Use of Biochar Particles for Asphalts

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This entry is adapted from the peer-reviewed paper 10.3390/polym15020343

Char/biochar particles could be considered as a new kind of sustainable particle created from their “waste” feedstocks. Specifically, when also considering the circular principles, the conversion of polymer waste, food waste, and biomasses, through thermal treatment at high temperatures, gives an appropriate second life for these waste materials. The char/biochar particles, being particles mainly composed of carbon atoms and having a large surface, are very useful to formulate composites with improved mechanical resistance, i.e., elastic modulus and tensile strength, as well as improved oxidative and photooxidative resistance, while also considering the particles’ radicals scavenging abilities in comparison to the properties of neat matrices.

biochar particles asphalts polymers

1. Biochar Particles: Production, Characteristics, and Properties

An opportunity to convert solid/food waste and biomass includes the thermochemical decomposition processes that are being used with increasing frequency. The main thermochemical decomposition processes explored are slow, fast, and flash pyrolysis, torrefaction, gasification, and hydrothermal liquefaction. All of these processes essentially generate: i. a solid phase, named char or biochar (in the case of biomass feedstock), ii. fuel, a mixed liquid phase of the heaviest hydrocarbon, iii. syngas, and a mixed gas phase of the lightest hydrocarbons are produced ^[1]^[2]^[3]^[4]. Of course, depending on the chemical composition of the treated materials (i.e., biomass, mixed waste, synthetic polymers), and depending on the operative condition (i.e., temperature process, heating rate, presence or absence of oxygen, residence time), the relative ratio between these three main products could change. Slow pyrolysis, conducted in the absence of oxygen, is characterized by slow heating rates and long residence times, as well as atmospheric pressure with an operating temperature that can vary from 350 to 800 °C; the necessary energy to pyrolyze the feedstock is usually provided internally by combusting a portion of the feedstock. The main product is a high-carbon solid char, and the coproducts are watery, low molecular weight liquid and a low energy combustible gas ^[5]^[6]^[7]^[8]. Fast pyrolysis, like slow pyrolysis, is conducted in the absence of oxygen with a temperature range between 400 and 600 °C. In contrast to slow pyrolysis, it uses a very high heating rate under a vacuum atmosphere, a short residence time, and the rapid quenching of vapor, since the main goal of this process is to produce bio-oil ^[5]^[9]^[10]. Flash pyrolysis is a batch process with an operative temperature range between 300 and 800 °C, and is similar to slow pyrolysis but with a high heating rate that uses moderate pressure (between 2 and 25 atm) to condense volatile elements and to promote secondary formation, since the aim of this process is to produce a biocarbon liquid fraction or biochar solid phase ^[11]. Torrefaction is a slow pyrolysis method with a lower temperature range, between 200 and 300 °C, that mainly removes water and some volatiles from the biomass to produce a “brown” char that is easy to ground and is a stabilized and friable biomass. Gasification is characterized by a high process temperature (between 750 and 1800 °C) with a limited and controlled oxygen concentration (normally calculated as the amount relative to stoichiometric combustion) ^[12] and/or steam ^[13]; as the name suggests, the primary products are a non-condensable gas mixture, called syngas, which is essentially composed by the presence of CO, H₂, with a smaller amount of carbon dioxide, methane, and other low molecular weight hydrocarbons ^[14]. Lastly, hydrothermal liquefaction is a process conducted in the presence of water, with a 250–450 °C temperature range under 100–300 bar; the main product of this process is called bio-crude, which is an energy-dense intermediate renewable source equivalent to oil that can be fractionated to a variety of liquid fuels ^[15]. Under this thermochemical process, the biomass is involved in depolymerization reactions (hydrolysis, dehydration, or decarboxylation), which produce insoluble products, such as bio-crude oil or bio-carbon, as well as volatile components (CO₂, CO, H₂ or CH₄) or soluble organic substances (mainly acids or phenols). All these processes and their differences are summarized in Table 1.

Table 1. Thermochemical processes and their main differences in terms of operative conditions, time of reactions, and primary products.

Thermochemical Process	Temperature Range [°C]	Heating Rate	Pressure	Residence Time	Primary Product
Slow Pyrolysis	350–800	Slow (<10 °C/min)	Atmospheric	Hours—Days	Char
Fast Pyrolysis	400–600	Very Fast (~1000 °C/s)	Vacuum-Atmospheric	Seconds	Oil
Flash Pyrolysis	300–800	Fast	Moderate (2–25 atm)	Minutes	Biocarbon/ Char
Torrefaction	200–300	Slow (<10 °C/min)	Atmospheric	Minutes—Hours	Friable Biomass
Gasification	700–1800	Moderate-Vary Fast	AtmosphericModerate	Seconds—Minutes	Syngas/ Producer gas
Hydrothermal Liquefaction	250–450	Moderate	Elevated 100–300 atm	Minutes—Hours	Bio-crude (oil)

The focus of this research is biochar, which is essentially a carbon-made material that can potentially be produced through any thermochemical process, as a primary or auxiliary co-product, and from any feedstock. Feedstocks could include building materials, agricultural waste, forestry residues, municipal solid waste etc.

Biochar could be described as being divided into a “carbon” fraction, which includes carbon, hydrogen, and oxygen bonded together in different forms, and an ash inorganic fraction. For each thermochemical process employed, the temperature process, heating rate, and residence time affect the quality and the quantity of primary products and auxiliary co-products, and an operative parameter needs to be tailored to the feedstock, since the composition of potential biochar results may be affected by the feedstock characteristics. The primary analysis normally performed to characterize the feedstock is the operative temperature, and the relative char quality is the proximate analysis. This thermogravimetric analysis gives information about feedstock moisture content relative to the mass lost until 110 °C; volatile matter relative to the mass lost in an inert atmosphere at 950 °C; fixed carbon relative to mass lost in the air at 750 °C; and the remaining part relative to ash amount. Elemental analysis is normally employed to characterize the quality of char in terms of carbon content. This is a technique in which a sample is combusted at a very high temperature in a little chamber with an excess oxygen content, and the gasses relative to the combustion are trapped and, depending on the number of sensors available, it is possible to have, in terms of percentage in weight, information about carbon, hydrogen, nitrogen, CHN element amount (relative CO₂, H₂O, NO), sulfur content, CHNS, oxygen/sulfur contents, and CHNOS.

As discussed above, biochar is a carbon-rich material which can be prepared from various waste feedstock. Municipal solid waste and agricultural waste are only two examples of the many organic wastes that may be utilized as feedstock to create biochar. Sludge is a solid waste that must be treated and disposed of, since it is produced during the wastewater treatment process. However, because it includes abundant carbon and nutrients such as ammonia, it is a viable feedstock for the synthesis of biochar ^[16]. The high carbon content, high cation exchange capacity, vast surface area, and stable structure of biochar are only a few of its benefits ^[17].

In general, organic or synthetic material can be used as feedstock with different processes depending on the physiochemical characteristics and the product composition.

The value of a particular type of biomass depends on the chemical and physical properties of the molecules from which it is made. Biomass is the main feedstock used in the literature for BC production because of different advantageous reasons. First, for environmental reasons, biomass is more readily available in a renewable way, either through natural processes or as a product of human activities. Furthermore, when produced by sustainable means, biomass produces approximately the same amount of carbon during conversion as is taken up during plant growth, which reduces the CO₂ amount in the atmosphere ^[18].

Biomass is mainly composed of three different organic compounds: cellulose, hemicellulose, and lignin, which give different mechanical and physiochemical properties to the woods. Cellulose makes up between 40% and 50% of the weight of dried wood and gives the biomass its strength ^[19]. Hetero polymers coexist with cellulose in plant cell walls to form hemicellulose. They contain several sugar monomers, including glucose, mannose, galactose, and xylose, and have lower molecular weights than glucose. Hemicellulose makes up anywhere from 20% to 35% of the bulk of dried wood ^[20]. The secondary cell wall of plants is made of lignin, which is a complex chemical compound. It is a kind of cross-linked resin that is amorphous, and it accounts for 15% to 30% of the mass of hardwoods. Depending on how much cellulose, hemicellulose, and lignin they contain, various biomass feedstocks have variable volatile matter concentrations and heating values, as well as different feedstock properties ^[21]^[22].

Biochar has received increasing attention due to its specific characteristics, such as high carbon content, cation exchange capacity, large specific surface area, and stable structure.

With different types of feedstocks, biochar has different physiochemical characteristics. The most typical processes for producing biochar are pyrolysis, gasification, and hydrothermal carbonization. Acid, alkali, oxidizing substances, metal ions, carbonaceous compounds, steam, and gas purging can all modify biochar. The environmental application fields determine the modification techniques to use.

The primary method used by biochar to remove organic and heavy metal contaminants is adsorption. The physiochemical characteristics of biochar, such as surface area, pore size distribution, functional groups, and cation exchange capacity, are strongly related to its adsorption ability, whereas physiochemical characteristics alter according to the production circumstances ^[23].

In general, biochar produced at high temperatures has a higher surface area and carbon content, mainly due to the increase in micro-pore volume caused by the removal of volatile organic compounds ^[24]. However, biochar yields decrease with temperature increases ^[25]. Therefore, an optimal strategy is required in terms of biochar yields and adsorption capacity. To sum up, the direct chemical composition of products and bioproducts is strictly connected to operative conditions (i.e., temperature, pressure and heating rate), which depend on the thermochemical process employed.

The physiochemical characteristics of biochar have been adjusted using metal ions, acids, alkalis, and oxidizing agents to make them better for various environmental processes ^[26].

Biochar has been widely employed in environmental applications, such as soil remediation, carbon sequestration, water treatment, and wastewater treatment because of its unique properties, which include high surface area, recalcitrant, and catalysis.

Common wastes, such as sludge and agricultural wastes, are produced in great quantities in the world. Sludge production alone reached 6.25 million tons in 2013 in China ^[27].

Converting common household wastes into biochar could be an option for environmental sustainability. Different feedstock has different proportions of element composition, and thus exhibits different properties, so the biochar derived from different feedstocks has various performances. The ways to deal with these wastes are directly linked to the impact they have on the environment.

Distinct feedstocks show varied qualities due to the different proportions of their elemental makeups, and, as a result, the biochar produced from those feedstocks performs differently. For instance, the pH (9.5) and potassium content (961 mg kg⁻¹) of straw-derived biochar were greater than those of wood biochar (349 mg kg⁻¹) ^[28]. Additionally, the biochar made from straw had more volatile material than non-volatile material, which is easier to remove during the pyrolysis process. Therefore, the high volatile component of the feedstock may contribute to poor biochar yields. Additionally, the content of pig and cow manures differed in terms of proportions ^[29]. Moreover, volatile content can be more easily removed than non-volatile content during pyrolysis. Therefore, the feedstock containing a high content of volatile content may result in low yields of biochar.

The type of feedstock has a significant effect on the physiochemical properties of biochar ^[30]. Therefore, the content of carbon in biochar is an important parameter, and different feedstocks can be converted into char using thermochemical decomposition processes, as was already described before (see Table 2).

Table 2. Proximate analysis of different biomass raw materials and relative elemental composition after pyrolysis process.

Feedstock	Proximate Analysis			Elemental Analysis
Feedstock	Volatile Matter [wt.%]	Fixed Carbon [wt.%]	Ash [wt.%]	C [wt.%]	H [wt.%]	N [wt.%]	O [wt.%]
Alfalfa ^[31] (Medicago sativa)	78.90	15.80	5.30	49.90	6.30	2.80	40.80
Almond Shell ^[32]	74.90	21.80	3.30	50.30	6.20	1.00	42.50
Bagasse ^[33]	71.00	13.70	2.10	51.71	5.32	0.33	42.64
Bamboo ^[34]	81.60	17.50	0.90	52.00	5.10	0.40	42.50
Carob Waste ^[6]^[35]	38.80	52.80	3.80	46.94	1.63	5.44	-
Coconut Fiber ^[36]	80.85	11.10	8.05	47.75	5.61	0.90	45.51
Corncob ^[37]	69.50	15.90	2.90	48.12	6.48	-	43.51
Cornstalk ^[37]	65.30	15.60	11.70	46.21	6.01	-	45.87
Cocopeat ^[33]	49.10	25.30	4.60	61.57	4.37	1.02	33.04
Dead Eucalyptus leaves ^[38]	77.60	16.90	0.80	52.90	8.10	0.30	47.90
Hamlin citrus ^[31]	77.90	17.80	9.40	50.70	6.60	1.60	42.90
Hornbeam Shell ^[39]	78.83	9.37	9.52	41.78	5.36	0.60	52.26
Loblolly Pine ^[31] (Pinus taeda)	77.60	14.50	2.30	55.50	5.60	0.40	45.90
Maize straw ^[40]	-	-	5.31	42.20	7.21	1.28	49.20
Mesocarp Fiber ^[38] (Oil palm)	72.80	18.90	8.30	51.50	6.60	1.50	40.10
Oak sawdust ^[41]	69.24	16.51	0.81	52.28	5.74	0.06	41.92
Olive wood ^[42]	79.60	17.20	3.20	49.00	5.40	0.70	44.90
Paddy straw ^[33]	56.40	15.40	20.90	48.75	5.98	1.99	43.28
Pinewood ^[36]	85.45	13.15	1.40	48.15	6.70	1.35	43.60
Palm Kernel Shell ^[33]	66.80	17.90	3.40	55.82	5.62	0.84	37.73
Raw Pine sawdust ^[40]	83.10	16.80	3.76	50.60	6.18	0.05	43.10
Rice husk	62.80	19.20	18.00	49.30	6.10	0.80	43.70
Sawdust ^[37]	70.40	18.50	1.20	48.37	4.98	-	46.27
Tea waste ^[43]	70.29	18.57	3.88	48.60	5.43	3.80	42.17
Wood Stem ^[33]	80.10	10.70	0.40	50.52	5.81	0.23	43.44
Wood Bark ^[33]	68.90	16.30	4.90	53.42	6.12	1.40	39.06

Due to different compositions (carbon with the presence of alkali metals, e.g., Li, Na, and K or alkaline metals, e.g., Ca, Mg, and Ba metals) depending on the nature of the feedstock, biochar can have versatile properties leading to many applications, including bioenergy (co-gasification, co-firing, and combustion), chemical use (as a catalyst or catalyst support), agronomy (regarding water retention, plant nutrients, or soil conditioner), pharmacological use (regarding the adsorption of drugs and toxins), environment remediation (regarding carbon sequestration and the sorption of pollutants), and as biomaterials for the production of bio-composites, fuel cells, and photovoltaic plants ^[44].

2. Asphalts Composites Containing Biochar Particles

Using biochar particles as an asphalt binder modifying filler is going to become a new and interesting application field. In fact, nowadays in the construction sector, it is already used as a substitute for cement in mortar or concrete, thanks to its help with accelerating cement hydrating ^[45] and due to global CO₂ mitigation ^[46]. The new approach regards the addition of asphalt binders as an ageing protector, which are an essential component of asphalt concrete in addition to being the heaviest coproduct of the petroleum refining system, after distillation, to obtain fuels and lubricants ^[47]. The oxidation of asphalt binders is an inevitable phenomenon that plays an enormous role in the deterioration of asphalt binders. In fact, the life expectancy of usual binders is susceptible to ultraviolet (UV) rays, which cause faster oxidation of asphalts, with a sensitive reduction in rheological characteristics and a loss of rutting properties, which can lead to pavement distress ^[48]. Walters et al. ^[49] investigated the impact of added biochar particles (coming from a thermochemical process used to convert swine manure in bio-oil) or nano-clay (Cloesite 30B) on the rheological properties and ageing susceptibility of asphalt binder, and compared the results with a control asphalt (PG 64–22) binder. The introduction of BC to the asphalt binder led to a reduction in asphalt temperature susceptibility, and, regarding the shear susceptibility, its sensitivity decreased by adding 10 wt.% of BC to PG 64–22, which achieved a lower value than control asphalt. Contrary to the addition of BC, the addition of nano-clay generated an impact on the layer spacing, which appeared to be responsible for enchaining the high temperature performance and ageing resistance of asphalt binders. In a second study by Walters et al. ^[48] a composite with both biochar (3 wt.%) particles and nano-clay (3 wt.%) was produced that resulted in a lower viscosity than the ones with only nano-clay, while the ageing susceptibility was improved significantly. This happens because biochar seems to have a role in the flow modifiers alleviating the stiffening effect of nano-clay, which help the nano-clay to disperse better in an asphalt binder.

Zhao et al. ^[50] evaluated the properties and performance of asphalt binders and mixtures by adding 5 wt.% and 10 wt.% of biochar from the fast pyrolysis of switchgrass for biofuel production. In their work, the authors found that biochar significantly increased the rutting resistances at high service temperatures of both asphalt binders and asphalt mixtures. Moreover, the addition of 5 wt.% of biochar may be the optimum in modifying binders in terms of cracking resistance, while 10 wt.% shows little effect in comparison with 5 wt.%. Another study was conducted by the same research group by adding different BC particles to a commonly used asphalt binder (PG 64–22), which resulted in a different type of pyrolysis of switchgrass, while taking into account that BC results as a by-product for biofuel production, and comparing these lab-made BC particles with a commercially activated carbon ^[51]. In particular, the BC particles were produced by the following techniques: i. a microwave reactor in which switchgrass was mixed with silicon carbide to absorb enough microwaves, then the mixture was heated up until 500 °C in less than 1 min and the temperature was maintained for 15 min, and, then, after cooling down, the silicon carbide particles were sieved out to finally obtain BC particles with size diameters between 75 and 150 μm; ii. a tube furnace method in which feedstock was heated up until 400 or 500 °C with a heating rate of 15 °C/min to result in BC particles with diameters smaller than 75 μm for particles obtained at 400 °C and 500 °C, and for the ones obtained at 500 °C a diameter range between 75 and 150 μm was obtained as well; iii. an activated commercially available carbon was selected for comparison. The composites were characterized in terms of viscosity modification, ageing and fatigue resistance, and rutting properties of un-aged and aged composites. The addition of all bio-modifiers increased the viscosity of the asphalt binder at a high service temperature and exploited a positive effect in ageing resistance at a long time of UV exposition. Globally, except for particles with smaller diameters (<75 μm) produced at 400 °C that showed a positive effect on the specific properties or performance of the asphalt binders, the pyrolysis method appeared to have a negligible effect on the degree of modification. Another study published by Zhang et al. ^[52] focused on varying biochar loads and biochar diameter distributions by comparing the biochar contribution on varying properties with the ones obtained by graphite adding. The biochar used in the work was obtained from waste wood resources, at a temperature ranging from 500 and 650 °C, through a pyrolysis plant able to heat at 10 °C/s. Then, BC particles were sieved to separate the different size ranges, and the size range of previous work was studied, i.e., between 75 and 150 μm and lower than 75 μm; the biochar contents in PG 58–28 control asphalt were 2 wt.%, 4 wt.%, and 8 wt.%, respectively. The flake graphite with a diameter lower than 75 μm and content of 4 wt.% was also added to PG 58–28 for comparison. As was expected, BC addition resulted in higher porosity and micro-structure compared with dense and smooth graphite. This aspect of course led to a larger and better adhesion interaction in the asphalt binders of BC than that of graphite, and, as a result, BC modified binders had better high-temperature rutting resistance and better anti-ageing properties, especially for the BC-modified binder with a lower BC diameter at a higher content.

In conclusion, it seems that the addition of BC to asphalt seems to increase the thermal resistance during asphalt preparation and their oxygen resistance in service. This is another important result of asphalt reducing viscosity during processing, which helps the dispersion of other asphalts constituents in order to obtain a high-performance pavement.

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Contributors MDPI registered users' name will be linked to their SciProfiles pages. To register with us, please refer to https://encyclopedia.pub/register :

Giulia Infurna

Gabriele Caruso

Nadka Tz. Dintcheva

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Update Date: 08 Feb 2023

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1. Biochar Particles: Production, Characteristics, and Properties

2. Asphalts Composites Containing Biochar Particles

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