Pyrolytic Oil

Pyrolytic oil, also called pyrolysis oil or bio-oil is a synthetic fuel produced

through pyrolysis. Pyrolytic oil typically is a dark brown, free-flowing liquid

composed of a very complex mixture of oxygenated hydrocarbons with a

perceptible proportion of water from both the original moisture and reaction

product. [1].

All pyrolysis oils derived from biomass elementally resemble the source

biomass and consist of the main elements carbon (3248 wt%), oxygen (4560

wt%), hydrogen (6.98.6 wt%), sulfur (00.05 wt%), and nitrogen (00.2 wt%) [2].

Pyrolysis oils are principally composed of water (1530 wt%) and a wide variety of

organic components which include organic acids such as formic, acetic, and

propionic acids; carbonyl and hydroxycarbonyl compounds such as ketones and

aldehydes; sugars and anhydrosugars, and phenolic compounds including

pyrolytic lignin and phenols [3].

The oil is formed by rapidly quenching and thus freezing the intermediate

products of flash degeneration of hemicellulose, cellulose and lignin. The liquid

thus contains many reactive species, which contribute to its unusual attributes. [4].

Pyrolytic Oil Characteristics

Pyrolysis oil is a dark brown, acidic, viscous, and energy-rich liquid with a

distinctive smoky odor. Influenced by the presence of micro-carbon in the liquid

and chemical composition, the colour can be almost black through dark red brown

to dark green, depending on the initial feedstock and the mode of pyrolysis. [5]

The complex mixture is consist of both polar and non-polar chemicals of

different molecular weights that are mainly derived from rapid and simultaneous

depolymerization and fragmentation of the three building blocks of lignocellulose:

cellulose, hemicellulose, and lignin. The abundance of organic acids within the

pyrolysis oil leads to a low pH of 23. [6] It is miscible with polar solvents such as

methanol, acetone, etc. but totally immiscible with petroleum-derived fuels. This is

due to the high oxygen content similar to that of biomass, and is responsible for

chemical instability and leads to a wide range of both boiling point temperature and

viscosity (351000 cP at 40C).

The effect of water in oil is also complex and important. The oil contains

varying quantities of water, which forms a stable single-phase mixture, ranging

from about 15 wt.% to an upper limit of about 30-50 wt.% water, depending on the

feed material, how it was produced and collected. Pyrolysis liquids can tolerate the

addition of some water, but there is a limit to the amount of water which can be

added to the liquid before phase separation occurs, in other words the liquid cannot

be dissolved in water. Water addition reduces viscosity, which is useful; reduces

heating value which means that more liquid is required to meet a given duty; and

can improve stability.

The density of the oil is very high at around 1200 kg t-1, compared with light

fuel oil at around 0.85 kg/L. This means that the liquid has about 42% of the energy

content of fuel oil on a weight basis, but 61% on a volumetric basis. This has
implications for the design and specification of equipment such as pumps and

atomisers in boilers and engines. [7]

Temperatures between 500 and 600 C provide the highest yields of oil,

when biomass is processed with heating values of around 15 20 MJ/kg. On the

other hand, pyrolytic oil from plastics has a higher heating value, about 30 45

MJ/kg, depending on the polymer and it contains a smaller aqueous fraction.

Physical properties such as viscosity, the research octane number and the motor

octane number, pour point, flash point or Diesel index could be a good indication

of pyrolytic oil quality as a fuel [8]. The heating value of oils from mixed plastic

waste could be estimated at 40 MJ/kg [9].

Pyrolysis liquids cannot be completely vaporised once they have been

recovered from the vapour phase. If the liquid is heated to 100 C or more to try to

remove water or distil off lighter fractions, it rapidly reacts and eventually produces

a solid residue of around 50 wt.% of the original liquid and some distillate

containing volatile organic compounds and water. While bio-oil has been

successfully stored for several years in normal storage conditions in steel and

plastic drums without any deterioration that would prevent its use in any of the

applications tested to date, it does change slowly with time, most noticeably there

is a gradual increase in viscosity. More recent samples that have been distributed

for testing have shown substantial improvements in consistency and stability,

demonstrating the improvement in process design and control as the technology

develops. [10]
Uses of Pyrolytic Oil

The properties of pyrolysis oil, such as its high corrosiveness, high viscosity,

instability, highly oxidative character, complexity, and diversity make its application

very challenging. Current reports of potential applications of pyrolysis oil mainly

include being a substitute for fuel oil or diesel in many static applications including

boilers, furnaces, engines and turbines for electricity generation [11-13], its

upgrading to potential transport fuels [14], or its utilization as a feedstock for the

production of adhesives [15], resins [16], and fertilizers [17]. It is also used as a

commercial food flavoring such as barbecue flavor [18]. Because of their high

oxygen and water contents, pyrolysis oils exhibit heating values of about 13 18

MJ/kg, which is only 4050% of that for hydrocarbon fuels [19]. Also due to the

presence of phenolic compounds in high concentrations (up to 50 wt. %),

consisting of relatively small amounts of phenol, eugenol, cresols, xylenols, and

much larger quantities of alkylated (poly-) phenols [20], they can be used for the

production of heat, electricity, synthetic gas or chemicals.

Pyrolytic Char

Pyrolysis conditions are usually optimized in order to maximize the liquid

and gas products; however, a solid fraction called pyrolytic char is also produced.

This char is mainly composed of a carbon-rich matrix that contains almost all the

inorganic compounds present in the raw wastes and a significant amount of

condensed by-products formed during the pyrolysis process and dispersed

throughout the solid porous structure [21].

The by-product pyrolytic char or biochar is typically about 15 wt.% of the

products but about 25% of the energy of the biomass feed. It can be used within

the process to provide the process heat requirements by combustion or it can be

separated and exported, in which case an alternative fuel is required. Depending

on the reactor configuration and gas velocities, a large part of the char will be of a

comparable size and shape as the biomass fed. The fresh char is pyrophoric i.e. it

spontaneously combusts when exposed to air so careful handling and storage is

required. This property deteriorates with time due to oxidation of active sites on the

char surface.

Characteristics of Pyrolytic Char

The heating value of char obtained from co-pyrolysis of waste (mixture of

biodegradable and nonbiodegradable) is approximately 34 MJ/kg [22], which is

comparable with typical coal. However, as expected some heavy metals and other

hazardous elements, like S, Cl and N, may also be retained in the solid products.
Therefore, it is important to fully characterize chars to assess their impact on the

environment and humans.

Uses of Pyrolytic Char

Biochar is a solid decomposition product of lignocellulosic biomass, its main

constitutes being carbon and a varying content of ash. It can be used as

replacement for pulverized coal, or as a natural soil amendment to restore soil

productivity. Recent research reported biochar as a promising colorant as well as

a reactive or non-reactive filler when used as additive for plastics and composites

[23]. This product can also be combusted to provide energy for the pyrolysis

process or other purposes. Char obtained in pyrolysis is not only a good fuel, but

it can also be processed into activated carbon. This possible application was

investigated by Zeng et al. [24].

REFERENCES

[1] Toft AJ. PhD Thesis, Aston University; 1998.

[2]. Oasmaa, A. and Czernik, S. (1999) Fuel oil quality of biomass pyrolysis

oils state of the art for the end users. Energy Fuels 13, 914921

[3]. . Piskorz, J. et al. (1988) Composition of oils obtained by fast pyrolysis of

different woods. In Pyrolysis Oils from Biomass (ACS Symposium Series), pp.

167178, American Chemical Society

[4]. Oasmaa A, Peacocke GVC. VTT Technical Research Centre

of Finland, Espoo, Finland. A guide to physical property

characterisation of biomass derived fast pyrolysis liquids,

vol. 450. VTT Publication; 2001;

[5] Oasmaa A, Peacocke GVC. VTT Technical Research Centre

of Finland, Espoo, Finland. Properties and fuel use of

biomass derived fast pyrolysis liquids, vol. 731. VTT

Publication; 2010.

[6] Piskorz, J. et al.Composition of oils obtained by fast pyrolysis of different

woods.
Pyrolysis Oils from Biomass (ACS Symposium Series). American Chemical

Society, ; 1988: 167178

[7] Diebold JP, Milne TA, Czernik S, Oasmaa A, Bridgwater AV,

Cuevas A, et al. Proposed specifications for various grades of

pyrolysis oils. In: Bridgwater AV, Boocock DGG, editors.

Developments in thermochemical biomass conversion;

1997. p. 433e47.

[8] Khan MZH, Sultana M, Al-Mamun MR, Hasan MR. Pyrolytic Waste Plastic

Oil and Its Diesel

Blend: Fuel Characterization. J Environ Public Health 2016;2016.

doi:10.1155/2016/7869080.

[9] Lpez A, de Marco I, Caballero BM, Laresgoiti MF, Adrados A, Torres A.

Pyrolysis of

municipal plastic wastes: Influence of raw material composition. Waste Manag

2010;30:620

7. doi:10.1016/j.wasman.2011.05.021.

[10] Diebold JP. A review of the chemical and physical

mechanisms of the storage stability of fast pyrolysis biooils.

In: Bridgwater AV, editor. Fast pyrolysis of biomass,

a handbook, vol. 2. UK: CPL Press; 2002. p. 243e92.

[11] Beran, M. and Axelsson, L.-U. (2014) Application of pyrolysis oil in the

OP16 gas turbine development of a low calorific fuel combustor. PyNe

Newslett. 35, 1617

[12] Kasper, J.M. et al. (1983) Use of pyrolysis-derived fuel in a gas turbine

engine. In Turbo Expo: Power for Land, Sea, and Air (Vol. 3): Coal, Biomass and

Alternative Fuels; Combustion and Fuels; Oil and Gas Applications; Cycle

Innovations, p. 83-GT-96, American Society of Mechanical Engineers

[13] Oasmaa, A. et al. (2001) Pyrolysis oil combustion tests in an industrial

boiler. In Progress in Thermochemical Biomass Conversion (Bridgwater, A.V.,

ed.), pp. 14681481, Wiley-Blackwell

[14] Yang, H. et al. (2014) Overview of upgrading of pyrolysis oil of biomass.

Energy Procedia 61, 13061309

[15] Fini, E. et al. (2001) Characterization and application of manurebased

bio-binder in asphalt industry. In TRB 89th Annual Meeting Compendium of

Papers. Transportation Research Board

[16] Sukhbaatar, B. et al. (2009) Use of lignin separated from bio-oil in oriented

strand board binder phenol-formaldehyde resins. BioResources 4, 789804

[17] Radlein, D. St. A.G. et al. Method of producing slow-release nitrogenous

organic fertilizer from biomass, 1997, US 5676727.

[18] Underwood, G. and Graham, R.G. Ensyn Engineering Associates Inc.

Method of using fast pyrolysis liquids as liquid smoke, 1991, US 4876108.

[19] Oasmaa, A. and Czernik, S. (1999) Fuel oil quality of biomass pyrolysis

oils state of the art for the end users. Energy Fuels 13, 914921

[20] Mohan D, Pittman CU, Steele PH. Pyrolysis of wood/biomass for bio-oil:

A critical review.

Energy and Fuels 2006;20:84889. doi:10.1021/ef0502397.

[21] Muhammad C, Onwudili JA, Williams PT. Catalytic pyrolysis of waste

plastic from electrical

and electronic equipment. J Anal Appl Pyrolysis 2015;113:3329.

doi:10.1016/j.jaap.2015.02.016.

[22] Widiyannita AM, Cahyono RB, Budiman A, Sutijan, Akiyama T. Study of

pyrolysis of ulin

wood residues 2016:50004. doi:10.1063/1.4958487.

[23] Mohanty, A. et al. Hybrid sustainable composites and methods of making

and using thereof, 2015, CA2014/050886.

[24] Zeng K, Minh DP, Gauthier D, Weiss-Hortala E, Nzihou A, Flamant G.

The effect of

temperature and heating rate on char properties obtained from solar pyrolysis of

beech wood.

Bioresour Technol 2015;182:1149. doi:10.1016/j.biortech.2015.01.112.