i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 2 2 3 6 8 e2 2 3 8 4

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Hydrogen production from dairy wastewater using

catalytic supercritical water gasification:
Mechanism and reaction pathway

Reza Khorasani, Mohammad Saleh Khodaparasti, Omid Tavakoli*

School of Chemical Engineering, College of Engineering, University of Tehran, Tehran, 14176, Iran

highlights graphical abstract

The higher temperature and pro-

longed residence time enhanced
the hydrogen production and
gasification efficiency.

The order of catalytic activity for
the hydrogen production was
MnO2> Formic acid > MgO.

Increasing temperature resulted
on elimination of acidic/phenol
compounds and reducing the
nitrogen-containing compounds.

A reaction pathway of supercriti-
cal water gasification of cheese-
based wastewater was proposed.

article info abstract

Article history: The supercritical water gasification (SCWG) of real dairy wastewater (cheese-based or
Received 23 December 2020 whey) was performed in a batch reactor in presence of two catalysts (MnO2, MgO) and one
Received in revised form additive (formic acid). The operational conditions of this work were at a temperature range
4 April 2021 of 350e400 C and the residence time of 30e60 min. The catalysts and formic acid were
Accepted 15 April 2021 applied in 1 wt%, 3 wt%, and 5 wt% to determine their effect on hydrogen production. The
Available online 27 May 2021 concentrations of catalysts and formic acid were calculated based on the weight of feed-
stock without ash. The results showed that increased temperature and prolonged resi-
Keywords: dence time contributed to the hydrogen production (HP) and gasification efficiency (GE).
Supercritical water gasification The gas yield of hydrogen in the optimum condition (400 C and 60 min) was achieved as
Dairy wastewater 1.36 mmol/gr DAF (dry ash free). Formic acid addition was favored towards enhancing
Catalyst hydrogen content while the addition of metal oxides (MnO2 and MgO) had an apex in their
Formic acid hydrogen production and they reached the highest hydrogen in 1 wt% concentration then
Reaction pathway ebbed. Moreover, GE was increased by the addition of the catalysts and formic acid con-
centrations. The highest hydrogen content (35.4%) was obtained in 1 wt% MnO2 and the

* Corresponding author.
E-mail address: otavakoli@ut.ac.ir (O. Tavakoli).
https://doi.org/10.1016/j.ijhydene.2021.04.089
0360-3199/© 2021 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 2 2 3 6 8 e2 2 3 8 4
highest GE (32.22%) was attained in the 5 wt% formic acid concentration. A reaction
pathway was proposed based on the GC-MS data of feedstock and produced liquid phase at
different condition as well as similar studies.
© 2021 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
Introduction
Global warming and climate change; stem from fossil fuels
usage, have become a serious problem over the world with
lots of adverse impacts on the natural environment [1,2]. The
advancement of the technologies and industries has resulted
in demanding more energy. In contrast, the fossil fuels are an
essential agent for meeting the energy needs of the humanity,
resulting in depleting the natural fossil resources and
increasing the price of the fuels [3].
Hydrogen is recognized the most promising alternative
fuel which its gravimetric energy density is 142 kJ/gr
comparing to the methane gas of 55.5 kJ/gr, gasoline of 46.2 kJ/
gr and diesel of 45.4 kJ/gr [4,5]. There are some technologies for
hydrogen production including steam reforming, gasification,
electrolysis, photolysis and biological methods. However,
among them, SCWG is the promising technology for hydrogen
production from biomass; besides, it is approximately
believed that is a self-sustainable and cost-effective process,
also the persistence organic pollutant can be degraded using
the SCWG system. Another merit of the SCWG is elimination
of energy consumption to dry biomass and/or organic wastes
prior to any treatment [6]. When the temperature and pres-
sure of water are above the 375  C and 22.1 MPa respectively,
the properties of the water change toward an excellent solvent
and medium for the decomposition of organic matters due to
its unique characteristics such as lower dielectric constant,
high solubility, low viscosity and finally the emergence of the
free radicals, so these privileges make the SCW an organic
solvent with high diffusivity [7e11].
In preceding decades, wastewater of various industries has
had a profound effect on water resource and environmental
pollution since the industrial sectors consume a considerable
amount of water. Because of increasing wastewater and
decreasing the water resources, the wastewater and its po-
tential for energy recovery and water reuse has been
becoming the big deal over the world [12]. One of the critical
wastewater types is dairy wastewater which is one of the most
polluting agents due to having diverse fats and oils. However,
dairy wastewater is biodegradable and cost-effective, and
high-efficiency technology are required to treat this waste-
water [13e15].
A review on prior researches on hydrothermal gasification
of industrials and dairy wastewaters with transition metal
catalysts is shown in Table 1. Sonil Nanda et al. [16] conducted
supercritical water gasification of lactose as a model com-
pound of dairy wastewater. It was illustrated that by
increasing the temperature from 550  C to 700  C, the
hydrogen yield was increased from 1.8 mol/mol lactose to
22369
16 mol/mol lactose and by applying 0.8 wt% Na2CO3 as a
catalyst the H2 yield reached to the maximum value of
22.4 mol/mol lactose [16]. Eyup Yildirir et al. [17] investigated
supercritical gasification of wet sludge produced from bio-
logical treatment of textile and leather wastewater. The ex-
periments were carried out at the temperature range of 400  C
to 550  C and reaction time of 0 up to 60 min. The results
elucidated that an increase in temperature from 400  C to
550  C leads to augmenting gasification yield and increasing
the methane gas composition from 23 to 38 mol/kg sludge and
4.3 vol% to 27.6 vol% respectively.
Changqing Cao [18] conducted hydrothermal co-
gasification of wheat straw and black liquor in an auto-clave
reactor, it was found that an increase in temperature and
residence time culminated to increasing the hydrogen and
gasification efficiency, H2 yield and gasification efficiency was
increased from 12.29 mol/kg up to 46.02 mol/kg, 66.71%e
162.05% when the temperature raised from 500  C up to 750  C
respectively.
The main objective of this research is to investigate the
hydrothermal and supercritical water gasification of cheese-
based dairy wastewater with the domain of reaction time
between 30 and 60 min and temperature range of 350e400  C.
Formic acid, as an additive and MnO2, MgO as catalysts were
added separately. The effects of changing temperature and
residence time were examined in a batch reactor made of
stainless steel 316. A reaction pathway of hydrothermal
gasification of dairy wastewater was introduced based on GC-
MS analysis and previous literatures. There is no any recent
publication related to the hydrothermal gasification of real
dairy wastewater with and without the catalysts and formic
acid additive. Besides, the reaction pathway of supercritical
water gasification of dairy wastewater enhancing the novelty
of this work.
Experimental
Feedstock
The dairy wastewater was obtained from the Teravat Factory
located in Semnan province, Iran (this factory is producing
milk, cheese and yoghurt). The calculation in this work is
based on dry whey; the whey contained 86.34% water. A
furnace with a temperature of 90  C was used for drying the
sample for 24 h. An elemental analysis (dry base) and a ther-
mogravimetric analysis (TGA) were used to determine char-
acteristics of feedstock.
Fig. 1 presents the TGA/DTG of cheese-based wastewater.
Since the feedstock contains degradable organic compounds
 22370
Table 1 e Summary of operating conditions and results in previous studies on hydrothermal gasification of industrial and dairy wastes.
Author (Ref.) Feedstock (Feed Reactor type Temperature Pressure Time/Residence Catalysts/ Highlighted results
Concentration) (Material) (⁰C) (MPa) time additives
(Catalysts
Concentration)

i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 2 2 3 6 8 e2 2 3 8 4
Sawai et al. [19] Domestic Batch (SS 316) 500 25 5e60 min Nickel 65 wt% on
The pretreatment conditions: T ¼ 250  C,
wastewater silica/alumina 35 wt Time ¼ 30 min, Viscosity of treated sludge ¼ 0.003
(Not mentioned) % (10e500 wt%) [Pa.s]

The pretreatment prompted the hydrogen and cold
gas efficiencies to soar up to 88% and 72% respectively,
with adding catalyst.
P. Casademont Olive mill Batch (SS 316) 530e544 25.2e26.4 20 min KOH, NaOH, Na2CO3,
Most favorable experimental condition: T ¼ 530  C,
et al. [6] wastewater K2CO3 (0.4, 0.9, 12, 14, P ¼ 256 bar, Residence time ¼ 20 min, 58 wt% KOH.
(Not mentioned) 58 wt%)
COD removal range: 73e89%.

The highest percentage of COD removal was observed
in the presence of Carbonate catalysts.
Sonil Nanda fruit wastes and Batch (SS 316) 400e600 23e25 15e45 min NaOH, K2CO3 (1, 1.5,
Maximum H2 yield (0.91 mmol/g) and total gas yield
et al. [2] agro-food residues 2 wt%) (5.5 mmol/g) conditions: feed ¼ orange peel, feed
(0.1, 0.2 wt%) concentration ¼ 1:10 biomass-to-water ratio, reaction
time ¼ 45 min, temperature ¼ 600  C.

In comparison to the 2 wt% NaOH, K2CO3 with the
same concentration made the H2 yield and selectivity
increase to 4.78 mmol/g and 45.8% respectively for the
coconut shell feedstock.
Rattana Muangrat Dairy waste Batch 300e390 9.5e24.5 0e120 min H2O2, NaOH (1.5,
The theoretical hydrogen production was obtained
et al. [20] (5, 10, 15% w/v) 3.00, 5.68 wt%) 40% at 390  C.

The liquid effluent possessed over 80% of whey ni-
trogen content.

The hydrogen gas yield was decreased above the 1.5 wt
% H2O2 because the oxidizing condition was
predominant.
Leandro Ferreira- Lactose Continuous flow 550e700 22.5 30 min NaOH, KOH, Na2CO3
A decrease of 92% on the TOC (total organic carbon)
Pinto et al. [21] monohydrate reactor (SS 316) (0.1, 0.3, 0.5, 2.5 wt%) and 0.45 M fraction of H2 production was obtained,
(0.5e2.5 wt%) related to lactose gasification at a concentration of
0.5 wt%.

The increase in temperature is also a critical factor in
the efficient reduction of TOC, as, in reactions at
550  C, the reduction in TOC was ~50%, while the
700  C reduction was ~96%.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 2 2 3 6 8 e2 2 3 8 4 22371

with simple structures (like lipids, proteins, amino acids, and

Maximum H2 yield: Non catalytic (16 mol/mol), K2CO3

MnO2, MgO and formic acid is favorable for increasing

Optimum conditions for maximum H2 production (H2

35.4%), 1 wt% MgO (H2 mole composition 33%), 5 wt%

carbon gasification efficiency and H2, CO2, CH4 yields:
aliphatic compounds, etc), then the TGA/DTG figure is divided

mole composition 23%): T ¼ 400  C, Residence time:

H2 production: 1 wt% MnO2 (H2 mole composition

Optimum condition (maximize of total gas yields,

into 4 sections. The preheated region which caused almost 4%

T ¼ 700  C, feed concentration of 4 wt% lactose,

weight reduction at the temperatures below 150  C is associ-

Formic acid (H2 mole composition 33.38%).

ated with water molecules and volatile matters vaporization.
In the second section, approximately 39% mass reduction near
(21.5 mol/mol), Na2CO3 (22.4 mol/mol).

the temperature range of 150e400  C is observed which can be

traced back to the decomposition of organic materials like
hydrocarbons, proteins, carboxylic acids, etc. The peak at
234.99  C is due to hydrocarbons decomposition and a peak at
340.54  C is because of protein decomposition. Sunooj et al.
RT ¼ 60 s, P ¼ 25 MPa.

[22] observed that the maximum peak which was ascribed to

protein decomposition of cow milk and fat milk occurred in
327  C and 413  C respectively. Mocanu et al. [23] also reported
that casein was the main important substance in milk. The
60 min.

casein decomposition happened above 176  C continuing to

610  C and the maximum peak was seen at 310  C. The third
section which occurs between 400  C and 800  C is termed the
stable phase. In this region, the residual of hydrocarbons and
Na2CO3, K2CO3 (0.2,

MnO2, MgO/Formic

non-biodegradable compounds slowly decompose. The fourth

acid (1, 3, 5 wt%)

section above 800  C is related to mineral decomposition and

0.5, 0.8 wt%)

the peak at 828.19  C is due to collapsing the remains of solids

(char). The results of the elemental analysis, TGA, and HHV
calculation [24] are summarized in Table 2.

Experimental apparatus
(Residence time)

The schematic of the batch reactor is presented in Fig. A1. The

30e60 min

experiments were carried out in autoclave reactor which its

30e75 s

volume was 130 ml and made of stainless steel. A PID

controller designated the pressure and temperature equipped
with an analogue pressure gage (for the pressure inside the
reactor) and digital pressure gage. The maximum pressure
and temperature that the reactor can tolerate are 250 bar and
25

23

410  C, for safety against a sudden increase in pressure, a VEE-

LOK 6000 psi safety valve was installed on the apparatus that
its functional pressure was on 280 bar. A VEE-LOK sample
550e700

350e400

valve was mounted for getting some gaseous products and

purging remaining air. To collect the gaseous product, a 1 L
Tedlar gas bag from American SKC company with a PTFE valve
for entering and exiting gas was used. Argon gas was used as
Continuous flow
tubular reactor

Batch (SS 316)

an agent carrier to take remaining air out of the reactor. The

reactor was sealed with a spiral wound between reactor flange
(SS 316)

and its body. A 1000 W-heater and electrical fan cooler was
Dairy waste

Dairy waste
(4e10 wt%)
Lactose
Sonil Nanda
et al. [16]

This work

Fig. 1 e The TGA/DTG analysis for dry dairy wastewaters.

22372 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 2 2 3 6 8 e2 2 3 8 4

Table 2 e Characteristics of dairy wastewaters samples utilized in this study.

 
Feed Water content Proximate analysisa (wt.%) Elemental analysis (wt.%) MJ Density Color
HHVe
(wt.%) Kg Kg
m3
Dairy waste 86.34 VMb FCc Ash C H N S Od 7.406 1055.2 White
43 32 25 25.72 4.23 4.00 0 41.05
a
Dry basis.
b
Volatile matter and moisture.
c
Fixed carbon.
d
By difference (O% ¼ 100  C%  H%  N%  S%  Ash%).
   
e MJ O
By (HHV ¼ 0:338C þ 1:428 H  þ 0:095S) [24].
Kg 8

used for heating and cooling the reactor. The reactor specifi-
cations are illustrated in Table 3.
Experimental method
Firstly, feedstock was measured based on the designated
temperature and pressure and loaded into the reactor. The
reactor was sealed with six steel alloy screw between its body
and foundations. The remaining air was purged with argon
gas for three times, and then the reactor was embedded inside
the electrical heater to reach set point. At the end of experi-
ment and to terminate the reaction, fan cooler was used to
cool the reactor to the 60  C. The gas bag after evacuating to
make sure there is no air inside, was connected to the sample
valve to gather the gaseous products prior detection with gas
chromatography.
Analysis
prepared oil phase underwent chromatography tests for
organic compounds using a GC-MS system (GC-Agilent Tech-
nology) equipped with a mass spectrometer (MS-5973
Network Mass Selective Detector). Helium was a carrier gas to
separate the organic fractions on an HP-5 capillary column
(30 m length, 0.25 mm I. D, 0.25-mm film thickness). The initial
temperature in the used oven was 50  C and then was
increased to 250  C with a 10  C/min ratio. The temperatures
of the injection port and detector were 250  C and 230  C,
respectively. Some parameter definitions were used to eval-
uate the results of supercritical water gasification as follow:
P*V
GP ðmmolÞ ¼ (1)
R*T
moles all spieces in produced gas
GYt ðmmol=grÞ ¼
mass of ash  free dry matter in feedstock
(2)

moles of each spieces in produced gas

The gas products including H2, CO2, CH4 and CO were detected GYi ðmmol=grÞ ¼
mass of ash  free dry matter in feedstock
by gas chromatography (GC-2550TG), equipped with thermal
(3)
conductivity detector (TCD) and flame ionization detector
(FID).
mass of produced gas
To determine the quality of extant compounds in the GE ð%Þ ¼ (4)
mass of ash  free dry matter in feedstock
cheese wastewater, the GC-MS analysis was applied. 1 mL of
the sample was mixed with 1 mL of dichloromethane for Amount of gas production (GP) was calculated using final
1 min. The blend was kept in the test tube for 60 min to temperature and pressure after cooling until 60  C based on
separate the oil and aqueous phases. The bottom phase was the head-space volume and ideal gas rule. The head-space
the oil phase, expected to have hydrocarbons content. The volume is computed by the difference between internal vol-
ume (130 ml) and residual liquid after finishing the experi-
ment. The mole composition of each produced gas was
calculated by GC apparatus results. Gasification efficiency (GE)
Table 3 e Apparatus specifications and technical features. was used for accounting the conversion of feedstock to
Apparatus part Specification gaseous product. All aforementioned equations were based on
1 Reactor/piping material Stainless steel 316 L the amount of the feedstock without its ash (DAF) since ash
2 Total reaction volume 130 ml cannot be gasified.
3 Reactor inner diameter 42.3 mm
4 Temperature measurement K-type Thermocouple in a
thermowell
Results and discussion
5 Pressure measurement Pressure transducer and gauge
6 Temperature controller PID type
7 Pressure safety valve VEE-LOK (Set-point: 280 bar) Liquid results
8 Mechanical Seal Spiral wound gaskets
9 Sampling valve and VEE-LOK (6000 psi) The chromatogram graphs of GC-MS analysis for feedstock
connections and produced liquid phases at the temperature of 350  C and
10 Heating system Electrical heater (1 kW) 375  C at constant residence time of 60 min were illustrated in
11 Cooling system Air fan
Fig. A2, A3, and A4, respectively. Detected compounds for
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 2 2 3 6 8 e2 2 3 8 4 22373

three specimens (feedstock, liquid phases of 350  C and 375  C) other words, with incrementing the temperature the number
were summarized in Tables 4 and 5, respectively. of small compounds was increased as a result of breaking the
As shown in Fig. 2a the feedstock consists of 76.84% long-chain molecules.
alkane, 11.14% ketones, 1.29% aromatic matters, 4.07% acids, The phenols and acidic compounds plummeted to the point
2.74% esters, and 3.92% other compounds. As presented in of zero when the temperature soared. In contrast, the ketones
Fig. 2b the liquid analysis was conducted at two different were heightened. One of the reasons for increasing ketones is
temperatures (350, 375  C). According to the GC-MS results, to decrease the number of other compounds, yet the trans-
gasification was conducive to a decrease in alkanes and ar- formation of phenols as a result of hydrogenation and the cy-
omatic compounds (with and without nitrogen). This phe- clic ketone production was reported in previous investigations
nomenon is indicated the dominance of dehydrogenation [26]. On the other hand, not only did the phenols not converted
reaction; hence, the hydrogen gas was increased. It is overly into the organic acids or phenolic resins (of which migrate to
attributed to the Diels-Alder mechanism. An increase in the solid phase) but also, they might be transmuted to alde-
nitrogen-containing compounds could be due to the hydro- hydes which are activations of gasification reactions. Phenols
lysis reaction and dissolving the proteins under supercritical can react with the hydrogen and yield alcoholic rings com-
conditions [25]. pounds like Benzenemethanol. In higher temperatures, the
The important effect of temperature increase was reducing opening of the rings compounds was intensified which can
the number of compounds and their molecular weights. In culminate in olefinic alcohol production. The methanol can
easily turn into gas; on the contrary, phenols are more resistant
to gasification. The free-radical mechanism was responsible
for converting the phenols compounds to the ketones, aro-
Table 4 e Major organic compounds in feedstock (dairy
matics, and alcohol compounds [16].
wastewater) detected by GC/MS analysis.
Sonil Nanda and et al. [16] studied supercritical water
Compound Name Area (%) gasification of lactose. Concerning the results, decanoic acid
Alkanes 76.838 that was an intermediate compound was gasified owing to
1 Cyclohexane 2.991 proceeding the oxidation reaction. Organic acids usually turn
2 Ethane, 1,1,2,2-tetrachloro- 2.060 into ketones and alcohols and aromatics because of the
3 Dodecane 0.978 presence of OH. and H. radicals which were results from
4 Tridecane 0.880 splitting water. Ketones were preponderance in the liquid
5 Dodecane, 2,6,10-trimethyl- 0.461
phase and there was no trace of organic acids; thus, this
6 Tetradecane 3.401
7 Dodecane, 2,6,10-trimethyl- 2.887
observation implies that organic acids were completely
8 pentadecane 6.055 decomposed.
9 Hexadecane 5.441 Nitrogen-containing compounds were reduced when the
10 Pentatriacontane 2.862 temperature soared. Reduction or elimination of nitrogen-
11 Heptadecane 5.537 containing aromatics was ascribed to the fact that ring-
12 Pentadecane, 2,6,10,14- 2.144
opening reaction which was usually aligned with the in-
tetramethyl-
crease of temperature, took place severely. Most of the com-
13 Tetradecane 8.739
14 Nonadecane 5.285 pounds possessed one or more nitrogen atoms in their
15 Eicosane 6.089 structure. In this regard, nitrogen atoms either were migrated
16 Heneicosane 5.610 to the gas phase or transmuted to the ammonia or ammonium
17 Docosane 5.703 in the liquid phase. Lee et al. [27] showed that nitrogen atoms
18 Pentatriacontane 1.437 that did not convert to the nitrogen-containing compounds or
19 Hexadecane 4.430
ammonia, converted to nitrogen gas and migrated to the gas
20 Tetracosane 2.657
phase.
21 Pentacosane 1.191
According to the aforementioned points, it can be
Ketones 11.143
concluded that increasing the temperature not only is useful
22 2-Pyrrolidinone, 1-methyl- 5.689 but also enhances hydrogen production.
23 1-Ethyl-2-pyrrolidinone 5.453

Aromatics 1.294 Gas results

24 Toluene 1.294
Effect of temperature
Acids 3.918
The effect of temperature in the range of 350  Ce400  C at
25 Hexanoic acid 3.918 residence time of 60 min for whey wastewater was studied. As
Ester 2.740 seen from Fig. 3a, the gas production was entirely dependent
26 Hexadecanoic acid, methyl ester 1.532 on temperature. When the temperature was increased from
27 Bis(2-ethylhexyl) phthalate 1.209 350  C up to 400  C, the gaseous production was augmented
Others 4.067
from 20.54 mmol to 32.21 mmol. The gasification efficiency of
whey wastewater presents in Fig. 3b. As it was expected, the
28 Ethane, 1,1-diethoxy- 1.754
temperature had a considerable effect on GE, when the tem-
29 Triacetin 2.313
perature was 350  C, the gasification efficiency was 13.4%, and
Totals 100
when the temperature was incremented to 400  C, the
22374 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 2 2 3 6 8 e2 2 3 8 4

Table 5 e Major organic compounds in liquid products at 350  C and 375  C and constant residence time of 60 min detected
by GC/MS analysis.
Compound Name Area (%)

350 C 375  C
Nitrogen containing compounds 28.946 22.824

1 Pyrrolidine, 1-methyl- 5.260 e

2 Pyridine 0.560 0.624
3 Pyridine, 2-methyl- 4.744 3.479
4 Piperidine, 1,3-dimethyl- 1.157 e
5 Piperidine, 1-ethyl- 3.507 5.233
6 Piperidine, 5-ethyl-2-methyl- e 1.910
7 1-Butylpyrrolidine 2.531 1.553
8 Piperidine, 2,6-dimethyl- 0.270 e
9 Pyrazine, 2,5-dimethyl- 1.517 1.190
10 Pyridine, 2,3-dimethyl- 0.783 0.795
11 Pyridine, 3-ethyl- 1.043 1.359
12 Piperidine, 1-butyl- 0.508 0.624
13 Pyridine, 3,5-dimethyl- 0.843 0.644
14 Thiazole, 4-(1,1-dimethylethyl)- 0.777 e
15 Pyridine, 5-ethyl-2-methyl- 2.003 2.210
16 Pyridine, 3-ethyl-4-methyl- 0.380 0.555
17 Pyridine, 3-ethyl-5-methyl- 0.515 e
18 Piperidine, 1-pentyl- 1.259 1.813
19 Pyridine, 3-ethyl-2,6-dimethyl- 1.115 e
20 4-Methyl-3-(N-ethylamino)-phenol 0.174 0.384
21 3-Piperidino-2-pentene e 0.450

Nitrogen and oxygen containing compounds 9.956 11.475

22 1-Butanamine, n-ethyl- 0.407 e

23 1-Pentanamine, N, N-dimethyl- 0.941 1.204
24 1-Pentanamine, N-ethyl- 0.695 e
25 (1-Isopropylcyclobutyl) methylamine 0.734 e
26 Butanamide, N-ethyl- 1.207 e
27 1-Butanamine, N, N-dimethyl- e 0.363
28 N-(3-Methylbutyl) acetamide 0.900 e
29 Pyrrolidine, 1-acetyl- 2.365 2.833
30 Piperidine, 1-acetyl- 0.535 1.307
31 Benzenamine, 2,5-dimethoxy- 0.490 e
32 Pyrrolidine, 1-(1-oxobutyl)- 0.292 0.830
33 2,5-Dihydro-4-ethyl-5-methyl-2-oxo-3-propyl-1H-pyrrole 0.232 0.275
34 Acetamide, N-(2-phenylethyl)- 0.381 e
35 Butanenitrile, 4-(dimethylamino)- $$ Butyronitrile, 4-(dimethylamino)- e 2.638
36 2-Diethylaminomethyl-1,3-butadiene e 0.261
37 1-(3-Methylbutyryl) pyrrolidine e 0.253
38 Acetamide, N-(2-phenylethyl)- e 0.533
39 5-Formyl-6-methyl-2,3-dihydro-1H-pyrrolizine 0.671 0.781
40 N, N-DIMETYLPALMITAMIDE 0.105 e
41 2-Acetyl-3-amino-6,6-dimethylbicyclo [3.1.0] hex-2-ene e 0.197

Ketones 51.062 60.460

42 2-Pentanone 0.967 e
43 3-Pentanone 0.594 e
44 2-Pentanone, 3-methyl- 0.423 e
45 3-Hexanone 0.190 e
46 Cyclopentanone, 2-methyl- 0.684 e
47 Cyclohexanone 0.257 e
48 2-Cyclopenten-1-one, 2-methyl- 1.840 1.396
49 2-Cyclopenten-1-one, 3-methyl- 0.445 0.664
50 2-Cyclopenten-1-one, 3,4-dimethyl- 0.606 1.605
51 2,3-Dimethyl-2-cyclopenten-1-one 1.648 e
52 2-Pyrrolidinone, 1-methyl- 13.634 15.443
53 2-Pyrrolidinone, 1-propyl- 1.830 e
54 2-Pyrrolidinone, 1-butyl- e 7.134
55 2-Cyclopenten-1-one, 2,3,4-trimethyl- 0.462 2.435
56 1-Ethyl-2-pyrrolidinone 23.625 25.698
57 1,5-dihydro-3,5-dimethyl-1-ethyl-2(2H)-pyrrolone 0.383 e
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 2 2 3 6 8 e2 2 3 8 4 22375

Table 5 e (continued )
Compound Name Area (%)
350  C 375  C
58 1,3-diaza-4-imino-5,5-diethyl-cyclohexane-2,6-dione e 3.708
59 Hexahydropyrrolizin-3-one 1.232 1.502
60 2-Pyrrolidinone, 1-(phenylmethyl)- e 0.175
61 Pyrrolo [1,2-a] pyrazine-1,4-dione, hexahydro-3-(2-methylpropyl)- 1.423 e
62 Dipyrrolo [1,2-a:10 ,20 -d] pyrazine-5,10-dione, octahydro- 0.817 0.700

Phenol 1.304 0

63 Phenol 1.304 e

Acids 1.373 0

64 Decanoic acid 1.373 e

Alcohols 4.942 4.597

65 1-Butanol, 3-methyl- (impure) 1.036 0.982

66 Benzenemethanol 1.488 0.420
67 Benzeneethanol 2.418 2.907
68 1-Propanol, 3-(methylthio)- e 0.288

Others 2.415 0.645

69 Methane, diethoxy- 0.830 0.645

70 Cyclohexene, 1-ethyl- 0.393 e
71 1,1-(Dimethyl) spiro [2.4]] hepta-4-ene 1.192 e

Totals 100 100

gasification efficiency reached approximately 17%. It was
found that the temperature was favorable to gas production
and gasification efficiency. The reason of this phenomenon is
explained from two aspects thermodynamically and kineti-
cally. From the thermodynamically facet, a high amount of
energy is required for breaking the complicated bonds of
feedstock, so the higher temperature justifies this case [28].
Also from the kinetic aspect, it is understood that most of the
involved reactions in SCWG such as decomposition, hydroly-
sis, steam reforming are endothermic, so the temperature is
considered as a prominent parameter and increasing the
temperature proceeds gasification [29,30]. Moreover, the va-
riety of temperature had a significant effect on the composi-
tions of produced gases. As it is presented in Fig. 3c, with the
increased temperature, the gas yields of all detected compo-
nents were increased. When the temperature was increased
from 350  C up to 400  C the gas yield of H2, CO2, CO, CH4 was
increased from 0.1 mmol/gr DAF, 2.7 mmol/gr DAF, 0.51
mmol/gr DAF, 0.01 mmol/gr DAF to 1.36 mmol/gr DAF, 2.82
mmol/gr DAF, 1.2 mmol/gr DAF, 0.54 mmol/gr DAF, respec-
tively. It is also shown that the rate of the increase of H2 yield
in the range of 375e400  C was much higher than 350e375  C.
Mi Yan et al. [31] investigated on the SCWG of waste food with
the temperature range of 420e500  C Residence time of
20e60 min, feedstock concentration of 2e10 wt%. They re-
ported that higher temperature favored gaseous products in
which H2 yield was 3.92 mmol/gr DAF when the temperature
was 420  C and with an increase in temperature the H2 yield
reached to 7.91 mmol/gr DAF when the temperature was
500  C. It can be ascribed to the endothermic nature of steam
reforming reaction. It is also conspicuous that CO2 yield was
dominant in comparison with other gaseous products. It is
also attributed to the decarboxylation reaction of produced
intermediates by hydrolysis of organic matters. CH4 yield was
increased almost fifty-fold (0.01 mmol/gr DAF to 0.54 mmol/gr
DAF) to upon increasing the temperature from 350  C up to
400  C. Progression of methanation reaction compared to the
WGS reaction can be the reason for the sharp the increase of
methane [17].
Effect of residence time
According to Fig. 3d, the effect of residence time was investi-
gated at a constant temperature of 400  C and the constant
pressure of 23 MPa. As the residence time was prolonged from
30 min to 60 min, the hydrogen yield was significantly esca-
lated by 91% from 0.71 mmol/gr DAF to 1.36 mmol/gr DAF. The
range of increasing H2 yield is divided into two sections; sec-
tion Introduction from 30 to 45 min and section Experimental
from 45 to 60 min. So, as it is shown in Fig. 3d. The H2 yield was
slowly incremented by 16% from 0.71 mmol/gr DAF to 0.83
mmol/gr DAF for section Introduction, the H2 yield was
sharply increased by 61% from 0.83 mmol/gr DAF to 1.36
mmol/gr DAF for section Experimental. The CO2 yield was
dominant compared to other products, and almost it was fixed
when the residence time changed. CH4 and CO yield increased
from 0.2 mmol/gr DAF, 0.74 mmol/gr DAF to 0.54 mmol/gr DAF
and 1.2 mmol/gr DAF, when the residence time was prolonged
from 30 to 60 min, respectively. Long-chain molecules are
broken by increasing the temperature and augmenting the
CH4, H2, and CO was due to of methanation reaction from CO2
and improving the steam reforming reaction against the WGS
reaction. Proceeding the steam reforming reaction resulted in
producing hydrogen and carbon dioxide gases. Generally,
longer reaction time favored hydrogenation and methanation
22376 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 2 2 3 6 8 e2 2 3 8 4

Fig. 2 e The GC-MS results of a) feedstock (dairy wastewater), b) liquid products at different temperature and residence time
of 60 min.

reaction. WGS reaction consumed CO as a reactant to produce
CO2, so intervening the polymerization can lead to keeping
CO2 fixed [17,32e35]. The residence time had a significant ef-
fect on gasification efficiency (GE). It is found that the pro-
longed of residence time was in favor of GE. According to
Fig. 3e, the gasification efficiency was slightly improved from
14.86% to 17% with the lengthening residence time from
30 min up to 60 min. It can be explained that extended resi-
dence leads to breaking bonds of molecules and decomposi-
tion of long-chain molecules to smaller molecules [20].
Effect of catalysts
The main aim of SCWG of biomass is to generate H2; as it was
discussed, the temperature played a vital role in SCWG, more
H2 yield was obtained at a higher temperature, and in terms of
the economic aspect, reaching the higher temperature in-
creases operational cost. To tackle this issue, catalysts and
additives are proposed. Previous sections helped us determine
the optimal conditions for the SCWG of whey. As it was
mentioned, higher temperature and residence time were
favorable to GP and HP. The temperature of 400  C and resi-
dence time of 60 min were designated to conduct catalytic
experiments. The used catalysts in this work were MgO and
MnO2. The experiments were performed at diverse catalyst
loadings (1 wt%, 3 wt%, and 5 wt%). The concentration of
catalyst was calculated concerning the quantity of feedstock,
on the other hand, the ‘‘catalyst loading’’ term was concluded
as the weight of catalyst based on the weight of the feedstock.
Fig. 4a and b illustrate the effect of MnO2 and MgO loading on
gas composition respectively. According to Fig. 4a, the content
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 2 2 3 6 8 e2 2 3 8 4 22377

Fig. 3 e Effect of reaction temperature at constant residence time of 60 min on a) Gas production, b) gasification efficiency, c)
gas yield, as well as effect of residence time at constant temperature of 400  C on d) gas yield, and e) gasification efficiency.

of hydrogen was 23% when the experiment was conducted
without a catalyst. When the loading of the catalyst was 1 wt
%, the content of hydrogen promoted to 35.4% while
increasing catalyst loading to 3% led to an unexpected
decrease, the hydrogen content in 3 wt% MnO2 was reached to
31.2% and by increasing the catalyst loading to 5 wt% the
hydrogen content plummeted to 29.5%. As it was inferred, the
MnO2 catalyst had a positive impact on hydrogen production
up to a certain point and after that, the hydrogen content was
reduced. The mole composition of CO was declined after
loading MnO2 to 1 wt%. The mole composition of CO was
20.27% when there was no amount of catalyst inside the
reactor, and by increasing catalyst loading to 1 wt%, 3 wt%,
5 wt%, the mole composition of CO was decreased to 15%, 18%,
and 19.3% respectively. A peak in 1 wt% of MnO2 was observed
for CO production like H2 production. Fig. 4b represents the
effect of MgO catalyst loading on detected gas composition.
There is a climax for hydrogen and carbon monoxide pro-
duction in 1 wt% of catalyst loading. It can also have the same
reason as the MnO2 does. The increase of H2 and the decline of
CO can be explained by promoting WGS reaction in which the
presence of metal oxide as an active phase catalyst leads to
releasing active oxygen in reaction space. Active oxygen
causes hydrogen production and breaking large-chain
22378 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 2 2 3 6 8 e2 2 3 8 4

Fig. 4 e Effect of catalysts/additive loading on gas composition for a) MnO2, b) MgO, c) formic acid as well as gasification
efficiency for d) MnO2, e) MgO, f) formic acid at 400  C and 60 min.

molecules to form smaller molecules. This phenomenon is
organic compound oxidation. MgO and MnO2 are metal oxides
that contain oxygen. Although the active oxygen first caused
more feedstock decomposition and hydrogen production, it
can also consume the hydrogen because the oxidization re-
action is a great factor that proceeds by increasing the loading
of the MgO and MnO2 catalysts [36]. The metal oxides were
responsible for promoting the water-gas shift reaction
because the hydrogen and carbon monoxide were increased
and decreased respectively. Carbon monoxide is a reactant of
water-gas shift reaction. Conversely, the carbon dioxide was
increased erratically when the catalyst loading soared but the
carbon dioxide fraction was not as much as the state that no
catalyst was added. The reason was absorbing the carbon di-
oxide by unsupported catalyst [37].
Fig. 4a and b shows the effects of MnO2 and MgO catalysts
on gasification efficiency at 400  C and 60 min respectively. As
it is represented in Fig. 4d, the GE for the non-catalytic con-
dition was obtained 16.91% while by adding 1 wt% MnO2 the
GE was reached 16.61% which is almost as every bit equal as
the non-catalytic condition. By increasing the MnO2 loading
the GE was increased. When the test possessed 3 wt%, 5 wt%
MnO2, the GE was enhanced to 18.36% and 23.87% respec-
tively. This phenomenon occurred when MgO was applied to
the reactor. According to Fig. 4e, the GE has reached points of
16.57%, 19.79%, and 22.66% when 1 wt%, 3 wt%, and 5 wt%
MgO were added. The results complied with a work of
Changqing Cao et al. [36] which alluded that metal oxides
were responsible for promoting the decomposition reaction
not only by providing active sites but also by introducing
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 2 2 3 6 8 e2 2 3 8 4
active oxygen molecules which are great factors in augment-
ing gasification.
The reason that the metal oxide catalysts were used in this
research was to investigate the effectiveness of metal oxide
catalysts for hydrogen production to gain a profound under-
standing of these metal oxides for real catalysts synthesis,
secondly, for introducing metal oxides as alternatives of oxi-
dants of the supercritical water environment. Because metal
oxides do not have any corrosion or hot spot problems of
oxidants in supercritical water partial oxidation [36,38].
Effect of formic acid additive
Organic solvent formic acid has been determined as a reaction
medium to promote hydrolysis of organic feedstock in order to
break long chain molecules and improve rate of hydrogen
generation [39]. In order to investigate the effect of formic acid
additive, the experiments were conducted at optimum con-
ditions (temperature of 400  C and residence time of 60 min)
with catalyst loading of 1 wt%,3 wt%,5 wt%. Definition of ad-
ditive loading is as same as catalyst loading and it is calculated
based on the feedstock weight. Fig. 4c shows the effect of
formic acid loading on gas composition of detected gases. As it
is represented, when the SCWG of whey was performed
without any additives and catalysts, the gas composition of H2
and CO2 were obtained 23% and 47.53% and by adding more
catalyst loading up to 1 wt% into reaction space, the content of
H2 and CO2 reached to 28.34% and 50% and when the catalyst
loading continued to increase up to 5 wt%, there was an in-
crease in the content of H2 and CO2, so the content of H2 and
CO2 33.38% and 54.36% respectively.
There are different types of articles related to formic acid
decomposition and its effect on hydrolysis. Formic acid is a
hydrolysis agent for organic matters, so that increasing in
temperature can promote hydrolysis reaction. Formic acid is
not degradable up to 200  C and decomposition of formic acid
near the critical point and supercritical point of water is
divided into two pathways: 1-dehydration reaction 2-decar-
boxylation reaction; an increase in temperature causes
domination of decarboxylation reaction. Intermediate of
decomposition of formic acid is hydrogen free radical that can
result in speeding up the decomposition of organic matters
because of having high reactivity. It is believed that hydrolysis
is the most important reaction for producing hydrogen that
free radicals play crucial role in producing hydrogen; addi-
tionally, the reason of adding catalysts and additives is
improving the free radical reactions. Free radicals of hydrogen
have a high reactivity in hydrocracking reactions and are
agents for suppressing the polymerization and condensation
reactions. As it is shown in Fig. 4e, hydrogen production was
increased by loading formic acid into reaction space.
Hydrogen production from formic acid under these conditions
and this quantity of formic acid is not that much considerable.
Results showed that presence of formic acid caused promot-
ing the steam reforming and WGS reactions [40e43].
Fig. 4f represents the effect of formic acid on gasification
efficiency of whey at supercritical water. It can be seen that in
SCWG of whey, gasification efficiency with the presence of
formic acid was more effective compared to the SCWG
without any formic acid. The GE for the SCWG of whey
without formic acid was 16.91% and by loading formic acid
22379
into reactor up to 1 wt% the GE was increased slightly to
17.82%. At the point of 3 wt% of formic acid the GE significantly
soared to 22.2% and by adding more formic acid concentration
up to 5 wt%, the GE was augmented to the point of 32.22%. It
was obvious that the trend on Fig. 4e complies with the
exponential trend line.
Fig. 5 illustrates the effects of MnO2, MgO, and formic acid
in diverse concentrations. As it is presented, the highest
hydrogen fraction was obtained in 1 wt% MnO2 and by
increasing MnO2 loading the hydrogen production was sub-
sided while the hydrogen production was increased by adding
formic acid into the reactor. The hydrogen production was
almost as much as the highest occurring in 1 wt% MnO2. The
addition of formic acid may surpass the highest hydrogen
content occurring currently.
Reaction pathway
In order to investigate the reaction pathway of supercritical
water gasification of real biomass we have to gain insight into
reaction routes of similar feeds. In this way, a short preview of
sundry work was conducted then, in accordance with GC-MS
analysis of this work, a reaction pathway was proposed. Pro-
posing a mechanism route in supercritical water condition,
we have to have a profound understanding of the cheese-
based feedstock. The main part of cheese-based wastewater
consists of lactose, protein, and inorganic materials [16]. Ac-
cording to the aforementioned sections, the major routes of
biomass decomposition under supercritical water conditions
are hydrolysis, pyrolysis, synthetic, steam-reforming, and
dehydrogenation reactions. Insoluble organic matters turn
into short-chained molecules (finer molecules) via breaking
the CeC bonds of long-chain molecules and consequently, gas
is produced. The organic acid conversion to gas is due to the
decarboxylation reaction [44,45]. The mechanism of polycyclic
compounds production can be conducted in two ways: 1-
using recombination reaction 2- using Diels-Alder reaction.
The alkanes and alkenes can be yields; furthermore, the long
reaction time and higher temperature can assist in producing
free radicals which are the main grounds of further decom-
position and gaseous products [46].
Azadi et al. [47] illustrated the catalytic decomposition of
organic materials under supercritical water conditions. The
results presented that in the beginning, the monomers and
oligomers were produced, in this regard, the alcoholic and
acidic intermediates were generated. Then, the CeC bonds of
materials were broken due to the contacting the metal sur-
face, and gaseous products which were mainly composed of
hydrogen and carbon dioxide were simultaneously produced
by using a water gas shift reaction. The oxygenated methane
could be created by breaking CeO bonds.
Pinkard et al. [48] studied supercritical water gasification
of ethanol and methanol in the temperature range of
500e560  C and residence time of 3e8 s. The results showed
that methanol can be converted into hydrogen, carbon
monoxide, carbon dioxide, and little formaldehyde. The
formaldehyde was recognized as an intermediate product
which was short-lived. Gong et al. [49] examined the super-
critical water gasification of humic substances as a model
22380 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 2 2 3 6 8 e2 2 3 8 4
Fig. 5 e The comparison of produced hydrogen content at different concentrations of catalysts at 400  C and 60 min.
compound of sewage sludge. The FTIR results of humic
feedstock and produced char in the temperature range of
325e600  C was emblematic of the composition of humic
acid which was chiefly constructed of carboxylates and
phenols. When the temperature was increased, the dehy-
drogenation, dihydroxylation, deamination, demethylation
reactions were activated. Chao Zhu et al. [50] inquired about
the mechanism and reaction pathway of supercritical water
gasification of guaiacol in the quartz reactor. The residual
intermediates of liquid products primarily contained phe-
nols, arens, cyclopentanones, alcohols, and organic acids.
The results indicated that guaiacol due to the removal of
methoxy groups convert into methanol and phenol. Meth-
anol, on the contrary to phenols, can easily be gasified.
Phenols can react with hydrogen and yield cyclohexanol
which can turn into hexanol and hexanone owing to the
ring-opening reaction. Hexanol and hexanone are aliphatic
hydrocarbons which can be easily changed into gaseous
products. These open-ring compounds can react with su-
percritical water to generate smaller molecules like ketones,
alcohols, organic acids, and alkanes. It seems that these
compounds are not stable in a supercritical water environ-
ment and with more conducting reactions, they can create
hydrogen-rich gas. Phenols can turn into the alkyl phenol via
alkylation reaction which cannot be effortlessly converted
into gas. Monocyclic, polycyclic, and heterocyclic aromatic
compounds can be produced by more reactions of alkyl
phenols which can be transmuted to tars and chars.
D. Klingler et al. [51] launched an investigation on hydro-
thermal gasification of alanine and glycine. One of the greatest
advantages of this work was having a similarity of tempera-
ture range with ours up to a certain point. The results showed
that there was a competition between decarboxylation and
deamination reaction. Alanine could be decomposed via three
reactions (hydrolysis, deamination, and decarboxylation);
therefore, lactic acid and ethylamine were produced. The
production of ethylamine was along with carbon dioxide
production. Ethylamine was recognized as a persistent com-
pound to be gasified. Lactic acid decomposed to acetaldehyde
and Propionic acid. The discrepancy between lactic acid
decomposition and acetaldehyde production was to produce
carbon dioxide, carbon monoxide, and methane. According to
the results of glycine decomposition, in the higher tempera-
ture glycine could be degraded quickly; therefore, the ethyl-
amine was produced. There is a noteworthy point that by
producing an ethylamine molecule, a carbon dioxide molecule
was produced. Methylamine like ethylamine was identified as
a persistent element. The dimerization of glycine was
responsible for diketopiperazine production along with water
production. The diketopiperazine decomposed to glycolic acid
via hydrolysis and deamination reactions. The results eluci-
dated that there was a little amount of glycolic acid in the
liquid phase because glycolic acid decomposed to formalde-
hyde due to further reactions consequently the formaldehyde
decomposed to gases.
Jale Yanik et al. [52] looked into the protein decomposition
based on the collected evidence. The proteins hydrolyzed to
amino acids then, amino acids decomposed to smaller mole-
cules and carboxylic acids, finally to the smaller compounds like
formic acid and acetic acids. Generally, the carbonic acids and
amines were produced from amino acids via decarboxylation
reaction, and ammonia and organic acids were produced via
deamination reaction. It should be mentioned that the propor-
tion of deamination to decarboxylation reaction rate depended
on the type of amino acid. As a result, organic acids were con-
verted into carbon dioxide, carbon monoxide, and hydrogen.
According to a work published by Rattana Muangrat et al.
[20], It can be expected that functional nitrogen-containing
groups like nitriles, amines, and amides produced ammonia.
With increasing the temperature, inorganic ions decreased
except NHþ 4 ion. This increase was attributed to two agents
first the proceeding hydrolysis of proteins second, the higher
concentration of Hþ; furthermore, the ammonia production
hindered the hydrogen production.
A synopsis of several researches on protein and cellulose
decomposition conducted by Saqib Sohail Toor et al. [53]. By
investigations related to this issue, sugars and amino acids
were produced via hydrolysis of biomass. These compounds
yielded nitrogen-containing cyclic organic compounds like
pyridines and pyrroles using the Millard reaction. These
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 2 2 3 6 8 e2 2 3 8 4 22381

Fig. 6 e Proposed reaction pathway of hydrothermal and supercritical water gasification of dairy wastewater (The bold lines
were detected by GC-MS analysis as well as conducted literature review, yet the dash-lines were detected by only literature
review).

compounds impeded the free-radical chain reactions which
were substantial to hydrogen production.
Sonil Nanda et al. [16] studied supercritical water gasifi-
cation of lactose as a model compound for dairy effluent. The
main part of the liquid phase was composed of ketones and
phenols which can be the result of complete degradation of
organic acids and finally they formed gaseous products via
methanation, steam-reforming, and water gas shift reactions.
The alcohol production was due to the free-radical mecha-
nism reaction, on the contrary, the phenols' and organic acids’
productions were because of the ionic mechanism reaction.
Aldehydes production was due to both ionic and free-radical
mechanisms in tandem. The phenolic compounds can form
ketones, aldehydes, and aromatic via a free-radical mecha-
nism reaction. Also, lipids can be converted into fatty acids
and glycerol which can degrade to acetaldehydes, acrolein,
and allyl alcohol.
In a study conducted by Yulin Hu et al. [54], the chemical
components derived from catalytic hydrothermal liquefaction
of algal lipid were designated by GC-MS analysis. The data
showed that the bio-oil was mainly comprised of hydrocar-
bons, phenols, nitrogenated compounds, oxygenated com-
pounds and other aromatics. As reported, the high amount of
nitrogenated compounds is attributed to protein degradation.
These nitrogenated matters and oxygen-containing com-
pounds were formed by Millard's reaction between sugars
derived from carbohydrates and amino acids decomposed
from protein.
Sonil Nanda et al. [55] investigated the waste cooking oil
(WSO) decomposition in supercritical water. Based on this
research, the WSO feedstock goes through 3 stages of
decomposition, respectively; first hydrolysis, decomposition,
and depolymerization reactions into the long-chain fatty
acids, second CeC bond cleavage and thermal cracking into
the short-chain and saturated fatty acids and third decar-
boxylation reactions into aliphatic hydrocarbons like meth-
anol, glycerol, and so on. Aromatic can be formed by the
removal of hydrogen from cyclic compounds. The aromatic
and cyclic compounds are persistent to be gasified because of
their high stability. On the contrary, the short-chain and
aliphatic hydrocarbons can be easily transformed into
gaseous products by thermal cracking and steam reforming.
The water-gas shift and methanation reactions were also
active among H2, CO, CO2, and CH4.
All aforementioned studies and the results of GC-MS
analysis can lead us to determine a reaction pathway of
22382 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 2 2 3 6 8 e2 2 3 8 4

Table 6 e SCWG reaction type corresponding to different range of operational parameters.

Experiment Water gas shift Steam Methanation Methanation
reforming from CO2 from CO
T ¼ 350  C, different time þ þ
T ¼ 375  C, different time þ þ
T ¼ 400  C, different time þ þ
t ¼ 30 min, different temperature þ þ
t ¼ 45 min, different temperature þ þ
t ¼ 60 min, different temperature þ þ
Additive: Formic acid þ þ
Catalyst: MnO2 þ
Catalyst: MgO þ

supercritical water gasification of real dairy wastewater which augmented. MnO2 was a promising catalyst that enabled us to
is the first work-related. The reaction mechanism of super- reach the highest hydrogen content (35.4%) in 1 wt% concen-
critical water gasification of dairy wastewater is represented tration and Formic acid addition in 5 wt% brought about the
in Fig. 6. As we know, dairy wastewater contains alkanes, highest GE (32.22%). GC-MS analysis and literature review of
acids, proteins, lipids, and lactose. Acids and alkanes are previous researches related to proposing a reaction pathway
converted into alkenes via dehydration and Diels-Alder reac- were come to suggest a reaction mechanism of supercritical
tion. Alkenes turn into aromatics via cyclization and aroma- water gasification of cheese-based wastewater.
tization reactions. The high temperature causes the aromatic
to form polycyclic aromatic hydrocarbon. The existent pro-
teins after breaking into amino acids undergo decomposition, Declaration of competing interest
deamination, decarboxylation, and recombination reactions
which bring about nitrogen-containing aromatics like pyri- The authors declare that they have no known competing
dines, organic acids like propionic acids, amines like dime- financial interests or personal relationships that could have
thylamine and the compounds result from dimerization like appeared to influence the work reported in this paper.
diketopiperazine. Breaking the CeO bonds of glucose and
fructose compounds which derive from lactose can lead to
alcohols and phenols production, then alcohols turn into
Acknowledgment
gaseous and light products. Phenols turn into aromatics
without nitrogen via alkylation reaction. Also, cyclohexanes
This research was fully supported by “Green Technology
are produced from phenols by striking the hydrogen-free
Laboratory” at School of Chemical Engineering, College of
radicals which are highly reactive. Cyclohexanols turn into
Engineering, University of Tehran, Iran.
hexanons and hexanols via ring-opening reactions which give
rise to the production of intermediates like aldehydes, alco-
hols, ketones, and alkanes, and finally, the gaseous products
Appendix A. Supplementary data
will be yielded. The higher temperature is favored to the ar-
omatics without nitrogen and compounds which are yields of
Supplementary data to this article can be found online at
dimerization reaction then, the polycyclic aromatic hydro-
https://doi.org/10.1016/j.ijhydene.2021.04.089.
carbons will be produced.

Nomenclature table
Conclusion

The dairy wastewater was used to produce hydrogen via su- Abbreviation signsDefinition
percritical water gasification (SCWG). Different parameters GP Gas Product
like temperature and residence time were examined. A con- GYt Gas Yieldt
dition that temperature and residence time was 400  C and GYi Gas Yieldi
60 min was recognized as an optimum condition in terms of GE Gasification Efficiency
hydrogen yield (1.36 mmol/gr DAF). Effects of two catalysts TGA Thermogravimetric analysis
(MgO and MnO2) and one additive (formic acid) were investi- TCD Thermal conductivity detectors
gated. Four reactions were responsible for gasification and DTG Derivative thermogravimetry
among them the water gas shift and steam reforming were FID Flame ionization detector
desirable to produce hydrogen. In Table 6, reactions that were DAF Dry ash free
dominant in each experiment are summarized. The results WGS water-gas shift
also represented that by increasing the catalysts loading, the SCWG Supercritical water gasification
hydrogen production (HP) was first increased and then HP Hydrogen production
decreased, on the contrary, the gasification efficiency (GE) was GC-MS Gas chromatographyemass spectrometry
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 2 2 3 6 8 e2 2 3 8 4 22383

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