Biofuels from Syngas

An attractive approach to converting biomass into liquid or gaseous fuels is direct gasification, followed by conversion of the gas to final fuel. Ethanol can be produced this way, but other fuels can be produced more easily and potentially at lower cost, though none of the approaches is currently inexpensive.

The choice of which process to use is influenced by the fact that lignin cannot easily be converted into a gas through biochemical conversion. Lignin can, however, be gasified through a heat process. The lignin components of plants can range from near 0% to 35%. For those plants at the lower end of this range, the chemical conversion approach is better suited. For plants that have more lignin, the heat-dominated approach is more effective.

Once the gasification of biomass is complete, the resulting gases can be used in a variety of ways to produce liquid fuels discussed, in brief, below

Fischer-Tropsch (F-T) fuels

The Fischer-Tropsch process converts “syngas” (mainly carbon monoxide and hydrogen) into diesel fuel and naphtha (basic gasoline) by building polymer chains out of these basic building blocks. Typically a variety of co-products (various chemicals) are also produced.  Figure 2.1 shows the production of diesel fuel from bio-syngas by Fisher-Tropsch synthesis (FTS).

The Fisher-Tropsch process is an established technology and has been proven on a large scale but adoption has been limited by high capital and O&M costs. According to Choren Industries, a German based developer of the technology, it takes 5 tons of biomass to produce 1 ton of biodiesel, and 1 hectare generates 4 tons of biodiesel.

Methanol

Syngas can also be converted into methanol through dehydration or other techniques, and in fact methanol is an intermediate product of the F-T process (and is therefore cheaper to produce than F-T gasoline and diesel). Methanol is somewhat out of favour as a transportation fuel due to its relatively low energy content and high toxicity, but might be a preferred fuel if fuel cell vehicles are developed with on-board reforming of hydrogen.

Dimethyl ether

DME also can be produced from syngas, in a manner similar to methanol. It is a promising fuel for diesel engines, due to its good combustion and emissions properties. However, like LPG, it requires special fuel handling and storage equipment and some modifications of diesel engines, and is still at an experimental phase. If diesel vehicles were designed and produced to run on DME, they would become inherently very low pollutant emitting vehicles; with DME produced from biomass, they would also become very low GHG vehicles.

A Primer on Waste-to-Energy

Waste-to-Energy is the use of modern combustion and biochemical technologies to recover energy, usually in the form of electricity and steam, from urban wastes. These new technologies can reduce the volume of the original waste by 90%, depending upon composition and use of outputs.

Energy is the driving force for development in all countries of the world. The increasing clamor for energy and satisfying it with a combination of conventional and renewable resources is a big challenge. Accompanying energy problems in different parts of the world, another problem that is assuming critical proportions is that of urban waste accumulation.

The quantity of waste produced all over the world amounted to more than 12 billion tonnes in 2006, with estimates of up to 13 billion tonnes in 2011. The rapid increase in population coupled with changing lifestyle and consumption patterns is expected to result in an exponential increase in waste generation of upto 18 billion tonnes by year 2020.

Waste generation rates are affected by socio-economic development, degree of industrialization, and climate. Generally, the greater the economic prosperity and the higher percentage of urban population, the greater the amount of solid waste produced. Reduction in the volume and mass of solid waste is a crucial issue especially in the light of limited availability of final disposal sites in many parts of the world. Millions of tonnes of household wastes are generated each year with the vast majority disposed of in open fields or burnt wantonly.

The main categories of waste-to-energy technologies are physical technologies, which process waste to make it more useful as fuel; thermal technologies, which can yield heat, fuel oil, or syngas from both organic and inorganic wastes; and biological technologies, in which bacterial fermentation is used to digest organic wastes to yield fuel.

The three principal methods of thermochemical conversion are combustion in excess air, gasification in reduced air, and pyrolysis in the absence of air. The most common technique for producing both heat and electrical energy from wastes is direct combustion. Combined heat and power (CHP) or cogeneration systems, ranging from small-scale technology to large grid-connected facilities, provide significantly higher efficiencies than systems that only generate electricity.

Biochemical processes, like anaerobic digestion, can also produce clean energy in the form of biogas which can be converted to power and heat using a gas engine. In addition, wastes can also yield liquid fuels, such as cellulosic ethanol, which can be used to replace petroleum-based fuels. Cellulosic ethanol can be produced from grasses, wood chips and agricultural residues by biochemical route using heat, pressure, chemicals and enzymes to unlock the sugars in biomass wastes.

Waste-to-energy plants offer two important benefits of environmentally safe waste management and disposal, as well as the generation of clean electric power.  The growing use of waste-to-energy as a method to dispose of solid and liquid wastes and generate power has greatly reduced environmental impacts of municipal solid waste management, including emissions of greenhouse gases.

Pyrolysis of Municipal Wastes

Pyrolysis-MSWPyrolysis is rapidly developing biomass thermal conversion technology and has been garnering much attention worldwide due to its high efficiency and good eco-friendly performance characteristics. Pyrolysis technology provides an opportunity for the conversion of municipal solid wastes, agricultural residues, scrap tires, non-recyclable plastics etc into clean energy. It offers an attractive way of converting urban wastes into products which can be effectively used for the production of heat, electricity and chemicals.

Pyrolysis of Municipal Wastes

Pyrolysis process consists of both simultaneous and successive reactions when carbon-rich organic material is heated in a non-reactive atmosphere. Simply speaking, pyrolysis is the thermal degradation of organic materials in the absence of oxygen. Thermal decomposition of organic components in the waste stream starts at 350°C–550°C and goes up to 700°C–800°C in the absence of air/oxygen.

Pyrolysis of municipal wastes begins with mechanical preparation and separation of glass, metals and inert materials prior to processing the remaining waste in a pyrolysis reactor. The commonly used pyrolysis reactors are rotary kilns, rotary hearth furnaces, and fluidized bed furnaces. The process requires an external heat source to maintain the high temperature required. Pyrolysis can be performed at relatively small-scale which may help in reducing transport and handling costs.  In pyrolysis of MSW, heat transfer is a critical area as the process is endothermic and sufficient heat transfer surface has to be provided to meet process heat requirements.

The main products obtained from pyrolysis of municipal wastes are a high calorific value gas (synthesis gas or syngas), a biofuel (bio oil or pyrolysis oil) and a solid residue (char). Depending on the final temperature, MSW pyrolysis will yield mainly solid residues at low temperatures, less than 4500C, when the heating rate is quite slow, and mainly gases at high temperatures, greater than 8000C, with rapid heating rates. At an intermediate temperature and under relatively high heating rates, the main product is a liquid fuel popularly known as bio oil.

Wide Range of Products

Bio oil is a dark brown liquid and can be upgraded to either engine fuel or through gasification processes to a syngas and then biodiesel. Pyrolysis oil may also be used as liquid fuel for diesel engines and gas turbines to generate electricity Bio oil is particularly attractive for co-firing because it can be relatively easy to handle and burn than solid fuel and is cheaper to transport and store. In addition, bio oil is also a vital source for a wide range of organic compounds and specialty chemicals.

Syngas is a mixture of energy-rich gases (combustible constituents include carbon monoxide, hydrogen, methane and a broad range of other VOCs). The net calorific value (NCV) of syngas is between 10 and 20MJ/Nm3. Syngas is cleaned to remove particulates, hydrocarbons, and soluble matter, and then combusted to generate electricity. Diesel engines, gas turbines, steam turbines and boilers can be used directly to generate electricity and heat in CHP systems using syngas and pyrolysis oil. Syngas may also be used as a basic chemical in petrochemical and refining industries.

The solid residue from MSW pyrolysis, called char, is a combination of non-combustible materials and carbon. Char is almost pure carbon and can be used in the manufacture of activated carbon filtration media (for water treatment applications) or as an agricultural soil amendment.

Thermal Conversion of Tannery Wastes

tannery-wastesTanneries generate considerable quantities of sludge, shavings, trimmings, hair, buffing dusts and other general wastes and can consist of up to 70% of hide weight processed. Thermal technologies, gasification in particular, by virtue of chemically reducing conditions, provides a viable alternative thermal treatment for Chrome containing materials, and generates a chrome (III) containing ash. This ash has significant commercial value as it can be reconstituted.

All of the wastes created by the tannery can be gasified following pre-treatment methods such as maceration, drying and subsequent densification or briquetting. A combined drying and gasification process could eliminate solid waste, whilst providing a combustible gas as a tax-exempt renewable energy source, which the tannery can directly reuse. Gasification trials have illustrated that up to 70% of the intrinsic energy value of the wastes currently disposed can be recovered as “synthesis gas” energy.

Gasification technology has the potential to provide significant cost benefits in terms of power generation and waste disposal, and increase sustainability within the leather industry. The gasification process converts any carbon-containing material into a combustible gas comprised primarily of carbon monoxide, hydrogen and methane, which can be used as a fuel to generate electricity and heat.

A wide range of tannery wastes can be macerated, flash dried, densified and gasified to generate a clean syngas for reuse in boilers or other Combined Heat and Power systems. As a result up to 70% of the intrinsic energy value of the waste can be recovered as syngas, with up to 60% of this being surplus to process drying requirements so can be recovered for on-site boiler or thermal energy recovery uses.

A proprietary technology has been in commercial operation at a tanyard on the West Coast of Norway since mid 2001. The process employs gasification-and-plasma-cracking and offer the capability of turning the tannery waste problem to a valorising source that may add values to the plant owner in terms of excessive energy and ferrochrome, a harmless alloy that is widely used by the metallurgical industry. The process leaves no ashes but a non-leaching slag that is useful for civil engineering works, and, hence, no residues for landfill disposal

Biomass Gasification Process

Biomass gasification involves burning of biomass in a limited supply of air to give a combustible gas consisting of carbon monoxide, carbon dioxide, hydrogen, methane, water, nitrogen, along with contaminants like small char particles, ash and tars. The gas is cleaned to make it suitable for use in boilers, engines and turbines to produce heat and power (CHP).

Biomass gasification provides a means of deriving more diverse forms of energy from the thermochemical conversion of biomass than conventional combustion. The basic gasification process involves devolatization, combustion and reduction.

During devolatization, methane and other hydrocarbons are produced from the biomass by the action of heat which leaves a reactive char.

During combustion, the volatiles and char are partially burned in air or oxygen to generate heat and carbon dioxide. In the reduction phase, carbon dioxide absorbs heat and reacts with the remaining char to produce carbon monoxide (producer gas). The presence of water vapour in a gasifier results in the production of hydrogen as a secondary fuel component.

There are two main types of gasifier that can be used to carry out this conversion, fixed bed gasifiers and fluidized bed gasifiers. The conversion of biomass into a combustible gas involves a two-stage process. The first, which is called pyrolysis, takes place below 600°C, when volatile components contained within the biomass are released. These may include organic compounds, hydrogen, carbon monoxide, tars and water vapour.

Pyrolysis leaves a solid residue called char. In the second stage of the gasification process, this char is reacted with steam or burnt in a restricted quantity of air or oxygen to produce further combustible gas. Depending on the precise design of gasifier chosen, the product gas may have a heating value of 6 – 19 MJ/Nm3.

Layout of a Typical Biomass Gasification Plant

The products of gasification are a mixture of carbon monoxide, carbon dioxide, methane, hydrogen and various hydrocarbons, which can then be used directly in gas turbines, and boilers, or used as precursors for synthesising a wide range of other chemicals.

In addition there are a number of methods that can be used to produce higher quality product gases, including indirect heating, oxygen blowing, and pressurisation. After appropriate treatment, the resulting gases can be burned directly for cooking or heat supply, or used in secondary conversion devices, such as internal combustion engines or gas turbines, for producing electricity or shaft power (where it also has the potential for CHP applications).

 

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A Glance at Drop-in Biofuels

drop-in-biofuelsBiofuel commercialization has proved to be costly and lingering than expected due to its high production cost and modification to flexibility in engines. Drop-in fuels are alternatives to existing liquid fuels without any significant modification in engines and infrastructures. According to IEA, “Drop-in biofuels are liquid bio-hydrocarbons that are functionally equivalent to petroleum fuels and are fully compatible with existing petroleum infrastructure”.

What are Drop-in Biofuels

Drop-in biofuels are can be produced from oilseeds via trans-esterification, lignocellulosic biomass via thermochemical process, sugars and alcohol via biochemical conversion or by hybrids of the above methods. Drop-in fuels encompass high hydrogen to carbon ratio with no/low sulfur and oxygen content, low water solubility and high carbon bond saturation. In short drop-in fuel is a modified fuel with close functional resemblance to fossil fuel.

Existing biofuels – bioethanol and biodiesel – have wide variation from fossil fuels in their blend wall properties – high oxygen content, hydrophilicity, energy density and mainly compatibility in existing engines and infrastructures. Oxygenated groups in biofuel have a domino effect such as reduction in the energy density, production of impurities which are highly undesirable to transportation components, instability during storage etc.

Major advantages of drop-in fuels over existing fuels are as follows:

  • Reduced sulphur oxide emissions by ultra low sulphur content.
  • Reduced ignition delay by high cetane value
  • Reduced hydrocarbons and nitrogen oxides emissions
  • Low aromatic content
  • Low olefin content, presence of olefin compounds undergo auto-oxidation leading to surface depositions.
  • High saturates, therefore leaving minimum residues
  • Low particulate emissions
  • No oxygenates therefore has high stability.

Potential Biomass Feedstock

Drop-in biofuels can be produced from various biomass sources- lipids (vegetable oils, animal fats, greases, and algae) and lignocellulosic material (such as crop residues, woody biomass, and dedicated energy crops). The prominent technologies for biomass conversion to drop-in fuel are the thermochemical and the biochemical process.

The major factor playing role in selection of biomass for thermochemical methods is the energy content or heating value of the material, which is correlated with ash content. Wood, wood chips accounts for less than 1% ash content, which is favorable thermal processing than biochemical process, whereas straws, husks, and majority of the other biomass have ash content ranging up to 25% of dry mass.

Free sugar generating plants such as sugarcane and sweet sorghum, are desirable feedstock for Acetone-Butanol-Ethanol fermentation and have been widely implemented. Presently there is a focus to exploit lignocellulosic residues, rich in hydrocarbon, for fuel production. However, this biomass requires harsh pretreatment to remove lignin and to transform holocellulose (cellulose & hemicelluloses) into fermentable products.

The lignocellulose transformation technology must be circumspectly chosen by its life cycle assessment, as it resists any changes in their structural integrity owing to its complexity. Lignocellulosic biomass, when deoxygenated, has better flexibility to turn to drop-in fuels. This is because, in its native state of the feedstock, each oxygen atom consumes two hydrogen atoms during combustion which in turn reduces effective H: C ratio. Biomass feedstock is characterized with oxygen up to 40%, and higher the oxygen content higher it has to be deoxygenated.

Thermochemical Route

Thermochemical methods adopted for biomass are pyrolysis and gasification, on thermolysis of biomass produce intermediate gas (syngas) and liquid (bio crude) serving as precursors for drop-in fuel. Biomass when exposed to temperature of 500oC-600oC in absence of oxygen (pyrolysis) produce bio-oil, which constitutes a considerable percentage of oxygen. After down streaming by hydroprocessing (hydrotreating and hydrocracking) the rich hydrocarbon tar (bio-oil) can be converted to an efficient precursor for drop-in fuel.

At a higher temperature, above 700, under controlled oxygen, biomass can be converted to liquid fuel via gas phase by the process, gasification. Syngas produced is converted to liquid fuel by Fischer-Tropsch with the help of ‘water gas shift’ for hydroprocessing. Hydroprocessing after the thermochemical method is however costly and complex process in case of pyrolysis and inefficient biomass to fuel yield with gasification process.

Biochemical Pathway

The advanced biocatalytic processes can divert the conventional sugar-ethanol pathway and convert sugars to fatty acids. Modified microbial strain with engineered cellular machineries, can reroute the pathway to free fatty acid that can be transformed into butanol or drop-in fuel with necessary processing.

Schematic for the preparation of jet fuel from biomass

Schematic for the preparation of jet fuel from biomass

Biological processing requires operation under the stressful conditions on the organisms to reroute the pathways, in additional to lowering NADPH (hydrogen) consumption. Other value added products like carboxylic acid, polyols, and alcohol in the same biological routes with lower operational requirements have higher market demands and commercial success. Therefore little attention is given by chemical manufacturers to the biological pathways for drop-in fuel production.

The mechanisms of utilization of lignocellulosic biomass to fuel by biological pathway rely heavily on the availability of monomeric C5 and C6 sugars during fermentation. Ethanol is perhaps the best-known and commercially successful alcohol from ABE fermentation. However, butanol has various significant advantages over ethanol- in the perception of energy content, feasibility to existing infrastructures, zero blend wall, safety and clean aspects. Although butanol is a closer drop-in replacement, existing biofuel ethanol, is a major commercial competitor. Low yield from fermentation due to the toxicity of butanol and complexity in down streaming are the vital reasons that hamper successful large scale butanol production.

Challenges to Overcome

Zero oxygen and sulphur content mark major challenges for production of drop-in fuels from conventional biomass. This demands high hydrogen input on the conventional biomass, with H: C ratio below 0.5, like sugar, starch, cellulose, lignocellulose to meet the effective hydrogen to carbon ratio of 2 as in drop-in fuel. This characterizes most of the existing biomass feedstock as a low-quality input for drop-in fuels. However oleochemicals like fats, oils, and lipids have closer H: C ratio to diesel, gasoline and drop-in fuels, thus easier to conversion. Oleochemical feedstock has been commercially successful, but to prolong in the platform will be a major challenge. Lipid feedstock is generally availed from crop-based vegetable oil, which is used in food sectors. Therefore availability, food security concerns, and economics are the major constraints to sustaining the raw material. Consequently switching to lignocellulosic biomass feedstock for drop-in holds on.

Conclusions

Despite the hurdles on biomass characteristics and process technology for drop-in fuel, it is a vital requirement to switch to better replacement fuel for fossil fuel, considering environmental and economic benefits. Understanding its concepts and features, drop-in fuel, can solve existing greenhouse emission debate on current biofuels. Through crucial ambiguities existing on future of alternative fuels, drop-in fuel has a substantial potential to repute itself as an efficient sustainable eco-friendly fuel in the naear future.

References

  • Neal K Van Alfen: ENCYCLOPEDIA OF AGRICULTURE AND FOOD SYSTEMS, Elsevier, Academic Press.
  • Pablo Domínguez de María John: INDUSTRIAL BIORENEWABLES:A Practical Viewpoint: Wiley & Sons.
  • Ram Sarup Singh, Ashok Pandey, Edgard Gnansounou: BIOFUELS- PRODUCTION AND FUTURE PERSPECTIVES, CRC Press.
  • Satinder Kaur Brar, Saurabh Jyoti Sarma, Kannan Pakshirajan : PLATFORM CHEMICAL BIOREFINERY-FUTURE GREEN CHEMISTRY, Elsevier.
  • Sergios Karatzos, James D. McMillan, Jack N. Saddle: Summary of IEA BIOENERGY TASK 39 REPORT-THE POTENTIAL AND CHALLENGES OF DROP-IN BIOFUELS, IEA Bioenergy.
  • Vijai Kumar Gupta, Monika Schmoll, Minna Maki, Maria Tuohy, Marcio Antonio Mazutti: APPLICATIONS OF MICROBIAL ENGINEERING, CRC Press.

Gasification of Municipal Wastes

utishinai-gasification-plantGasification of municipal wastes involves the reaction of carbonaceous feedstock with an oxygen-containing reagent, usually oxygen, air, steam or carbon dioxide, generally at temperatures above 800°C. The process is largely exothermic but some heat may be required to initialise and sustain the gasification process. The main product of the gasification process is syngas, which contains carbon monoxide, hydrogen and methane. Typically, the gas generated from gasification has a low heating value (LHV) of 3 – 6 MJ/Nm3.The other main product produced by gasification is a solid residue of non-combustible materials (ash) which contains a relatively low level of carbon. Syngas can be used in a number of ways, including:

  • Syngas can be burned in a boiler to generate steam for power generation or industrial heating.
  • Syngas can be used as a fuel in a dedicated gas engine.
  • Syngas, after reforming, can be used in a gas turbine
  • Syngas can also be used as a chemical feedstock.

Gasification has been used worldwide on a commercial scale for several decades by the chemical, refining, fertilizer and electric power industries. MSW gasification plants are relatively small-scale, flexible to different inputs and modular development. The quantity of power produced per tonne of waste by gasification process is larger than when applying the incineration method. The most important reason for the growing popularity of gasification of municipal wastes has been the increasing technical, environmental and public dissatisfaction with the performance of conventional incinerators.

Plasma Gasification

Plasma gasification uses extremely high temperatures in an oxygen-starved environment to completely decompose input waste material into very simple molecules in a process similar to pyrolysis. The heat source is a plasma discharge torch, a device that produces a very high temperature plasma gas. It is carried out under oxygen-starved conditions and the main products are vitrified slag, syngas and molten metal.

plasma-gasification

Vitrified slag may be used as an aggregate in construction; the syngas may be used in energy recovery systems or as a chemical feedstock; and the molten metal may have a commercial value depending on quality and market availability. The technology has been in use for steel-making and is used to melt ash to meet limits on dioxin/furan content. There are several commercial-scale plants already in operation in Japan for treating MSW and auto shredder residue.

Advantages of Gasification

There are numerous solid waste gasification facilities operating or under construction around the world. Gasification of solid wastes has several advantages over traditional combustion processes for MSW treatment. It takes place in a low oxygen environment that limits the formation of dioxins and of large quantities of SOx and NOx. Furthermore, it requires just a fraction of the stoichiometric amount of oxygen necessary for combustion. As a result, the volume of process gas is low, requiring smaller and less expensive gas cleaning equipment.

The lower gas volume also means a higher partial pressure of contaminants in the off-gas, which favours more complete adsorption and particulate capture. Finally, gasification generates a fuel gas that can be integrated with combined cycle turbines, reciprocating engines and, potentially, with fuel cells that convert fuel energy to electricity more efficiently than conventional steam boilers.

Disadvantages of Gasification

The gas resulting from gasification of municipal wastes contains various tars, particulates, halogens, heavy metals and alkaline compounds depending on the fuel composition and the particular gasification process. This can result in agglomeration in the gasification vessel, which can lead to clogging of fluidised beds and increased tar formation. In general, no slagging occurs with fuels having ash content below 5%. MSW has a relatively high ash content of 10-12%.

The Concept of Biorefinery

A biorefinery is a facility that integrates biomass conversion processes and equipment to produce fuels, power, and value-added chemicals from biomass. Biorefinery is analogous to today’s petroleum refinery, which produces multiple fuels and products from petroleum. By producing several products, a biorefinery takes advantage of the various components in biomass and their intermediates, therefore maximizing the value derived from the biomass feedstock.

A biorefinery could, for example, produce one or several low-volume, but high-value, chemical products and a low-value, but high-volume liquid transportation fuel such as biodiesel or bioethanol. At the same time, it can generate electricity and process heat, through CHP technology, for its own use and perhaps enough for sale of electricity to the local utility. The high value products increase profitability, the high-volume fuel helps meet energy needs, and the power production helps to lower energy costs and reduce GHG emissions from traditional power plant facilities.

Biorefinery Platforms

There are several platforms which can be employed in a biorefinery with the major ones being the sugar platform and the thermochemical platform (also known as syngas platform).

Sugar platform biorefineries breaks down biomass into different types of component sugars for fermentation or other biological processing into various fuels and chemicals. On the other hand, thermochemical biorefineries transform biomass into synthesis gas (hydrogen and carbon monoxide) or pyrolysis oil.

The thermochemical biomass conversion process is complex, and uses components, configurations, and operating conditions that are more typical of petroleum refining. Biomass is converted into syngas, and syngas is converted into an ethanol-rich mixture. However, syngas created from biomass contains contaminants such as tar and sulphur that interfere with the conversion of the syngas into products. These contaminants can be removed by tar-reforming catalysts and catalytic reforming processes. This not only cleans the syngas, it also creates more of it, improving process economics and ultimately cutting the cost of the resulting ethanol.

Plus Points

Biorefineries can help in utilizing the optimum energy potential of organic wastes and may also resolve the problems of waste management and GHGs emissions. Biomass wastes can be converted, through appropriate enzymatic/chemical treatment, into either gaseous or liquid fuels. The pre-treatment processes involved in biorefining generate products like paper-pulp, HFCS, solvents, acetate, resins, laminates, adhesives, flavour chemicals, activated carbon, fuel enhancers, undigested sugars etc. which generally remain untapped in the traditional processes. The suitability of this process is further enhanced from the fact that it can utilize a variety of biomass resources, whether plant-derived or animal-derived.

Future Perspectives

The concept of biorefinery is still in early stages at most places in the world. Problems like raw material availability, feasibility in product supply chain, scalability of the model are hampering its development at commercial-scales. The National Renewable Energy Laboratory (NREL) of USA is leading the front in biorefinery research with path-breaking discoveries and inventions. Although the technology is still in nascent stages, but it holds the key to the optimum utilization of wastes and natural resources that humans have always tried to achieve. The onus now lies on governments and corporate sector to incentivize or finance the research and development in this highly promising field.

Biomass Pyrolysis Process

Pyrolysis is the thermal decomposition of biomass occurring in the absence of oxygen. It is the fundamental chemical reaction that is the precursor of both the combustion and gasification processes and occurs naturally in the first two seconds. The products of biomass pyrolysis include biochar, bio-oil and gases including methane, hydrogen, carbon monoxide, and carbon dioxide.

Depending on the thermal environment and the final temperature, pyrolysis will yield mainly biochar at low temperatures, less than 450 0C, when the heating rate is quite slow, and mainly gases at high temperatures, greater than 800 0C, with rapid heating rates. At an intermediate temperature and under relatively high heating rates, the main product is bio-oil.

Pyrolysis can be performed at relatively small scale and at remote locations which enhance energy density of the biomass resource and reduce transport and handling costs.  Pyrolysis offers a flexible and attractive way of converting solid biomass into an easily stored and transported liquid, which can be successfully used for the production of heat, power and chemicals.

A wide range of biomass feedstocks can be used in pyrolysis processes. The pyrolysis process is very dependent on the moisture content of the feedstock, which should be around 10%. At higher moisture contents, high levels of water are produced and at lower levels there is a risk that the process only produces dust instead of oil. High-moisture waste streams, such as sludge and meat processing wastes, require drying before subjecting to pyrolysis.

The efficiency and nature of the pyrolysis process is dependent on the particle size of feedstocks. Most of the pyrolysis technologies can only process small particles to a maximum of 2 mm keeping in view the need for rapid heat transfer through the particle. The demand for small particle size means that the feedstock has to be size-reduced before being used for pyrolysis.

Pyrolysis processes can be categorized as slow pyrolysis or fast pyrolysis. Fast pyrolysis is currently the most widely used pyrolysis system. Slow pyrolysis takes several hours to complete and results in biochar as the main product. On the other hand, fast pyrolysis yields 60% bio-oil and takes seconds for complete pyrolysis. In addition, it gives 20% biochar and 20% syngas.

Bio-oil

Bio-oil is a dark brown liquid and has a similar composition to biomass. It has a much higher density than woody materials which reduces storage and transport costs. Bio-oil is not suitable for direct use in standard internal combustion engines. Alternatively, the oil can be upgraded to either a special engine fuel or through gasification processes to a syngas and then bio-diesel. Bio-oil is particularly attractive for co-firing because it can be more readily handled and burned than solid fuel and is cheaper to transport and store.

Bio-oil can offer major advantages over solid biomass and gasification due to the ease of handling, storage and combustion in an existing power station when special start-up procedures are not necessary. In addition, bio-oil is also a vital source for a wide range of organic compounds and speciality chemicals.

Pyrolysis of Scrap Tires

scrap-tires-pyrolysisPyrolysis of scrap tires offers an environmentally and economically attractive method for transforming waste tires into useful products, heat and electrical energy. Pyrolysis refers to the thermal decomposition of scrap tires either in the absence or lack of oxygen. The principal feedstocks for pyrolysis are pre-treated car, bus or truck tire chips. Scrap tires are an excellent fuel because of their high calorific value which is comparable to that of coal and crude oil. The heating value of an average size passenger tire is between 30 – 34MJ/kg.

Pyrolysis is the most recommended alternative for the thermochemical treatment of waste tires and extensively used for conversion of carbonaceous materials in Europe and the Asia-Pacific. Pyrolysis is a two-phase treatment which uses thermal decomposition to heat the rubber in the absence of oxygen to break it into its constituent parts, e.g., pyrolysis oil (or bio oil), synthetic gas and char. Cracking and post-cracking take place progressively as the material is heated to 450-500°C and above.

Process Description

The pyrolysis method for scrap tires recycling involves heating whole or halved or shredded tires in a reactor containing an oxygen free atmosphere and a heat source. In the reactor, the rubber is softened after which the rubber polymers disintegrate into smaller molecules which eventually vaporize and exit from the reactor. These vapors can be burned directly to produce power or condensed into an oily type liquid, called pyrolysis oil or bio oil. Some molecules are too small to condense and remain as a gas which can be burned as fuel. The minerals that were part of the tire, about 40% by weight, are removed as a solid. When performed well a tire pyrolysis process is a very clean operation and has nearly no emissions or waste.

The heating rate of tire is an important parameter affecting the reaction time, product yield, product quality and energy requirement of the waste tire pyrolysis process. If the temperature is maintained at around 450oC the main product is liquid which could be a mixture of hydrocarbon depending on the initial composition of waste material. At temperature above 700oC, synthetic gas (also known as syngas), a mixture of hydrogen and carbon monoxide, becomes the primary product due to further cracking of the liquids.

Schematic for Pyrolysis of Scrap Tires

Schematic for Pyrolysis of Scrap Tires

The nature of the feedstock and process conditions defines the properties of the gas, liquid and solid products. For example, whole tires contain fibers and steel while shredded tires have most of the steel and sometimes most of the fiber removed. Processes can be either batch or continuous. The energy required for thermal decomposition of the scrap tires can be in the form of directly-fired fuel, electrical induction and or by microwaves (like a microwave oven). A catalyst may also be required to accelerate the pyrolysis process.

Useful Products

The high acceptance of pyrolysis for the treatment of scrap tires is due to the fact that the derived oils and syngas can be used as biofuels or as feedstock for refining crude oil or chemical products. The pyrolysis oil (or bio oil) has higher calorific value, low ash, low residual carbon and low sulphur content.

The use of pyrolysis oil in cement kilns, paper mills, power plants, industrial furnaces, foundries and other industries is one of the best uses of scrap tires.  Pyrolysis of scrap tyres produces oil that can be used as liquid fuels for industrial furnaces, foundries and boilers in power plants due to their higher calorific value, low ash, residual carbon and sulphur content.

The solid residue, called char, contains carbon black, and inorganic matter. It contains carbon black and the mineral matter initially present in the tire. This solid char may be used as reinforcement in the rubber industry, as activated carbon or as smokeless fuel.