Operating conditions of various pyrolysis processes and their product fractions (bio-oil, biochar, and gas) [2].
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IntechOpen Book Series will also publish a program of research-driven Thematic Edited Volumes that focus on specific areas and allow for a more in-depth overview of a particular subject.
\\n\\nIntechOpen Book Series will be launching regularly to offer our authors and editors exciting opportunities to publish their research Open Access. We will begin by relaunching some of our existing Book Series in this innovative book format, and will expand in 2022 into rapidly growing research fields that are driving and advancing society.
\\n\\nLaunching 2021
\\n\\nArtificial Intelligence, ISSN 2633-1403
\\n\\nVeterinary Medicine and Science, ISSN 2632-0517
\\n\\nBiochemistry, ISSN 2632-0983
\\n\\nBiomedical Engineering, ISSN 2631-5343
\\n\\nInfectious Diseases, ISSN 2631-6188
\\n\\nPhysiology (Coming Soon)
\\n\\nDentistry (Coming Soon)
\\n\\nWe invite you to explore our IntechOpen Book Series, find the right publishing program for you and reach your desired audience in record time.
\\n\\nNote: Edited in October 2021
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\n\nDesigned to cover fast-moving research fields in rapidly expanding areas, our Book Series feature a Topic structure allowing us to present the most relevant sub-disciplines. Book Series are headed by Series Editors, and a team of Topic Editors supported by international Editorial Board members. Topics are always open for submissions, with an Annual Volume published each calendar year.
\n\nAfter a robust peer-review process, accepted works are published quickly, thanks to Online First, ensuring research is made available to the scientific community without delay.
\n\nOur innovative Book Series format brings you:
\n\nIntechOpen Book Series will also publish a program of research-driven Thematic Edited Volumes that focus on specific areas and allow for a more in-depth overview of a particular subject.
\n\nIntechOpen Book Series will be launching regularly to offer our authors and editors exciting opportunities to publish their research Open Access. We will begin by relaunching some of our existing Book Series in this innovative book format, and will expand in 2022 into rapidly growing research fields that are driving and advancing society.
\n\nLaunching 2021
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\n\nVeterinary Medicine and Science, ISSN 2632-0517
\n\nBiochemistry, ISSN 2632-0983
\n\nBiomedical Engineering, ISSN 2631-5343
\n\nInfectious Diseases, ISSN 2631-6188
\n\nPhysiology (Coming Soon)
\n\nDentistry (Coming Soon)
\n\nWe invite you to explore our IntechOpen Book Series, find the right publishing program for you and reach your desired audience in record time.
\n\nNote: Edited in October 2021
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As such, this book focuses on metal oxides, which present a large diversity of electrical, magnetic, optical, optoelectronic, thermal, electrochemical, and catalytic properties, making them suitable for a wide range of applications. By bringing together scientific contributions with special emphasis on the interrelations between materials chemistry, processing, microstructures, and properties of stoichiometric and nonstoichiometric metal oxides, this book highlights the importance of tightly integrating high-throughput experiments (including both synthesis and characterization) and efficient and robust theory for the design of advanced materials.",isbn:"978-1-78985-452-7",printIsbn:"978-1-78985-451-0",pdfIsbn:"978-1-83969-130-0",doi:"10.5772/intechopen.77573",price:119,priceEur:129,priceUsd:155,slug:"structure-processing-properties-relationships-in-stoichiometric-and-nonstoichiometric-oxides",numberOfPages:102,isOpenForSubmission:!1,isInWos:null,isInBkci:!1,hash:"e41f9a3546e36dbf70a36974f74e9845",bookSignature:"Speranta Tanasescu",publishedDate:"November 4th 2020",coverURL:"https://cdn.intechopen.com/books/images_new/7760.jpg",numberOfDownloads:3893,numberOfWosCitations:1,numberOfCrossrefCitations:2,numberOfCrossrefCitationsByBook:0,numberOfDimensionsCitations:8,numberOfDimensionsCitationsByBook:0,hasAltmetrics:0,numberOfTotalCitations:11,isAvailableForWebshopOrdering:!0,dateEndFirstStepPublish:"January 28th 2019",dateEndSecondStepPublish:"March 14th 2019",dateEndThirdStepPublish:"May 13th 2019",dateEndFourthStepPublish:"August 1st 2019",dateEndFifthStepPublish:"September 30th 2019",currentStepOfPublishingProcess:5,indexedIn:"1,2,3,4,5,6,7",editedByType:"Edited by",kuFlag:!1,featuredMarkup:null,editors:[{id:"24934",title:"Dr.",name:"Speranta",middleName:null,surname:"Tanasescu",slug:"speranta-tanasescu",fullName:"Speranta Tanasescu",profilePictureURL:"https://mts.intechopen.com/storage/users/24934/images/system/24934.jpg",biography:"Speranta Tanasescu, PhD, is Senior Researcher I and head of the Laboratory of Chemical Thermodynamics in the “Ilie Murgulescu” Institute of Physical Chemistry of the Romanian Academy, Bucharest. Dr. Tanasescu obtained a PhD in Physical Chemistry from the Romanian Academy in 1979 and has served as a supervisor in chemistry since 2002. She received the “Gh. Spacu” Award from the Romanian Academy in 1972. Her thematic research focuses on activities with impact in the following domains: materials science, nanoscience and nanotechnologies, new sources of energies, nanosafety, and nanomedicine. Her research is significant for understanding processing-structure relationships as well as for finding key parameters in relation to bio-reactivity of the nanomaterials with impact in both nanosafety and nanomedicine research.",institutionString:"Ilie Murgulescu Institute of Physical Chemistry of the Romanian Academy",position:null,outsideEditionCount:0,totalCites:0,totalAuthoredChapters:"3",totalChapterViews:"0",totalEditedBooks:"1",institution:{name:"Romanian Academy",institutionURL:null,country:{name:"Romania"}}}],equalEditorOne:null,equalEditorTwo:null,equalEditorThree:null,coeditorOne:null,coeditorTwo:null,coeditorThree:null,coeditorFour:null,coeditorFive:null,topics:[{id:"492",title:"Solid-State Chemistry",slug:"chemistry-inorganic-chemistry-solid-state-chemistry"}],chapters:[{id:"72732",title:"Introductory Chapter: Structure-Processing-Properties Relationships in Stoichiometric and Nonstoichiometric Oxides",doi:"10.5772/intechopen.92861",slug:"introductory-chapter-structure-processing-properties-relationships-in-stoichiometric-and-nonstoichio",totalDownloads:483,totalCrossrefCites:0,totalDimensionsCites:0,hasAltmetrics:0,abstract:null,signatures:"Speranta Tanasescu",downloadPdfUrl:"/chapter/pdf-download/72732",previewPdfUrl:"/chapter/pdf-preview/72732",authors:[{id:"24934",title:"Dr.",name:"Speranta",surname:"Tanasescu",slug:"speranta-tanasescu",fullName:"Speranta Tanasescu"}],corrections:null},{id:"70119",title:"Role of Neutron Diffraction in Identifying Stoichiometry and Nonstoichiometry in the Compounds",doi:"10.5772/intechopen.89461",slug:"role-of-neutron-diffraction-in-identifying-stoichiometry-and-nonstoichiometry-in-the-compounds",totalDownloads:654,totalCrossrefCites:0,totalDimensionsCites:1,hasAltmetrics:0,abstract:"In this chapter we introduce stoichiometry and nonstoichiometry from crystal structure point of view along with some examples. We also discussed about the importance of nonstoichiometry in the application oriented research work and their use in the technological applications. We further discuss the ways to identify stoichiometry through various methods. We then introduce neutron diffraction and briefly describe how neutrons and X-ray interacts with matter and the difference in their interaction with matter. We then focus upon its (neutron) usability to identify nonstoichiometry by using some examples available in the literatures. High-temperature superconductivity-based research has seen the importance of neutron diffraction and scattering in identifying the structural modification which leads to superconductivity in the compounds.",signatures:"Som Datta Kaushik and Anil Kumar Singh",downloadPdfUrl:"/chapter/pdf-download/70119",previewPdfUrl:"/chapter/pdf-preview/70119",authors:[{id:"298294",title:"Dr.",name:"S D",surname:"Kaushik",slug:"s-d-kaushik",fullName:"S D Kaushik"},{id:"313769",title:"Dr.",name:"A. K.",surname:"Singh",slug:"a.-k.-singh",fullName:"A. K. Singh"}],corrections:null},{id:"69391",title:"On Application of Hyperfree Energy for the Description of Thermodynamics of Mobile Components in Nonstoichiometric Partially Open Ceramic Systems",doi:"10.5772/intechopen.89584",slug:"on-application-of-hyperfree-energy-for-the-description-of-thermodynamics-of-mobile-components-in-non",totalDownloads:508,totalCrossrefCites:0,totalDimensionsCites:1,hasAltmetrics:0,abstract:"Nonstoichiometric oxides form a new chapter in tailored materials. Founding and construction of thermodynamic functions related to solid (geologic, metallurgic) materials is traced showing interactions between Czech Professor F. Wald and Russians R.S. Kurnakov and D.S. Korzhinskiĭ and further developed by Czech P. Holba in the initial phase definition and related characterization of partially open systems. A gradual increase in thermodynamic concepts related to solid-state description is investigated in more detail. For the associated thermodynamic definition of the mobile component, the previously formulated hyperfree energy function, which was recently applied to several systems, was used. As a measure of the material disposition for the absorption of the free component, an innovative term of plutability is proposed, which allows the introduction of various forecaster variables such as temperature, pressure, and activity. Examples of practical application are examples of high-temperature superconducting materials, where the Czech school of thermodynamics is emphasized.",signatures:"Jaroslav Šesták",downloadPdfUrl:"/chapter/pdf-download/69391",previewPdfUrl:"/chapter/pdf-preview/69391",authors:[{id:"302126",title:"Emeritus Prof.",name:"Jaroslav",surname:"Sestak",slug:"jaroslav-sestak",fullName:"Jaroslav Sestak"}],corrections:null},{id:"69496",title:"Nonstoichiometry Role on the Properties of Quantum-Paraelectric Ceramics",doi:"10.5772/intechopen.89499",slug:"nonstoichiometry-role-on-the-properties-of-quantum-paraelectric-ceramics",totalDownloads:638,totalCrossrefCites:0,totalDimensionsCites:1,hasAltmetrics:0,abstract:"Among the lead-free perovskite-structure materials, strontium titanate (SrTiO3—ST) and potassium tantalate (KTaO3—KT), pure or modified, are of particular importance. They are both quantum paraelectrics with high dielectric permittivity and low losses that can find application in tunable microwave devices due to a dependence of the permittivity on the electric field. Factors as Sr/Ti and K/Ta ratio in ST and KT ceramics, respectively, can alter the defect chemistry of these materials and affect the microstructure. Therefore, if properly understood, cation stoichiometry variation may be intentionally used to tailor the electrical response of electroceramics. The scientific and technological importance of the stoichiometry variation in ST and KT ceramics is reviewed and compared in this chapter. The differences in crystallographic phase assemblage, grain size, and dielectric properties are described in detail. Although sharing crystal chemical similarities, the effect of the stoichiometry is markedly different. Even if the variation of Sr/Ti and K/Ta ratios did not change the quantum-paraelectric nature of ST and KT, Sr excess impedes the grain growth and decreases the dielectric permittivity in ST ceramics, while K excess promotes the grain growth and increases the dielectric permittivity in KT ceramics.",signatures:"Alexander Tkach and Paula M. 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The effect of different compositional variables and oxygen stoichiometry on the structure and thermodynamic stability of the BaxSr1-xCo1-yFeyO3-δ (x = 0.2, 0.4, 0.5, 0.6, 0.8; y = 0.2, 0.4, 0.6, 0.8, 1) perovskite-type compositions were investigated by solid electrolyte electrochemical cells method and scanning electron microscopy (SEM). The thermodynamic quantities represented by the partial molar free energies, enthalpies and entropies of oxygen dissolution in the perovskite phase, as well as the equilibrium partial pressures of oxygen were obtained in the temperature range of 823–1273 K. The in situ change of oxygen stoichiometry and the determination of thermodynamic parameters of the new oxygen-deficient BSCF compositions were studied via coulometric titration technique coupled with electromotive force (EMF) measurements. The effect of A- and B-site dopants concentration correlated to the variation of oxygen stoichiometry on the thermodynamic stability and morphology of the BSCF samples was evidenced.",signatures:"Florentina Maxim, Alina Botea-Petcu, Florina Teodorescu, Ludwig J. Gauckler and Speranta Tanasescu",downloadPdfUrl:"/chapter/pdf-download/73533",previewPdfUrl:"/chapter/pdf-preview/73533",authors:[{id:"24934",title:"Dr.",name:"Speranta",surname:"Tanasescu",slug:"speranta-tanasescu",fullName:"Speranta Tanasescu"},{id:"321069",title:"Dr.",name:"Florina",surname:"Teodorescu",slug:"florina-teodorescu",fullName:"Florina Teodorescu"},{id:"323964",title:"Dr.",name:"Florentina",surname:"Maxim",slug:"florentina-maxim",fullName:"Florentina Maxim"},{id:"323965",title:"Dr.",name:"Alina",surname:"Botea-Petcu",slug:"alina-botea-petcu",fullName:"Alina Botea-Petcu"},{id:"323968",title:"Prof.",name:"Ludwig J.",surname:"Gauckler",slug:"ludwig-j.-gauckler",fullName:"Ludwig J. Gauckler"}],corrections:null},{id:"70161",title:"Stoichiometric and Nonstoichiometric Compounds",doi:"10.5772/intechopen.89402",slug:"stoichiometric-and-nonstoichiometric-compounds",totalDownloads:1194,totalCrossrefCites:2,totalDimensionsCites:5,hasAltmetrics:0,abstract:"This chapter gives a general overview of synthesis and recent development of nickel oxide as a nonstoichiometric compound. We establish the synthesis chemistry of nickel oxide as a nonstoichiometric material, and hence successively introduce definitions and classifications of nonstoichiometric compounds as well as their point defects. The samples of nonstoichiometric nickel oxide are synthesized by thermal decomposition method. The nonstoichiometry of samples was then studied chemically by iodometric titration, and the results are further corroborated by excess oxygen obtained from the thermo-gravimetric analysis (TGA). X-ray diffraction (XRD) and Fourier transformed infrared (FTIR) techniques are used to analyze structural phase of nonstoichiometric nickel oxide. The change in oxidation state of nickel was studied by X-ray photoelectron spectroscopy (XPS) analysis. 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Khalid Ijaz",coverURL:"https://cdn.intechopen.com/books/images_new/11006.jpg",licenceType:"CC BY 3.0",editedByType:"Edited by",editors:[{id:"104702",title:"Dr.",name:"Raymond W.",middleName:null,surname:"Nims",slug:"raymond-w.-nims",fullName:"Raymond W. Nims"}],productType:{id:"1",title:"Edited Volume",chapterContentType:"chapter",authoredCaption:"Edited by"}}},ofsBook:{item:{type:"book",id:"11946",leadTitle:null,title:"Field-Programmable Gate Arrays",subtitle:null,reviewType:"peer-reviewed",abstract:"\r\n\tField programmable array (FPGA) is a programmable device that uses prebuilt logic blocks and routing resources to implement the system without adding additional fabrication steps. The reconfigurable system has applications in computational acceleration and prototyping application-specific integrated circuits (ASIC). The final design of ASIC or processor using FPGA will be continue reprogrammed until we have a bug-free design. The demand for FPGA is expected to increase continuously due to increased adoption of FPGA in areas of enterprise businesses as well as ASIC design because they can be dynamically reprogrammed. The optimized FPGAs are more power-efficient than running equivalent workloads on a CPU. The combination of versatility, efficiency, and performance of FPGAs make the design process more data at a lower total cost of ownership (TCO). Seeing the numerous application of FPGAs irrespective of the domain, it is necessary to understand FPGA in-depth in terms of architecture and applications.
",isbn:"978-1-80356-675-7",printIsbn:"978-1-80356-674-0",pdfIsbn:"978-1-80356-676-4",doi:null,price:0,priceEur:0,priceUsd:0,slug:null,numberOfPages:0,isOpenForSubmission:!0,isSalesforceBook:!1,isNomenclature:!1,hash:"d23889b993e9babdb668001a673adb9a",bookSignature:"Dr. Ajay Kumar Singh",publishedDate:null,coverURL:"https://cdn.intechopen.com/books/images_new/11946.jpg",keywords:"Field Programmable Array, Architecture, Algorithm, Logic Design, Validation, Logic Simulation, Logic Gate, Challenges in FPGA Design, Power-Efficient, Energy Conversion, Embedded System, Low Power Applications",numberOfDownloads:null,numberOfWosCitations:0,numberOfCrossrefCitations:null,numberOfDimensionsCitations:null,numberOfTotalCitations:null,isAvailableForWebshopOrdering:!0,dateEndFirstStepPublish:"March 22nd 2022",dateEndSecondStepPublish:"June 1st 2022",dateEndThirdStepPublish:"July 31st 2022",dateEndFourthStepPublish:"October 19th 2022",dateEndFifthStepPublish:"December 18th 2022",dateConfirmationOfParticipation:null,remainingDaysToSecondStep:"a month",secondStepPassed:!0,areRegistrationsClosed:!1,currentStepOfPublishingProcess:3,editedByType:null,kuFlag:!1,biosketch:"Dr. Singh's areas of interest are modeling of submicron MOS devices, Low power VLSI circuit design, Nanotechnology, and Renewable energy sources. He has published more than 95 research papers in various International Journals and conferences and reviewed many research papers submitted to various international journals. He has more than 27 years of teaching experience for graduate and undergraduate students. Dr.Singh is a Senior Member of IEEE and Fellow IETE-India.",coeditorOneBiosketch:null,coeditorTwoBiosketch:null,coeditorThreeBiosketch:null,coeditorFourBiosketch:null,coeditorFiveBiosketch:null,editors:[{id:"192404",title:"Dr.",name:"Ajay",middleName:"Kumar",surname:"Singh",slug:"ajay-singh",fullName:"Ajay Singh",profilePictureURL:"https://mts.intechopen.com/storage/users/192404/images/system/192404.jpg",biography:"Dr Singh is working as Professor in the Electronics and Communication Engineering of NIIT University-Neemarana Rajasthan India. Prior to joining this Unversity, he was Associate Professor in Faculty of Engineering and Technology, Multimedia University-Melaka Malaysia. He has more than 27 years of teaching experience for graduate and undergraduate students. He has successfully supervised 4 PhDs and 7 Master thesis. His areas of interest are modeling of submicron MOS devices, Low power VLSI circuit design, Nanotechnology and Renewable energy sources. He has published more than 95 research papers in various International Journals and conferences and reviewed many research papers submitted to various international journals. He is associated with many research journals in their editorial board. 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Hydraulic fracture propagation in fractured porous media leads to an alternation next to all mechanisms of fracture and propagation characteristics because of the interaction between the weak interface of the natural fracture. The behavior of hydraulic fracture at the collision stage to the natural fracture may lead to the intersection, diversion, or containment. The hydraulic fracture interaction at the interface of the natural fracture is an important factor on the fracture propagation further direction in rock. Natural fracture orientation has to be determined before the operation. Many parameters can influence on the properties of crack at the fracturing process such as pore pressure of the reservoir, rock and fluid properties, state of stress, and many other factors. The coupling of hydraulic fracturing and complex fracture network deformation plays a key role in the naturally fractured porous media.
\nThe creation of complex fracture networks in the naturally fractured media depends on the mechanism of interaction between the induced fracture and the preexisting fracture. Many authors have investigated the effect of NF on the geometry and propagation of induced fracture and some solutions have been provided by most of them for predicting the interaction mechanism [1–4]. Hubbert and Willis specified the minimum fracturing pressure with respect to the state of stress concentration around the borehole [5]. The difference of pore pressure and fracturing fluid pressure effects on the fracturing direction initiation [6]. Other research established correlations between the magnitude of horizontal stress and natural fracture characteristic in the generation of complexity network during fracturing operation [7]. The displacement of the adjacent blocks in edge-to-edge contact in shearing and slipping mode is a significant parameter in hydraulic fracturing propagation in naturally fractured porous media [8]. The extended finite element method (XFEM) is a novel technique for tracking the fracture propagation in naturally fractured reservoirs, which have been extensively used in order to facilitate fracturing interaction mechanism as no–re-meshing domain [9]. Belytschko and Zi used the extended finite element method (XFEM) and cohesive modeling to model crack-propagation paths by the division of the crack tip into the cracked and uncracked regions [10]. Taheri Shakib et al. showed that hydraulic and natural fracture characteristics and situations affect the production rate of fractured reservoirs [11]. They also showed the effect of horizontal stress orientation in stochastic fracture distributed at the hydraulic fracture operation [12]. Also, the interaction scenario of hydraulic fracture propagation in orthogonal and non-orthogonal approaching angle has been investigated [13].
\nThe present paper aims to model the propagation of hydraulic fracture in the naturally fractured reservoirs by the implementation of XFEM. The governing equation of XFEM has been described in this paper. We represent the propagation of hydraulic fracture and the interaction between the hydraulic and natural fractures by XFEM. The research results will provide a theoretical and industrial basis for the application of hydraulic fracturing technology in the effective development of naturally fractured reservoirs.
\nThe methodology of extended finite element method was first proposed by Belytschko and Black to simulate plane-strain fracture propagation problems and modeling discontinuities by using enriched function with the degree of freedom. In extended finite element method, the re-meshing technique in order to track hydraulic fracture propagation and capture the evolved fracture surface is eliminated [14]. The extended finite element form in order to compute the displacement field can be expressed by the following expression:\n
where
where
Here, (
In this study, fracture modeling is carried out using cohesive behavior at the crack tip. Barenblatt modeled cracking as a cohesive behavior in a model that predicted a nonlinear zone at the crack tip to overcome the limitation within Griffith’s theory. This model can estimate the uncracked structure behavior which is a defect in many other models. Moreover, the cohesive model does not regard singularities in stress behavior as necessary, and removes them from the initial consideration which is a great advantage [15]. In this model, the cohesive crack zone is specified by the relation between the displacement of the fracture face and the cohesion stress applied to the interface. By assuming singular crack propagation within a fractured medium and an advancement of the crack at the tip of the hydraulic fracture, cohesive modeling can be used to calculate nonlinear fracture behavior. The criterion for a fracture to propagate at the cohesive zone is that the energy-release rate must overcome the dissipation-energy rate [16, 17]. Assuming the cohesive zone within the propagated hydraulic fracture, three distinct zones will contribute in the fracturing stage, which are the fully opened zone, partially damaged zone and non-damaged zone.
\nThe elastic model of mass rock applied by the dynamic modulus.
The fully opened zone is the section that fully separates the upper and lower parts of the crack from the fluid flow. The partially damaged zone or process zone is located around the crack tip where the total stress acts to this zone lower than the critical stress (Figure 1). In addition to the two mentioned zones, non-damaged zone is located beyond the process zone and with no possibility of fracturing fluid.
\n\nThe tension at the cohesive fracture tip
Here,
The hydraulic fracture propagation in cohesive zone model can be applied by the traction-separation law:\n
where
where
Here,
Hydraulic fracture in naturally fractured reservoirs is faced with a unique situation which may increase the possibility of deviation from symmetrical propagation. Experimental results reveal that three scenarios may occur at the propagation stage and beyond the collision stage of fluid-driven in hydraulic fracture interaction with the natural fracture, namely diversion, penetration, and containment. Diversion is the situation in which the collided hydraulic fracture has an effective stress too low to initiate new fracture at the front wall of preexisting joint, and as a result the fluid-driven propagates along the natural fracture axis. Many studies have been investigated in order to specify the possibility of occurrence of these scenarios.
\nHanson et al. and later Shaffer et al. represented that the magnitude of difference between the young modulus of the two intersected interface has significant influence on increasing the possibility of arresting hydraulic fracture [21, 22]. Based on their experimental reports, as the hydraulic fracture propagates from higher modulus into lower interface, the arresting phenomena increase. In addition to the young modulus, experimental results and numerical analysis reveal the effect of the frictional coefficient on the containment of hydraulic fracture. These results show that if the hydraulic fracture propagates from higher frictional coefficient pathway and collides to lower frictional coefficient interface at the natural fracture, the strain increases parallel to the hydraulic fracture due to the increase in the motion rate at interface region. This increase may result in an abrupt fracture seizing. Daneshy also discussed about the possibility of seizing the growth of hydraulic fracture at the intersection stage based on the opening interface of the natural fracture [23]. Another significant parameter that can influence the crossing criteria of hydraulic fracture is the approaching angle. Blanton using different angle-approaching experiments concluded that the presence of high differential stress and high intersection angle can improve the crossing of hydraulic fracture.
\nThe hydraulic fracture can keep on planar propagation beyond the collision point. However, because of the energy dissipation at the contacting stage, the crossing criteria cannot exactly determine if the hydraulic fracture will penetrate through the other side of weakness plane. The fluid-driven energy must be high enough in order to separate the natural fracture bonding at the intact side of the wall. However, breakage at the other side of the wall might have some offset with the collision point, which originates from the preexisted flaw or mini-cracks along the intact side. Based on Blanton’s results, the reduction of the stress anisotropy and treatment pressure may lead to increase in the possibility of diversion and dissipation of fluid-driven along the natural fracture path and also to complex natural fracture network [24, 25]. Later, Beugelsdijk using laboratory experimental results concluded that at high principle stress difference, the hydraulic fracture may have no interaction with the preexisting discontinuities and may turn around them [26]. In addition to the mentioned scenarios, hydraulic fracture may also cause dilation, long slippage along the natural fracture interface, or may turn around and bypass discontinuities. Inclined weakness plane at the propagation path of induced fracture has high tendency to divert the fluid-driven. However, all of the mentioned scenarios can only be estimated and visually represented using an experimental method. The containment stage is the only stage which can approximate the interaction on the natural fracture and fluid-driven. Beyond this stage, no other method can exactly approve the crossing criteria or diversion.
\nHydraulic fracture propagation in the naturally fractured reservoirs plays a different role than the conventional porous media. As the hydraulic fracture passes beyond the induced stress of drilled well, the hydraulic fracture propagation reorientates through the maximum stress principle. The hydraulic fracture propagation in homogeneous porous media is approximately near to the straight path; however, in a real reservoir rock media, because of discontinuities and inhomogeneity, the induced fracture trajectory waver is perpendicular with the minimum compressional stress. The hydraulic fracture tip tends to propagate through the local direction, which has the maximum energy release rate and minimum resistance. Still, there is the possibility of curving and increasing the deviation of hydraulic fracture from straight trajectory by increasing the shearing intensity factor. As long as the induced fracture propagates in opening mode, its fracture trajectory is near to the straight line. When the fracture faced the two materials with different Young’s modulus, the angle of deflection tends to rematch the tip direction in accordance with the lower Young’s modulus material. By increasing the hydraulic fracture length by the propagation of the tip of the hydraulic fracture away from the wellbore, the curvature of hydraulic fracture tends to be decreased. In addition to the rock mechanic properties, the fracturing fluid properties and flow rate injection also have a great impact on the straightness stability. Also, increasing the fracturing fluid viscosity will decrease the leak-off rate and tortuosity of the fracture, but it requires a higher rate of treatment pressure [27]. However, increasing the fluid viscosity in fracturing treatment leads to an abrupt increase in fluid pressure at the fracture path and reduces the flow rate at the fracture tip, because of the uniformity in pressure profile within the hydraulic fracture path. High rate of pressure difference between the fracture tip and the mouth region causes an inhomogeneity in the geometry of the fracture path and lowers the rate of growth [28]. Unlike the high viscosity, lower viscosity will cause a uniform pressure profile within the hydraulic fracture path increasing fluid leakage rate to the adjacent layer. Increasing the fluid leak-off rate will cause a perturbation in the local stress regime and increase the possibility of zigzag fracture pattern. Natural fractures have different response in alteration of the rate of injection and fracturing fluid properties. In the naturally fractured reservoir, increasing the flow rate injection will increase the leak-off rate to the adjacent layer and subsequently cause debonding of the natural fracture in tensile mode [29]. From the studies, reducing the fluid flow injection rate and viscosity of fracturing fluid in fractured media will greatly reduce the possibility of complex fracture network generation [30].
\nAfter initiation and propagation stage of hydraulic fracture beyond the far-field stress region, the hydraulic fracture tries to rematch its orientation by the maximum stress principle. The hydraulic fracture direction is almost parallel with the orientation of maximum stress principle but not exactly perpendicular to the minimum compressional stress, because it tends to orient its trajectory in porous media along the path of minimum resistance. Despite the stress direction in the local field, the induced fracture trajectory may have a wavy shape because of the inhomogeneity of the porous media along its path. The local stress component at the neighborhood of the fracture tip can be expressed by the following equation:\n
where (
where
In numerical modeling, we can only predict the local displacement within the natural fracture only at the
where
where
where
where
As mentioned earlier, when the hydraulic fracture propagates through the 90° natural fracture, at the early stage of approaching, the natural fracture is almost closed. By approaching the hydraulic fracture to the natural fracture interface, some activation may occur which may change the local physical properties at that region. In addition to the hydraulic fracture acting stress, the natural fracture also perturbs the stress regime around its area, which is directly proportional to its length. In reality, we cannot represent that if the approaching angle is 90°, then the collision angle is orthogonal too. This is due to the fact that the local perturbation and acting stress in coalescence process are mutual. Natural fracture by acting stress to the tip of the hydraulic fracture will cause deviation on its overall propagation, which may lead to deviation from the 90°. The magnitude of this stress can be expressed by the following equation [33]:\n
where
From Figure 2, assume that the approaching angle is the same as collision angle which is 90°. As seen in Figure 2, the hydraulic fracture approaches the natural fracture in an orthogonal angle. The tensile and shear debonding can be evaluated at the approaching stage of the hydraulic fracture tip to the natural fracture interface in a, b and c areas. a and b areas are located, respectively, at 10- and 5-cm distances from the 50-cm length natural fracture interface, and c area is precisely located at the collision point of the hydraulic fracture to the natural fracture. Stress condition is assumed to be isotopic.
\nEvaluated areas for debonding of natural fracture when induction fracture is 90° angle.
The maximum opening and shearing displacement in perpendicular approaching stage approximately occurs at the 20-cm distance from the north tip of the natural fracture. The maximum tensile and debonding size and location in the orthogonal approaching stage are the same. Moreover, debonding evaluation indicates that the minimum debonding size occurs at the 30-cm distance from the north of the natural fracture tip. As already mentioned, in the realistic-induced fracture propagation, debonding displacement alteration in tensile and shearing mode happens because changing the propagation angle at the perturbed stress region is not monotonic.
\nPerturbation of stress regime around the approaching hydraulic fracture tip will lead to the activation of natural fracture interface prior to the collision stage. In normal opening mode prior to the collision stage, debonding occurs at the time that the pore pressure within the natural fracture dominates the normal closure stress of the natural fracture (
Tensile and shear displacements along the deboned zone shown in
Approaching stage of hydraulic fracture and shear dilation caused by remote stress around induced fracture.
Another main approaching angle, which can be investigated in our study, is an inclined natural fracture with the 45° angle with respect to the propagated hydraulic fracture. In an inclined mode, the lower rate of energy is required in order to reactivate the natural fracture interface at the same distance compared with the perpendicular mode (Figure 5). Unlike many earlier models, the hydraulic fracture is propagated through the interface of the natural fracture, which means that the touching moment of the left side is the same as the right side. Tensile and shear displacements along the debonded crack (45°) are shown in Figure 6. When the induction with 45° angle is close to the natural fracture in the c area, tensile failure phenomenon is such that the natural fracture had an angle of 90°, because the middle area of the natural fracture becomes debonded and the maximum value of debonding occurs at the collision point. But with less distance between the natural and induced fractures, the condition is slightly different. When the hydraulic fracture approaches the 10-cm distance from the natural fracture, the 12-cm distance from the north tip of the natural fracture becomes compressed and the other part becomes debonded. The maximum value of debonding is at the collision point but the symmetry of the debonding zone in the natural fractures with 90° angle does not take place here. After the cutoff point, the natural fracture by hydraulic fracture (c area) of the upper part of the kink point becomes debonded and the lower part becomes compressed (Figure 6). In 45° angle propagation angle, the shear displacement magnitude has a higher value than the tensile opening. In this case, the lower part of the coalescence point has the tendency to bind because of the compression and the upper part in tension turns into debonding (Figure 7).
\nAreas of study for debonding investigation when natural fracture with a 45° angle relative to the hydraulic fracture spread.
Tensile and shear displacements along the debonded zone shown in
In low approaching angle (45°) at the isotropic stress ratio, the shearing displacement is much larger than the tensile mode; however, with an increase in the stress ratio the difference between shearing and tensile opening remains closed to each other [34]. The natural fracture length increases the remote stress caused by the tip of the hydraulic fracture that has a tendency to increase the debonding of the natural fracture [35, 36].
\nDebonding induced by the approaching hydraulic fracture to natural fracture.
The approaching stage of the hydraulic fracture was not fully investigated and carried out in a numerical way. As mentioned previously, considering stress regime perturbation around the natural fracture location will cause a deflection on the approaching angle of the hydraulic fracture. As the hydraulic fracture grows toward the natural fracture, influenced by the interaction stress of the natural fracture, the nearest tip edge will be active in a shorter time leading to the propagation of hydraulic fracture in a mixed mode. By increasing the shearing intensity factor, the hydraulic fracture path tends to be more kinked and deviates through the natural fracture interface. The following equation can compute the deflection angle of induced fracture (α) under mixed-mode propagation:\n
The curvature of the hydraulic fracture by the propagation of the hydraulic fracture will dramatically increase in stress-perturbed zone [33]. If the opening mode dominates in the tip of the hydraulic fracture, the fracture trajectory will tend to be more singular and straight. The rate of the hydraulic fracture deflection highly depends on the treatment pressure, leak-off rate, length of the natural fracture, and stress anisotropy. In this study, we assume that the hydraulic fracture is subjected to an isotropic principle stress. At the early stage of deviation, the natural fracture walls tend to stick together and are almost completely closed. In parallel natural fracture case, in addition to the distance parameter, the alteration of the approaching angle is another factor which was considered. Figure 8 shows the distance from the deviated hydraulic fracture tip on the natural fracture at 10 (a) and 5 m (b) and the exact coalescence (c) of the hydraulic and natural fractures. When the hydraulic fracture reaches the point a, the natural fracture reaches the activation threshold. When the hydraulic fracture approaches the natural fracture (Figure 8b and c), normal displacement occurs, and the natural fracture interface nearly fully separates. As seen in Figure 8, the approaching of the induced fracture will lead to an abrupt increase in the propagation angle and oriented near to perpendicularly. Increases in the values for the deviation angle and interaction stress increase the possibility of natural fracture collision.
\nApproaching stage of induced fracture and shear dilation caused by remote stress around hydraulic fracture.
If the collision point in the approaching stage of the hydraulic fracture is assumed to lie at the midpoint of the natural fracture in the isotropic principle stress situation, the tensile displacement is as shown in Figure 9. At the approaching stage, the shear displacement increases nonlinearly because, at a constant shear stress, the shear displacement is also a function of the normal displacement. By increasing the normal displacement of natural fracture interface, the shear displacement has lower resistance to shearing. Moreover, because of continuous changing of approaching angle besides the distance, the shearing, and opening displacement both of them have non-monotonic behavior. As the hydraulic fracture approaches the natural fracture, the approaching angle of the hydraulic fracture increases with respect to the natural fracture location, which leads to a decrease in shearing compression. Surprisingly, the influence of the approaching angle on the shear slippage as the hydraulic fracture approaches the natural fracture is greater than the influence of the distance. As Figure 9 shows, the approaching angle of the hydraulic fracturing tip is 66 (a), 49 (b), and 34° (c). As seen in Figure 10, the deviation of the intersection angle from the perpendicular will result in discrepancies in the natural fracture tip displacement. As the hydraulic fracture interacts with the natural fracture, the pore pressure within the natural fracture changes, which leads to compression and extension within the natural fracture.
\nTensile and shear displacements along the debonded zone shown in
Deviation of the intersection angle from the perpendicular will result in discrepancies in natural fracture tip displacement.
Formerly, re-meshing technique has been greatly implemented in order to align the mesh with the tip of the hydraulic fracture for tracking the propagating direction. However, in our study by utilizing the XFEM as no-re-meshing tools can greatly track the hydraulic fracture trajectory to capture the stress and strain field around the tip of the hydraulic fracture. The accuracy of fracture propagation trajectory by refining the mesh around the crack tip can be improved. Stress singularity at the fracture tip is eliminated by the implementation of cohesive zone model in XFEM. Refining the mesh can provide more accurate calculation in the propagation of hydraulic fracture through natural fractures based on shearing or opening mode by computation stress concentration around the fracture tip. The number of iteration to reach convergence in our fracture tip is 5–7. The error between our numerical result and the analytical result is lower than 1%.
\nNatural fractures can have a significant effect on the hydraulic fracture growth and achieve successful treatment. Spacing and trajectory of natural fractures in fractured blocks with respect to the induced fracture propagation has a significant effect on the accuracy of interaction prediction. Numerical analysis of hydraulic fracturing propagation in the naturally fractured reservoir and the interaction between the induced fracture and the natural fracture are the main objectives of this paper. Numerical simulation can be used as a tool to solve this engineering problem.
\nIn this paper, the extended finite element method (XFEM) has been implemented to simulate the coalescence stage of hydraulic fracture and natural fractures. Analysis of interaction between the induced and natural fractures in the fractured reservoirs was discussed in this study. The interaction between the induced and natural fractures depends on the collide angle. Induced fracture causes the opening of the preexisting natural fractures. The tensile and shear debonding of natural fractures in 90 and 45° displayed different behavior caused induced and variations in stresses at the natural fractures. A critical point in interaction between the hydraulic fracture and the natural fractures is the dilation caused by shearing and opening from the northing to the southing along the natural fracture in both degrees which play different scenarios. Decreasing the approaching angle from perpendicular to 45° intensifies the displacement by shearing much more than tensile. In low collision angle, the top stage of the interception point has the maximum debonding in shearing mode and the lower stage has the maximum bonding.
\nThe current global energy supply is, to a large extent, based on fossil fuels (oil, natural gas, and coal) of which the reserves are finite. As a result of industrialization, population growth, and urbanization, there has been a rapid increase in global energy demand and consumption. The necessity for long-term alternative energy sources is obvious due to the increasing energy consumption, high prices and limited reserves of fossil fuels and evidence of global warming, environmental pollution, and climate change. As a result, there is renewed interest in producing and using renewable energy resources, such as biomass, wind, solar, geothermal, and tidal. Bioenergy is a sustainable form of energy derived from biomass sources [1, 2, 3, 4]. Recently, bioenergy is getting more attention because of its potential advantages, including renewable fuel for boilers, engines, turbines, power generation and industrial processes; inexpensive and CO2 neutral; utilization of nonfood and waste second-generation biomass feedstocks; easy to store and transport as liquid fuels; high-energy density compared to atmospheric biomass gasification fuel gases [2, 5, 6]. Biomass is a promising eco-friendly alternative source of renewable bioenergy because of its abundant availability, relatively lower price, and zero greenhouse gas emissions in the context of current energy scenarios. However, the only renewable energy resource that can be used to produce transport fuels is biomass [2, 4].
Biomass is plant or animal-based organic matter that is living or was living in the recent past. Various biomass components, such as sugars, starches, and lignocellulosic (non-starch fibrous part of the plant) materials, can be converted to liquid transport fuels, reducing the use of fossil fuels. A promising alternative to reduce environmental issues related to waste disposal and management is converting biomass residues and wastes (such as crop residues, food wastes, animal manure, and municipal solid wastes) into useful bioenergy. Some of the advantages of converting biomass residues and wastes into bioenergy include (a) reducing the burden on waste management, (b) converting waste into valuable energy reduces the dependence on fossil fuels, (c) reducing decomposing waste and associated issues such as water contamination, greenhouse gas emissions, pests and insects breeding, and foul odor. [4, 7, 8, 9, 10].
The biomass feedstocks can be transformed into biofuels through biochemical and thermal conversion processes. The thermal conversion approach, such as pyrolysis, gasification, and torrefaction, are applicable for a wide range of biomass types using different temperatures to breakdown the bonds of organic matter in a relatively short period of time, unlike the biochemical processes [2, 5, 6]. Lignocellulosic biomass, such as agricultural crop residues, wood and forestry residues, are readily available, inexpensive, and promising resources for biofuels. Biomass can be considered one of the best options for sustaining future energy demand. The more efficient biomass production and conversion processes are essential for the efficient utilization of biomass resources [11]. Biomass is a valuable fuel source that is considered renewable as it can be produced year after year. Compared to fossil fuels, biomass has the potential to reduce combustion emissions, such as CO2, SOX, and NOX [12, 13].
A commonly used biomass classification is based on the origin of biomass, such as agricultural crop residues, forestry and wood processing residues, purposely grown dedicated energy crops, aquatic biomass, animal, food, industrial and municipal waste, sewage sludge, digestate, and industrial crops. Various types of wastes, such as wastepaper, sewage sludge, cow manure, poultry litter, municipal, and many industrial wastes, are treated as biomass because these are a mixture of organic (and nonorganic) compounds. Biomass is also classified based on its chemical composition as carbohydrates, lignin, essential oils, vegetable oils, animal fats, natural resins (gums), etc. Lignocellulosic biomass is the most abundant biomass on the earth and it represents a major carbon source for bioenergy, biofuels, and chemical compounds [2, 4].
Agricultural crop biomasses are natural products of agriculture, including food-based and nonfood-based portions of crops. The food-based portion comprises simple carbohydrates and oils from crops, such as corn, sugarcane, sugar beet, rapeseed, soybean, and sunflower. The nonfood-based portion is commonly discarded, which comprises complex carbohydrates of crops that are not harvested for commercial use or byproducts from harvesting or processing, such as corn stover, sugarcane bagasse, straw residues, waste from food processing, horticulture, and food crops [4, 7, 14]. Forestry and wood processing residues include trees that are not valuable as timber and not harvested during logging, crowns and branches from fully-grown trees that are removed during logging in commercial forests, waste from forest and wood processing (such as wood pellets, woodchips, leaves, lumps, barks, and sawdust) as well as materials removed during forest management operations. Most of the biomass used today are derived from agricultural crop, forestry, and wood biomass [7, 15].
Another expanding and potentially larger source of biomass is dedicated energy crops that are grown specifically for their fuel value on marginal land unsuitable for agriculture. These are high-yield and low-maintenance crops that produce maximum energy yield. There are two types of energy crops, herbaceous and short-rotation woody crops. Herbaceous energy crops include perennial grasses, such as switchgrass, miscanthus, bluestem, elephant grass, bamboo, and wheatgrass, that are harvested annually after maturity. In 2–3 years, herbaceous energy crops reach complete production and do not require replanting for 15 years or more. The drawback of most nonwoody energy crops is that their chemical properties (high ash and salt content) make them less suitable for combustion. Woody crops are grown on short rotations, generally with more intensive management than timber plantations. These fast-growing hardwood trees include poplar, willow, maple, cottonwood, black walnut, and sweetgum. The woody crops are harvested within 5–8 years of planting [4, 14, 15, 16, 17].
Aquatic biomass includes different types of algae, plants, and microbes found in water, such as aquatic plants, water hyacinth, seaweed, kelp, macroalgae, and microalgae [18]. Another primary biomass source is municipal, industrial, food, and animal waste. Municipal solid waste includes waste from commercial, industrial, and residential sectors containing a significant amount of biomass with energy content. The industrial waste includes waste from textile and food processing industries and waste from various industrial and manufacturing processes, such as sugar cane residues and paper sludge. Food waste includes postconsumer waste, animal fat, used cooking oil, residues from food and drink manufacturing, preparation and processing, etc. Animal and human waste includes cooked or uncooked food, fruits, paper, manure of different animals, and waste from farm and processing operations. The problem of disposing of waste is reduced to a certain extent when waste materials are treated and converted to useful energy products. Primarily, animal and human waste are free of harmful materials. In contrast, industrial waste may contain different harmful additives and toxic chemicals [4, 14, 15, 19].
Plant biomass has a carbon-to-oxygen (C/O) ratio of almost one. Because of the high level of oxygen, the energy density of biomass is relatively lower than fossil fuels, which means that issues associated with land use must be considered. The potential benefit of biomass can be reduced by environmental damage due to the expansion of land use for biomass production, leading to a high potential for deforestation, emissions, erosion, nutrient runoff, etc. When sufficient land areas are available, large-scale cultivation of energy crops for bioenergy is feasible. The agricultural lands must be used to grow food crops. Land for energy crops needs to be selected carefully to avoid food versus energy conflict. Identifying lands with minimal disturbance to food production is critical for technically and economically feasible biomass production. To achieve sustainable large-scale biomass production, infertile/marginal or abandoned agricultural land with little fertilizer or pesticides and potentially needing minimal water has been widely considered important. Energy crops are adaptive to infertile/marginal or abandoned agricultural land. Energy crops, such as switchgrass and miscanthus, generally require much less water to grow and are suitable to replace dryland crops partially. Energy crops should not be grown at the expense of biodiversity. Beyond the vast land areas needed to grow energy crops, the long-term impact of soil quality due to repeated removal of biomass and water usage are major concerns [4, 20, 21].
Plants absorb atmospheric CO2 and produce carbohydrates in photosynthesis that form the building blocks of biomass. Water and sunlight are the other two key ingredients of photosynthesis. The burning of biomass does not add to the total CO2 inventory of the earth as it releases CO2 back into the atmosphere that the plants have absorbed recently in photosynthesis producing biomass. Therefore, biomass is considered the most important carbon-neutral or green carbon fuel source. But the overall biomass chain needs to be considered for true carbon neutrality of biomass. Significant cost, energy needs, and CO2 emissions account for biomass harvesting, drying, handling, transportation, processing, and storage, which need to be considered in life-cycle analysis for sustainability. Biomass plays an integral part in the overall sustainable energy solution. Biochar facilitates the conversion of marginal lands to lands suitable for agriculture by improving soil quality. The impacts of adding biochar to soils may include reduced land area required for food production as a result of increased productivity and making marginal lands economically productive [4, 12, 20, 22].
The chemical composition of biomass is different from fossil fuels. Lignocellulosic biomass is a complex mixture of biopolymers consisting of three key elements, carbon (C), oxygen (O), and hydrogen (H). The percentages in dry matter of C, O, and H are 42–47%, 40–44%, and 6%, respectively, whose total content reaches typically above 95%. In addition, depending on the plant species and environment, plant biomass also contains various macronutrients, micronutrients, trace elements, and other heavy metals [4, 18]. The non-starch fibrous part of the plant (lignocellulosic) material is the major component of plant biomass. Three major constituents of lignocellulosic biomass comprising the cell wall of plants are cellulose, hemicellulose, and lignin. Cellulose, the main component of the plant cell wall, provides structural support. The second most abundant polymer in lignocellulosic biomass is hemicellulose. The third most abundant polymer in lignocellulosic biomass is lignin. Usually, cellulose is the major component in wooden biomasses, whereas hemicellulose is the key component in leaves and grasses and lignin in shells. Hemicellulose is thermally less stable than cellulose. Lignin is the most stable of all three. Knowledge of biomass composition in terms of cellulose, hemicellulose, and lignin can be helpful in controlling the product chemistry [2, 4, 23, 24].
The other compounds present in biomass include inorganic compounds and organic extractives. These nonstructural components include fats, waxes, proteins, terpenes, simple sugars, gums, resins, starches, and essential oils that do not constitute the cell walls or cell layers. Often these compounds are responsible for the smell, color, flavor, and natural resistance to decaying of some species. The inorganic compounds constitute less than 10% by weight of biomass, forming ash in the pyrolysis process. Depending on the type of biomass, the cellulose, hemicellulose, and lignin content fall in the range of 40–60%, 15–30%, and 10–25%, respectively. Fermentable sugars produced by hydrolyzing carbohydrates (cellulose and hemicellulose) can be converted into fuels and chemicals. The content of cellulose, hemicellulose, and lignin in wood biomass is high (~90%), while more extractives and ash are present in agricultural and herbaceous biomass [2, 4, 24].
Analysis of biomass feedstock is an essential part of understanding the behavior of biomass in energy use. The proximate analysis, ultimate analysis, and higher heating value (HHV) of biomass feedstock can provide a clear understanding of its thermochemical conversion characteristics. The proximate analysis gives information on biomass composition in terms of volatile matter (VM), fixed carbon (FC), ash content, and moisture (M) content. VM is the condensable and non-condensable vapors/gases released from biomass during heating. The amount of VM depends on the heating rate and the final biomass temperature. FC is the solid carbon (nonvolatile) that remains in the char after devolatilization. FC and VM indicate the percentage of biomass burned in solid and gaseous states, respectively. Ash is the noncombustible solid residue remaining after biomass is completely burned. These are of fundamental importance for bioenergy use. These data provide the essential information for the furnace design, including sizing and location of primary and secondary air supplies, refractory, ash removal, and exhaust handling equipment. [4, 25, 26].
The ash contains mostly inorganic residues and its composition depends on the biomass type. The inorganics in ash include silica, calcium, iron, aluminum, and small amounts of potassium, sodium, magnesium, and titanium. The content of ash in biomass is generally small. But if biomass contains alkali metals or halides, ash may play a significant role in biomass combustion or gasification. Agricultural residues, grasses, and straw generally contain potassium compounds and chlorides are particularly susceptible to this problem and can cause severe corrosion, fouling, and agglomeration in boilers or gasifiers. Burning biomass at lower temperatures mitigates the problems of corrosion and slagging. The ash produced during biomass conversion does not necessarily come from biomass itself but also from other sources like contamination as well. Biomass can pick up dirt, soil, rock, and other impurities during collection and handling, partly contributing to ash content [4, 14, 25].
The relationship between FC and char yield in biomass is positive, while VM and ash relate negatively to char yield. The greater biomass VM is expected to lead to greater gas production instead of the solid phase. Moisture content has a significant impact on the biomass conversion process. High moisture content is a major concern in biomass conversion. Thermochemical conversion processes generally require biomass with low moisture content. However, biochemical conversion processes can use biomass with high moisture content. Some moisture is required in the gasification process to produce hydrogen and with increasing moisture content, the amount of hydrogen increases. The moisture content can be very high (>90%) in some wet biomass (such as water hyacinth). As the energy used in the evaporation of moisture is not recovered, moisture drains much of the deliverable energy during conversion [4, 25, 26, 27].
The ultimate analysis provides the composition of biomass on a gravimetric basis, including major elements (C, H, O, S, and N), moisture, and ash. The ultimate analysis is usually reported on a dry and ash-free basis. These are useful for performing mass balances on biomass conversion processes. Elemental chemical composition, volatiles, moisture, and ash are essential for thermochemical conversions of biomass. Additionally, information on the polymeric composition of biomass is required for conversions, such as torrefaction, pyrolysis, and gasification. The ultimate analysis helps calculate the quantity of combustion air needed to sustain the combustion reactions. Usually, the sulfur and nitrogen content of biomass is very low and produces minimal pollutants SOX and NOX [25, 27].
Biomass can be converted to end products (such as heat, biofuels, or chemicals) through chemical, biochemical, and thermochemical conversion processes. Selection of the conversion process depends on number of factors, such as the desired form of end products, biomass feedstock available, environmental standards, policy, economic conditions, and specific factors related to the project. In most situations, the selection of the conversion process is based on two factors, the desired form of end products and biomass feedstock available. The moisture content of biomass primarily determines the biomass conversion process. Dry biomasses (such as wood or straw) are required for thermochemical conversions, such as pyrolysis, gasification, or combustion. Low-energy density due to higher moisture content makes wet biomass unsuitable for these processes. Transportation and energy costs significantly increased due to the high moisture content. Hydrothermal and biochemical processing are wet conversion processes that have gained growing attention and are more suitable for processing high moisture content biomass, including aquatic biomass, sewage sludge, food waste, and manure. Compared with thermochemical conversion, biochemical conversion consumes less energy but requires more time. Consequently, cost-effective hydrothermal processing has been given more attention than thermochemical conversion (with drying). If moisture content lies between wet and dry regions, additional parameters (such as cost and feasibility of drying) need to be considered in selecting a suitable conversion process [1, 2, 4, 10, 28, 29, 30].
Thermochemical conversion processes usually offer many advantages over biochemical conversion processes, including better conversion efficiency, handling a wide variety of feedstocks, shorter reaction times, and high-energy efficiency. As a result, thermochemical conversion processes have recently received greater attention for biofuel production. Many thermochemical conversion processes are available to convert biomass into products (solid, liquid, and gaseous). Thermochemical conversion processes use high temperatures to breakdown the bonds of biomass organic matter. These are classified according to the oxygen content used in the process, including combustion (complete oxidation), gasification (partial oxidation), and pyrolysis (thermal degradation in the absence of oxygen). Torrefaction, a mild form of pyrolysis, is also performed in the absence of oxygen. Hydrothermal processing, a thermal degradation in the absence of oxygen, is an alternative route to process wet biomass. The typical products of the thermochemical conversion of biomass are biochar (carbon-rich solid residue), bio-oil (liquid fraction, condensable vapors), and non-condensable gases. The distribution of products (biochar, bio-oil, and gases) depends primarily on the conversion process [2, 4, 9].
Pyrolysis is one of the thermal decomposition processes conducted in the absence of oxygen to convert biomass into three distinct product fractions—solid residue (biochar), condensable vapors resulting in liquid product fraction (bio-oil), and non-condensable gaseous products. In the absence of oxygen, combustion cannot occur; instead, pyrolysis happens. Pyrolysis processes can be classified as torrefaction, slow pyrolysis, intermediate pyrolysis, fast pyrolysis, flash pyrolysis, microwave pyrolysis, and hydrothermal processing. These pyrolysis processes differ from one another based on the operating conditions such as residence time, heating rate, and pyrolysis temperature, which in turn affect the yield of products (gas, bio-oil, and biochar) [3, 4]. Moderate temperatures and short residence times tend to produce more liquids. The operating conditions of these different thermal conversion processes, along with their product distribution and biomass feed particle size needed, are shown in Table 1.
Mode | Condition | Liquid (bio-oil) | Solid (biochar) | Gas (syngas) | Heating rate | Particle Size (mm) |
---|---|---|---|---|---|---|
Slow pyrolysis | Low to moderate temperatures (300–550°C), Long residence time (hours to days) | 30% | 35% | 35% | 1–0.8°C/s | 5–50 |
Intermediate pyrolysis | Low to moderate temperatures (450–550°C), Moderate residence time (10–20 s) | 50% | 25% | 25% | 1–10°C/s | 1–5 |
Fast pyrolysis | Moderate temperatures (425–600°C), Short vapor residence time (<2 s) | 75% | 12% | 13% | 10–1000°C/s | < 1 |
Flash Pyrolysis | (750–1000°C), (0.5 seconds) | >1000°C/s | <0.2 | |||
Microwave- Assisted Pyrolysis | (400–800°C) | |||||
Torrefaction | (450–550°C), (< 2 hours) | 20% | 75% | 5% | < 1°C/s | |
Hydrothermal Carbonization | (<200°C), (minutes to hours) | 35–80% | < 1°C/s | |||
Hydrothermal Liquefaction | (200–350°C), 5–20 MPa | |||||
Hydrothermal Gasification | (400–600°C), 23–45 MPa, short residence time | |||||
Gasification | High temperature (>800°C), Long vapor residence time | 5% tar (55% water) | 10% | 85% |
Operating conditions of various pyrolysis processes and their product fractions (bio-oil, biochar, and gas) [2].
The three pathways char formation, depolymerization, and fragmentation describe the primary conversion of biomass during the pyrolysis process. Intra- and intermolecular rearrangement reactions generally favor char formation resulting in higher thermal stability of the residue. The formation of benzene rings and the combination of these rings into an aromatic polycyclic structure characterize char formation. The release of water or non-condensable gas (devolatilization) generally accompanies these rearrangement reactions. The breaking of polymer bonds characterizes depolymerization, a dominant reaction during the initial stages of pyrolysis. When the temperature is sufficiently greater than the activation energies for the bond dissociation, depolymerization occurs, increasing the concentration of free radicals. It is followed by stabilization reactions producing monomer, dimer, and trimer units. These volatile condensable molecules at ambient conditions are found in the liquid fraction. Fragmentation involves breaking polymer bonds and even monomer bonds, resulting in the formation of non-condensable gases and a range of organic vapors that are condensable under ambient conditions [4, 31, 32, 33].
The decomposition of three lignocellulose components (hemicellulose, cellulose, and lignin) releases condensable vapors and non-condensable gases. The condensable vapor includes methanol, acetic acid, acetone (mainly from hemicellulose), anhydrous monosaccharides, hydroxyacetaldehyde (mainly from cellulose), phenols, and heavier tars (from lignin decomposition) apart from water vapor. The water-insoluble heavier tars contain larger molecules obtained from splitting ether and C-C bonds in lignin. The condensable vapors are condensed to form bio-oil (a dark brown and free-flowing organic liquid mixture). It usually contains 15–35 wt.% water resulting from the original moisture and as a pyrolysis product. Pyrolysis temperature determines the degree of devolatilization of biomass. There are significant differences between the pyrolysis behaviors of hemicellulose, cellulose, and lignin, which are responsible for most physical and chemical property modifications during the pyrolysis process. Hemicellulose and cellulose decompose over a narrow temperature range. Lignin decomposes over a wider temperature range than hemicellulose and cellulose [4, 31, 32, 34, 35].
Fast pyrolysis typically involves high temperatures (450 and 550°C), high heating rates (10–1000°C/s), and short residence times (0.5–2 s) [36]. It is the most promising thermal process to produce a higher amount of liquid fuel (bio-oils) than other thermal conversion processes. Fast pyrolysis can produce up to 75 wt% bio-oil [37], which can be used directly or as an energy carrier after upgrading.
Fast pyrolysis suppresses secondary reactions (cracking and repolymerization) by having short vapor residence times (rapid removal and quenching of condensable primary volatile vapors) and maintaining high heating rates, thereby maximizing the yield of condensable vapors (bio-oil). This results from rapid quenching and condensing intermediate degradation products of hemicellulose, cellulose, and lignin to bio-oil without further reactions, such as breaking down larger molecular weight (MW) components into smaller MW gaseous products. The rapid quenching of intermediates results in bio-oil having many reactive species, contributing to its unusual characteristics. Rapid and simultaneous depolymerization and fragmentation of cellulose, hemicellulose, and lignin fractions with a rapid increase in temperature form condensable vapors. Rapid removal and quenching shorten the residence time at high temperatures and trap many of these fractions inhibiting further reactions (depolymerize, decompose, degrade, crack or condense with other molecules) to form more non-condensable gases [4, 38, 39].
The main product of the fast pyrolysis process is bio-oil (65–75%), with smaller amounts of biochar (10–25%) and non-condensable gases (10–20%). The distribution of bio-oil, biochar, and gases depends on the biomass composition, rate, and duration of heating. The fast pyrolysis process has the capability to produce bio-oil with high fuel-to-feed ratios. To strike a balance between thorough devolatilization and minimal secondary cracking of vapors, the optimum pyrolysis temperature range for bio-oil production is 425–600°C, with a maximum yield of around 500°C [10]. Due to the higher cellulose and hemicellulose content in wood than in energy crops and agricultural residues, woody biomass (poplar, sawdust, forest, and wood residue) produces the highest bio-oil yield of around 75%, followed by energy crops (reed) and agricultural residues (wheat straw, flax straw, etc.). Product yield in fast pyrolysis is affected by the feed particle size. Smaller particle size increases the heat transfer rate, thus, increasing bio-oil yield. Feedstock particle size and pyrolysis temperature need to be optimized for maximum bio-oil yield [4, 36, 39]. A finely ground (usually <1 mm) biomass feed is required to achieve very high heat transfer rates, thereby very high heating rates reducing heat and mass transfer limitations. Due to the absence of secondary reactions, the overall fast pyrolysis process is highly endothermic. Fast pyrolysis favors low moisture content biomass (<10 wt.%) to minimize water content in bio-oil. Low moisture content also facilitates grinding the feed to give sufficiently small particles to ensure rapid heating and hence fast pyrolysis [4, 37].
The central part of the pyrolysis process is the reactor used, where the thermal conversion reactions occur. Many reactors are used in the pyrolysis process, such as entrained flow reactor, fluidized bed reactor, fixed bed reactor, autoclave, rotating cone reactor, and plasma reactor [40]. These reactors can be classified into subcategories according to the flow of material and phenomena, such as circulating, co-current, counter-current, and crossflow. The amount of bio-oil depends on the reactors used and the operating conditions. The continuous developments in pyrolysis technologies explore many reactor designs to optimize pyrolysis performance and produce high-quality bio-oil. Because of its moisture contents, a higher heating value (HHV) of the bio-oil produced is half the HHV of crude oil. However, each reactor type has specific characteristics, bio-oil yielding capacity, advantages, and limitations. The crucial characteristic steps of the fast pyrolysis process are: the pyrolysis reaction takes place with high heat and heat transfer rates, thus, the particle sizes of biomass materials need to be small enough to enhance such heat transfer; the pyrolysis reaction temperature ranges from 450 to 550°C in the vapor phase; short residence times for the vapor up to two seconds; rapid quenching and condensing the vapors into bio-oil. Common reactor types used for fast pyrolysis are described below [41, 42, 43, 44, 45].
The packed bed pyrolysis reactor system contains a reactor with a gas cooling and cleaning system. These reactors are common types of reactors with cylindrical shapes and packed with solid packing materials, such as firebricks, steel, or concrete; they can be packed with catalysts too. The feed enters from one side and the product is obtained from the other. The relatively fine biomass solids move down and contact a counter-current upward-moving product gas stream. The catalyst pellets are packed in a given section and are unmovable where the pyrolysis reactions occur in this section. Some of the advantages of these packed bed reactors are catalyst recovery and recycling, which gives good economic impacts [41, 42].
Fluidization is a phenomenon in which fine solids are transformed into a fluid-like state through contact with a gas or liquid. The particles in the fluidized bed are present in a semi-suspended state when the gas velocity maintains a critical value known as the minimum fluidization velocity. The fixed bed transforms into a fluidized bed at this stage when the fluid drag is equal to the particle weight. Bubbles are made at the openings at which the fluidizing gas enters the bed, where the packing solids above the gas entrance are pushed aside until they create a void space through which the gas can enter at the initial fluidization velocity. Uniform mixing, uniform temperature distribution, and operation in a continuous state are the main advantages of bubbling fluidized-bed reactors [43, 44].
A circulating fluidized-bed reactor works on the same principle as the bubbling fluidized bed except that the bed is highly expanded and solids continuously recycle around an external loop comprising a cyclone and loop seal. In this circulating fluidized bed, the reactor does not contain any bed and does not have any separate upper surface. The most important advantages of circulating fluidized-bed reactors over other reactor configurations include internal recycling of huge bulk particles reaching the top of the vessel back to its bottom, a good void range, and no distinct upper bed surface in the column [42, 45].
Ablative pyrolysis reactor is basically different in concept compared to the other methods of fast pyrolysis. In ablative pyrolysis, biomass is pressed against a heated surface and rapidly moved during which the biomass melts at the heated surface and leaves an oil film behind which evaporates. In the other reactors mentioned above, the rate of reaction is limited by the rate of heat transfer through a biomass particle, that is why fine particles are required. This ablative process uses larger biomass particles and is typically limited by the heat supply rate to the reactor. The rate of reaction is strongly affected by pressure, the relative velocity of biomass on the heat exchange surface, and the reactor surface temperature [41, 42].
Biomass materials are typically wet and have a moisture content range of up to 95 wt.%. Biomass with more than 30 wt.% moisture content is not suitable for pyrolysis. It needs to be dried before being suitable for pyrolysis, which requires a large amount of energy. It becomes a net energy consumption for biomass with high moisture content because the heat available from the biomass is less than the heat of moisture evaporation. Hydrothermal processing involves applying heat and pressure in the presence of water (subcritical or supercritical). Biomass typically with 70 wt.% or more water can be converted into carbonaceous end products without atmospheric oxygen. Water plays an active role as a solvent and reactant in hydrothermal processing. It is a promising technique for converting wet biomass into carbonaceous solids at relatively high yields without energy-intensive drying before or during the process. Depending on the operating conditions (temperature, pressure, and residence time), hydrothermal processes are classified as hydrothermal carbonization (HTC), hydrothermal liquefaction (HTL), and hydrothermal gasification (HTG) [2, 4].
When biomass feedstock in water is heated at temperatures below 200°C in a sealed vessel at autogenous pressure, mostly solids (hydrochar) are formed in a process known as HTC. The residence time of HTC varies from minutes up to several hours. Hemicellulose and cellulose decomposition temperature in subcritical water is usually around 160°C and 180 to 200°C, respectively, while lignin decomposes above 220°C. HTC converts biomass into three distinct product fractions: solid residue (hydrochar), bio-oil mixed with water in liquid fraction (aqueous solution), and a small volume of gases (consisting mainly of CO2). HTC aims to maximize the hydrochar yield. The three factors (type of biomass, pH, and maximum temperature used) primarily influence the product distribution and characteristics. The other factors, such as solids concentration (in biomass water mixture) and reaction time, have a relatively smaller influence. The overall extent of hydrochar formation from glucose is negligible below 160°C and yield is maximum at 200°C. Hydrochar formation is reduced with the increase in temperature above 200°C as a result of gasification reactions converting part of the hydrochar formed into volatile compounds. Process conditions and the type of biomass feed are the two factors that influence energy requirements and final product composition. Hydrochar has high hydrophobic and homogeneous properties and can be easily separated from the liquid fraction. Dried hydrochar pellets can be produced from the separated solid fraction, which can be used for energy production. The liquid fraction can be used to recover mono sugars. The gas fraction has less CO and CO2 and is less harmful. The hydrochar has carbon content similar to lignite and the yield of hydrochar varies from 35% up to 80% [2, 4, 46, 47, 48].
The HTC reduces both the oxygen and hydrogen content of the biomass through dehydration and decarboxylation. During HTC, hemicelluloses and cellulose are hydrolyzed to oligomers/monomers, whereas lignin mostly remains unchanged. The reaction mechanism of the HTC process mainly involves dehydration, decarboxylation, and polymerization. Dehydration is favored at temperatures less than 300°C. The hydroxymethylfurfural (HMF) generated from hexose (D-fructose and D-glucose) and furfural generated from pentoses (D-xylose) are well-known dehydration products of sugars. The hydrothermal process under acidic conditions allows the effective conversion of D-glucose to HMF. D-glucose first isomerizes to D-fructose and then undergoes dehydration to form HMF. The HMF, in turn, decomposes into levulinic acid, formic acid, and soluble polymeric carbonaceous material with increasing residence time [49, 50].
Hydrochar has a higher energy content than the feedstock used and lower O/C and H/C ratios than the feedstock. Hydrochar has higher H/C ratios than biochar specifications. HTC is a high-energy-consuming process. Solar energy appears to be an attractive renewable energy source to combine with HTC. HTC can combine with other processes to produce hydrochar with characteristics (morphology, porosity, conductivity, H/C ratio, O/C ratio, energy content, elemental composition, etc.) suitable for applications in many fields such as solid fuel in power generation, soil amendment, adsorbent in water purification and carbon capture. Hydrochar can be further processed to use as carbon electrodes or nanocomposites. HTC process was initially used for the degradation of organic materials, production of liquid and gaseous fuels, and production of basic chemicals. In recent years, the technology gained research interest to produce solid hydrochar and as a technique to synthesize nano- and micro-size carbon particles [46, 47, 51, 52].
The hydrochar produced by HTC directly from carbohydrates or biomass lacks porosity. Only a tiny porosity is developed even after further carbonization at a higher temperature. This is due to hydrochar being pre-carbonized material produced under autogenic pressures and temperatures between 160 and 200°C. For most industrial applications such as adsorption or catalysis, the high surface area and porosity of hydrochar are essential. This would ensure efficient transport and diffusion throughout the material. Different techniques have been developed to improve the porosity of hydrochar [47]. Some of the advantages of the HTC process include low carbonization temperatures, can be synthesized in the aqueous phase (no drying is required), and inexpensive process. Hydrochar obtained from HTC has the following properties: (a) uniform spherical micro-sized particles; (b) oxygenated functional groups at the surface (OH, C=O, COOH groups); (c) controlled porosity can be easily introduced using activation procedures, thermal treatments, etc.; (d) easily controlled surface chemistry and electronic properties via additional thermal treatment; (e) special physicochemical properties can be obtained by adding other components (such as inorganic nanoparticles) to biomass [49, 50].
At temperatures between 200 and 350°C and pressures of 5–20 MPa, biomass is primarily converted to a liquid fraction (aqueous soluble) in a process known as HTL. Leading reactions in HTL are considered to be free radical and ionic reactions. At ambient conditions, the dielectric constant (a measure of hydrogen bonding) of water is about 80 F/m. It decreases rapidly with increasing temperature, at 250°C and 5 MPa dielectric constant is about 27 F/m and at 350°C and 25 MPa about 14 F/m. Due to decreasing dielectric constant (number of hydrogen bonds), water displays less polar behavior. An increase in temperature increases the dissociation of water. The ionic product of water (pKw) at 25°C is 14 and decreases to 11 at 250°C. With increasing temperature, mass transfer is enhanced because of accelerated mass-transfer-limited chemical reactions resulting from a decrease in the viscosity of water [4, 53, 54].
The primary conversion of biomass during the HTL comprises three pathways; depolymerization, decomposition, and recombination. Higher MW biomass is depolymerized and decomposed into smaller MW compounds. These compounds are highly reactive and recombined (repolymerized) to form bio-oil, gaseous and solid products. The parameters such as temperature and pressure are important for the depolymerization of long-chain polymer structures to shorter-chain hydrocarbons. The decomposition step involves three steps: dehydration (loss of water molecule), decarboxylation (loss of CO2 molecule), and deamination (removal of amino acid content). The dehydration and decarboxylation steps remove oxygen from the biomass in the form of H2O and CO2, respectively. Macromolecules of biomass are hydrolyzed to form polar monomers and oligomers. Subcritical water at HTL temperatures and pressure breaks down the hydrogen bonds of the cellulose structure to form sugar monomers. It is rapidly degraded by different reactions (such as isomerization, hydrolysis, dehydration, reverse aldol defragmentation, rearrangement, and recombination) into a series of products. Most of the degradation products such as polar organic molecules, furfurals, phenols, glycolaldehyde, and organic acids are highly soluble in water. Recombination and repolymerization of light MW compounds occur due to the unavailability of the hydrogen compound or excess oxygen [53, 55, 56].
During HTL of lignin, hydrolysis and splitting of the ether and C-C bond, demethoxylation, alkylation, and condensation reactions occur. Competition occurs between these main reactions. The gaseous, liquid, and solid yield of HTL of biomass depends on several parameters, including biomass feedstock, temperature, heating rate, residence time, pressure, mass ratio of water/biomass, and catalyst. The main product of HTL is the liquid fraction (bio-oil). The temperature and pressure directly (activation energy, reaction equilibria) and indirectly (solvent properties) impact the reaction. During HTL, the major components of biomass cellulose, hemicellulose, and lignin behave differently. In general, biomass with high cellulose and hemicellulose produces higher bio-oil yields. Higher bio-oil yields have been reported from hardwood samples (cherry) than softwood (cypress). Softwood contains higher lignin than hardwood, hence, lower bio-oil yield [54, 57]. Other studies have also shown that both temperature and lignin contents of wood had a marked effect on bio-oil yield. Bio-oil production was maximum for wood with low lignin contents [58, 59]. Subcritical water in HTL acts as a heat transfer medium to overcome the heat transfer limitations. As a result, biomass particle size has negligible to minimal effects on HTL. Excessive size reduction of biomass feedstock is not required [54, 58].
Usually, the effect of temperature on the bio-oil yield is synergetic due to the increased fragmentation of biomass at higher temperatures. Depolymerization occurs when the temperature is sufficient for bond dissociation. The competition among hydrolysis, fragmentation, and repolymerization reactions describes the role of temperature during the HTL process. Depolymerization is a dominant reaction during the initial stages of HTL. Repolymerization becomes active at later stages of HTL, leading to the formation of hydrochar. Intermediate temperatures usually produce higher bio-oil yields [54, 58]. The increase in HTL temperature not only enhances the reaction rates but also changes the reaction mechanisms. Hence, lower temperatures favor ionic reactions; higher temperatures promote the formation of radicals by homolytic bond breakage. Radical reactions usually lead to a diverse product spectrum and finally to gas formation [54, 60, 61]. Various authors have observed increased bio-oil yields with increasing temperature during the HTL process. Different authors have proposed various optimum temperatures for a variety of biomasses. It can be assumed that the temperature range of 280–350°C would be suitable for the decomposition of biomass under both subcritical and supercritical conditions. Final HTL temperature varies with the type of biomass [54, 58].
The temperature gradients during the heating of biomass are important for the sequence and extent of chemical reactions. Due to the better dissolution and stabilization of fragmented compounds in subcritical water, the effect of heating rates on the product distributions in HTL is minimal compared to pyrolysis. Because of secondary reactions, slow heating rates typically tend to yield solid fraction (hydrochar). Secondary reactions are also dominant at very high heating rates and yield more gases. Furthermore, bio-oil yield is not significantly affected by large variations in high heating rates. Moderate heating rates may be suitable to overcome heat transfer limitations leading to extensive fragmentation and minimal secondary reactions. Many researchers have investigated the effect of residence times on product distribution during the HTL process. Duration of reaction time may characterize the product compositions and the overall biomass conversion. Short residence times are usually preferred during the HTL of biomass. Longer residence times can decompose preasphaltenes and asphaltene into lighter products enhancing the yield of bio-oil and gases. It is essential to inhibit the decomposition of lighter products to obtain a high liquid oil yield. Generally, bio-oil yield attains a maximum before decreasing for extended residence times, whereas gas yield and biomass conversion increase continuously until reaching saturation [54, 55, 56, 58].
Pressure helps maintain single-phase media for HTL to avoid large heat inputs required for phase change. Two-phase systems need a large heat supply to maintain the temperature of the system. Pressure increases solvent density and a high-density medium penetrates effectively into molecules of biomass components resulting in improved decomposition and extraction. Many investigations have been performed to study the influence of different solvents (such as subcritical and supercritical alcohols) on the liquefaction yield of lignocellulosic biomass. Critical temperatures and pressures of alcohols are lower than in water and significantly milder reaction conditions could be used. Alcohols are expected to dissolve relatively high MW products derived from cellulose, hemicelluloses, and lignin due to their lower dielectric constants than water. Ethanol and methanol have been widely employed for biomass liquefaction. The mass ratio of biomass/water is considered a vital parameter for the HTL process. Different authors investigated the effect of water density on HTL yield. All solvolytic conversions are benefitted from the dilution of reactants, intermediates, and products during the reaction. This dilution minimizes cross-reactions and produces a more distinct product spectrum. Higher substrate concentrations inevitably lead to cross-reactions leading to undesirable polymerization of the reaction products. Such processes have been observed for HTL of biomasses, promoting the formation of solid fractions. Catalysts are important in the HTL of biomass. A range of homogeneous catalysts (such as mineral acids, organic acids, and bases) and heterogeneous catalysts (such as zirconium dioxide, anatase, and other materials) has been proposed to tailor the reaction toward a specific product and enhance the reaction rates [54, 55, 56, 62].
HTG operates near or above the critical point of water at 400–600°C and 23–45 MPa. The primary product of HTG is a mixture of non-condensable gases (H2, CO, CH4, and CO2), which can produce syngas enriched with H2. At the critical point (374°C and 22.1 MPa) of water, the conversion efficiency is improved. Biomass polysaccharides split in the presence of supercritical water (SCW). Due to higher reaction temperatures, HTG reactions progress at a faster rate and complete decomposition of biomass is achieved. This is a distinctive feature of HTG compared to other hydrothermal treatments (HTC and HTL). One of the problems with HTC and HTL is the difficulty in byproduct treatment due to undesirable byproducts being occasionally dissolved in the liquid fraction. The conversion rate of HTG is typically higher than 80% that decomposes biomass into gaseous products. Consequently, post-treatment of liquid fraction is not required or easily carried out because only a small amount of organic compounds remain in the liquid. Conventional gasification can be effectively employed when biomass is not wet, but it is ineffective when biomass has a high moisture content (> 80%). The syngas of conventional gasification is partially diluted with nitrogen (due to partial oxidation using air) and contains tar. Syngas from HTG is not diluted with nitrogen and do not contain tars. Tar, if produced, remains in the liquid fraction [2, 4, 63].
The HTG performance is strongly dependent on the operating conditions, including biomass characteristics, temperature, pressure, residence time, feedstock concentration, and catalyst. The rate of hydrolysis and decomposition is relatively fast in the HTG process; hence, short residence times are expected to degrade biomass successfully. Optimization of residence times is required for the efficient destruction of biomass organic compounds. Pressure helps maintain single-phase media for HTG to avoid large heat inputs required for phase change. Two-phase systems need a large heat supply to maintain the temperature of the system. The rate of hydrolysis and biomass dissolution can be controlled by maintaining pressure higher than the supercritical pressure, which may enhance favorable reaction pathways for bio-oil or gas yield. Pressure imparts minor or negligible influence on bio-oil or gas yield in supercritical conditions. This is because, in the supercritical region, the effect of pressure on the properties of water is minimal [54, 58, 64].
SCW exhibits a unique property; the density, viscosity, ionic product, and dielectric constant change significantly when water changes from ambient conditions (25°C and 0.1 MPa) to the supercritical condition. At ambient conditions, the dielectric constant of water is about 80 F/m and water is a polar solvent due to a high dielectric constant (a large number of hydrogen bonds). At supercritical conditions (400°C and 25 MPa), the dielectric constant is about 6 F/m; because of the decrease in the number of hydrogen bonds, water begins to display the behavior of a nonpolar solvent that can completely dissolve many organic compounds, hydrocarbons, and gases (such as CO2, CH4, H2, and N2). This results in poor solubility of inorganic polar compounds in SCW. Many rapid homogeneous reactions involving organic compounds occur at supercritical conditions due to the absence of phase boundaries. In subcritical water, inorganic polar compounds (such as NaCl, KCl, and CaSO4) are usually soluble. But these compounds are insoluble in supercritical water and easily separated from the reaction products. SCW exhibits gas-like properties and using SCW as the reaction medium in HTG has several advantages: low viscosity creates a high diffusion coefficient and enhances mass transfer, low density improves the solvation properties, creates a single-phase reaction environment in the reactor by complete miscibility with different organics and gases, enhance mass transfer, prevent poisoning of catalyst (if used) and coke formation and product gas (syngas) does not have tar and has a high heating value. Syngas can be converted to liquid fuels or value-added chemicals via different gas-to-liquid conversions, such as Fischer-Tropsch synthesis or to ethanol and butanol through syngas fermentation using microorganisms [9, 53, 54, 63].
Biomass is a sustainable energy source and a promising eco-friendly alternative source of renewable bioenergy. The most abundant biomass, lignocellulose, represents a significant carbon source for bioenergy. Lignocellulosic biomass is a complex mixture of biopolymers. The three major biopolymers are cellulose, hemicellulose, and lignin. Inorganic compounds and organic extractives are among other compounds present in lignocellulosic biomass. The selection of the process to convert biomass to end products depends on several factors, but the desired form of end products and available biomass feedstock are the two key factors usually considered. Thermochemical conversion processes usually offer many advantages over biochemical conversion processes.
Thermochemical conversions convert biomass into liquid, gaseous and solid products. The product distribution depends on the conversion process employed, that is, operating conditions (heating rate, residence time, and temperature). More liquids are produced at moderate temperatures and short residence times. Bio-oil is the desired product in fast pyrolysis and bio-oil yield is maximized at high heating rates, short vapor residence times, and around 500°C. A finely ground dry biomass feed is essential for high heat transfer rates. Due to the higher cellulose and hemicellulose content, woody biomass produces the highest bio-oil yield.
High moisture content is a major barrier in biomass processing for bioenergy. It has a significant impact on the biomass conversion process. High moisture biomass requires a large amount of energy to evaporate moisture to make it suitable for pyrolysis.
Hydrothermal processing is useful for biomass feedstocks with high moisture as it does not require drying, thereby reducing energy costs. Hydrothermal processing has been given more attention in recent years and can be classified into HTC, HTL, and HTG based on the reaction temperature, pressure, and residence time. HTC, HTL, and HTG are aimed to maximize the production of solid (hydrochar), liquid (bio-oil/water), and gas (non-condensable) fractions, respectively. More research is required on hydrothermal processing to investigate reaction kinetics and chemistry, heat transfer, energy and heat recovery, combinations with other technologies, such as solar, technical, and economic aspects and the effect of operational parameters.
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Global cocoa production has been rising fairly steadily over the years by increasing production in growing countries with most of the production taking place in areas of high pathogen biodiversity. Thus, the sustainability of the cocoa economy is under threat as diseases of various statuses now constitute the most serious constraint to production. Most important among these is the black pod disease caused by Phytophthora genus with annual losses of 30–90% of the crop. This economically important pathogen is very diverse in nature and varied across growing countries including species such as palmivora, megakarya, capsici and citrophthora distinguished based on chromosome number, sporangial characteristics and pedicel length. World losses of 20–25% in cacao production are due to black pod disease, an estimate of 700,000 metric tons on global scale reducing global cocoa production. High cacao loss to diseases is a prime factor limiting production; consequently, significant effort is required to deal with problems associated with disease control to ensure a sustainable cacao. The effective and sustainable management of black pod disease requires integrated approach encompassing different control measures.",book:{id:"7005",slug:"theobroma-cacao-deploying-science-for-sustainability-of-global-cocoa-economy",title:"Theobroma Cacao",fullTitle:"Theobroma Cacao - Deploying Science for Sustainability of Global Cocoa Economy"},signatures:"Dele Adeniyi",authors:null},{id:"67634",title:"Cacao Growth and Development Under Different Nursery and Field Conditions",slug:"cacao-growth-and-development-under-different-nursery-and-field-conditions",totalDownloads:1255,totalCrossrefCites:2,totalDimensionsCites:2,abstract:"Experiments were conducted between 2004 and 2018 to examine cacao growth, development, establishment and yield under varying experimental conditions comprised of seed mucilage handling before sowing, sowing methods and its effects on seedling growth and development, timing of mycorrhizal inoculation on root and shoot growth and development and effects of shade and dry season drip irrigation on growth and yield of field-grown cacao. Results show that cleaning cacao seed mucilage before sowing enhanced sprouting rate and percent germination. The use of manure mixed with sawdust and loamy soil aided excellent seed germination, seedling vigor and root development. Inoculating cacao seeds with arbuscular mycorrhizal fungi (AMF) at point of sowing and early stages in the nursery aided root development and enhanced field establishment and survival during the dry season. Dense shade retarded cacao growth and development during the rainy season, while no shade enhances optimum growth and canopy development. The use of drip irrigation strategies in young cacao plantations increased seedling survival from less than 45% under no irrigation to above 95% at the end of the second dry season. This showed that irrigation during dry season can significantly enhance cacao establishment and survival.",book:{id:"7005",slug:"theobroma-cacao-deploying-science-for-sustainability-of-global-cocoa-economy",title:"Theobroma Cacao",fullTitle:"Theobroma Cacao - Deploying Science for Sustainability of Global Cocoa Economy"},signatures:"Idowu Babadele Famuwagun and Samuel Ohi Agele",authors:null},{id:"68383",title:"Major Natural Vegetation in Coastal and Marine Wetlands: Edible Seaweeds",slug:"major-natural-vegetation-in-coastal-and-marine-wetlands-edible-seaweeds",totalDownloads:756,totalCrossrefCites:0,totalDimensionsCites:1,abstract:"For thousands of years, seaweeds grown in coastal and marine have been used as food, materials and medicines by the people. Edible seaweeds directly consumed, especially in Asian, are used for preparing food due to the their components containing minerals, essential trace elements, and various natural compounds. At the last decades, they have been getting more and more attention in food and pharmaceutical industries because of their biological activities such as anti-cancer, anti-obesity, anti-diabetes, anti-microbial, and anti-oxidant activity. Therefore, in the present study, we have worked on to understand the structure of edible seaweeds. It is worthy to mention that they can be considered as source of some proteins, polyunsaturated fatty acids, minerals, vitamins, dietary fibers, antioxidants, and phytochemicals.",book:{id:"8667",slug:"plant-communities-and-their-environment",title:"Plant Communities and Their Environment",fullTitle:"Plant Communities and Their Environment"},signatures:"Ilknur Babahan, Birsen Kirim and Hamideh Mehr",authors:null},{id:"67540",title:"Aphid-Plant Interactions: Implications for Pest Management",slug:"aphid-plant-interactions-implications-for-pest-management",totalDownloads:1073,totalCrossrefCites:2,totalDimensionsCites:4,abstract:"Aphids are important herbivores and important pest of many field and forest crops. They have specialized long and flexible stylets which are adapted to feeding on phloem sap. To establish successful feeding on host plant, they need to counter a range of both physical and chemical defenses. The defenses employed by plants can have direct effect on the aphid species through difficulty in establishing successful feeding due to the presence of trichomes, thick cell wall, etc. or effect on their biology with lethal consequences in extreme cases (direct defenses). In contrast to this, plants can attract natural enemies of aphids through the release of volatile compounds (the so-called “cry or call for help”) (indirect defense). The information on different defense strategies employed by plants can be utilized to enhance the level of resistance (R) to develop sustainable pest management strategies.",book:{id:"8667",slug:"plant-communities-and-their-environment",title:"Plant Communities and Their Environment",fullTitle:"Plant Communities and Their Environment"},signatures:"Sarwan Kumar",authors:null},{id:"72336",title:"Plant Phenology and An Assessment of the Effects Regarding Heavy Metals, Nanoparticles, and Nanotubes on Plant Development: Runner Bean, Artichoke, and Chickpea Seedlings",slug:"plant-phenology-and-an-assessment-of-the-effects-regarding-heavy-metals-nanoparticles-and-nanotubes-",totalDownloads:654,totalCrossrefCites:0,totalDimensionsCites:0,abstract:"The relationship between environmental pollution and nutrition in particular, which forms the basis of health, is fundamentally important for protecting human health. Therefore, the data obtained from the examination of how plants and animals consumed as food are affected by environmental pollution can be seen as an indicator of their effects on humans. On the other hand, the role of technology and nanotechnology in life has been increasing in this century, and a considerable amount of heavy metals, nanoparticles (NPs), and nanotubes (NTs) are released to the environment. The results of morphological or anatomical examination of runner bean (Phaseolus coccineus L) and artichoke (Cynara scolymus L.) plants subjected to copper (Cu) and lead (Pb) heavy metals and chickpea (Cicer arietinum L) plants subjected to Au nanoparticles and C70 single-walled carbon nanotubes (SWNTs) are presented with this study in the point of their phenological development process. The three taxa belonging to Fabaceae and Asteraceae families with high economic status and having flowers with characteristic features were chosen deliberately as representatives. This chapter presents a study that will shed light on future biomonitoring-based studies focusing on the impact of environmental pollution on plants phenology with economic value.",book:{id:"8667",slug:"plant-communities-and-their-environment",title:"Plant Communities and Their Environment",fullTitle:"Plant Communities and Their Environment"},signatures:"Feyza Candan",authors:[{id:"155281",title:"Associate Prof.",name:"Feyza",middleName:null,surname:"Candan",slug:"feyza-candan",fullName:"Feyza Candan"}]}],onlineFirstChaptersFilter:{topicId:"141",limit:6,offset:0},onlineFirstChaptersCollection:[],onlineFirstChaptersTotal:0},preDownload:{success:null,errors:{}},subscriptionForm:{success:null,errors:{}},aboutIntechopen:{},privacyPolicy:{},peerReviewing:{},howOpenAccessPublishingWithIntechopenWorks:{},sponsorshipBooks:{sponsorshipBooks:[],offset:8,limit:8,total:0},allSeries:{pteSeriesList:[{id:"14",title:"Artificial Intelligence",numberOfPublishedBooks:9,numberOfPublishedChapters:89,numberOfOpenTopics:6,numberOfUpcomingTopics:0,issn:"2633-1403",doi:"10.5772/intechopen.79920",isOpenForSubmission:!0},{id:"7",title:"Biomedical Engineering",numberOfPublishedBooks:12,numberOfPublishedChapters:104,numberOfOpenTopics:3,numberOfUpcomingTopics:0,issn:"2631-5343",doi:"10.5772/intechopen.71985",isOpenForSubmission:!0}],lsSeriesList:[{id:"11",title:"Biochemistry",numberOfPublishedBooks:31,numberOfPublishedChapters:314,numberOfOpenTopics:4,numberOfUpcomingTopics:0,issn:"2632-0983",doi:"10.5772/intechopen.72877",isOpenForSubmission:!0},{id:"25",title:"Environmental Sciences",numberOfPublishedBooks:1,numberOfPublishedChapters:11,numberOfOpenTopics:4,numberOfUpcomingTopics:0,issn:"2754-6713",doi:"10.5772/intechopen.100362",isOpenForSubmission:!0},{id:"10",title:"Physiology",numberOfPublishedBooks:11,numberOfPublishedChapters:141,numberOfOpenTopics:4,numberOfUpcomingTopics:0,issn:"2631-8261",doi:"10.5772/intechopen.72796",isOpenForSubmission:!0}],hsSeriesList:[{id:"3",title:"Dentistry",numberOfPublishedBooks:8,numberOfPublishedChapters:129,numberOfOpenTopics:2,numberOfUpcomingTopics:0,issn:"2631-6218",doi:"10.5772/intechopen.71199",isOpenForSubmission:!0},{id:"6",title:"Infectious Diseases",numberOfPublishedBooks:13,numberOfPublishedChapters:113,numberOfOpenTopics:3,numberOfUpcomingTopics:1,issn:"2631-6188",doi:"10.5772/intechopen.71852",isOpenForSubmission:!0},{id:"13",title:"Veterinary Medicine and Science",numberOfPublishedBooks:11,numberOfPublishedChapters:105,numberOfOpenTopics:3,numberOfUpcomingTopics:0,issn:"2632-0517",doi:"10.5772/intechopen.73681",isOpenForSubmission:!0}],sshSeriesList:[{id:"22",title:"Business, Management and Economics",numberOfPublishedBooks:1,numberOfPublishedChapters:18,numberOfOpenTopics:2,numberOfUpcomingTopics:1,issn:"2753-894X",doi:"10.5772/intechopen.100359",isOpenForSubmission:!0},{id:"23",title:"Education and Human Development",numberOfPublishedBooks:0,numberOfPublishedChapters:5,numberOfOpenTopics:1,numberOfUpcomingTopics:1,issn:null,doi:"10.5772/intechopen.100360",isOpenForSubmission:!0},{id:"24",title:"Sustainable Development",numberOfPublishedBooks:0,numberOfPublishedChapters:14,numberOfOpenTopics:5,numberOfUpcomingTopics:0,issn:null,doi:"10.5772/intechopen.100361",isOpenForSubmission:!0}],testimonialsList:[{id:"13",text:"The collaboration with and support of the technical staff of IntechOpen is fantastic. 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