1 - 1.509 -Phenol, 2-propyl- 13:18.9 - - 0.718Phenol, 3,4-diethyl 13:19.4 - 0.343 -Phenol, 2-ethyl-4,5-dimethyl- 13:37.5 2.954 - -Phenol, 2-methyl-6-propyl- 14:01.8 - - 0.113Phenol, 4-(1,1-dimethylethyl)-2-methyl- 14:36.4 0.120 - -Phenol, 4-pentyl- 14:42.8 - - 0.220

Oxygenated 2.646 0.841 1.409Benzene, 1-ethoxy-4-methyl- 10:49.1 - 0.240 -3,4-Dimethyldihydrofuran-2,5-dione 11:13.5 1.862 - -2-Hexenoic acid, 3,4,4-trimethyl-5-oxo-, (Z)- 11:45.8 - - -Benzeneacetic acid, à-oxo-, ethyl ester 12:03.0 - 0.296 -Benzene, 2-methoxy-4-methyl-1-(1-methylethyl)- 13:11.7 0.117 - -Benzeneacetic acid, 4-methoxy-, methyl ester 15:43.0 0.221 - -

18

Benzenepropanoic acid, 4-methoxy-, methyl ester 16:55.2 0.316 - -3(2H)-Benzofuranone, 2,7-dimethyl- 17:27.9 0.129 - -1-Hexene, 6-phenyl-4-(1-phenylethoxy)- 18:55.4 - 0.304 1.409

Aromatics 4.220 2.989 8.230Toluene 04:34.0 0.260 0.935 -Naphthalene, 2,6-dimethyl- 15:41.8 0.113 - -Cyclobutane, 1,2-diphenyl- 17:07.2 0.122 - -Benzene, (1-pentylhexyl)- 18:06.1 - - 0.187Benzene, (1-butylheptyl)- 18:08.4 0.265 - 0.519Benzene, (1-propyloctyl)- 18:15.7 0.179 - 0.324Benzene, (1-ethylnonyl)- 18:30.2 0.215 - 0.284Benzene, (1-methyldecyl)- 18:55.1 - - 0.513Benzene, (1-methylhexyl)- 18:55.5 - 0.456 -Benzene, (1-pentylheptyl)- 19:11.1 0.468 0.477 0.844Benzene, (1-butyloctyl)- 19:14.4 0.878 0.466 0.862Benzene, (1-propylnonyl)- 19:22.5 0.342 - 0.671Benzene, 1,1′-(1,2-cyclobutanediyl)bis-, cis- 19:35.4 - - 0.266Benzene, (1-ethyldecyl)- 19:37.0 0.310 - 0.605Benzene, (1-methylnonyl)- 20:01.5 0.457 - -Benzene, (1-pentyloctyl)- 20:13.8 0.610 0.655 1.278Benzene, (1-butylnonyl)- 20:18.3 - - 0.829Benzene, (1-propyldecyl)- 20:26.4 - - 0.596Benzene, (1-ethylundecyl)- 20:41.2 - - 0.452

Hydrocarbon 2.264 0.000 4.7511,2-Butadiene 11:55.0 0.270 - -Propane, 2-cyclopropyl- 12:06.9 0.617 - -Hexadecane 15:13.3 0.250 - 0.787Cetene 16:23.0 - - 0.142Octadecane 16:28.5 - - 0.181Heptadecane 16:28.9 - - 1.2255-Eicosene, (E)- 17:09.2 - - 0.597Nonadecane 17:40.9 - - 0.484Pentadecane 17:41.0 0.744 - -Heneicosane 18:48.1 - - -Eicosane 18:48.9 0.230 - 0.393Pentadecane, 2,6,10-trimethyl- 18:52.3 - - 0.235Tetracosane 23:42.3 - - 0.4141-Docosene 24:31.1 - - 0.175Cholest-4-ene 28:57.1 0.153 - 0.117

Nitrogenated 25.282 37.529 38.5701-Butanamine, N,N-dimethyl- 06:17.6 0.268 - -Pyridine, 3-methyl- 06:32.6 - 1.476 -Pyridine, 3-ethyl- 08:23.2 - 2.948 -Pyridine, 2-propyl- 09:06.6 - 0.764 -Pyridine, 2,4-dimethyl- 09:14.2 - 0.585 -Pyridine, 5-ethyl-2-methyl- 09:36.0 - 6.684 -Pyridine, 3-ethyl-4-methyl- 09:46.4 - 5.450 -2-Pyrrolidinone, 1-methyl- 09:53.7 1.381 - 1.705Pyridine, 4-propyl- 10:10.8 - 0.566 -1-Piperidinecarboxaldehyde 10:15.7 0.172 - -2-Pyrrolidinone 10:18.6 - 1.858 2.6253-Pyridinol 10:31.4 - 0.588 5.108Pyridine, 2,3,6-trimethyl- 10:38.4 - 0.588 -2,5-Pyrrolidinedione, 1-methyl- 10:43.0 0.562 0.386 0.9842-Pyrrolidinone, 1,5-dimethyl- 10:46.3 0.195 - -2-Pyrrolidinone, 1-ethyl- 10:59.5 - 1.130 0.9643-Quinuclidinol 10:59.8 1.085 - 1.597Piperidine, 1-ethyl-2-methyl- 11:04.7 0.195 - -4-Piperidone, 1-ethyl- 11:04.9 - - 0.172Pyrrolidine, 2,2-dimethyl-N-ethyl 11:07.5 0.233 - 0.1083-Pyridinol, 2-methyl- 11:16.1 - - 1.781

19

N-n-Propylmaleimide 11:20.4 - - -5-Dimethylamino-furan-2-carbaldehyde 11:20.5 1.950 - -2,5-Pyrrolidinedione, 1-ethyl- 11:26.5 - 2.501 -Pyridine, 5-ethoxy-2-methyl- 11:34.8 - 0.375 -Pyridine, 3-butyl- 11:47.5 - 0.830 -2-Piperidinone, 1-methyl- 11:48.3 0.140 - -3-Pyridinol, 6-methyl- 11:50.6 - - 3.269Pyridine, 3-ethyl-2,6-dimethyl- 11:52.7 - 1.241 -2-Piperidinone 12:06.6 - - 0.6342-(3-Pentyl)pyridine 12:17.0 - 0.341 -à-Propylsuccinimide, à-methyl- 12:23.2 - - 0.4332-Pyrrolidinone, 1-propyl- 12:23.4 - - 0.489Caprolactam 12:23.4 0.484 - -Pyrrole, 3-formyl-4,5-dimethyl- 12:24.0 - - 0.8762-(5-Ethylpyridin-2-yl)ethanol 12:27.6 - 1.027 -2,5-Pyrrolidinedione, 3-ethyl-1,3-dimethyl- 12:33.4 - - 0.193Benzoic acid, 4-methyl-, hydrazide 12:34.5 0.202 - -2-Pentene, 3-(dimethylamino)-, (E)- 12:41.2 - 0.451 -2-Butanone, diethylhydrazone- 12:44.7 0.589 - -2-Pyrrolidinone, 4,4-dimethyl-5-methylidene- 12:45.5 0.212 - -2(1H)-Pyridinone, 1,3-dimethyl- 12:53.6 0.459 - -2(1H)-Pyridinone, 3,6-dimethyl- 12:53.7 - - 0.2562,3-xylidine, N-ethyl- 12:55.1 - 1.189 -1-Propylpyrrole, 2,5-dimethyl- 12:57.4 0.753 - -2(1H)-Pyridinone, 3-acetyl-4-hydroxy-6-methyl- 13:04.2 - 0.610 -2-Propenenitrile, 3-phenyl-, (E)- 13:06.7 - - 0.3923-Pyridinol, 2-ethyl-6-methyl- 13:12.7 - - 0.146Cyclohexanamine, N-butyl- 13:15.1 - 0.439 -Pyrazole, 3-amino-5-tert-butyl- 13:27.0 3.252 - -N-[2-Hydroxyethyl]succinimide 13:31.0 - - 0.7915-Butylpyridine, 2-methyl- 13:39.4 - 0.549 -Piperidine, 1-amino-2,6-dimethyl- 13:47.8 - - 0.144Phenol, 3-(ethylamino)-4-methyl- 13:51.1 0.115 - -1-(Piperidin-1-yl)dodecan-1-one 13:53.2 - - -Indole 13:53.6 - - 0.733Pyrazine, 2-oxo-1-methyl-3-isopropyl- 14:04.3 - 0.338 -2-Cyclopentenone, 2-methyl-3-propylamino- 14:09.6 - - -N-Ethyl-desoxy-veratramine 14:09.9 0.251 - -Benzenamine, 3,4-dimethoxy- 14:10.1 0.173 - -Pyrrolidine, N-methyl-2-(propionylmethylene)- 14:24.3 4.210 - -2-Pyrrolidinone, 1-butyl- 14:35.7 - - 4.0971H-Indole, 1,3-dimethyl- 14:55.3 0.326 - -2-n-Propylpyridine, 3,5-diethyl- 14:57.6 - 0.190 -Quinoline, 4-methyl- 15:05.2 - - 0.8412-Oxazoline, 2-methyl-4,5-tetramethylene-5-ethyl- 15:07.6 0.304 - -Alanine, N-methyl-n-propargyloxycarbonyl-, dodecyl ester 15:07.9 0.439 - -Indole, 3-methyl- 15:10.1 1.116 - 2.7501H-Indole, 4-methyl- 15:10.5 - 0.938 -2,4(1H,3H)-Pyrimidinedione, 1,3-dimethyl- 15:16.5 0.834 - -Pyrrolidine, 2,3-Bis(1-methylallyl)- 15:20.4 0.626 - -p-Toluidine, N-methyl-N-nitroso- 15:38.2 - 0.905 -Pyrrolidine, 1-(1-cyclohexen-1-yl)- 15:40.9 0.209 - -2H-pyrrolo[2,3-b]pyridin-2-one, 1,3-dihydro-1,3,3-trimethyl- 15:47.6 0.154 - -6-Undecylamine 15:51.7 - - -Tropidine, 2-acetyl-8-demethyl- 15:56.2 0.188 - -2,4(1H,3H)-Pyrimidinedione, 1,3,5-trimethyl- 15:59.7 0.801 - -Benzonitrile, 2,4,6-trimethyl- 16:24.2 - 1.263 1.1361H-Indole, 2,3-dimethyl- 16:31.1 0.291 - 0.6601H-Tetrazole, 5-(1,5-dimethyl-1H-pyrrol-2-yl)- 17:13.2 0.336 - -1H-Indole, 5,6,7-trimethyl- 17:20.4 - 0.724 0.590Acetamide, N-(2-acetylphenyl)- 17:21.2 0.321 - -2,3,7-Trimethylindole 17:25.8 - - 0.107

20

Salicylaldehyde, 4-(diethylamino)- 17:38.1 - 0.174 -1H-Indole, 2,3-dihydro-1,3,3-trimethyl-2-methylene- 17:42.6 - 0.422 -Acetamide, N-[3-(1-methyl-1H-1,3-benzimidazol-2-yl)propyl]- 17:50.6 0.137 - -Benzylamine, à-methyl-N-(2-butylidene-4-chloro-3,3-dimethyl)- 18:55.8 0.327 - -2-Biphenylamine, 3-methyl- 18:56.8 - - -Piperidine, 1-(2-phenylethyl)- 19:30.0 - - 1.5535H-Indeno[1,2-b]pyridine 20:30.6 - - 0.331Caffeine 20:33.2 0.645 - -1H-Indole-3-propanoic acid, methyl ester 21:13.2 0.115 - -9H-Pyrido[3,4-b]indole, 1-methyl- 21:30.9 0.257 - 0.652Acridine, 1,2,3,4-tetrahydro-4,9-dimethyl- 21:40.7 - - -1-Naphthalenecarbonitrile, 4-amino- 21:52.7 - - 0.557Dodecanamide 23:34.2 - - 0.4919-Octadecenamide, (Z)- 25:08.4 0.976 - 1.409

Others 1.501 1.112 1.652Butanoic acid, 4-chloro- 05:00.5 0.247 - -Diethyl disulfide 07:43.7 - 0.613 -Trisiloxane, 1,1,1,5,5,5-hexamethyl-3-[(trimethylsilyl)oxy]- 09:07.5 - 0.218 -2(3H)-Furanone, 3-(2-bromoethyl)dihydro- 10:00.8 0.147 - -Benzoyl bromide 10:51.1 0.263 - -Ethyl n-butyl disulfide 11:10.0 - 0.281 -Methylphosphonic acid, 2TMS derivative 13:25.3 - - 0.7141-Iodo-2-methylundecane 16:01.9 0.180 - -Sulfurous acid, butyl tridecyl ester 17:14.6 - - 0.205Undecanoic acid, 11-bromo-, methyl ester 18:41.4 0.392 - -Trichloroacetic acid, tridecyl ester 19:16.3 - - 0.269Succinic acid, 2,4,6-trichlorophenyl phenethyl ester 21:05.7 0.272 - -Cholestane, 3-(ethylthio)-, (3á,5à)- 28:36.0 - - 0.2845á-Cholestan-3à-ol, trifluoroacetate 28:48.1 - - 0.180

Total 90.503 88.355 90.704

21

0 20 40 60 80 100 1200

10

20

30

40

50

60

70

80

90

100

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.00.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4

1.6

1.8

2.0

(c)

Yie

ld (w

t%) a

nd C

onve

rsio

n (%

)

Time (min)

Conversion

Bio-oil

LHCs

Coke

Gas products

(a)

6

5R

4

(b)

H/C

O/C

R Dried Sewage Sludge3 400 oC, 30 min, 9.1 wt% sludge4 400 oC, 10 min, 9.1 wt% sludge5 400 oC, 60 min, 9.1 wt% sludge6 400 oC, 120 min, 9.1 wt% sludge

3

Oil

Coal

Lignite

Peat

Biomass

Anthracite

10 30 60 1200

10

20

30

40

50

60

70

80

90

100

C4+ C

3H

6 + C

3H

8

C2H

4 + C

2H

6

CH4

CO2

CO H2

Gas

com

posi

tion

(mol

%)

Time (min)

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

Tota

l am

ount

of g

as (L

)

10 30 60 1200

10

20

30

40

50

60

70

80

90

100(d)

Others Nitrogenated Hydrocarbon Aromatic Oxygenated Phenol Ester Acid Ketone Aldehyde Alcohol

GC

-MS

rela

tive

peak

are

a (%

)

Time (min)

Fig. S7. Effects of reaction time on (a) product yields, (b) H/C and O/C ratios (on a van Krevelen diagram), (c) gas composition, and (d) bio-oil composition.

As shown in Fig. S7a, at a constant temperature of 400 °C, the product yields are not strongly

dependent on the reaction time. These results are quite different from those reported previously for

the liquefaction of sewage sludge in scH2O [2], where increasing the liquefaction time resulted in

more active hydration; thus, water-soluble oil is preferably formed, which lowers the yield of heavy

oil from 37 wt% at 20 min to 10 wt% at 120 min. In the scMeOH medium, extending the reaction

time did not cause a significant change in the yield of coke (8.6–9.9 wt%), indicating that the

formation of coke is effectively retarded. On increasing the reaction time from 10 to 120 min, the

gas yield increased slightly from 1.7 to 5.3 wt%, suggesting that gas formation during liquefaction

is not significant. Notably, even at a short reaction time of 10 min, very effective liquefaction of 22

sewage sludge occurred, with a conversion of 91%, a bio-oil yield of 52.4 wt%, and a total liquid

yield of 89.1 wt%. In addition, as shown in Fig. S7b and listed in Table S3, the bio-oil produced at

10 min exhibited a high calorific value of 32.7 MJ kg−1 and a low O/C ratio of 0.13. With a further

increase of the reaction time to 120 min, the HHV increased slightly to 34.6 MJ kg−1 and the O/C

ratio decreased to 0.1. This observation clearly indicates that scMeOH is a very effective solvent for

the rapid conversion of dried sewage sludge into bio-oil.

Fig. S7c shows the compositions of the gases produced at different liquefaction times. With

increasing reaction time, the H2 content decreased significantly from 20.3 to 1.8 mol%; this high

degree of H2 consumption is attributed to the enhancement of cracking. In fact, bio-oil obtained at

10 min did not flow at room temperature, while that produced at 120 min was apparently free

flowing. The contents of CO and CO2, which were the main gas products, did not significantly

change with reaction time, ranging from 60 to 62 mol%, suggesting that decarbonylation and

decarboxylation are the main pathways for deoxygenation.

23

8 10 12 14 16 18 20 22 24 260

10

20

30

40

50

60

70

80

90

100

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.00.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4

1.6

1.8

2.0(a)

Yie

ld (w

t%) a

nd C

onve

rsio

n (%

)

Concentration (wt%)

Conversion

Bio-oil

LHCs

Coke

Gas products

3

R

8

(b)

H/C

O/C

R Dried Sewage Sludge3 400 C, 30 min, 9.1 wt% sludge7 400 C, 30 min, 16.7 wt% sludge8 400 C, 30 min, 25.0 wt% sludge

7

Oil

Biomass

Peat

Lignite

Coal

Anthracite

9.1 16.7 250

10

20

30

40

50

60

70

80

90

100(c)

C4+ C3H6 + C3H8 C2H4 + C2H6 CH4 CO2 CO H2

Gas

com

posi

tion

(mol

%)

Concentration (wt%)

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

Tota

l am

ount

of g

as (L

)

9.1 16.7 250

10

20

30

40

50

60

70

80

90

100 Others Nitrogenated Hydrocarbon Aromatic Oxygenated Phenol Ester Acid Ketone Aldehyde Alcohol

GC

-MS

rela

tive

peak

are

a (%

)

Concentration (wt%)

(d)

Fig. S8. Effects of biomass concentration on (a) product yields, (b) H/C and O/C ratios (on a van Krevelen diagram), (c) gas composition, and (d) bio-oil composition.

The concentration of dried sewage sludge in methanol was adjusted by controlling the loading

amount of biomass while maintaining the solvent filling ratio in the reactor. As shown in Fig. S8a,

on increasing the sewage sludge concentration from 9.1 to 25.0 wt%, the yield of bio-oil increased

considerably from 51.0 to 66.9 wt%, while the amount of LHCs decreased from 36.0 to 20.2 wt%.

Under methanol-deficient conditions, the increase in the yield of bio-oil and decrease in the LHC

amount indicated that a lower degree of solvolysis occurred, and the amount of recoverable

products (which did not evaporate during vacuum drying) increased. In addition, on increasing the

concentration from 9.1 to 25.0 wt%, the yield of coke only increased slightly from 8.6 to 12.0 wt%,

24

and the gas yield decreased from 4.4 to 1.0 wt%, suggesting that even at high concentrations,

almost complete conversion of solid sewage sludge into the liquid phase occurred.

The change in concentration did not strongly affect the calorific value and O/C ratio of bio-oils

(Fig. S8b), as the bio-oils produced at different concentrations exhibited similar calorific values

(34.1–35.0 MJ kg−1) and similar O/C ratios (0.10–0.13). With increasing concentration, the increase

in the content of water in the liquid mixture is attributed to the high amount of lipids or reaction

intermediates that are converted to their corresponding esters, producing water as a byproduct

(Table S3).

Fig. S8c shows the gas composition at different concentrations. On increasing the

concentration from 9.1 to 25.0 wt%, the H2 content in the produced gases decreased significantly

from 23.6 to 1.5 mol%, while the CH4 content increased considerably from 7.7 to 61.0 mol%.

Under methanol-deficient conditions, the decrease of H2 content is quite understandable because the

amount of the hydrogen-generating source in the reactor was low. It is not clear what causes the

significant increase in CH4 at high concentrations, but enhanced incorporation of methanol into the

reaction intermediates generated from the sewage sludge may be responsible for the increased

amount of CH4 as a byproduct.

25

0 30 50 70 1000

10

20

30

40

50

60

70

80

90

100 C4+ C

3H

6 + C

3H

8

C2H

4 + C

2H

6

CH4

CO2

CO H

2

Gas

com

posi

tion

(mol

%)

Methanol (vol%)

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0(a)

Tota

l am

ount

of g

as (L

)

0 30 50 70 1000

10

20

30

40

50

60

70

80

90

100 C4+ C

3H

6 + C

3H

8

C2H

4 + C

2H

6

CH4

CO2

CO H

2

(b)

Gas

com

posi

tion

(mol

%)

Ethanol (v%)

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

Tot

al a

mou

nt o

f gas

(L)

Fig. S9. Composition of the gas produced at various (a) methanol–water ratios and (b) ethanol–water ratios

26

(a)

(b)

Fig. S10. GC-TOF/MS chromatograms of the bio-oil produced at 400 °C for 30 min in (a) scMeOH–scH2O mixture (3:7, v/v) and (b) scEtOH–scH2O mixture (3:7, v/v) with a S/N (signal/noise) ratio of 400.

27

Table S6. Chemical compounds in the bio-oil produced in various water to alcohol mixtures

Sample Case 1170 vol%scMeOH

Case 1250 vol%scMeOH

Case 1330 vol%scMeOH

Case 1470 vol%scEtOH



Name of compound Retention time (min)

Alcohols 3.358 1.467 1.015 6.297 1.624 3.2931-Butanol 02:49.3 - - - 0.735 - -1-Butanol, 2-ethyl- 06:06.1 - - - 0.334 - -1-Hexanol 06:41.0 - - - 2.177 - -1-Hexanol, 2-ethyl- 09:41.6 - - - 0.559 - -Phenylethyl alcohol 11:09.6 0.875 - - 2.022 1.624 2.931Benzeneethanol, á-methyl- 12:05.6 1.351 1.222 0.632 - - -3-Phenylpropanol 12:57.5 0.578 - - - - -á-Ethylphenethyl alcohol 13:17.0 - - - 0.471 - -1,4-Benzenediol, 2,3,5-trimethyl- 15:47.9 - - 0.383 - - -Benzenemethanol, 4-(1,1-dimethylethyl)- 17:00.2 0.554 0.246 - - - -n-Heptadecanol-1 19:16.5 - - - - - 0.362

Aldehydes 0.000 0.000 0.000 0.277 0.950 0.594Cyclopentanecarboxaldehyde, 2-methyl-3-methylene- 13:04.5 - - - 0.277 0.408 0.5941,3-Cyclohexadiene-1-carboxaldehyde, 2,6,6-trimethyl- 13:19.4 - - - - 0.542 -

Ketones 3.453 3.396 2.136 0.324 0.837 2.6972-Pentanone, 4-hydroxy-4-methyl- 06:07.7 - - - 0.324 - -2-Cyclopenten-1-one, 2,3-dimethyl-

09:53.4 - - - - - 0.596Ethanone, 1-(1-cyclohexen-1-yl)- 10:44.9 - - - - - 0.1913-Penten-2-one, 3-ethyl-4-methyl- 11:36.0 - 2.389 1.245 - - -2-Hepten-4-one, 2-methyl- 11:36.0 1.783 - - - - -Cyclopentanone, 2-methyl- 11:38.0 - - - - 0.592 0.9033-Cyclopenten-1-one, 2,2,5,5-tetramethyl- 11:45.7 - - - - 0.245 0.8511-Propanone, 1-cyclohexyl- 12:50.9 0.998 - 0.891 - - -1,3-Cyclohexanedione, 2-methyl- 13:26.0 - - - - - 0.1561,3-Cyclopentanedione, 2-methyl- 13:31.6 - 0.548 - - - -Duroquinone 14:20.8 - 0.458 - - - -2H-Inden-2-one, 1,4,5,6,7,7a-hexahydro-7a-methyl-, (S)- 14:47.6 0.672 - - - - -

Acids 4.387 6.284 6.584 10.617 15.161 2.881Propanoic acid 03:17.8 1.155 1.276 0.672 1.232 1.044 -Butanoic acid 05:10.6 - - - 5.720 10.113 1.692Butanoic acid, 3-methyl- 06:12.6 1.555 2.787 2.245 2.245 2.870 0.731Butanoic acid, 2-methyl- 06:23.8 - 0.844 0.644 0.560 0.721 -Pentanoic acid, 3-methyl- 08:16.3 - - 0.112 0.588 - -Pentanoic acid, 4-methyl- 08:17.5 - - 0.380 - - -Octanoic acid 11:59.9 - - 0.455 - - -Benzeneacetic acid, 4-hydroxy-3,5-dimethyl- 16:42.8 0.946 0.827 0.516 - - -Undecanoic acid 17:12.7 - - 0.371 - - -Mandelic acid, 2,4,6-trimethyl 17:49.4 0.408 - - - - -Tetradecanoic acid 19:27.2 - - 0.263 - - -

28

n-Hexadecanoic acid21:30.3 0.322 0.551 0.926 0.273 0.413 0.458

Esters 17.683 9.484 7.225 8.489 5.941 2.493Octanoic acid, ethyl ester 12:22.8 - - - 0.155 - -Benzeneacetic acid, ethyl ester 13:08.1 - - - 1.729 0.650 -Benzenepropanoic acid, methyl ester 13:35.8 0.260 - - - - -Benzenepropanoic acid, ethyl ester 14:36.5 - - - 0.603 0.379 0.269Benzeneacetic acid, 4-hydroxy-, methyl ester 15:53.3 - - - - 0.271 -Dodecanoic acid, methyl ester 16:47.0 1.015 0.577 0.321 - - -Dodecanoic acid, ethyl ester 17:36.7 - - - 0.414 0.311 0.485Methyl tetradecanoate 19:05.3 - - - - -Tridecanoic acid, methyl ester 19:05.3 - - 0.671 - - -Methyl tetradecanoate 19:05.3 1.547 0.930 - - - -Pentadecanoic acid, methyl ester 19:46.2 1.688 1.023 0.781 - - -Decanoic acid, ethyl ester 19:49.4 - - - 0.541 - -Octadecanoic acid, ethyl ester 19:49.4 - - - - 0.419 -Tridecanoic acid, 12-methyl-, methyl ester 19:51.6 0.795 - 0.371 - - -Undecanoic acid, ethyl ester 20:28.7 - - - 0.581 0.458 0.282Tetradecanoic acid, ethyl ester 20:34.0 - - - 0.337 - -Pentadecanoic acid, 14-methyl-, methyl ester 20:48.3 0.317 - 3.909 - - -Hexadecanoic acid, methyl ester 21:10.5 8.802 5.181 - - - -Hexadecanoic acid, 15-methyl-, methyl ester 21:47.5 0.414 - - - - -Hexadecanoic acid, ethyl ester 21:49.9 - - - 3.051 2.619 1.457Methyl stearate 23:04.4 2.846 1.773 0.924 - - -Eicosanoic acid, ethyl ester 23:40.0 - - - - 0.834 -Pentadecanoic acid, ethyl ester 23:40.0 - - - 1.079 - -Diisooctyl phthalate 26:37.7 - - 0.247 - - -

Phenols 11.594 15.038 14.842 7.815 9.424 14.227Phenol 08:54.8 - - - 0.675 0.979 1.726p-Cresol 10:31.1 - - - 2.626 2.359 4.401Phenol, 2,6-dimethyl- 11:02.0 1.014 1.090 0.632 - - -Phenol, 2-ethyl- 11:31.6 - - - 0.562 0.767 4.719Phenol, 2,3-dimethyl- 11:41.0 - 0.534 1.071 - - -Phenol, 4-ethyl- 11:58.4 - - - 1.848 2.537 -Phenol, 2,4,6-trimethyl- 12:32.9 4.443 5.298 4.960 - - -Phenol, 2-ethyl-6-methyl- 12:53.0 - - - 1.521 1.933 1.847Phenol, 2,3,6-trimethyl- 12:58.8 0.363 - - - - -Phenol, 4-ethyl-3-methyl- 13:02.6 - 0.568 - - - -Phenol, 2-butyl- 13:19.3 - - - - - 0.687Phenol, 2-methyl-6-propyl- 13:28.5 - - 0.259 - - -Phenol, 2,5-diethyl- 14:05.2 - - - 0.583 0.850 0.848Phenol, 4-(1,1-dimethylethyl)-2-methyl- 14:36.7 - 0.267 - - - -Phenol, 2-ethyl-4,5-dimethyl- 14:47.6 5.171 7.282 7.921 - - -Phenol, 4-(1,1-dimethylpropyl)- 17:12.6 0.603 - - - - -

Oxygenated 3.910 3.122 6.268 1.489 0.000 1.604Acetic anhydride 03:34.8 2.367 - - - - -2(3H)-Furanone, dihydro-5-methyl- 08:20.0 - - - 0.320 - -Furan, 2,4-dimethyl- 10:41.6 - - - - - 0.281Dihydrofuran-2,5-dione, 3,4-dimethyl 11:13.5 - - 1.787 - - -Oxetane, 3,3-dimethyl- 12:06.8 - 0.789 - - - -Cyclohexanepropanenitrile, 2-oxo- 12:23.7 - - 0.717 - - -1-Pentyne, 3-ethoxy-3-ethyl- 12:50.8 - 0.878 - - - -

29

Benzene, 1-ethoxy-4-ethyl- 13:19.5 - - - 0.471 - -Ethanone, 1-(6-methyl-7-oxabicyclo[4.1.0]hept-1-yl)- 13:31.7 - - 0.407 - - -Benzene, 2-methoxy-1-methyl-4-(1-methylethyl)- 14:36.6 - - 0.328 - - -Benzene, 2-methoxy-4-methyl-1-(1-methylethyl)- 14:46.8 - - 0.475 - - -Benzene, 1-methoxy-4-(1-methylpropyl)- 15:02.8 0.684 1.126 1.375 - - -1-Hexene, 3-methyl-6-phenyl-4-(1-phenylethoxy)- 21:05.2 - 0.329 0.716 - - -1-Hexene, 6-phenyl-4-(1-phenylethoxy)- 21:05.2 0.859 - 0.463 0.698 - 1.323

Aromatics 2.676 2.071 4.371 2.893 2.470 1.891Benzene, 2-methoxy-4-methyl-1-(1-methylethyl)- 14:46.8 - 0.459 - - - -Benzene, (1-methylhexyl)- 18:55.4 - 0.340 0.464 - 0.280 -Benzene, (1-pentylheptyl)- 19:11.5 0.520 0.538 0.673 0.444 0.464 0.587Benzene, (1-butyloctyl)- 19:14.8 0.541 - 0.732 0.848 0.456 -Benzene, (1-propylnonyl)- 19:22.9 0.433 - - 0.355 0.372 0.498Benzene, (1-ethyldecyl)- 19:37.4 - - - 0.336 - -Benzene, (1-methylundecyl)- 20:01.9 - - - - 0.466 -Benzene, (1-pentyloctyl)- 20:14.2 0.721 0.734 0.982 0.616 - 0.807Benzene, (1-butylnonyl)- 20:18.5 0.462 - 0.675 - 0.432 -Benzene, (1-propyldecyl)- 20:26.6 - - 0.500 0.294 - -Benzene, (1-propyldecyl)- 20:26.7 - - - - -Phenanthrene, 7-ethenyl-1,2,3,4,4a,4b,5,6,7,8,8a,9-dodecahydro-1,1,4b,7-tetramethyl-, [4aS-(4aà,4bá,7à,8aà)]- 27:24.6 - - 0.346 - - -

Hydrocarbon 0.958 1.079 3.178 3.988 5.691 7.182Cyclobutane, methyl- 10:59.8 - - 1.001 - - -Cyclopentene, 1-ethyl-5-methyl- 11:12.6 - - - - - 0.1701-Heptene, 2-methyl- 11:46.7 - - - 0.876 1.234 3.1521-Hexene, 2-methyl- 12:06.8 - - 0.680 - - -Cyclobutane, ethyl- 12:06.8 0.542 - - - - -Dodecane 12:25.9 - - - - 0.439 0.503Tetradecane 16:28.9 - 0.451 - 0.907 1.468 1.057Hexadecane 17:40.6 - - 0.431 0.489 1.856 1.559Heptadecane 17:40.6 0.417 - - 0.377 0.695 -Nonadecane 18:48.5 - - 0.479 0.523 - 0.428Eicosane 18:48.5 - 0.628 - 0.394 - 0.3131-Pentadecene, 2-methyl- 19:16.6 - - 0.587 - - -3-Tetradecene, (E)- 19:16.6 - - - 0.422 - -

Nitrogenated 40.152 44.550 45.220 43.846 46.523 48.6901-Butanamine, N-ethyl- 04:48.9 - - - 2.246 - -Acetamide, N-ethyl- 06:59.9 - - - 1.288 1.960 1.655Formamide, N,N-diethyl- 07:59.8 - - - 0.978 1.222 -Acetamide, N,N-diethyl- 09:13.5 - - - 2.207 2.527 1.267Pyridine, 5-ethyl-2-methyl- 09:36.9 - - - 4.018 2.954 2.4652-Pyrrolidinone, 1-methyl- 09:53.6 3.468 3.103 4.431 - 0.377 0.658Hexylamine, N,N-diethyl- 10:06.7 - - - 0.347 - -Pyridine, 4-propyl- 10:11.1 - - - 0.323 - -2-Pyrrolidinone 10:19.3 2.665 - - 5.420 3.767 1.115Propionamide, N,N-diethyl- 10:23.8 - - - 0.380 0.372 -Pyridine, 3-ethyl-5-methyl- 10:25.6 - - - - - 0.262Pentanamide, N-ethyl- 10:39.8 - - - 0.293 0.429 0.501Pyridine, 3-ethyl-4-methyl- 10:43.4 - - - - 0.720 0.3262,5-Pyrrolidinedione, 1-methyl- 10:43.5 0.622 - 0.299 0.390 - -2-Pyrrolidinone, 1,5-dimethyl- 10:47.2 0.352 0.474 0.630 0.232 - -2-Pyrrolidinone, 1-ethyl- 10:58.5 - - - 3.139 7.278 10.9421H-Imidazole, 1-methyl-4-nitro- 10:59.7 1.053 0.960 - - - -Aziridine, 2-tert-butyl-1,3-dimethyl-, trans- 11:07.9 - - 0.270 - - -

30

Ethane, diazo- 11:13.4 1.980 2.352 - - - -1-Butanamine, N,N-diethyl- 11:15.5 - - - - 0.497 -Furan-2-carbaldehyde, 5-dimethylamino- 11:20.5 1.813 0.965 1.011 - - -2,5-Pyrrolidinedione, 1-ethyl- 11:26.4 - - - 2.361 2.301 5.371Pyridine, 5-ethoxy-2-methyl- 11:34.8 - - - 0.195 - -Pyrrolidine, 2,2-dimethyl-N-ethyl- 11:40.3 - - - - 1.078 -2H-Pyrrole, 5-ethoxy-2-ethoxymethyl-3,4-dihydro- 11:40.3 - - - 0.765 - 1.2872,5-Cyclohexadien-1-one, 4-ethyl-3,4-dimethyl- 11:41.2 - - - - - 0.2122-Piperidinone, 1-methyl- 11:48.5 0.681 0.709 0.577 - - -2H-Benzo[1,4]oxazine-6-sulfonic acid, 3-oxo-3,4-dihydro-, (1,3,5-trimethyl-1H-pyrazol-4-yl)amide 11:50.6 0.408 - - - - -Pyridine, 3-ethyl-2,6-dimethyl- 11:52.7 - - - 0.401 0.443 0.538Aziridine, 2-(1,1-dimethylethyl)-1-ethyl-3-methyl-, trans- 11:54.5 - - - - 0.301 0.4323-Pyridinol, 2,6-dimethyl- 12:03.1 - - 0.550 - - -2-Piperidinone 12:07.6 - - 0.562 0.681 - 0.505Formamide, N-butyl-N-(1-methylethyl)- 12:11.6 - - - 0.633 - 0.349à-propylsuccinimide, à-methyl- 12:23.3 - - 0.413 - - -5-Cyclopropylpyrazole, 3-amino- 12:23.8 - - - - - 0.8402,6-Xylidine 12:27.7 - - - 0.652 - -Benzenamine, 2-ethyl- 12:27.7 - - - - 0.771 0.331L-Proline, 1-methyl-5-oxo-, methyl ester 12:30.4 - - 0.486 - - -2,5-Pyrrolidinedione, 3-ethyl-1,3-dimethyl- 12:33.5 0.346 0.409 0.336 - - -Aziridine, 1-ethyl-2-methyl-3-(1-methylethyl)-, trans- 12:36.0 - - - - - 0.3542H-Azepine, 3,4,5,6-tetrahydro-7-methoxy- 12:36.1 - - - 0.226 - -Hexahydro-1H-azepine, N-ethyl- 12:36.1 - - - - 0.310 -2,5-Pyrrolidinedione, 3-methyl-4-propyl-, cis- 12:41.3 - - - 0.293 0.287 -3-(Dimethylamino)-2-pentene, (E)- 12:41.3 - - - - - 0.185Benzenamine, 4-butyl- 12:46.7 - - - - - 0.484Pyridine, 2-methyl-5-butyl- 12:46.7 - - - 1.044 1.183 -o-Toluidine, 5-isopropyl- 12:55.2 - - - - - 0.316Benzenamine, N-ethyl-N,3-dimethyl- 12:55.3 - - - - 0.666 -2,3-Xylidine, N-ethyl- 12:55.3 - - - 0.626 - -Neopentylamine 12:55.5 - - - 0.588 - -2-Pyrrolidone, 3-ethylidene-1-vinyl-, cis- 12:57.1 1.747 - - - - -1-Propylpyrrole, 2,5-dimethyl- 12:57.2 - 1.192 1.761 - - -Phenol, 3,4,5-trimethyl-, methylcarbamate 12:58.9 - - 0.283 - - -2H-Azepin-2-one, hexahydro-3-methyl- 13:00.4 - - - 1.491 2.253 -Pyridin-3-ol, 2-ethyl-6-methyl- 13:01.9 0.667 1.097 1.822 0.607 0.746 0.8182(1H)-Pyridinone, 3-acetyl-4-hydroxy-6-methyl- 13:04.2 - - - - - 0.550Phenol, 4-(methylamino)- 13:04.2 - - - - 0.750 -2,5-Pyrrolidinedione, 1,3-diethyl-3-methyl- 13:05.3 - - - 0.197 0.285 0.4543-Pyridinol, 2-ethyl-6-methyl- 13:12.2 - - 0.313 - - -Cyclohexanamine, N-butyl- 13:15.0 - - - 0.510 0.737 -Phenol, 5-amino-2-methoxy- 13:26.9 - 6.330 - - - -Pyrazole, 3-amino-5-tert-butyl 13:26.9 3.679 - 3.738 - - -Pyrrolidine, 1-(1-cyclohexen-1-yl)- 13:42.7 - 0.409 0.531 - - -2-Pyrrolidinone, 1-butyl- 13:48.9 - - - - 0.213 0.856Indole 13:54.3 - - - 0.169 - -2,4(1H,3H)-Pyridinedione, 3-acetyl-1,6-dimethyl- 13:54.8 - - - - 0.918 0.599Benzenamine, N,N,3,5-tetramethyl- 13:57.3 0.380 - - - - -3-Isoquinoline acetic acid, perhydro-, methyl ester 13:58.2 0.590 0.526 - - - -Pyridine, 4-amino-3,5-diethyl- 13:58.2 - - - 0.238 - -3-Pyridinemethanol, 5-hydroxy-4,6- 14:09.8 - 0.270 - - - -

31

dimethyl-Bupivacaine 14:18.4 - 0.933 - - - -Pyrimidine, 2,4-dihydroxy-5,6-dimethyl- 14:18.8 - - 1.387 - - -Arecoline 14:18.8 1.477 - - - - -Pyrrolidine, N-methyl-2-(propionylmethylene)- 14:23.9 4.918 4.428 2.623 - - -2H-Pyrrole-2-carboxylic acid, 5-ethoxy-3,4-dihydro-, ethyl ester 14:32.6 - - - - - 1.2861-Oxaspiro[4.5]decane-2,4-dione 14:36.0 - - - - 0.356 -2-Cyclopentenone, 2-methyl-3-propylamino- 14:39.5 - 0.267 - - - -Imidazo[1,2-a]pyrimidine, 1,6-dimethyl-5-oxo-1,2,3,5-tetrahydro- 14:42.7 0.347 0.509 - - - -Isoquinoline, 1,2,3,4-tetrahydro-6,7-dihydroxy-1-methyl- 14:47.6 - - - 0.446 - -1H-Indole, 1,2-dimethyl- 14:54.9 0.296 - - - - -1H-Indole, 1,3-dimethyl- 14:55.0 - 0.333 - - - -2-Piperidinecarboxylic acid, 5-butyl- 15:06.5 0.897 0.348 - - - -Indolizidine, 3-ethyl-5-methyl 15:07.2 0.282 - - - - -Indole, 3-methyl- 15:10.5 1.398 1.876 2.646 0.911 0.981 1.2336,7-Isoquinolinediol, 1,2,3,4-tetrahydro-1,1-dimethyl- 15:15.7 - - - 0.170 - -Pyrrolidine, 2,3-bis(1-methylallyl)- 15:20.0 1.120 - - - - -Isoquinoline, 1-[(3,5-dihydroxy)benzyl]-N-formyl-1,2,3,4,5,6-hexahydro- 15:46.4 - - - 0.312 - -Anisole, 3-dimethylamino- 15:57.6 0.330 0.258 0.250 - - -1H-Isoindole-1,3(2H)-dione, N-ethyl- 16:15.6 - - - 0.177 - -Benzonitrile, 2,4,6-trimethyl- 16:24.2 - 0.374 0.562 1.570 1.993 2.5191H-Indole, 2,3-dimethyl- 16:31.0 1.724 2.780 3.786 0.164 - -2-Methyl-5-(1-butyn-1-yl)pyridine 16:31.2 - - - - 0.218 0.351Quinoline, 8-methoxy-2,2,4-trimethyl-1,2,3,4-tetrahydro 16:35.0 - - - 0.219 - -1-Naphthalenamine, 5-methoxy- 16:45.3 - - - 0.118 - 0.1621H-Indole, 1,2,3-trimethyl- 17:02.3 1.224 2.067 2.102 - - -1H-Indole, 5,6,7-trimethyl- 17:20.4 0.908 1.473 1.925 0.921 1.169 -Indolizine, 2-methyl-6-ethyl- 17:20.4 - - - - - 1.568Salicylaldehyde, 4-(diethylamino)- 17:21.6 - - - - 0.220 -1H-Indole, 2,3,5-trimethyl- 17:25.8 - - 0.486 - - -2,3,7-Trimethylindole 17:25.8 0.251 0.464 0.273 - - -Salicylaldehyde, 4-(diethylamino)- 17:38.2 - - - 0.776 - -1H-Indole, 2,3-dihydro-1,3,3-trimethyl-2-methylene- 17:46.7 0.991 1.510 0.310 0.564 0.785 0.983Benzaldehyde, 4-(diethylamino)-2-methoxy- 18:10.6 - - - 0.292 0.224 0.161DL-Tryptophan, 6-methyl- 18:16.4 - 0.188 0.238 - - -Quinoline, 1,2-dihydro-2,2,4-trimethyl- 18:28.5 - - - 0.135 - 0.336Indole, 1,2,3,7-tetramethyl- 18:32.7 0.929 2.012 1.693 - - -Pyridine-3,5-dicarbonitrile, 1,2,4,4,6-pentamethyl-1,4-dihydro- 18:42.9 - - - 0.130 0.181 -1H-pyrrolo[2,3-b]pyridine, 2,3-dihydro-1,3,3-trimethyl-2-methylene- 18:46.6 - - 0.253 - - -2-Biphenylamine, 3-methyl- 18:57.3 - 0.505 - - - -Ethanone, 1-(1,3-dimethyl-1H-indol-2-yl)- 19:14.0 - 0.554 - 0.130 0.170 0.1731H-Indole, 1,2,3,5,7-pentamethyl- 19:21.0 - 0.322 - - - -1H-Isoindol-1-one, 2,3-dihydro-4,5-dimethyl-3-(2-methylpropylidene)- 19:41.5 - - - 0.126 - -Indole, 1,2,3,4,7-pentamethyl 20:17.6 0.264 0.373 0.500 - - -5H-Indeno[1,2-b]pyridine 20:31.2 - - 0.260 - - -4-Biphenylamine, 2,3-dimethyl- 20:33.9 - 0.387 - - - -p,p′-Ditolylamine 20:33.9 0.382 - - - - -5-Isopropylidene-3,3-dimethyl-dihydrofuran-2-one 21:28.6 - - - - - 0.5441H,6H-dipyrrolo[1,2-a:1′,2′-d]pyrazine, 5,10-diethoxy-2,3,7,8-tetrahydro- 21:28.7 - 0.791 1.364 0.919 0.998 -Norharmane, N-methyl- 21:30.7 0.559 0.565 - - - -

32

Dodecanamide 23:34.7 - - 0.473 0.360 0.473 0.991Dodecanamide, N-methyl 23:53.6 - - 0.474 - - -Dodecanamide, N,N-dimethyl 24:14.1 - - 0.813 - - -Myristamide, N-ethyl- 24:15.2 - - - 0.561 - -Dodecanamide, N-ethyl- 24:15.2 - - - 0.218 1.353 2.0439-Octadecenamide, (Z)- 25:08.8 1.403 2.434 4.789 1.688 2.056 2.668

Others 0.968 1.879 0.512 1.019 0.000 0.985Methyl ethyl disulfide 05:58.5 - - - - - 0.270Diethyl disulfide 07:43.7 - - - 0.306 - 0.343Silane, diethoxydimethyl- 08:48.8 - - - 0.275 - -Cyclotetrasiloxane, octamethyl- 09:07.8 - - - 0.198 - -Trisiloxane, 1,1,1,5,5,5-hexamethyl-3-[(trimethylsilyl)oxy]- 09:07.8 0.226 - - - - 0.158Trisulfide, diethyl- 11:35.9 - - - - - 0.214Bicyclo[3.3.1]non-1(8)-ene, 3-bromomethyl- 17:12.6 - 0.922 - - - -Benzene, (2-iodoethyl)- 18:55.4 0.353 - - - - -Undecanoic acid, 11-bromo-, methyl ester 19:51.6 - 0.545 - - - -Cholestane, 3-(ethylthio)-, (3á,5à)- 28:36.4 0.389 0.413 0.512 0.239 - -

Total 89.138 88.370 91.949 87.055 88.621 87.042

33

(a) 0 vol% EtOH (b) 30 vol% EtOH (c) 50 vol% EtOH (d) 70 vol% EtOH

Fig. S11. Separation of the oil and water phases.

34

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