Abstract

Introduction

Literature review

Sewage statistic

• Current status on the statistic of waste water in Ho Chi Minh city

• Types of sewage
• Wastewater sludge
• Algae
• Wastewater sludge management

Fundamentals of HTL

• Hydrothermal liquefaction of biomass

• Feedstocks and Their Primary Compounds
• Possible Hydrothermal Pathways
• Bio-Oil Production from Sludge through HTL
• Solvent

Effects of Operating Process on HTL

• Effects of Type and Composition of Feedstock

• Effects of Catalyst
• Effects of Reaction Temperature
• Effects of pressure
• Effects of Residence Time
• Effects of Water to Biomass Ratio
• Heating rate (heating value)

Research Approaches and Methodology

• Batch and continuous flow reactor

• Review of subcritical water technologies
• Pilot plant testing for HTL

Abstract
The volume of industrial, commercial and domestic waste produced in a megacity is enormous.
Similarly, society in megacities have an insatiable appetite for energy. There is a need to find
sustainable solutions to manage waste and produce energy, which in terms of scale may be
commercially viable within a megacity if waste and energy production are synergistically
managed. The project aims to quantify the scale and composition of waste typically found in a
megacity and determine how these wastes can be sustainably converted to energy. The wastes
are to be classified in their suitability for existing and emerging waste-to-energy technologies. In
particular, a focus will be on the production of renewable transportation fuels from organically
rich waste streams, where hydrothermal processes will be investigated. Once the wastes have
been quantified, synthetic representations of these wastes will be prepared and converted via
hydrothermal processing technologies to quantify their economic and technical feasibility.
Introduction

Municipal wastewater (MWW) management is a major issue in the countries worldwide. This
problem is more sensitive in developing countries, because the total amount of MWW has
dramatically increased due to rapid urbanization and industrialization in the cities of developing
countries, in particular, the present of megacity (Manaf, et al., 2009; Refee et al., 2008). Due to
the lack of effective management programs, regulations, and policies; wastewater is causing
sever health hazards including several communicable diseases, bad odors, nuisance, and
environmental impacts, such as, water pollution, soil pollution, and air pollution, if the untreated
wastewater is discharged into environment. Most of Southeast Asian Cities are lacking policies,
regulations, basic-infrastructure, and efficient MWW management programs (UNEP, 2004).

Ho Chi Minh is the core of Vietnam’s largest urban area, heading towards a population of 12
million in 2025, including peri-urban areas . It is a mega city and the economic center of the
country. The administrative area covers 2095 km2.Currently, about 8.2 millions inhabitants live
in the entire territory of the city, resulting in an average density of 3400 persons/km2. With rapid
economic growth, and increasing population with their higher income and better lifestyle, the
quantity of MWW and problems associated with wastewater as well as sludge are becoming a
serious problem in Ho Chi Minh (Dhokhikah and Trihadiningrum, 2012). Wide range of
industrial teachnology are commonly utilized to deminish high toxic ingredients in wastewater
into the standard level before the water source is reused or sent into the rivers. However, while
the treated water resource is able to be discharge into receiving sources in accordance with
National Regulation and Policy , the treatment of sludge is much more complicated. Most sludge
treatment plant and technologies do not meet the standards when discharging into the
environment. Moreover, the sludge also account for a relatively large volume of very different
components which have not had adequate attention, or more precisely work of the state
administration for this type of waste is not fully implemented; it can say almost loose due to
many causes, as well as subjective. Over time and with the increasing demands on quality of life
as well as environmental protection requirements of the city, the sludge are paid more attention
due to their ability to pollute the environment and affect our urban landscape.

In this study, quantified wastewater generation and analyzed its composition is conducted in
order to propose appropriate methods of management. Further to this, we analyzed gaps in
regards to waste management technology. A novel process for co-production of biogas and bio-
crude oil from high-water content wastewater sludge through hydrothermal liquefaction (HTL)
treatments is developed. Hydrothermal liquefaction is a thermochemical process where raw
sludge can be heat treated directly in the absence of oxygen and in the presence of water as the
reaction medium mostly in subcritical or near critical conditions. This eliminates the need to
dewater/dry biomass which can be a major energy input for biofuel production via other
processes such as pyrolysis or gasification. Since hydrothermal liquefaction is a promising
technology for conversion of high-water-content biomass without the need of costly sludge
dewatering, it could replace the conventional sludge treatment by making valuable energy
products out of a waste material.
Literature review
Sewage statistic

Current status on the statistic of waste water in Ho Chi Minh city

Types of sewage

Wastewater sludge

Algae

Wastewater sludge management

Fundamentals of HTL

Hydrothermal liquefaction of biomass

Hydrothemal liquefaction (HTL) involves biomass direct liquiefaction process for

reduction of complex organic into biofuel and other ingredient with presence of solvent ( the
popular solvent is water). The operating conditions for this process requires the high pressure of
100-300 bar and moderate temperatures of 200-350oC (14) compared to pyrolysis
which operates at and high temperatures (> 500oC) and mild pressure (0.1-0.5 MPa) (2) (3) (4)
Pyrolysis is method using heat for decomposition of organic ingredients in the absence
of air (oxygen) (3). In industry application possibility, fast pyrolysis ( rapid heating of
dry biomass material) is the only possible realized teachnology for bio-fuel production.
However, pyrolysis processes requires the relatively dry feedstock, which narrows its
application for wastewater streams and wet material ( up to 90% water). Furthermore,
the drying process consumes intensive energy, and hence it could not economically
efficient.

One benefit of HTL compared to pyrolysis is that there is present of water as a solvent,
mostly in near critical or subcritical conditions (T < 374oC and P < 22.1 MPa). This makes
HTL becomes a promising conversion process, which eliminates the need of drying/ de-watering
process for wastewater biomass. There is a wide range of valuable product covered from HTL
includes: char solid, syngas, water soluble products and bio-oils. In particular, HTL is the
potential process produce bio-oils with high heating values (31- 35 MJ/kg) since produced oils
have lower water and oxygen content (5% and 10-20%, respectively) compared to bio-oils
produced from pyrolysis process (5)

Wastewater Sludge

Wastewater sludge is the main waste from wastewater treatment, containing high percentage of
water (> 90% on wet mass basis). The U.S. is currently producing 6.9 Million dry tons of sewage
sludge annually and Canada produces more than 0.66 million dry tones (2.5 million wet tones) of
biosolids and sludges per year. (6) (7) The City of London operates six Wastewater Treatment
Plants namely: Greenway, Pottersburg, Vauxhall, Adelaide, Oxford and Lambeth (Southland).
The average daily flow through all the treatment plants is approximately 209,000 cubic metres
per day based on data on 2013.(8)

Sewage sludge is generally the solid residue from the wastewater stream and can be produced in
two steps during the treatment of the effluent. Primary sludge is generated during the removal of
insoluble matters such as grit, grease, and scum from wastewater by screening followed by
coagulation and sedimentation. The settled primary sludge contains mainly water (between 97%
and 99%) and highly putrescible organic matters. The secondary sludge or waste activated
sludge (WAS) is generated as a result of biological treatment of the effluent from primary
treatment rich with dissolved organic matter, and it consists of a complex activated sludge.
Generally, sludge is a mixture of organic or volatile matters (such as proteins, carbohydrates and
lipids), inorganic matters and associated water. Typical characteristics of the two different sludge
types are listed in Table. As shown in Table , primary sludge typically has higher percentage of
total solids (TS) compared to the activated sludge. The two types of sludge contain resources
such as nitrogen (1.5-4 % for primary and 2.4-5 % for activated sludge) and phosphorous (0.17-
0.6 for primary and 0.6-2.3% for activated sludge) which could be recovered and used as
fertilizers or soil conditioners. According to Table , primary sludge usually has higher energy
content because it is captured via gravity and therefore its energy content has not yet been
consumed, while during the secondary treatment the microorganisms have consumed most of
their energy content leaving behind mainly inert biomass.
Feedstocks and Their Primary Compounds + Possible Hydrothermal Pathways

The reaction pathways for hydrothermal liquefaction of biomass depend on the components

of the biomass. Each type of biomass has its own specific composition. The main biomass

components are :

 Carbohydrates.

 Lignin.

 Protein.

 Lipids.

The degradation products of these components in sub-critical water differ significantly for each
specific type of biomass; however the basic reaction mechanisms for HTL remain the same. The
basic reaction mechanisms can be described as :

 Depolymerization of the biomass.

 Decomposition of biomass monomers by cleavage, dehydration, decarboxylisation

 and deammination.

 Recombination of reactive fragments

Solvent

In general, previous researches indicated that using water as solvent, oil yields increased
comparing to oil yields collected from alcohols and acetone under similar temperature
conditions (9-13). The Figure illustrates the phase diagram of water where at high
pressure ranging from 100-250 bar and moderate temperature 200-350℃, the properties
of near- supercritical water ( sub- critical water) is formed in liquid state. El-Rub (2004)
indicated that sub-critical water is used as optimal solvent, catalyst and reactant for liquefaction
conversion (14-15). Moreover, this type of water is an excellent medium for efficient and
homogenous reactions since it is highly soluble in organic subtances and has a low viscosity,
relative high density and dissociation constant (14). The combination of these properties
allows ionic reaction occurs completely. Sub-critical watet acts as a catalyst and reactant, which
promotes the molecues transformation through a cascade of complicated reactons into bio-oils
product. H+ from the water is added to break carbon bonds, which causes disintegration and
reformation of organic material into fregments and then into hydrocarbons transfromation (16)
.This cascade is drived by the acidic and basic nature of hot water.

Effects of Operating Process on HTL

The impact of various operative conditions on the bio-oil production from HTL technology was
extensively investigated in previous literature. The parameters includes temperature,
solvent to biomass ratio, heating rate, residence time and pressure have important
contribution to the quality of the end product (17).

Temperature
Biomass liquefaction reaction is endothermic at the low temperatures and exothermic at high
temperature (17). Since the properties of water changes rapidly within near critical conditions ,
the optimun temperature for achiving maximum oild yield is sequential (14). Initially, increasing
temperature gradually enhences the bio- oil yield efficiency and then gaining a certain peak for
the bio-oil yield. However, a further increasing in temperature reduces the bio-oil percentage in
the final product. This behavior could be explained by two mechanism from El-Rub research in
2004:
• The secondary decompositions and Bourdard gas reactions become active at high temperatures
which lead to the formation of gases (18).
•The recombination of free radical reactions leads to the char formation due to their high
concentrations (17).
Residence time
Duration of reaction has the certain contribution on the distribution of the final product and
overall conversion of HTL. The effect of residence time on bimass hydro liquefaction has been
discovered in previous researches. Qu et al. (20) and Yin et al. (21) suggested that 10-min
holding time at a specificed temperature was sufficient for woody biomass and cattle manure to
form oily subtance in the presence of NaOH as a catalyst, giving the highest bio-oil yield.
However, Yin et al. (21) also indicated that a higher residence time effects negatively on the bio-
oil yield (increase time from 15 to 40 minutes resulted in oily yield decrease from 39.6% to
13%). Similar results were obtained by Anastasakis and Ross (19), where the highest oil yield
from seaweed was achieved in a residence time of 15 minutes.The explaination for this trend is
as a result of restriction of secondary or tertiary reactions that reversely convert the heavy oil
into water, solid residue and bio gaseous product (22-23).

Solvent to biomass ratio

There has been a lot of previous research about the effect of water to biomass ratio or solvent
density on HTL oil yield. In HTL, mass ratio of biomass to water plays a significant role since it
acts as both a solvent for hydrolyzing carbonhydrates which have high molecular weight presents
in biomass and a hydrogen donor (19). Sun (22, 24) reported that low moisture content in reactor
feed could restrict the hydrolysis of biomass, which leads to smaller production of bio-oil and
higher yield of char or solid residue. In contrast, increasing the water concentration leads to the
higher oil yield, possibly because denser solvent medium enhances the extraction (14). For
instance, Yin et al. (23) reported that bio-oil yield decreased aggressively from 49% to 1.5 wt%
when corresponding mass ratio of water to cattle manure was decrease from 2 to 0.5. , Yin et al
(23) believed the decrease was due to the conversion of bio-oil/intermediates into solid residue
through self-condensation reactions. Boocock and Sherman (25) also observed greatly reduced
oil yields at high wood-to-water ratios during HTL of polar wood at 350 oC, suggesting the
critical solvent/reactant roles of water in biomass HTL process, which contribute to hydrolytic
degradation of lignocellulosic biomass and stabilising the product oils.

Pressure
In supercritical medium, the low pressure has negative impact on the yield of bio- oil yield. The
main aim of pressure is to remain one single phase during HTL reaction. Single phase
liquefaction is critical to prevent large enthalpy inputs required for phase change of solvent
(17).However, the pressure has negligible role in improving the bio- oil percentage once the
conditions for HTL is set up (17)

Catalyst
Hydroxides, carbonates, bicarbonates and formates of the alkali metal are used as catalysts
during hydrothermal liquefaction in general. It has been widely demonstrated in many studies
that use of a catalyst in HTL of biomass could effectively promote liquefaction efficiency
leading to higher biomass conversion and bio-oil yields as well as improved oil quality (heating
values). Different kinds of homogeneous and heterogeneous catalysts have been employed in
hydrothermal liquefaction process, but the most common catalysts used were alkali metal
compounds, e.g. Na2CO3, NaOH, K2CO3, KOH, LiOH, RbOH, and CsOH.

Heating rate (heating value)

Quang et.al (28) indicated that the heating rate has strong impact on the product yield. It has
been confirmed that during HTL processes higher heating rates significantly contributed to the
oily yield. Although the chemical properties behind this impact has not been yet fully
understood, Quang et.al (28) summarized some possible explanations:

 Rapid heating accelerates the degradation reactions of biomass materials.

 Rapid heating reduces unwanted side reactions and promotes reactions forming more bio-
oil.
 Rapid heating accelerates the breaking of biomass cell and thus eases the releasing of cell
contents into the hydrothermal media for subsequent reactions.
 Rapid heating minimizes the char formation and/or the re-polymerization.

Research Approaches and Methodology

Batch and continuous flow reactor

Most of researches preferred the HTL reaction was occurred in batch reactor. However, from the
economic perspective, continuous flow reactors are suitable for large- scale applications of the
HTL technologies, which lead to economically feasible process and energy utilization efficiency.
One disadvantage of batch reactor is that it could be not possible to achieve high bio-oil yield in
the short residence time. In additional, continuous flow reactor could control residence time to
achieve the maximum higher bio-oil yield.
In a HTL of Chlorella and Spirulina microalgae study, Jazrawi et al (26) used a continuous flow
reactor of 2L volume, the operating condition included pressure of 150-200 bar, temperature of
250-350oC and residence time of 3-5 min. The author discovered highest bio-oil yield of 41.7 %
was achieved at 350oC and residence time of 3 min. In other study in three types of sludge (one
waste water sludge with 7.7% solid concentration, two industrial sludge samples), .
Hammerschmidt et al. used (27) a continuous flow reactor of 127 ml with feed flow of 5.2 and
10.5g/min, temperature ranging from 300-350oC and pressure of 25 MPa were set up. This study
firstly mixed homogeneous catalyst K2CO3 with feed stream and then the mixture was pumped to
the reactor filled with ZrO2 as a heterogeneous catalyst. Although the residence time in the
catalytic bed was controlled to be 10 minutes in most runs, a longer residence time and higher
catalyst concentration of the feed resulted in greater bio-oil yields.

Review of subcritical water technologies

Pilot plant testing for HTL

Knowledge Gap and Project Objectives
The main important knowledge gaps are listed below:
 Not enough data are available on HTL of wastewater sludge. The reported bio-oil yields
are usually low due to low solid concentration of sludge.
 Very few studies have been performed on the effects of co-feeding of different
 feedstocks.
 Most of the HTL experiments are performed in batch reactors. Very few continuous
reaction data are available.
 More research is still required to develop a relatively low cost and environmentally
friendly process for recovering energy from waste water such as wastewater sludge, algae