Thermochemical processes for biofuels production from biomass
© Canabarro et al.; licensee Chemistry Central Ltd. 2013
Received: 11 September 2013
Accepted: 17 November 2013
Published: 20 November 2013
The contribution of biomass to the world’s energy supply is presently estimated to be around 10% to 14%. The conversion of biomass to biofuels can be achieved primarily via biochemical and thermochemical processes. Recently, the use of thermochemical processes as pyrolysis and gasification has received great attention. The biomass composition and form of process conduction can affect greatly the efficiency of conversion for both gasification and pyrolysis. This review compiles recent thermochemical studies using several kinds of biomass to obtain biofuels and, additionally, it presents a brief description of main gasification and pyrolysis processes employed. Publications in Patent database also were reported and compiled.
Recently there has been a renewed interest in using biomass as an energy source due to the increasing demand in global energy coupled with environmental concerns of using fossil fuels. The contribution of biomass to the world’s energy supply is presently estimated to be around 10% to 14% . The conversion of biomass to biofuels can be achieved primarily via biochemical and thermochemical processes. The thermochemical processes can convert both food and nonfood biomass to fuel products via pyrolysis and gasification . Thermochemical gasification is a promising technology that can exploit the embedded energy in various types of biomass and convert to valuable products suitable for different industrial applications. Common feedstock for gasification includes agricultural crop residues, forest residues, energy crops, organic municipal wastes, and animal waste [2, 3].
Pyrolysis, like gasification, is an advanced thermal treatment that converts a material into a syngas but at lower temperatures and in the absence of oxygen. It is always also the first step in combustion and gasification processes where it is followed by total or partial oxidation of the primary products [4, 5]. Despite the calorific value of a gas derived from pyrolysis being higher than that of gasification, the volume of gas produced is usually much lower due to the lack of the oxygen carrier [6–8].
Both pyrolysis and gasification of biomass are complex processes and depends on several factors such as the composition of lignocellulosic material, heating rate and content of inorganic material etc. The amounts of cellulose, hemicellulose and lignin present in the biomass affect the pyrolysis and gasification, implying in great variation in the efficiency among different biomass and process employed. In this sense, the objective of this review is to compile the main biomass used in thermochemical studies. In addition, it will be presented a brief description of main gasification and pyrolysis processes employed as well as the main technologies cited in patent database.
For the synthesis of liquid fuels and other chemicals only a nitrogen-free syngas is suitable. Several studies on nitrogen conversion in different gasification processes are available in the literature. Fixed bed and fluidized bed gasification are more common. Different gasification agents can be applied, as air, oxygen or steam [14, 15].
The use of air as a gasifying agent is most common in industry but yields low heating value gas (4–7 MJ/Nm3) that is only suitable for heat and power applications. On the other hand, steam and oxygen can increase the heating value of syngas (10–18 MJ/Nm3) and the H2/CO ratio. A high H2/CO ratio is required for producing liquid fuels through Fischer–Tropsch synthesis and also benefits the production of H2 for use in fuel cells. However, high capital costs and complex system design have hindered the applications of steam and oxygen gasification at a large industrial scale [2, 16].
Comparison of different types of biomass and gasification process
Dual fluidized bed gasifier
Input fuel power: 90 kWth;
A lower amount of steam and the high catalytic activity of the lignite caused a better performance of the gasification reactor.
Particle size: 370 and 510 μm;
Steam-to-carbon ratio: 1.3 and 2.1 KgH2O/Kgcarbon.
The reduction of particle size increases product gas yield in +15.7%.
Waste wood; Bark; Plastic residues
Input fuel power: 100 kW; Nitrogen content: 0.05 to 2.70 wt.-%. Temperature: 850°C
The DFB gasifier is suitable for the conversion of fuels with higher loads of nitrogen.
Water: 6.1 wt.-% (waste wood); 11.9 wt.-% (Bark)
Empty fruit bunches
Moisture: more than 50 wt.%;
The gasification efficiency decreases as the moisture content increases.
A high content of moisture and oxygen resulted in a low calorific value.
Particle size: less than 1.0 mm;
Fluidized bed gasifier
Pine, maple-oak mixture, and discarded seed corn
Gasifying agent: Oxygen and steam
The gasification is most effective for feedstock with low nitrogen and moisture contents.
Input fuel power: 800 kW
Supercritical water gasification
Reaction times: 3 –80 min
The yield of CH4 increased significantly as the indole concentration increased.
Temperature: 550 and 700°C
Hydrogen and carbon gasification efficiencies exhibited values up to 79% and 20%, respectively.
Initial indole concentration: 0.2 mol/L
Pressure: 30 MPa
Temperature: 300 - 430°C.
The highest rate of coke formation occurred in the temperature range of 350 –370°C, and long residence times.
Residence times: 5–120 min.
Feed concentrations: 10, 20 e 30 wt.%
Pressure: 30 MPa.
Temperature: 800, 900 and 1000°C;
The increase in reactor temperature resulted in an increase in energy yield and apparent thermal efficiency.
Gasifying agent: 8 g/min of steam;
The enhancement in syngas quality at the 1000°C case resulted in an increase of energy yield.
Tracer gas: 2.33 g/min of nitrogen;
Sample: 15 g of sugarcane bagasse.
Biomass not specified.
Temperature: 800°C to 1200°C.
Higher gasification temperature leads to higher energy efficiencies of product gas and lower energy efficiencies of tar.
Raw bamboo; Torrefied bamboo; High-volatile bituminous coal
Gasification agent: Oxygen;
The carbon conversions of the three fuels are higher than 90%.
Sizes of the particles: 44 – 250 μm;
fuel temperature: 300 K;
Pressure: 2 Mpa.
Atmospheric pressure gasifier and the pressurized gasifier.
Moisture: 10 – 20%;
In comparison with fuels and chemicals from conventional feedstocks, biomass based
Feedstock size: 20 – 80 mm.
fuels and chemicals are expensive.
Fixed bed reactor
Crude glycerol with olive kernel
H2 concentration increased from 19 to 33% (v/v) and the tar yield decreased from 19.5 to 2.4 wt% at conditions of T = 850°C and λ = 0.4.
Air ratios of λ = 0.2–0.4
Pine; Red oak; Horse manure; Cardboard
Moisture: 12.2 wt.% (Pine), 14.8 wt.% (Red oak) 18.33 wt.% (Horse manure) 12.6 wt.% (Cardboard)
efficiencies for the gasifier were found in the range of 81.7–84.6%
Mixture of polypropylene and poplar sawdust
Temperature: 400 to 800°C; Particle size: 2 mm (sawdust); 3 mm (polypropylene)
The increase of temperature led to the decrease of the solid residues fraction and an increase in the gas yield.
Optimum temperature: 700°C
Dual fluidized bed gasification (DFB)
The DFB gasifier consists of two reactors, where gasification and combustion take place separately . Circulating bed material between these two reactors carries the heat from the combustion reactor to the gasification reactor . In the DFB gasifier, biomass is gasified with steam. Due to steam gasification, there is virtually no nitrogen in the producer gas and the hydrogen content amounts to about 40%. The average heating value is around 12–14 MJ/Nm3 (Nm3 = at 273.15 K and 101.325 Pa, referred to as dry gas). Producer gas from steam gasification is well suitable not only for heat and electricity production, but also for chemical synthesis .
Fixed bed gasification
Supercritical water gasification (SCWG)
This process has the potential to convert biomass with water contents up to 80% directly without the need for an energy-expensive drying step . An advantage of processing wet biomass hydrothermally, rather than drying it, is that doing so avoids the energy penalty associated with the phase change of the water. This leads to an improvement in economic performance compared with a conventional gasification process . These systems make use of the conditions of the critical point of water at 647.3 K and a pressure of 22.1 MPa as a favorable environment for wet biomass gasification reactions .
Plasma is considered to be the fourth state of matter, consisting of a mixture of electrons, ions and neutral particles, although overall it is electrically neutral. The degree of ionization of a plasma is the proportion of atoms that have lost (or gained) electrons. Plasma technology involves the creation of a sustained electrical arc by the passage of electric current through a gas in a process referred to as electrical breakdown. Because of the electrical resistivity across the system, significant heat is generated, which strips away electrons from the gas molecules resulting in an ionized gas stream, or plasma [15, 34]. Plasma gasification processes may reach temperatures from 2,000 to 30,000°C .
A general analysis of data compiled in Table 1 reveals that fluidized and fixed-bed reactors are more usual in gasification procedures. The variable more studied is temperature, where it is seen that at high temperature the energy production and the syngas quality increases, beyond that decrease the tars production. The particle size and the moisture have a significant influence in the gasification process, but if the particle size is reduced the syngas production increases and at high moisture contents the efficiency of gasification decrease.
Pyrolysis is an advanced thermal treatment that converts a material into a syngas at temperatures around 1000°C and in the absence of oxygen. Pyrolysis also can be described as the direct thermal decomposition of the organic matrix that could obtain solid, liquid and gas products [35–37]. Temperature is the most important factor for the product distribution of pyrolysis, most interesting range for the production of the pyrolysis products is between 625 and 775 K. The charcoal yield decreases as the temperature increases. Yield of products resulting from biomass pyrolysis can be maximized as follows: charcoal (a low temperature, low heating rate process), liquid products (a low temperature, high heating rate, short gas residence time process), and fuel gas (a high temperature, low heating rate, long gas residence time process) [8, 38, 39].
Lower process temperature and longer vapour residence times favour the production of charcoal. High temperature and longer residence time increase the biomass conversion to gas and moderate temperature and short vapour residence time are optimum for producing liquids [4, 40]. Short residence time pyrolysis of biomass at moderate temperatures has generally been used to obtain high yield of liquid products. For highly cellulosic biomass feedstocks, the liquid fraction usually contains acids, alcohols, aldehydes, ketones, esters, heterocyclic derivatives and phenolic compounds [35, 41, 42].
Comparison of different types of biomass and pyrolysis process
Moderate temperature, short residence time vapour
Fluid Bed 500°C
41,67% C 7,87% H 50,46% O
43,13% C 8,14% H 0,22% N 48,51% O
43,66% C 7,67% H
39,45% C 7,96% H 0,001% N 52,58% O
39,44% C 8,01% H 0,30% N 52,25% O
41,27% C 7,79% H
0,01% N 50,93% O
32,64% C 8,01% H
0,35% N 58,31% O
Phenol, furans, ethers, acids, single-ringaromatic
Residence times 1–3 s
E- Biooil wt%
22.56% C 10,8% H 0,3% N 63,34% O
Celulose, sugar cane bagasse
Fixed Bed with H2
Hidropyrolysis 10 Mpa
Oil palm shell
Fluidised Bed with N2
High fraction of phenol
Pine and spruce
Oxygenated organic compounds aldehydes, acids, ketones and metoxylated phenols
Circulating Fluidised Bed
Non-hidrocarbons and alkanes-aromatics
Rape seed grains
Wood chips and rice shell
Powder-particle; Catalitic; Fluidised Bed 427°C
Birch bark, birch sapwood
One step and stepwise
Tubular Batch with N2
43,21% C 5,94% H
45,50% O 0,65% N 1,24% S
38% oil, large pore size, high clorific value
45,3% C, 5,6% H, 1% N,
0,8% S, 47,2% O
49,4% C, 5,8% H, 1,3% N
1,3% S, 42,3% O
Palm leaf stem
36,1% C, 5,2% H, 0,7% N,
0,7% S, 57,2% O
Palm bituminous coal
73,1% C, 5,5% H, 1,4% N,
1,7% S, 8,7% O
0,50% N, 38,16% C,
5,40% H, 55,94% O
0,21% N, 42,93% C,
6,16% H, 50,70% O
Posidonea Oceanic seaweed
0,71% N, 34,85% C,
4,54% H, 0,62% S, 59,28% O
agricultural urban pruning waste
2,09% N, 48,06% C,
5,81% H, 44,04% O
waste of forest pruning
0,65% N, 40,12% C,
5,44% H, 53,79% O
Steam pyrolysis; 5X105 Pa
Biomass is pyrolysed at slow heating rates (5–7 K/min). This leads to less liquid and gaseous product and more of char production, at low temperature (675–775 K), and/or gas, at high temperature. Significant amount of work has been done on this process. The most used reactors in this process are fixed bed and tubular reactor .
Fast pyrolysis is a process in which a material, such as biomass, is rapidly heated to high temperatures in the absence of air (specifically oxygen). It involves fast heating of biomass but not as fast as flash pyrolysis. Heating rate is somewhere about 300°C/min. Generally, fast pyrolysis is used to obtain high-grade bio-oil. Fast pyrolysis is successful with different reactors configurations, some of them are fluidized-bed reactors, entrained flow reactor, wire mesh reactor, vacuum furnace reactor, vortex reactor, rotating reactor, circulating fluidized bed reactor. If the purpose was to maximize the yield of liquid products resulting from biomass pyrolysis, a low temperature, high heating rate, short gas residence time process would be required. If the purpose were to maximize the yield of fuel gas resulting from biomass pyrolysis, a high temperature, low heating rate, long gas residence time process would be preferred [9, 53–55].
Flash pyrolysis is the process in which the reaction time is of only several seconds or even less. The heating rate is very high. This requires special reactor configuration in which biomass residence times are only of few seconds. Two of appropriate designs are entrained flow reactor and the fluidized-bed reactor. Flash pyrolysis of any kind of biomass requires rapid heating and therefore the particle size should be fairly small. Major problem of the present reactors for flash pyrolysis are the quality and the stability of the produced oil, strongly affected by char/ash content of bio-oil. Besides the known problems concerning solid particles in the bio-oil, char fines will catalyze repolymerization reactions inside the oil resulting in a higher viscosity. Flash pyrolysis is of following types: flash hydro-pyrolysis is flash pyrolysis done in hydrogen atmosphere, it is carried out at a pressure up to 20Mpa; rapid thermal process is a particular heat transfer process with very short heat residence times (between 30 ms and 1.5 s). It is done at temperatures between 400 and 950 1C; rapid de-polymerization and cracking of feed stocks takes place; rapid heating eliminates the side reactions whereby giving products with comparable viscosity to diesel oil; solar flash pyrolysis concentrated solar radiation can be used to perform flash pyrolysis; vacuum flash pyrolysis the process is done under vacuum, the vacuum facilitates the removal of the condensable products from the hot reaction zone [56–58].
Catalytic biomass pyrolysis
From literature it was seen that liquids obtained from biomass by slow, flash or fast pyrolysis process, could not be directly used as transportation fuel. This oil needs to be upgraded as they have high oxygen and water content. These oils are also found to be less stable and less miscible in conventional fuels. Catalytic biomass pyrolysis is introduced to improve the quality of the oil produced [38, 59, 60].
Recent technologies in gasification and pyrolysis process
Method and apparatus for coproduction of pig iron and high quality syngas.
WO 2012/018394 A3
Nanoparticle catalyst and method of using the same for biomass gasification.
US 2011/0315931 A1
Method of puryfing a gas.
US 2012/0202897 A1
Fluidized bed gasifier
Pretreatment of biomass feed for gasification.
US 2012/0266531 A1
Method and device for mixed flow type gasification of biomass.
US 2012/159469 A1
Fluidized bed and downstream edge
Method for producing production gas and apparatus using same.
US 2012/176611 A1
Ammonia production by integrated intencified process.
WO 2012/025767 A3
A processes and a system for the gasification and/or combustion of biomass and/or coal with and at least partial carbon dioxide separation.
WO 2012/103997 A1
Production of stable biomass pyrolysis oils using fractional catalytic pyrolysis
US 2010/0212215 A1
Producing of biofuel by fast pyrolysis of organic material, using a system of three interconnected serial fluidized bed reactors
Equipment and a method for generating biofuel based on rapid pyrolysis biomass
US 2011/0219680 A1
Producing substitute natural gas (hydrocarbons) from forestry residues by hydropyrolysis
Sorption enhanced methanation of biomass
US 2013/0017460 A1
Method and apparatus for pyrolysis and gasification of biomass
US 2013/0125465 A1
Reactor with rotational chamber for pyrolysis of biomass to conversion in energy
Reactor for pyrolysis of biomass
WO 2011/034409 A1
Process for catalytic hydrotratament of a pyrolysis oil
WO 2011/064172 A1
Pyrolytic conversion of biomass materials into stable fuels and other usable products
Production of pyrolysis oil
WO 2011/103313 A2
Effective pyrolysis of a biomass utilizing rapid heat transfer from a solid heat carrier or catalyst
Method and apparatus for pyrolysis of a biomass
WO 2012/012191 A1
The authors thank CAPES for scholarships.
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