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Hydrothermal Gasification Treatment for


Hydrogen Generation from Organic Wastes

Conference Paper November 2006

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Hydrothermal Gasification Treatment for Hydrogen Generation
from Organic Wastes
B. Garca Jarana1, J. Snchez-Oneto1, Juan R. Portela1, C. Mantell1, E. Nebot Sanz1, E. Martnez de la Ossa1.
1
Department of Chemical Engineering, Food Technologies and Environmental Technologies, Faculty of
Sciences, University of Cdiz
Box. 40, E-11510 Puerto Real, SPAIN.
belen.garcia@uca.es

ABSTRACT

Hydrothermal processes have demonstrated a great potential and effectiveness for the treatment of industrial
wastewaters with high organic concentration. Two different hydrothermal processes can be carried out: the first one
leads to the complete oxidation of the organic matter by using an oxidant stream (normally oxygen), and the second
one that leads to their gasification in absence or defect of dissolved oxygen. Both processes will be applied to
different industrial wastewaters containing a high concentration of organics, with a high energy potential. In this way,
besides the complete purification of industrial wastewaters, it is sought to carry out the use of their energy potential
with the hydrothermal gasification by burning the gas effluent generated (of great heating power due to its high
content in hydrogen and slight hydrocarbons).

At the moment, our research team in the University of Cdiz has proved the hydrothermal gasification, both at sub-
critical and supercritical conditions, of model compounds and industrial wastewaters. Nowadays, we have built a pilot
plant (25 kg/h) suitable to continue these studies.

Keywords:Gasification,hydrothermal, glucose ,lixiviate,vinasse.

1 INTRODUCTION

Hydrothermal gasification is a promising technology for gasifying biomass with high moisture content. Supercritical
water gasification (SCWG), in which supercritical water is not only a solvent for organic materials but also a reactant,
is one of the applications for producing fuel from organic resources. There exist many kinds of biomass that are not
considered as promising materials for the conventional gasification processes because of their high content of
moisture. In SCWG the water contained in wet biomass is used as solvent as well as reactant, for that reason the
drying procedure is not required for the gasification of wet biomass through this technology. Another advantage of the
supercritical water gasification process compared to conventional gasification, in that higher gasification efficiencies
are achieved at much lower temperatures of approximately 400C.

Biomass polymer is typically composed of cellulose, hemicellulose, lignin, and others. Cellulose is known as one of
the most refractory components for dissolving in hot water, [1]. The complete conversion of cellulose to glucose and
its oligomers can be achieved at temperatures as high as 400 C in supercritical water conditions, [2], while the
descomposition rate of glucose was inhibited by the increase in reaction pressure in supercritical water, [3]. Therefore,
gasification of glucose in supercritical water can be considered as a good model for gasification of more complex
cellulosic biomass in supercritical water. Yu et al. found that glucose at low concentrations (0.1M) can be completely
gasified in SCW at 600 C and 34.5MPa. [4]. The major products were hydrogen and carbon dioxide. No char or tar
products were detected. Schmieder et al. showed that the addition of KOH increase the production of H2, [5].

In this paper we studied on the sub- and supercritical water gasification of glucose as representative biomass model
compounds. The influence of pressure, concentration and excess of oxidant were examined in relation to the yield and
composition of the product gases. Some experiments at subcritical conditions have been carried out for wastewaters as
lixiviates from urban solid wastes and vinasses from alcohol distillery.
Hydrogen is an obvious alternative to hydrocarbon fuels. It has many potential uses, is safe to manufacture, and is
environmentally friendly. Hydrogen is expected to play a key role in the worlds energy future by replacing fossil
fuels. Hydrogen is gaining increasing attention as an encouraging future energy. [6]

2 EXPERIMENTAL

2.1 Equipment
2.1.1 Description of the batch reactor
The batch reactor, only used in the subcritical range, was a 316 stainless steel reactor (Autoclave Engineers) with a
capacity of 300mL. The vessel was fitted with a variable-speed stirrer (MagneDrive) and an electric furnace. A
constant temperature was maintained at 2 C from the set point by means of an electronic controller (PID). The
experimental system incorpored a rupture disk with a burst pressure of 20 Mpa as a safety device in case of presure
buildup in the reactor during an experiment. Figure 1 shows a schematic drawing of this apparatus used in this work.

Gas Sampler Pressure Gauge

Gas Inlet

Injector
Liquid Sampling
Tubes
Reactor

Synthetic Air
Aire

Magnetic Temperature
Stirrer Controller

Electric Furnace

Figure 1. Schematic diagram of the wet air oxidation reactor system

The reactor was charged with initial volume of the waste, pressurised with air or nitrogen and the system was heated
to the desired temperature for each experiment and the stirrer speed was adjusted to 7.5rev/s. The zero time for the
reaction was taken when the temperature set point had been reached. The reaction temperature and pressure were
maintained during the course of the experiment. At the end of each experiment, when room temperature had been
reached, gas effluent was depressurized slowly and passed through the gas sampler. A single gas sample was taken
and analyzed by gas chromatography in order to determine the gas product composition.

2.1.2 Description of the continuous flow reactor


The flow reactor operated both at sub- and supercritical conditions. Fig. 2 shows a schematic diagram of the
laboratory-scale, continuous flow reactor system. All wetted parts, from the pumps to the back-pressure regulator,
were made of stainless steel 316. The reactor was constructed from a 2.5m length of 1/4 in.-o.d. tubing. The oxidant
feed stream was prepared by dissolving hydrogen peroxide with deionized water in a feed tank. Another feed tank
equipped with a magnetic stirrer was loaded with an aqueus solution of glucose. The two feed streams were
pressurised in two different lines by two high-pressure metering pumps and then separately preheated. In order to
assure that all H2O2 is decomposed to give H2O and O2, two in series preheating systems were used for the oxidant
feed stream: (1) by flowing through 3 m. coiled 1/8-in.-o.d. tubing electrically heated and (2) by flowing through 5 m
of coiled 1/8-in.-o.d. tubing submerged in a fluidized sand bath (Techne Model SBL-2). Based on the studies of
Croiset et al. [7], it has been evidenced that H2O2 completely decomposed in the preheaters. The organic feed stream
was preheated by flowing through 3 m.coiled 1/8-in.-o.d. tubing submerged in the fluidized sand bath.
After preheating, the two lines were mixed at the reactor inlet. Upon exiting the reactor, the effluent was cooled
rapidly in a counter current heat exchanger and afterwards, the system pressure was reduced by using a back-pressure
regulator. The product stream was then separated into liquid and vapor phases.
Feed Tank
(Cutting fluid emulsion)
Oxidant Tank
(H2O2)

Check Valves Buble Flow Meter


High Pressure Pump

Oxidant Pressure Gas


Preheater P
Pressure 1
Gauge Pressure Sampler
P
Gauge Gauge
P
Feed Preheater 1 T T Cooling Water Cooling Water
Gas-Liquid
Separator
Filter Back
Pressure
Sand Bath Regulator
Coiled Reactor Liquid
Oxidant line
Feed Preheater 2 Preheater 2
T Temperature
Compressed Controller
Air

Figure 2. Schematic diagram of the continuous flow reactor system

2.2 Materials and analytical methods


Lixiviates from urban solid wastes were used. Dilutions of these feed stocks solutions for preparing feed solutions of
required concentrations were made. Table 1 shows the characteristics of the pure lixiviate.

Vinasses are organic wastes generated during the process of alcohol obtaining in the distillery industries, presenting a
high polluting character mainly due to their acidic state and the existence of a high organic load. The characteristics of
the concentrated vinasse are in Table 1

Table 1. Characteristics of the concentrated wastes


Conductivity
Waste DQO (mg O2/L) pH
(mS/cm)

Lixiviate 20657 8.66 35.20

Vinasse 27000 3.73 3.62

Gas samples were analyzed using an HP 6890 Series gas chromatograph with a Thermal Conductivity Detector
(TCD). Two in-series columns were used to separate CO from CO2: the first column is a Porapack-Q column and the
second is a molecular sieve Carvosieve column (Supelco). A temperature ramp form 55 to 160C (at 15C/min) was
used. The system was calibrated with a standard gas mixture containing H2, O2, N2, CO2, CO and CH4.
The COD measurements were obtained according to the dichromate standard method. [8].

3 RESULTS AND DISCUSSION

Experiments with glucose. Table3 shows the experimental results. The experiments at subcritical conditions were
conducted according to the work of Williams et al. [9] Better results were obtained at conditions of temperature and
pressure where the reaction medium was a gas phase. However, the yield of H2 is low because H2 is formed in the first
steps of reaction mechanism by water gas shift reaction but other studies show that H2 formed via the water gas shift
reaction can further react with organic compounds to form hydrogenated products, [10]. In this way, if the reaction
time decreases, there must be a reduction in CH4 and an increase of H2, CO and CO2. In the last experiment a small
increase of H2 is observed when the reaction time is lower.
In the subcritical region, intermediates like acids and aldehydes have been found but the yield of gases is low. Here
due to the relatively high ion product of water, ionic reactions can be dominant and free-radical reactions, which are
necessary to form gases, are less pronounced. At supercritical conditions, the density of water is lower. This means
that ionic product of water is much lower and ionic reactions are inhibited because of the low relative dielectric
constant of water. The lower density favors free-radical reactions, which are necessary to form gases such as H2 or
CH4. For that reason, we studied the gasification process at supercritical conditions.

Table 3 Summary of operating conditions and results from experiments conducted in the bath reactor.
Feed Initial T P Reaction Oxygen Elim % H2 CO2 CH4 CO O2 N2
COD (C) (bar) (Kg/m3) time order COD Gasif. (%) (%) (%) (%) (%) (%)
(mgO2/L) (min) (n) (%) (*)
0.5M
glucose
& 0.1M 106600 330 139 645 120 0.02 67.6 28.8 <0.01 9.1 <0.01 0.8 <0.01 90.1
H2 O2
0.5M
glucose 106600 305 122 709 120 0.02 69.8 42 <0.01 17.8 <0.01 1.8 <0.01 80.4
& 0.1M
H2 O2
0.5M
glucose 106600 300 117 719 120 0.02 81.8 30.2 <0.01 11.8 <0.01 0.9 <0.01 87.3
& 0.1M
H2O2
0.5M
glucose 106600 300 117 719 120 0.02 81.6 88.3 0.01 31.4 0.89 4.7 <0.01 63
& 0.1M
H 2 O2
1.1M
glucose 213100 330 130 642 120 0.02 51.3 58.9 0.02 37.3 4.9 8.5 <0.01 42.9
& 0.1M
H2O2
1.1M
glucose 213100 330 98 45.4 0 0.02 0.05 65.4 0.07 16.9 9.7 28.6 24.9 19.8
& 0.1M
H2O2

Lixiviate 1450 300 100 715 120 0.17 25 0.68 <0.01 15.4 0.8 <0.01 16.2 67.6

Lixiviate 1450 300 150 725 120 - 29 0.89 <0.01 0.4 <0.01 <0.01 <0.01 99.6

Lixiviate 1450 300 150 725 120 8.8 - 7.9 <0.01 2.1 <0.01 <0.01 19.2 78.7

Lixiviate 3390 275 180 776 120 1.2x10-3 77 1.31 <0.01 3.8 <0.01- <0.01 11.8 84.3

Lixiviate 3390 300 130 722 120 - 22 0.37 <0.01 2.3 <0.01 <0.01 <0.01 97.7

Lixiviate
&
1.2x10-3M 3390 300 160 728 120 - 32 0.29 <0.01 0.9 <0.01 <0.01 <0.01 99.1
KOH

Vinasses 2720 300 140 724 120 - 8 0.6 <0.01 0.6 <0.01 <0.01 <0.01 99.4

Vinasses
&
1.2x10-3M 2720 300 160 728 120 - 56 0.6 <0.01 0.6 <0.01 <0.01 <0.01 99.4
KOH

(*) %Gasification refers to the ratio = (Carbon amount in the gas product / Carbon amount in the feed) * 100
Table 4 shows the experimental results at supercritical conditions in the flow reactor. At supercritical conditions the
influence of the amount of oxygen was examined. A treatment with 100% of Stoichiometric Oxygen generates an
almost total decrease of COD. In the rest of experiments with a lower amount of oxygen generates a less decrease of
COD. These results suggest a oxidative character, that is a oxidation reaction for 100% of oxygen and a oxidation
partial for the rest of treatments. With 0% of Stoichiometric Oxygen generates low COD reduction, which suggests a
hydrolisis reactions and not oxidation. In all experiments there is not production of char.
A high concentration of CO is obtained in the experiments with certain amount of Stoichiometric Oxygen., which
suggests a partial oxidation in those cases, where there is a similar formation of fuel gases (H2 and CH4).
The yield of hydrogen is higher in the case of total absence of oxygen. For this reason these are the excellent
conditions to generate fuel gases. In this experiment, glucose produced 36% H2,, 32% CO2, 30% CO and 2% CH4.
In the future we will studied the influence of the presence of KOH in the feed with supercritical conditions for
increase the gasification efficiency.
Table 4 Summary of operating conditions and results from experiments conducted in the flow reactor.
Feedstock Initial Oxygen Elim. H2 CO2 CH4 CO O2 N2
COD ratio COD (%) (%) (%) (%) (%) (%)
(mgO2/L) (*) (%)

0.06M glucose 50415 1 96.15 12.67 42.64 2.65 33.79 <0.01 <0.01

0.06M glucose 50415 0.75 68.11 15.87 37.46 2.49 43.05 <0.01 <0.01

0.06M glucose 50415 0.5 66.72 12.89 37.66 2.85 46.56 <0.01 <0.01

0.06M glucose 50415 0.25 59.15 14.22 40.76 2.62 48.80 <0.01 <0.01

0.06M glucose 50415 0 30.71 36.06 32.04 1.93 30.19 <0.01 <0.01

(*) Oxygen ratio refers = Oxygen / Stoichiometric Oxygen

Experiments with lixiviate. The results are in Table 3.We conducted the experiment with a dilution of 1/10 and 1/5.
Finally we studied the effect of alkali additions on the gasification because according to literature adding some alkali
in the feedstock solution could decrease the CO yield, and increase the CO2 yield, [6] In this case, KOH is selected
like catalyst according to the studies made by Schmieder et al. [8] They showed that at 600C and 250 bar all
compounds are completely gasified by addition of KOH or K2CO3, forming a H2 rich gas containing CO2 as the main
carbon compound. In our case, at subcritical conditions the yield of gas are very low and H2 is not formed.
This waste was not studied at supercritical conditions because lixiviate has high conductivity, which would make
problems caused by salts.

Experiments with vinasses. The results with vinasses (Table 3) are similar to lixiviate, but in this case we will
conduct the experiments with vinasses in supercritical conditions.

In the future we will study the influence of the presence of KOH in the feed with supercritical conditions to increase
the gasification efficiency of glucose and vinasses.

Acknowledgements
We wish to thank the INTERREG III-B program from the European Community and the Spanish Ministry of Science
and Technology (project CTQ2004-05605) for the financial supports to this work.
4 REFERENCES

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