Você está na página 1de 12

Fuel Processing Technology 87 (2006) 461 – 472

www.elsevier.com/locate/fuproc

An overview of hydrogen production from biomass


Meng Ni, Dennis Y.C. Leung *, Michael K.H. Leung, K. Sumathy
Department of Mechanical Engineering, The University of Hong Kong, 7/F Haking Wong Building, Pokfulam Road, Hong Kong, China

Received 15 July 2004; received in revised form 8 November 2004; accepted 12 November 2005

Abstract

Hydrogen production plays a very important role in the development of hydrogen economy. One of the promising hydrogen production
approaches is conversion from biomass, which is abundant, clean and renewable. Alternative thermochemical (pyrolysis and gasification) and
biological (biophotolysis, water – gas shift reaction and fermentation) processes can be practically applied to produce hydrogen. This paper gives
an overview of these technologies for hydrogen production from biomass. The future development will also be addressed.
D 2005 Elsevier B.V. All rights reserved.

Keywords: Biomass; Pyrolysis; Gasification; Supercritical water; Fermentation; Biophotolysis

1. Introduction energy supply [4]. Biomass research is recently receiving


increasing attention because of the probable waste-to-energy
Dependence on fossil fuels as the main energy sources has application. For instance, 150 GT of vegetable bio-matter
led to serious energy crisis and environmental problems, i.e. generated globally every year can produce about 1.08  1010
fossil fuel depletion and pollutant emission. It has been GJ energy [5]. One of the major drawbacks is the low
reported that United Arab Emirates, one of the major oil efficiency of utilizing biomass. In China, biomass is widely
export countries, would fail to meet the share in the oil and used for cooking and heating through biomass burning with a
natural gas demands by 2015 and 2042, respectively [1]. The thermal efficiency only between 10% and 30%. Alternatively,
fossil fuel resources in Egypt would be exhausted within one to converting biomass into gaseous and aqueous fuels, electricity
two decades [2]. In China, Mao claimed that the imported oil and especially hydrogen is possibly a more efficient way of
amounted to 31% to meet the energy demand in 2000 and the biomass utilization. This paper aims to give an overview of
demand would reach 45 –55% in 2010 [3]. The increasing various methods of producing hydrogen from biomass and
energy demands will speed up the exhaustion of the finite fossil their development potential.
fuel. Moreover, combustion of fossil fuel produces substantial
greenhouse and toxic gases, such as CO2, SO2, NOx and other 2. Energy from biomass
pollutants, causing global warming and acid rain.
In response to the two problems stated above, continuous A variety of biomass resources can be used to convert to
effort has been made in exploration of clean, renewable energy. They can be divided into four general categories:
alternatives for a sustainable development. Biomass is one of
the most abundant renewable resources. It is formed by fixing (i) Energy crops: herbaceous energy crops, woody energy
carbon dioxide in the atmosphere during the process of plant crops, industrial crops, agricultural crops and aquatic
photosynthesis and, therefore, it is carbon neutral in its crops.
lifecycle. Biomass has been used for centuries. Currently, (ii) Agricultural residues and waste: crop waste and animal
biomass contributes about 12% of today’s world energy supply, waste.
while in many developing countries it contributes 40 –50% (iii) Forestry waste and residues: mill wood waste, logging
residues, trees and shrub residues.
* Corresponding author. Tel.: +852 2859 7911; fax: +852 2858 5415. (iv) Industrial and municipal wastes: municipal solid waste
E-mail address: ycleung@hkucc.hku.hk (D.Y.C. Leung). (MSW), sewage sludge and industry waste.
0378-3820/$ - see front matter D 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.fuproc.2005.11.003
462 M. Ni et al. / Fuel Processing Technology 87 (2006) 461 – 472

The available energy production processes from biomass Methane and other hydrocarbon vapors produced can be
can be divided into two general categories: thermochemical steam reformed for more hydrogen production:
and biological processes. Combustion, pyrolysis, liquefaction
CH4 þ H2 OYCO þ 3H2 ð2Þ
and gasification are the four thermochemical processes. Direct
biophotolysis, indirect biophotolysis, biological water –gas In order to increase the hydrogen production, water –gas shift
shift reaction, photo-fermentation and dark-fermentation are reaction can be applied as follows:
the five biological processes. Combustion is the direct
CO þ H2 OYCO2 þ H2 : ð3Þ
burning of biomass in air to convert the biomass chemical
energy into heat, mechanical power or electricity using Besides the gaseous products, the oily products can also be
equipment such as stoves, furnaces, boilers or steam turbines, processed for hydrogen production [7]. The pyrolysis oil can be
respectively. As the energy efficiency is low (10 – 30%) and separated into two fractions based on water solubility. The
the pollutant emissions are the by-products; combustion is not water-soluble fraction can be used for hydrogen production
a suitable hydrogen production for sustainable development. while the water-insoluble fraction for adhesive formulation.
In biomass liquefaction, biomass is heated to 525 – 600 K in The material flow is summarized in Fig. 1. Experimental study
water under a pressure of 5 – 20 MPa in the absence of air. has shown that when Ni-based catalyst is used, the maximum
Solvent or catalyst can be added in the process. The yield of hydrogen can reach 90%. With additional steam
disadvantages of biomass liquefaction are difficulty to achieve reforming and water – gas shift reaction, the hydrogen yield can
the operation conditions and low production of hydrogen. be increased significantly.
Therefore, liquefaction is not favorable for hydrogen produc- Temperature, heating rate, residence time and type of
tion. Other thermochemical processes (pyrolysis and gasifi- catalyst used are important pyrolysis process control para-
cation) and biological processes (biophotolysis, biological meters. In favor of gaseous products especially in hydrogen
water gas shift reaction and fermentation) are feasible and production, high temperature, high heating rate and long
receiving much attention in hydrogen production in recent volatile phase residence time are required [8]. These parameters
years. can be regulated by selection among different reactor types and
heat transfer modes, such as gas – solid convective heat transfer
and solid –solid conductive heat transfer. The heat transfer
3. Thermochemical processes for hydrogen production modes and features of various reactors are listed in Table 1 [9].
It can be seen from the table that fluidized bed reactor type
3.1. Hydrogen from biomass pyrolysis exhibits higher heating rates and thus it appears to be the
promising reactor type for hydrogen production from biomass
Pyrolysis is the heating of biomass at a temperature of pyrolysis.
650 –800 K at 0.1 – 0.5 MPa in the absence of air to convert Some inorganic salts, such as chlorides, carbonates and
biomass into liquid oils, solid charcoal and gaseous chromates, exhibit beneficial effect on pyrolysis reaction rate
compounds. Pyrolysis can be further classified into slow [10]. As tar is difficult to be gasified, extensive studies on the
pyrolysis and fast pyrolysis. As the products are mainly catalytic effect of inexpensive dolomite and CaO on the
charcoal, slow pyrolysis is normally not considered for
hydrogen production. Fast pyrolysis is a high temperature
process, in which the biomass feedstock is heated rapidly in Biomass Pyrolysis Carbon
the absence of air, to form vapor and subsequently
condensed to a dark brown mobile bio-liquid. The products
of fast pyrolysis can be found in all gas, liquid and solid
phases [6]: Bio-Fuel Co-Product

(i) Gaseous products include H2, CH4, CO, CO2 and other
gases depending on the organic nature of the biomass for
pyrolysis. Separation
Phenolic
(ii) Liquid products include tar and oils that remain in liquid Intermediates
form at room temperature like acetone, acetic acid, etc.
(iii) Solid products are mainly composed of char and almost
pure carbon plus other inert materials. H2O
Catalytic Steam
Reforming Resins
Although most pyrolysis processes are designed for bio-
fuel production, hydrogen can be produced directly through
fast or flash pyrolysis if high temperature and sufficient
volatile phase residence time are allowed as follows: H2 and CO2

Biomass þ heatYH2 þ CO þ CH4 þ other products ð1Þ Fig. 1. Biomass to hydrogen based on pyrolysis with a co-products strategy [7].
M. Ni et al. / Fuel Processing Technology 87 (2006) 461 – 472 463

Table 1 bed reactor and the production rates of 250 kg H2/day was
Pyrolysis reactor types, heat transfer modes and typical features [9] achieved. Padro and Putsche [24] estimated the hydrogen
Reactor type Mode of heat transfer Typical features production cost of biomass pyrolysis to be in the range of
Ablative 95% conduction Accepts large size feedstocks US$8.86/GJ to US$15.52/GJ depending on the facility size and
4% convection Very high mechanical char abrasion biomass type. For comparison, the costs of hydrogen produc-
from biomass
tion by wind-electrolysis systems and PV-electrolysis systems
1% radiation Compact design
Heat supply problematical are US$20.2/GJ and US$41.8/GJ, respectively. It can be seen
Heat transfer gas not required that biomass pyrolysis is a competitive method for renewable
Particulate transport gas not always hydrogen production.
required
Fluidized bed 90% conduction High heat transfer rates
9% convection Heat supply to fluidizing gas or to bed 3.2. Hydrogen from biomass gasification
directly
1% radiation Limited char abrasion
Biomass can be gasified at high temperatures (above 1000
Very good solids mixing
Particle size limit <2 mm in smallest K). The biomass particles undergo partial oxidation resulting in
dimension gas and charcoal production. The charcoal is finally reduced to
Simple reactor configuration form H2, CO, CO2 and CH4. This conversion process can be
Circulating 80% conduction High heat transfer rates expressed as:
fluidized
bed Biomass þ heat þ steamYH2 þ CO þ CO2
19% convection High char abrasion from biomass and
char erosion þ CH4 þ light and heavy hydrocarbons þ char: ð4Þ
1% radiation Leading to high char in product
Char/solid heat carrier separation Unlike pyrolysis, gasification of solid biomass is carried out
required in the presence of O2. Besides, gasification aims to produce
Solids recycle required gaseous products while pyrolysis aims to produce bio-oils and
Increased complexity of system charcoal. The gases produced can be steam reformed to
Maximum particle sizes up to 6 mm
produce hydrogen and this process can be further improved
Possible liquids cracking by hot solids
Possible catalytic activity from hot char
by water – gas shift reactions as discussed in the previous
Greater reactor wear possible section. The gasification process is applicable to biomass
Entrained 4% conduction Low heat transfer rates having moisture content less than 35% [25].
flow One of the major issues in biomass gasification is to deal
95% convection Particle size limit <2 mm with the tar formation that occurs during the process. The
1% radiation Limited gas/solid mixing
unwanted tar may cause the formation of tar aerosols and
polymerization to a more complex structure, which are not
decomposition of hydrocarbon compounds in tar have been favorable for hydrogen production through steam reforming.
conducted [11,12]. The catalytic effects of other catalysts (Ni- Currently, three methods are available to minimize tar
based catalysts [13], Y-type zeolite [14], K2CO3, Na2CO3 and formation: (i) proper design of gasifier, (ii) proper control
CaCO3 [15]) and various metal oxides (Al2O3, SiO2, ZrO2, and operation and (iii) additives/catalysts.
TiO2 [16] and Cr2O3 [15]) have also been investigated. Among The operation parameters, such as temperature, gasifying
the different metal oxides, Al2O3 and Cr2O3 exhibit better agent and residence time, play an important role in formation
catalytic effect than the others. Among the catalysts, Na2CO3 is and decomposition of tar. It has been reported that tar could be
better than K2CO3 and CaCO3. Although noble metals Ru and thermally cracked at temperature above 1273 K [26]. The use
Rh are more effective than Ni catalyst and less susceptible to of some additives (dolomite, olivine and char) inside the
carbon formation, they are not commonly used due to their gasifier also helps tar reduction [27]. When dolomite is used,
high costs [17]. 100% elimination of tar can be achieved [28]. Catalysts not
In order to evaluate hydrogen production through pyrolysis only reduce the tar content, but also improve the gas product
of various types of biomass, extensive experimental investiga- quality and conversion efficiency. Dolomite, Ni-based catalysts
tions have been conducted in recent years. Agricultural and alkaline metal oxides are widely used as gasification
residues [18], peanut shell [7], post-consumer wastes such as catalysts. Process modifications by two-stage gasification and
plastics, trap grease, mixed biomass and synthetic polymers secondary air injection in the gasifier are also useful for tar
[19] and rapeseed [20] have been widely tested for pyrolysis reduction [13].
for hydrogen production. In order to solve the problem of Another problem of biomass gasification is the formation
decreasing reforming performance caused by char and coke of ash that may cause deposition, sintering, slagging, fouling
deposition on the catalyst surface and in the bed itself, fluidized and agglomeration [29,30]. To resolve the ash-associated
catalyst beds are usually used to improve hydrogen production problems, fractionation and leaching have been employed to
from biomass-pyrolysis-derived bio-fuel [21,22]. Yeboah et al. reduce ash formation inside the reactor [30 – 33]. Though
[23] constructed a demonstration plant for hydrogen production fractionation is effective for ash removal, it may deteriorate
from peanut shells pyrolysis and steam reforming in a fluidized the quality of the remaining ash. On the other hand, leaching
464 M. Ni et al. / Fuel Processing Technology 87 (2006) 461 – 472

Table 2
Investigations on biomass gasification for hydrogen production
Feedstock Reactor type Catalyst used Hydrogen production (vol.%) References
Sawdust Not known Na2CO3 48.31 at 700 -C [35]
55.4 at 800 -C
59.8 at 900 -C
Sawdust Circulating fluidized bed Not used 10.5 at 810 -C [36]
Wood Fixed bed Not used 7.7 at 550 -C [37]
Sawdust Fluidized bed Not known 57.4 at 800 -C [38]
Not known Fluidized bed Ni 62.1 at 830 -C [39]
Sawdust Fluidized bed K2CO3 11.27 at 964 -C [40]
CaO 13.32 at 1008 -C
Na2CO3 14.77 at 1012 -C
Pine sawdust Fluidized bed Not known 26 – 42 at 700 – 800 -C [41]
Bagasse 29 – 38 at 700 – 800 -C
Cotton stem 27 – 38 at 700 – 800 -C
Eucalyptus gobulus 35 – 37 at 700 – 800 -C
Pinus radiata 27 – 35 at 700 – 800 -C
Sewage sludge Downdraft Not known 10 – 11 [43]
Almond shell Fluidized bed La – Ni – Fe 62.8 at 800 -C [44]
Perovskite 63.7 at 900 -C
Switchgrass Moving bed Cu – Zn – Al 27.1 [45]

can remove biomass’ inorganic fraction, as well as improve This reaction is exothermic and high yield of hydrogen can be
the quality of the remaining ash [30]. More recently, achieved at relatively low temperature (923 – 973 K). As
gasification of leached olive oil waste in a circulating fluidized compared with conventional gasification, the HyPr-RING
bed reactor was reported for gas production that demonstrated process, as illustrated in Fig. 3, can be conducted in a much
the feasibility of leaching as a pretreatment technique for gas simpler manner as the reaction for hydrogen production and
production [34]. gas separation are carried out in one single reactor at a lower
Hydrogen can be produced from the gasification gaseous temperature [48]. This novel gasification process has been
products through the same procedure of steam reforming and analyzed theoretically and demonstrated experimentally to be a
water –gas shift reaction as discussed in the pyrolysis section. very efficient technique for hydrogen production from biomass.
As the products of gasification are mainly gases, this process is When biomass has high moisture content above 35%, it is
more favorable for hydrogen production than pyrolysis. In likely to gasify biomass in a supercritical water condition.
order to optimize the process for hydrogen production, a Under the severe conditions obtained by heating water to a
number of efforts have been made by researchers to test temperature above its critical temperature (647 K) and
hydrogen production from biomass gasification with various compressing it to a pressure above its critical pressure (22
biomass types and at various operating conditions, as listed in MPa), biomass is rapidly decomposed into small molecules or
Table 2 [35 –45]. Using a fluidized bed gasifier along with gases in a few minutes at a high efficiency [53]. Supercritical
suitable catalysts, it is possible to achieve hydrogen production water gasification is a promising process to gasify biomass
about 60 vol.%. Such high conversion efficiency makes
biomass gasification an attractive hydrogen production alter- 11
native. In addition, the costs of hydrogen production by bio-
10.23
mass gasification are competitive with natural gas reforming as 10
illustrated in Fig. 2 [46]. Taking into account the environmental
benefit as well, hydrogen production from biomass gasification
Hydrogen Cost ($/GJ)

9
should be a promising option based on both economic and 8.76 8.74
Bagasse
environmental considerations. Switchgrass
In recent years, a novel gasification method, namely, 8 7.76
7.54
Hydrogen Production by Reaction Integrated Novel Gasifica- 7.46
tion (HyPr-RING) was proposed by Lin et al. [47 – 52]. HyPr- 7 Natural Gas $4.5/GJ
RING method is an integration of the water-hydrocarbon 6.67
reaction, water –gas shift reaction and absorption of CO2 and
6
other pollutants in a single reactor under both sub-critical and 5.85
Natural gas $3/GJ
supercritical water conditions. The main reaction for this new
method can be expressed as: 5
500 1000 1500 2000
Biomass feed to gasifier (tonnes/day)
0
C þ 2H2 O þ CaOYCaCO3 þ 2H2 ; DH298 ¼  88kJ =mol
Fig. 2. Estimated cost comparison of hydrogen production by biomass
ð5Þ gasification and natural gas steam reforming [46].
M. Ni et al. / Fuel Processing Technology 87 (2006) 461 – 472 465

(a) HyPr-RING process

Coal, Heavy oil, High pressure reactor


H2
biomass, water (923-973K)

C + 2H2O + CaO → CaCO3 + 2H2

Water Sorbent
CO2
clean Up regenerator

CaCl2, NaS Ash

(b) Conventional gasification hydrogen


process for hydrogen production
Sorbent CO2
Sorbent
S regenerator
regenerator

Steam
Synthesis
gas, CO, Clean gas,
CO2, H2 CO,CO2, CO2,
Coal,
H2O,H2S H2 H2 H2
Heavy Shift CO2
Oil, Gas Reaction
Gasifier clean up absorptor
Biomass (<673K)

> 1573K
Ash C + CO2 → 2CO
C + H2O → CO + H2 CO + H2O → CO2 + H2
O2

Air
Air
Separator

N2

Fig. 3. Comparison of HyPr-RING and conventional gasification hydrogen production process [48].

with high moisture contents due to the high gasification ratio as 873 K and 34.5 MPa, was different from the non-
(100% achievable) and high hydrogen volumetric ratio (50% supercritical water condition. One advantage is that, during
achievable). gasification, neither tar nor char formation occurs. This early
In recent years, extensive research has been carried out to finding stimulated extensive interests in supercritical water
evaluate the suitability of various wet biomass gasification in research. Recent attempts to produce hydrogen from biomass
supercritical water conditions. However, the works have been at supercritical water conditions are summarized in Table 3
mostly on a laboratory scale and in an early development [59 – 62]. Using glucose as a model compound, hydrogen
stage; hence, the principles and basic mechanisms are not yield of more than 50 vol.% can be achieved with the use of
well understood yet. The solubility of biomass components in proper catalysts in supercritical water condition. Tubular
hot compressed water has been first studied by Mok et al. reactors are widely used in supercritical water gasification
[54]. The results show that in hot compressed waters, about because of their robust structures to withstand high pressure.
40 –60% of the biomass sample is soluble though the reaction Although supercritical water gasification is still at its early
is maintained slightly below the critical water condition. development stage, the technology has already shown its
Minowa et al. [55 –57] reported hydrogen production from economic competitiveness with other hydrogen production
cellulose gasification in hot compressed water (subcritical) methods. Spritzer and Hong [63] have estimated the cost of
using nickel catalyst. Yu et al. [58] reported that the hydrogen produced by supercritical water gasification to be
gasification of glucose at supercritical water condition, such about US$3/GJ (US$0.35/kg).
466 M. Ni et al. / Fuel Processing Technology 87 (2006) 461 – 472

Table 3
Recent studies on hydrogen production by biomass gasification in supercritical water conditions
Feedstock Gasifier type Catalyst used Temperature and pressure Hydrogen yield References
Glucose Not known Not used 600 -C, 34.5 MPa 0.56 mol H2/mol of feed [59]
Glucose Not known Activated carbon 600 -C, 34.5 MPa 2.15 mol H2/mol of feed
Glucose Not known Activated carbon 600 -C, 25.5 MPa 1.74 mol H2/mol of feed
Glucose Not known Activated carbon 550 -C, 25.5 MPa 0.62 mol H2/mol of feed
Glucose Not known Activated carbon 500 -C, 25.5 MPa 0.46 mol H2/mol of feed
Glycerol Not known Activated carbon 665 -C, 28 MPa 48 vol.% [60]
Glycerol/methanol Not known Activated carbon 720 -C, 28 MPa 64 vol.%
Corn starch Not known Activated carbon 650 -C, 28 MPa 48 vol.%
Sawdust/corn Not known Activated carbon 690 -C, 28 MPa 57 vol.%
starch mixture
Glucose Tubular reactor KOH 600 -C, 25 MPa 59.7 vol.% [61]
(9.1 mol H2/mol glucose)
Catechol Tubular reactor KOH 600 -C, 25 MPa 61.5 vol.%
(10.6 mol H2/mol catechol)
Sewage Autoclave K2CO3 450 -C, 31.5 – 35 MPa 47 vol.%
Glucose Tubular reactor Not used 600 -C, 25 MPa 41.8 vol.% [62]
Glucose Tubular reactor Not used 500 -C, 30 MPa 32.9 vol.%
Glucose Tubular reactor Not used 550 -C, 30 MPa 33.1 vol.%
Glucose Tubular reactor Not used 650 -C, 32.5 MPa 40.8 vol.%
Glucose Tubular reactor Not used 650 -C, 30 MPa 41.2 vol.%
Sawdust Tubular reactor Sodium carboxymethyl- 650 -C, 22.5 MPa 30.5 vol.%
cellulose (CMC)

Hydrogen production from biomass thermochemical these works are in laboratory scale and the practical applica-
processes has already been shown to be attractive tions still need to be demonstrated. Biological hydrogen
economically and demonstrated to be a feasible option. production can be classified into five different groups: (i)
However, it should be noted that hydrogen gas is normally direct biophotolysis, (ii) indirect biophotolysis, (iii) biological
produced together with other gas constituents. Thus, water – gas shift reaction, (iv) photo-fermentation and (v) dark-
separation and purification of hydrogen gas are required. fermentation [66]. All processes are controlled by the
Nowadays, several methods, such as CO2 absorption, hydrogen-producing enzymes, such as hydrogenase and
drying/chilling and membrane separation [64 65], have nitrogenase. The major components of nitrogenase are MoFe
been successfully developed for hydrogen gas purification. protein and Fe protein. Nitrogenase has the ability to use
It is expected that biomass thermochemical conversion magnesium adenosine triphosphate (MgATP) and electrons to
processes, especially the newly developed gasification reduce a variety of substrates (including protons). This
types, will be available for large-scale hydrogen production chemical reaction yields hydrogen production by a nitroge-
in the near future. nase-based system [67]:

4. Biological process for hydrogen production 2e þ 2Hþ þ 4ATPYH2 þ 4ADP þ 4Pi ð6Þ

4.1. General aspects where ADP and Pi refer to adenosine diphosphate and
inorganic phosphate, respectively.
The phenomenon of biological hydrogen production was Hydrogenases exist in most of the photosynthetic micro-
observed one century ago. When the oil crisis broke out in organisms and they can be classified into two categories: (i)
1970s, the technology started receiving attention, especially in uptake hydrogenases and (ii) reversible hydrogenases. Uptake
hydrogen production by photosynthetic process. However, hydrogenases, such as NiFe hydrogenases and NiFeSe hydro-

Table 4
Comparative properties of nitrogenase and hydrogenase [51]
Property Nitrogenase Hydrogenase
Substrates ATP, H+ or N2, electrons H+, H2
Products H2 or NH+4 ATP, H+, H2, electrons
Number of proteins Two (Mo – Fe and Fe) One
Metal components Mo, Fe Ni, Fe, S
Optimum temperature 30 -C (A. vinelandii) 55 -C (R. rubrum), 70 -C (R. capsulatus)
Optimum pH 7.1 – 7.3 (A. vinelandii) 6.5 – 7.5 (R. sulfidophilus)
Inhibitors N2 (of H2 production), NH+4 , O2, high N to C ratio CO, EDTA (ethylenediaminetetraacetic acid), O2, presence of organic compound
Simulators Light H2 (R. sphaeroides), absence of organic compounds (R. rubrum, R. capsulatus)
M. Ni et al. / Fuel Processing Technology 87 (2006) 461 – 472 467

genases, act as important catalysts for hydrogen consumption Table 5


as follows: Comparison of hydrogen production by wild-type microorganisms and mutants
Name of Hydrogen production References
H2 Y2e þ 2Hþ ð7Þ microorganisms comparison between
mutants and wild-type
Reversible hydrogenases, as indicated by its name, have the microorganisms
ability to produce H2 as well as consume H2 depending on the Azotobacter vinelandii H2 oxidation/H2 evolution [70]
reaction condition, For wild-type: 46
For mutants: 1.5
H2 62e þ 2Hþ : ð8Þ Rhodobacter capsulatus Hydrogen from malate [71]
Koku et al. [68] have reported that though a variety of For wild-type: 25%
For mutants: 68%
substrates can be used for Rhodobacter sphaeroides growth, Anabaena Mutants show higher [72]
only some of them are suitable for hydrogen production. The oxygen tolerance
properties of nitrogenase and hydrogenase are summarized in than wild-type Anabaena
Table 4. hydrogen production not known
Rhodobacter sphaeroides Hydrogen production of the [73]
mutants 1.5 times higher than
4.2. Direct biophotolysis that of the wild-type
Rhodobacter sphaeroides 50% more hydrogen production [74]
Direct biophotolysis of hydrogen production is a biological for the mutants than the wild-type
process using microalgae photosynthetic systems to convert
solar energy into chemical energy in the form of hydrogen:
low. Recently, mutants derived from microalgae were reported
solar energy to have good O2 tolerance and thus higher hydrogen
2H2 O Y 2H2 þ O2 ð9Þ
production. The works reported on mutants for hydrogen
Two photosynthetic systems are responsible for photosynthesis production are listed in Table 5 [70 – 74]. It can be seen that,
process: (i) photosystem I (PSI) producing reductant for CO2 using mutants for hydrogen production, the efficiency can be
reduction and (ii) photosystem II (PSII) splitting water and increased significantly.
evolving oxygen. In the biophotolysis process, two photons Benemann [75] estimated the cost of direct biophotolysis for
from water can yield either CO2 reduction by PSI or hydrogen hydrogen production to be $20/GJ assuming that the capital
formation with the presence of hydrogenase. In green plants, cost is about US$60/m2 with an overall solar conversion
due to the lack of hydrogenase, only CO2 reduction takes place. efficiency of 10%. Hallenbeck and Benemann [67] performed
On the contrary, microalgaes, such as green algae and similar cost estimation and reported that the capital cost of
Cyanobacteria (blue-green algae), contain hydrogenase and, US$100/m2. In their estimation, some practical factors were
thus, have the ability to produce hydrogen. In this process, neglected, such as gas separation and handling.
electrons are generated when PSII absorbs light energy. The
electrons are then transferred to the ferredoxin (Fd) using the 4.3. Indirect biophotolysis
solar energy absorbed by PSI. The hydrogenase accepts the
electrons from Fd to produce hydrogen as shown in Fig. 4. According to Gaudernack [76], the concept of indirect
Since hydrogenase is sensitive to oxygen, it is necessary to biophotolysis involves the following four steps as illustrated
maintain the oxygen content at a low level under 0.1% so that in Fig. 5: (i) biomass production by photosynthesis, (ii)
hydrogen production can be sustained [67]. This condition can biomass concentration, (iii) aerobic dark fermentation yield-
be obtained by the use of green algae Chlamydomonas ing 4 mol hydrogen/mol glucose in the algae cell, along with
reinhardtii that can deplete oxygen during oxidative respiration 2 mol of acetates, and (iv) conversion of 2 mol of acetates
[69]. However, due to the significant amount of substrate being into hydrogen. In a typical indirect biophotolysis, Cyanobac-
respired and consumed during this process, the efficiency is teria are used to produce hydrogen via the following
reactions [66]:
H2
Solar 12H±2 O þ 6CO2 YC6 H12 O6 þ 6O2 ð10Þ
Energy
C6 H12 O6 þ 12H2 OY12H2 þ 6CO2 : ð11Þ

PSI and 2e- Markov et al. [77] investigated the indirect biophotolysis
Hydrogenase with Cyanobacterium anabaena variabilis exposed to light
PSII Fd
intensities of 45 –55 Amol 1 m 2 and 170 – 180 Amol 1 m 2
in the first stage and second stage, respectively. Photoproduc-
tion of hydrogen at a rate of about 12.5 ml H2/gcdw h (cdw:
O2
2H+
cell dry weight) was found. In the study on indirect
2H2O
biophotolysis with Cyanobacterium gloeocapsa alpicola by
Fig. 4. Schematics of direct biophotolysis. Troshina et al. [78], it was found that maintaining the medium
468 M. Ni et al. / Fuel Processing Technology 87 (2006) 461 – 472

Stage 1
CO2 H2
Solar Solar
Energy Energy
2e-
2e- Cell Bacterial Fd
PSI and PSII Fd Nitrogenase
Material Photosystem
4ATP
O2
2H2O
Stage 2 2H+
Organic Acids
Cell H2
Material Fig. 6. Photo-fermentation schematics.

2e- than 5 h by the oxidation of CO to CO2 coupled with the


Fermentation Hydrogenase
Fd reduction of protons to hydrogen. However, R. rubrum requires
light to grow and hydrogen production is inhibited by medium
2H+ CO partial pressure above 0.2 atm. An alternative new
chemoheterotrophic bacterium Citrobacter sp. Y19 was tested
Fig. 5. Indirect biophotolysis for hydrogen production. by Jung et al. [82] for hydrogen production using water – gas
shift reaction. The maximum hydrogen production activity was
at pH value between 6.8 and 8.3 yielded optimal hydrogen found to be 27 mmol/g cell h, which is about three times higher
production. Increasing the temperature from 30 -C to 40 -C can than R. rubrum.
increase the hydrogen production twice as much. The hydrogen Recently, Wolfrum et al. [83] have conducted a detailed
production rate through indirect biophotolysis is comparable to study to compare the biological water – gas shift reaction with
hydrogenase-based hydrogen production by green algae. The conventional water – gas shift processes. Their analysis showed
estimated overall cost is US$10/GJ of hydrogen [67]. However, that biological water – gas shift process was economically
it should be pointed out that indirect biophotolysis technology competitive when the methane concentration was under 3%.
is still under active research and development. The estimated The hydrogen production cost from biological water – gas shift
cost is subject to a significant change depending on the reaction ranged from US$1.75/kg (US$14.6/GJ) to around
technological advancement. US$2.25/kg (US$18.8/GJ) for a methane concentration be-
tween 1% and 10%. Compared with thermochemical water –
4.4. Biological water– gas shift reaction gas shift processes, the cost of biological water – gas shift
processes are lower due to the elimination of reformer and
Some photoheterotrophic bacteria, such as Rhodospirillum associated equipment.
rubrum can survive in the dark by using CO as the sole carbon
source to generate ATP by coupling the oxidation of CO to the 4.5. Photo-fermentation
reduction of H+ to H2 [79]:
Photosynthetic bacteria have the capacity to produce
CO þ H2 O6CO2 þ H2 ; DG0 ¼  20:1kJ =mol: ð12Þ
hydrogen through the action of their nitrogenase using solar
In equilibrium, the dominating products are CO2 and H2. energy and organic acids or biomass. This process is known as
Therefore, this process is favorable for hydrogen production. photo-fermentation, as shown in Fig. 6. In recent years, some
Organisms growing at the expense of this process are the attempts have been made for hydrogen production from
gram-negative bacteria, such as R. rubrum and Rubrivax industrial and agricultural wastes to effect waste management.
gelatinosus, and the gram-positive bacteria, such as Carbox- As summarized in Table 6 [84 – 87], hydrogen can be produced
ydothermus hydrogenoformans [80]. Under anaerobic condi- by photo-fermentation of various types of biomass wastes.
tions, CO induces the synthesis of several proteins, including
CO dehydrogenase, Fe –S protein and CO-tolerant hydroge-
Table 6
nase. Electrons produced from CO oxidation are conveyed
Example studies on hydrogen production by photo-fermentation
via the Fe –S protein to the hydrogenase for hydrogen
Biomass type Bacteria system Hydrogen conversion References
production [81]. efficiency
Biological water – gas shift reaction for hydrogen production
Lactic acid Rhodobacter sphaeroides 86% [84]
is still under laboratory scale and only few works have been immobilized
reported. The common objectives of these works were to Lactate feedstock Rhodobacter capsulatus 30% [85]
identify suitable microorganisms that had high CO uptake and Wastewater Rhodobacter sphaeroides 53% [86]
to estimate the hydrogen production rate. Kerby et al. [79] immobilized
observed that under dark, anaerobic conditions in the presence Sugar refinery Rhodobacter spaeroides 0.005 l H2/h/l [87]
wastewater O.U.001 culture
of sufficient nickel, the doubling time of R. rubrum was less
M. Ni et al. / Fuel Processing Technology 87 (2006) 461 – 472 469

H2 CO2

Gas Separation

Fermentative
Substrates such as
Biomass, Agricultural Pretreatment Fermentation
Products or other
organic wastes

Fig. 7. Hydrogen production by dark fermentation.

However, these processes have three main drawbacks: (i) use hydrogen production (14 mmol/g carbohydrate) from waste-
of nitrogenase enzyme with high-energy demand, (ii) low solar water by anaerobic microflora in the presence of chemostat
energy conversion efficiency and (iii) demand for elaborate culture. When HRT was increased from 0.5 day to 3 days,
anaerobic photobioreactors covering large areas [84]. Hence, at hydrogen production rate was reduced from 198 to 34 mmol
the present time, photo-fermentation process is not a compet- l 1 day 1, while the carbohydrates in the wastewater were
itive method for hydrogen production. decomposed at an increasing efficiency from 70% to 97%. Due
to the fact that solar radiation is not a requirement, hydrogen
4.6. Dark fermentation production by dark fermentation does not demand much land
and is not affected by the weather condition. Hence, the
Fermentation by anaerobic bacteria as well as some feasibility of the technology yields a growing commercial
microalgaes, such as green algae on carbohydrate-rich sub- value.
strates, can produce hydrogen at 30 -C to 80 -C especially in a
dark condition [88]. This process using dark fermentation for 5. Conclusions
hydrogen production is illustrated in Fig. 7. Unlike a
biophotolysis process that produces only H2, the products of Hydrogen is recognized as one of the most promising
dark fermentation are mostly H2 and CO2 combined with other energy carriers in the future. Many investigations on various
gases, such as CH4 or H2S, depending on the reaction process hydrogen production methods have been conducted over the
and the substrate used. With glucose as the model substrate, past several decades. Biomass is potentially a reliable energy
maximum 4 mol H2 is produced per mole glucose when the end resource for hydrogen production. Biomass is renewable,
product is acetic acid: abundant and easy to use. Over the life cycle, net CO2
C6 H12 O6 þ 2H2 OY2CH3 COOH þ 4H2 þ 2CO2 ð13Þ emission is nearly zero due to the photosynthesis of green
plants. The thermochemical pyrolysis and gasification hydro-
When the end product is butyrate, 2 mol H2 is produced: gen production methods are economically viable and will
C6 H12 O6 þ 2H2 OYCH2 CH2 CH2 OOH þ 2H2 þ 2CO2 become competitive with the conventional natural gas reform-
ing method. Biological dark fermentation is also a promising
ð14Þ
hydrogen production method for commercial use in the future.
However, in practice, the 4 mol H2 production/mol glucose With further development of these technologies, biomass will
cannot be achieved because the end products normally contain play an important role in the development of sustainable
both acetate and butyrate [89]. hydrogen economy.
The amount of hydrogen production by dark fermentation
highly depends on the pH value, hydraulic retention time Acknowledgements
(HRT) and gas partial pressure. For the optimal hydrogen
production, pH should be maintained between 5 and 6 [90 – The authors gratefully acknowledge the funding support
92]. Partial pressure of H2 is yet another important parameter from the CLP Research Institute Ltd.
affecting the hydrogen production. When hydrogen concentra-
tion increases, the metabolic pathways shift to produce more References
reduced substrates, such as lactate, ethanol, acetone, butanol or
[1] A. Kazim, T.N. Veziroglu, Utilization of solar-hydrogen energy in the
alanine, which in turn decrease the hydrogen production [93].
UAE to maintain its share in the world energy market for the 21st century,
Besides the pH value and partial pressure, HRT also plays an Renewable Energy 24 (2001) 259.
important role in hydrogen production. Ueno et al. [94] have [2] M.A.H. Abdallah, S.S. Asfour, T.N. Veziroglu, Solar-hydrogen energy
reported that an optimal HRT of 0.5 day could effect maximum system for Egypt, International Journal of Hydrogen Energy 24 (1999) 505.
470 M. Ni et al. / Fuel Processing Technology 87 (2006) 461 – 472

[3] Z.Q. Mao, Hydrogen—a future clean energy in china, Symposium on [24] C.E.G.. Padro, V. Putsche, Survey of the economics of hydrogen
Hydrogen Infrastructure Technology for Energy and Fuel Applica- technologies, National Renewable Energy Laboratory Technical Report,
tions, The Hong Kong Polytechnic University, Hong Kong, 2003 NREL/TP_570_27079, September, 1999.
(November 18). [25] A. Demirbas, Hydrogen production from biomass by the gasification
[4] A. Demirbas, Biomass resource facilities and biomass conversion process, Energy Sources 24 (2002) 59.
processing for fuels and chemicals, Energy Conversion and Management [26] T.A. Milne., N. Abatzoglou, R.J. Evans, Biomass gasifier _tars_: their
42 (2001) 1357. nature, formation, and conversion, National Renewable Energy Laborato-
[5] J. Larminie, A. Dicks, Fuel Cell Systems Explained, Wiley, Toronto, ry Technical Report, NREL/TP_570_25357, 1998.
2000. [27] J. Corella, M.P. Aznar, J. Gil, M.A. Caballero, Biomass gasification in
[6] R.K. Jalan, V.K. Srivastava, Studies on pyrolysis of a single biomass fluidised bed: where to locate the dolomite to improve gasification?
cylindrical pellet-kinetic and heat transfer effects, Energy Conversion and Energy and Fuels 13 (1999) 1122.
Management 40 (1999) 467. [28] D. Sutton, B. Kelleher, J. Ross, Review of literature on catalysts for
[7] R. Evans, L. Boyd, C. Elam, S. Czernik, R. French, C. Feik, S. Philips, E. biomass gasification, Fuel Processing Technology 73 (2001) 155.
Chaornet, Y. Parent, Hydrogen from biomass-catalytic reforming of [29] J.M. Wornat, R.H. Hurt, N.Y.C. Yang, T.J. Headley, Structural and
pyrolysis vapors, FY 2003 Progress Report, National Renewable Energy compositional transformations of biomass chars during combustion,
Laboratory, 2003. Combustion and Flame 100 (1995) 131.
[8] A. Demirbas, Gaseous products from biomass by pyrolysis and gasifica- [30] S. Arvelakis, E.G. Koukios, Physicochemical upgrading of agroresidues
tion: effects of catalyst on hydrogen yield, Energy Conversion and as feedstocks for energy production via thermochemical conversion
Management 43 (2002) 897. methods, Biomass and Bioenergy 22 (2002) 331.
[9] A.V. Bridgwater, Principles and practice of biomass fast pyrolysis [31] S. Arvelakis, P. Vourliotis, E. Kakaras, E.G. Koukios, Effect of leaching
processes for liquids, Journal of Analytical and Applied Pyrolysis 51 on the ash behavior of wheat straw and olive residue during fluidized bed
(1999) 3. combustion, Biomass and Bioenergy 20 (2001) 459.
[10] M.A. Rabah, S.M. Eldighidy, Low cost hydrogen production from waste, [32] S. Arvelakis, H. Gehrmann, M. Beckmann, E.G. Koukios, Effect of
International Journal of Hydrogen Energy 14 (1989) 221. leaching on the ash behavior of olive residue during fluidized bed
[11] P.A. Simell, N.A.K. Hakala, H.E. Haario, A. Krause, Catalytic decompo- gasification, Biomass and Bioenergy 22 (2002) 55.
sition of gasification gas tar with benzene as the model compound, [33] S.Q. Turn, C.M. Kinoshita, D. Ishimura, Removal of inorganic constitu-
Industrial and Engineering Chemistry Research 36 (1997) 42. ents of biomass feedstocks by mechanical dewatering and leaching,
[12] P.A. Simell, E.K. Hirvensalo, V.T. Smolander, A. Krause, Steam reforming Biomass and Bioenergy 12 (1997) 241 – 252.
of gasification gas tar over dolomite with benzene as a model compound, [34] P. Garcia-Ibanez, A. Cabanillas, J.M. Sanchez, Gasification of leached
Industrial and Engineering Chemistry Research 38 (1999) 1250. orujillo (olive oil waste) in a pilot plant circulating fluidized bed reactor.
[13] I. Narvaez, J. Corella, A. Orio, Fresh tar (from a biomass gasifier) Preliminary results, Biomass and Bioenergy 27 (2004) 183.
elimination over a commercial steam-reforming catalyst. Kinetics and [35] Y. Yongjie, Exploring energy from biomass—the gasification of residues
effect of different variables of operation, Industrial and Engineering from hydrolyzed sawdust, Acta Energiae Solaris Sinica 17 (1996) 209 (in
Chemistry Research 36 (1997) 317. Chinese).
[14] P.T. Williams, A.J. Brindle, Catalytic pyrolysis of tyres: influence of [36] W. Chuangzhi, Y. Xiuli, X. Bingyan, L. Zhengfan, L. Ping, The
catalyst temperature, Fuel 81 (2002) 2425. performance study of biomass gasification with oxygen-rich air, Acta
[15] G. Chen, J. Andries, H. Spliethoff, Catalytic pyrolysis of biomass for Energiae Solaris Sinica 18 (1997) 237 (in Chinese).
hydrogen rich fuel gas production, Energy Conversion and Management [37] Y. Xia, W. Dunsong, Study of gasification treatment of biomass in fixed
44 (2003) 2289. bed gasifier, Mei Qi Yu Re Li 20 (2000) 243 (in Chinese).
[16] D. Sutton, B. Kelleher, J. Ross, Catalytic conditioning of organic volatile [38] S. Turn, C. Kinoshita, Z. Zhang, D. Ishimura, J. Zhou, An experimental
products produced by peat pyrolysis, Biomass and Bioenergy 23 (2002) investigation of hydrogen production from biomass gasification, Interna-
209. tional Journal of Hydrogen Energy 23 (1998) 641.
[17] L. Garcia, R. French, S. Czernik, S. Chornet, Catalytic steam reforming of [39] S. Rapagna, N. Jand, P.U. Foscolo, Catalytic gasification of biomass to
bio-oils for the production of hydrogen: effects of catalyst composition, produce hydrogen rich gas, International Journal of Hydrogen Energy 23
Applied Catalysis A: General 201 (2000) 225. (1998) 551.
[18] J. Abedi, Y.D. Yeboah, M. Realff, D. McGee, J. Howard, K.B. Bota, An [40] J. Jian-chun, J. Chun, Z. Jin-Ping, Y. Hao, D. Wei-di, T. Yuan-bo,
integrated approach to hydrogen production from agricultural residues for Study on industrial applied technology for biomass catalytic gasifica-
use in urban transportation, Proceedings of the 2001 DOE Hydrogen tion, Chemistry and Industry of Forest Products 21 (2001) 21 (in
Program Review, NREL/CP-570-30535, National Renewable Energy Chinese).
Laboratory, 2001. [41] W. Zhiwei, T. Songtao, S. Xueyong, L. Zian, C. Congming, L. Dingkai, A
[19] S. Czernik, R. French, R. Evans, E. Chornet, Hydrogen from post- study on model for biomass pyrolysis and gasification in fluidized bed,
consumer residues, U.S.DOE Hydrogen and Fuel Cells Merit Review Journal of Fuel Chemistry and Technology 30 (2002) 342 (in Chinese).
Meeting, Berkeley, CA, 2003 (May 19 – 23). [42] C. Courson, L. Udron, D. Swierczynski, C. Petit, A. Kiennemann,
[20] O. Onay, O.M. Kockar, Fixed-bed pyrolysis of rapeseed (Brassica napus Hydrogen production from biomass gasification on nickel catalysts tests
L.), Biomass and Bioenergy 26 (2004) 289. for dry reforming of methane, Catalysis Today 76 (2002) 75.
[21] K.A.M. Bair, S. Czernik, R. French, Y. Parent, M. Ritland, E. Chornet, [43] A. Midilli, M. Dogru, G. Akay, C.R. Howarth, Hydrogen production from
Fluidizable catalysts for producing hydrogen by steam reforming biomass sewage sludge via a fixed bed gasifier product gas, International Journal of
pyrolysis liquids, Proceedings of the 2002 U.S. DOE Hydrogen Program Hydrogen Energy 27 (2002) 1035.
Review, NREL/CP-610-32405, National Renewable Energy Laboratory, [44] S. Rapagna, H. Provendier, C. Petit, A. Kiennemann, P.U. Foscolo,
2002. Development of catalysts suitable for hydrogen or syn-gas production
[22] K.A.M. Bair, S. Czernik, R. French, E. Chornet, Fluidizable catalysts for from biomass gasification, Biomass and Bioenergy 22 (2002) 377.
hydrogen production from biomass pyrolysis/steam reforming, FY 2003 [45] R.C. Brown, Biomass-derived hydrogen from a thermally ballasted
Progress Report, National Renewable Energy Laboratory, 2003. gasifier, FY 2003 Progress Report, National Renewable Energy Labora-
[23] Y. Yeboah, K. Bota, D. Day, D. McGee, M. Realff, R. Evans, E. tory, 2003.
Chornet, S. Czernik, C. Feik, R. French, S. Philips, J. Patrick, Hydrogen [46] D.A. Bowen, F. Lau, R. Zabransky, R. Remick, R. Slimane, S. Doong,
from biomass for urban transportation, Hydrogen, Fuel Cells and Techno-economic analysis of hydrogen production by gasification of
Infrastructure Technologies Program Review Meeting, Berkeley, CA, biomass, NREL FY 2003 Progress Report, National Renewable Energy
2003 (May 18 – 22). Laboratory, 2003.
M. Ni et al. / Fuel Processing Technology 87 (2006) 461 – 472 471

[47] S.Y. Lin, Y. Suzuki, H. Hatano, M. Harada, Hydrogen production from [71] H. Ooshima, S. Takakuwa, T. Katsuda, M. Okuda, T. Shirasawa, M.
hyrocarbon by integration of Water-Carbon Reaction and Carbon Dioxide Azuma, J. Kato, Production of hydrogen by a hydrogenase-deficient
Removal (HyPr-RING) Method, Energy and Fuels 15 (2001) 339. mutant of Rhodobacter capsulatu, Journal of Fermentation and Bioengi-
[48] S.Y. Lin, Y. Suzuki, H. Hatano, M. Harada, Development an innovative neering 85 (1998) 470.
method, HyPr-RING, to produce hydrogen from hydrocarbons, Energy [72] A.A. Tsygankov, L.T. Serebryakova, K.K. Rao, D.O. Hall, Acetylene
Conversion and Management 43 (2002) 1283. reduction and hydrogen photoproduction by wild-type and mutant strains
[49] S.Y. Lin, M. Harada, Y. Suzuki, H. Hatano, Gasification of organic of Anabaena at different CO2 and O2 concentrations, FEMS Microbiology
material/CaO pellets with high-pressure steam, Energy and Fuel 18 (2004) Letters 167 (1998) 13.
1014. [73] L. Vasilyeva, M. Miyake, E. Khatipov, T. Wakayama, M. Sekine, M. Hara,
[50] S.Y. Lin, M. Harada, Y. Suzuki, H. Hatano, Continuous experiment E. Nakada, Y. Asada, J. Miyake, Enhanced hydrogen production by a
regarding hydrogen production by coal/CaO reaction with steam (I) gas mutant of Rhodobacter sphaeroides having an altered light-harvesting
products, Fuel 83 (2004) 869. system, Journal of Bioscience and Bioengineering 87 (1999) 619.
[51] S.Y. Lin, M. Harada, Y. Suzuki, H. Hatano, Process analysis for hydrogen [74] T. Kondo, M. Arkawa, T. Hirai, T. Wakayama, M. Hara, J. Miyake,
production by reaction integrated novel gasification (HyPr-RING), Energy Enhancement of hydrogen production by a photosynthetic bacterium
Conversion and Management 46 (2005) 869. mutant with reduced pigment, Journal of Bioscience and Bioengineering 93
[52] S. Sato, S.Y. Lin, Y. Suzuki, H. Hatano, Hydrogen production from heavy (2002) 145.
oil in the presence of calcium hydroxide, Fuel 82 (2003) 561 – 567. [75] J.R. Benemann, Process analysis and economics of biophotolysis of water,
[53] Y. Matsumura, T. Minowa, Fundamental design of a continuous biomass IEA/H2/10/TR2-98, 1998.
gasification process using a supercritical water fluidized bed, International [76] B. Gaudernack, Photoproduction of hydrogen, IEA Agreement on the
Journal of Hydrogen Energy 29 (2004) 701. Production and Utilization of Hydrogen Annual Report, IEA/H2/AR-98,
[54] W.S.L. Mok, M. Jerry, J. Antal, Uncatalyzed solvolysis of whole biomass 1998.
hemicellulose by hot compressed liquid water, Industrial and Engineering [77] S.A. Markov, A.D. Thomas, M.J. Bazin, D.O. Hall, Photoproduction of
Chemistry Research 31 (1992) 1157. hydrogen by Cyanobacteria under partial vacuum in batch culture or
[55] T. Minowa, F. Zhen, T. Ogi, Cellulose decomposition in hot-compressed in a photobioreactor, International Journal of Hydrogen Energy 22
water with alkali or nickel catalyst, Journal of Supercritical Fluids 13 (1997) 521.
(1998) 253. [78] O. Troshina, L. Serebryakova, M. Sheremetieva, P. Lindblad, Production
[56] T. Minowa, T. Ogi, Hydrogen production from cellulose using a reduced of H2 by the unicellular Cyanobacterium gloeocapsa alpicola CALU 743
nickel catalyst, Catalysis Today 45 (1998) 411. during fermentation, International Journal of Hydrogen Energy 27 (2002)
[57] T. Minowa, S. Inoue, Hydrogen production from biomass by catalytic 1283.
gasification in hot compressed water, Renewable Energy 16 (1999) 1114. [79] R.L. Kerby, P.W. Ludden, G.P. Roberts, Carbon monoxide-dependent
[58] D.H. Yu, M. Aihara, M.J. Antal, Hydrogen production by steam reforming growth of Rhodospirillum rubrum, Journal of Bacteriology 177 (1995)
glucose in supercritical water, Energy and Fuels 7 (1993) 574. 2241.
[59] X. Xiaodong, M. Yukihiko, S. Jonny, J.A. Michael, Carbon-catalyzed [80] B. Soboh, D. Linder, R. Hedderich, Purification and catalytic properties of
gasification of organic feedstocks in supercritical water, Industrial and a CO-oxidizing: H2-evolving enzyme complex from Carboxydothermus
Engineering Chemistry Research 35 (1996) 2522. hydrogenoformans, Europe Journal of Biochemistry 269 (2002) 5712.
[60] M.J. Antal, X.D. Xu, Hydrogen production from high moisture content [81] S.A. Ensign, P.W. Ludden, Characterization of the CO oxidation/H2
biomass in supercritical water, Proceedings of the 1998 U.S.DOE evolution system of Rhodospirillum rubrum. Role of a 22-kDa iron –
Hydrogen Program Review, NREL/CP-570-25315, 1998. sulfur protein in mediating electron transfer between carbon monoxide
[61] H. Schmieder, J. Abeln, N. Boukis, E. Dinjus, A. Kruse, M. Kluth, G. dehydrogenase and hydrogenase, Journal of Biological Chemistry 266
Petrich, E. Sadri, M. Schacht, Hydrothermal gasification of biomass and (1991) 18395.
organic wastes, Journal of Supercritical Fluids 17 (2000) 145. [82] G.Y. Jung, J.R. Kim, J.Y. Park, S. Park, Hydrogen production by a new
[62] X.H. Hao, L.J. Guo, X. Mao, X.M. Zhang, X.J. Chen, Hydrogen chemoheterotrophic bacterium Citrobacter sp. Y19, International Journal
production from glucose used as a model compound of biomass gasified of Hydrogen Energy 27 (2002) 601.
in supercritical water, International Journal of Hydrogen Energy 28 [83] E. Wolfrum, P.C. Manese, A. Watt, G. Vanzin, J. Huang, S. Smolinski,
(2003) 55. Biological water gas shift, DOE Hydrogen, Fuel Cell, and Infrastructure
[63] M.H. Spritzer, G.T. Hong, Supercritical water partial oxidation, FY 2003 Technologies Program Review, 2003 (May 19 – 22).
Progress Report, National Renewable Energy Laboratory, 2003. [84] A.S. Fedorov, A.A. Tsygankov, K.K. Rao, D.O. Hall, Hydrogen
[64] Y.S. Lin, Microporous and dense inorganic membranes: current status and photoproduction by Rhodobacter sphaeroides immobilised on polyure-
prospective, Separation and Purification Technology 25 (2001) 39. thane foam, Biotechnology Letters 20 (1998) 1007.
[65] M.W. Reij, J.T.F. Keurentjes, S. Hartmans, Membrane bioreactors for [85] A.A. Tsygankov, A.S. Fedorov, T.V. Laurinavichene, I.N. Gogotov, K.K.
waste gas treatment, Journal of Biotechnology 59 (1998) 155. Rao, D.O. Hall, Actual and potential rates of hydrogen photoproduction
[66] D.B. Levin, L. Pitt, M. Love, Biohydrogen production: prospects and by continuous culture of the purple non-sulphur bacterium Rhodobacter
limitations to practical application, International Journal of Hydrogen capsulatus, Applied Microbiology and Biotechnology 49 (1998) 102.
Energy 29 (2004) 173. [86] H.G. Zhu, T. Suzuki, A.A. Tsygankov, Y. Asada, J. Miyake, Hydrogen
[67] P.C. Hallenbeck, J.R. Benemann, Biological hydrogen production; production from tofu wastewater by Rhodobacter sphaeroides immobi-
fundamentals and limiting processes, International Journal of Hydrogen lized in agar gels, International Journal of Hydrogen Energy 24 (1999)
Energy 27 (2002) 1185. 305.
[68] H. Koku, I. Eroglu, U. Gunduz, M. Yucel, L. Turker, Aspects of the [87] M. Yetis, U. Gunduz, I. Eroglu, M. Yucel, L. Turker, Photoproduction of
metabolism of hydrogen production by Rhodobacter sphaeroides, hydrogen from sugar refinery wastewater by Rhodobacter sphaeroides
International Journal of Hydrogen Energy 27 (2002) 1315. O.U.001, International Journal of Hydrogen Energy 25 (2000) 1035.
[69] A. Melis, L.P. Zhang, M. Forestier, M.L. Ghirardi, M. Seibert, Sustained [88] C.Y. Lin, C.H. Jo, Hydrogen production from sucrose using an anaerobic
photobiological hydrogen gas production upon reversible inactivation of sequencing batch reactor process, Journal of Chemical Technology and
oxygen evolution in the green algae Chlamydomonas reinhardtii, Plant Biotechnology 78 (2003) 678.
Physiology 122 (2000) 127. [89] F.R. Hawkes, R. Dinsdale, D.L. Hawkes, I. Hussy, Sustainable fermen-
[70] H. Mctavish, L.A. Sayavedrasoto, D.J. Arp, Substitution of Azotobacter tative hydrogen production: challenges for process optimisation, Interna-
vinelandii hydrogenase small-subunit cysteines by serines can create tional Journal of Hydrogen Energy 27 (2002) 1339.
insensitivity to inhibition by O2 and preferentially damages H2 oxidation [90] H.H.P. Fang, H. Liu, Effect of pH on hydrogen production from glucose
over H2 evolution, Journal of Bacteriology 177 (1995) 3960. by a mixed culture, Bioresource Technology 82 (2002) 87.
472 M. Ni et al. / Fuel Processing Technology 87 (2006) 461 – 472

[91] N. Kumar, D. Das, Enhancement of hydrogen production by Enterobacter lulosiruptor saccharolyticus, Biotechnology and Bioengineering 81
coacae IIT-BT 08, Process Biochemistry 35 (2000) 589. (2003) 255.
[92] S.K. Khanal, W.H. Chen, L. Li, S. Sung, Biological hydrogen production: [94] Y. Ueno, S. Otsuka, M. Morimoto, Hydrogen production from industrial
effects of pH and intermediate products, International Journal of wastewater by anaerobic microflora in chemostat culture, Journal of
Hydrogen Energy 29 (2004) 1123. Fermentation and Bioengineering 82 (1996) 194.
[93] E.W.J.V. Niel, P.A.M. Claassen, A.J.M. Stams, Substrate and production
inhibition of hydrogen production by the extreme thermophile Caldicel-

Você também pode gostar