The measured concentration of some pharmaceutical active compounds in some of the aquatic environment in European countries.
\r\n\tIn sum, the book presents a reflective analysis of the pedagogical hubs for a changing world, considering the most fundamental areas of the current contingencies in education.
",isbn:"978-1-83968-793-8",printIsbn:"978-1-83968-792-1",pdfIsbn:"978-1-83968-794-5",doi:null,price:0,priceEur:0,priceUsd:0,slug:null,numberOfPages:0,isOpenForSubmission:!1,hash:"b01f9136149277b7e4cbc1e52bce78ec",bookSignature:"Dr. María Jose Hernandez-Serrano",publishedDate:null,coverURL:"https://cdn.intechopen.com/books/images_new/10229.jpg",keywords:"Teacher Digital Competences, Flipped Learning, Online Resources Design, Neuroscientific Literacy (Myths), Emotions and Learning, Multisensory Stimulation, Citizen Skills, Violence Prevention, Moral Development, Universal Design for Learning, Sensitizing on Diversity, Supportive Strategies",numberOfDownloads:null,numberOfWosCitations:0,numberOfCrossrefCitations:null,numberOfDimensionsCitations:null,numberOfTotalCitations:null,isAvailableForWebshopOrdering:!0,dateEndFirstStepPublish:"September 14th 2020",dateEndSecondStepPublish:"October 12th 2020",dateEndThirdStepPublish:"December 11th 2020",dateEndFourthStepPublish:"March 1st 2021",dateEndFifthStepPublish:"April 30th 2021",remainingDaysToSecondStep:"3 months",secondStepPassed:!0,currentStepOfPublishingProcess:4,editedByType:null,kuFlag:!1,biosketch:"Dr. Phil. Maria Jose Hernandez Serrano is a tenured lecturer in the Department of Theory and History of Education at the University of Salamanca, where she currently teaches on Teacher Education. She graduated in Social Education (2000) and Psycho-Pedagogy (2003) at the University of Salamanca. Then, she obtained her European Ph.D. in Education and Training in Virtual Environments by research with the University of Manchester, UK (2009).",coeditorOneBiosketch:null,coeditorTwoBiosketch:null,coeditorThreeBiosketch:null,coeditorFourBiosketch:null,coeditorFiveBiosketch:null,editors:[{id:"187893",title:"Dr.",name:"María Jose",middleName:null,surname:"Hernandez-Serrano",slug:"maria-jose-hernandez-serrano",fullName:"María Jose Hernandez-Serrano",profilePictureURL:"https://mts.intechopen.com/storage/users/187893/images/system/187893.jpg",biography:"DPhil Maria Jose Hernandez Serrano is a tenured Lecturer in the Department of Theory and History of Education at the University of Salamanca (Spain), where she currently teaches on Teacher Education. She graduated in Social Education (2000) and Psycho-Pedagogy (2003) at the University of Salamanca. Then, she obtained her European Ph.D. on Education and Training in Virtual Environments by research with the University of Manchester, UK (2009). She obtained a Visiting Scholar Postdoctoral Grant (of the British Academy, UK) at the Oxford Internet Institute of the University of Oxford (2011) and was granted with a postdoctoral research (in 2021) at London Birbeck University.\n \nShe is author of more than 20 research papers, and more than 35 book chapters (H Index 10). She is interested in the study of the educational process and the analysis of cognitive and affective processes in the context of neuroeducation and neurotechnologies, along with the study of social contingencies affecting the educational institutions and requiring new skills for educators.\n\nHer publications are mainly of the educational process mediated by technologies and digital competences. Currently, her new research interests are: the transdisciplinary application of the brain-based research to the educational context and virtual environments, and the neuropedagogical implications of the technologies on the development of the brain in younger students. Also, she is interested in the promotion of creative and critical uses of digital technologies, the emerging uses of social media and transmedia, and the informal learning through technologies.\n\nShe is a member of several research Networks and Scientific Committees in international journals on Educational Technologies and Educommunication, and collaborates as a reviewer in several prestigious journals (see public profile in Publons).\n\nUntil March 2010 she was in charge of the Adult University of Salamanca, by coordinating teaching activities of more than a thousand adult students. She currently is, since 2014, the Secretary of the Department of Theory and History of Education. Since 2015 she collaborates with the Council Educational Program by training teachers and families in the translation of advances from educational neuroscience.",institutionString:"University of Salamanca",position:null,outsideEditionCount:0,totalCites:0,totalAuthoredChapters:"0",totalChapterViews:"0",totalEditedBooks:"0",institution:{name:"University of Salamanca",institutionURL:null,country:{name:"Spain"}}}],coeditorOne:null,coeditorTwo:null,coeditorThree:null,coeditorFour:null,coeditorFive:null,topics:[{id:"23",title:"Social Sciences",slug:"social-sciences"}],chapters:null,productType:{id:"1",title:"Edited Volume",chapterContentType:"chapter",authoredCaption:"Edited by"},personalPublishingAssistant:{id:"301331",firstName:"Mia",lastName:"Vulovic",middleName:null,title:"Mrs.",imageUrl:"https://mts.intechopen.com/storage/users/301331/images/8498_n.jpg",email:"mia.v@intechopen.com",biography:"As an Author Service Manager, my responsibilities include monitoring and facilitating all publishing activities for authors and editors. From chapter submission and review to approval and revision, copyediting and design, until final publication, I work closely with authors and editors to ensure a simple and easy publishing process. I maintain constant and effective communication with authors, editors and reviewers, which allows for a level of personal support that enables contributors to fully commit and concentrate on the chapters they are writing, editing, or reviewing. I assist authors in the preparation of their full chapter submissions and track important deadlines and ensure they are met. I help to coordinate internal processes such as linguistic review, and monitor the technical aspects of the process. As an ASM I am also involved in the acquisition of editors. Whether that be identifying an exceptional author and proposing an editorship collaboration, or contacting researchers who would like the opportunity to work with IntechOpen, I establish and help manage author and editor acquisition and contact."}},relatedBooks:[{type:"book",id:"6942",title:"Global Social Work",subtitle:"Cutting Edge Issues and Critical Reflections",isOpenForSubmission:!1,hash:"222c8a66edfc7a4a6537af7565bcb3de",slug:"global-social-work-cutting-edge-issues-and-critical-reflections",bookSignature:"Bala Raju Nikku",coverURL:"https://cdn.intechopen.com/books/images_new/6942.jpg",editedByType:"Edited by",editors:[{id:"263576",title:"Dr.",name:"Bala",surname:"Nikku",slug:"bala-nikku",fullName:"Bala Nikku"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}},{type:"book",id:"1591",title:"Infrared Spectroscopy",subtitle:"Materials Science, Engineering and Technology",isOpenForSubmission:!1,hash:"99b4b7b71a8caeb693ed762b40b017f4",slug:"infrared-spectroscopy-materials-science-engineering-and-technology",bookSignature:"Theophile Theophanides",coverURL:"https://cdn.intechopen.com/books/images_new/1591.jpg",editedByType:"Edited by",editors:[{id:"37194",title:"Dr.",name:"Theophanides",surname:"Theophile",slug:"theophanides-theophile",fullName:"Theophanides Theophile"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}},{type:"book",id:"3092",title:"Anopheles mosquitoes",subtitle:"New insights into malaria vectors",isOpenForSubmission:!1,hash:"c9e622485316d5e296288bf24d2b0d64",slug:"anopheles-mosquitoes-new-insights-into-malaria-vectors",bookSignature:"Sylvie Manguin",coverURL:"https://cdn.intechopen.com/books/images_new/3092.jpg",editedByType:"Edited by",editors:[{id:"50017",title:"Prof.",name:"Sylvie",surname:"Manguin",slug:"sylvie-manguin",fullName:"Sylvie Manguin"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}},{type:"book",id:"3161",title:"Frontiers in Guided Wave Optics and Optoelectronics",subtitle:null,isOpenForSubmission:!1,hash:"deb44e9c99f82bbce1083abea743146c",slug:"frontiers-in-guided-wave-optics-and-optoelectronics",bookSignature:"Bishnu Pal",coverURL:"https://cdn.intechopen.com/books/images_new/3161.jpg",editedByType:"Edited by",editors:[{id:"4782",title:"Prof.",name:"Bishnu",surname:"Pal",slug:"bishnu-pal",fullName:"Bishnu Pal"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}},{type:"book",id:"72",title:"Ionic Liquids",subtitle:"Theory, Properties, New Approaches",isOpenForSubmission:!1,hash:"d94ffa3cfa10505e3b1d676d46fcd3f5",slug:"ionic-liquids-theory-properties-new-approaches",bookSignature:"Alexander Kokorin",coverURL:"https://cdn.intechopen.com/books/images_new/72.jpg",editedByType:"Edited by",editors:[{id:"19816",title:"Prof.",name:"Alexander",surname:"Kokorin",slug:"alexander-kokorin",fullName:"Alexander Kokorin"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}},{type:"book",id:"1373",title:"Ionic Liquids",subtitle:"Applications and Perspectives",isOpenForSubmission:!1,hash:"5e9ae5ae9167cde4b344e499a792c41c",slug:"ionic-liquids-applications-and-perspectives",bookSignature:"Alexander Kokorin",coverURL:"https://cdn.intechopen.com/books/images_new/1373.jpg",editedByType:"Edited by",editors:[{id:"19816",title:"Prof.",name:"Alexander",surname:"Kokorin",slug:"alexander-kokorin",fullName:"Alexander Kokorin"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}},{type:"book",id:"57",title:"Physics and Applications of Graphene",subtitle:"Experiments",isOpenForSubmission:!1,hash:"0e6622a71cf4f02f45bfdd5691e1189a",slug:"physics-and-applications-of-graphene-experiments",bookSignature:"Sergey Mikhailov",coverURL:"https://cdn.intechopen.com/books/images_new/57.jpg",editedByType:"Edited by",editors:[{id:"16042",title:"Dr.",name:"Sergey",surname:"Mikhailov",slug:"sergey-mikhailov",fullName:"Sergey Mikhailov"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}},{type:"book",id:"371",title:"Abiotic Stress in Plants",subtitle:"Mechanisms and Adaptations",isOpenForSubmission:!1,hash:"588466f487e307619849d72389178a74",slug:"abiotic-stress-in-plants-mechanisms-and-adaptations",bookSignature:"Arun Shanker and B. Venkateswarlu",coverURL:"https://cdn.intechopen.com/books/images_new/371.jpg",editedByType:"Edited by",editors:[{id:"58592",title:"Dr.",name:"Arun",surname:"Shanker",slug:"arun-shanker",fullName:"Arun Shanker"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}},{type:"book",id:"878",title:"Phytochemicals",subtitle:"A Global Perspective of Their Role in Nutrition and Health",isOpenForSubmission:!1,hash:"ec77671f63975ef2d16192897deb6835",slug:"phytochemicals-a-global-perspective-of-their-role-in-nutrition-and-health",bookSignature:"Venketeshwer Rao",coverURL:"https://cdn.intechopen.com/books/images_new/878.jpg",editedByType:"Edited by",editors:[{id:"82663",title:"Dr.",name:"Venketeshwer",surname:"Rao",slug:"venketeshwer-rao",fullName:"Venketeshwer Rao"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}},{type:"book",id:"4816",title:"Face Recognition",subtitle:null,isOpenForSubmission:!1,hash:"146063b5359146b7718ea86bad47c8eb",slug:"face_recognition",bookSignature:"Kresimir Delac and Mislav Grgic",coverURL:"https://cdn.intechopen.com/books/images_new/4816.jpg",editedByType:"Edited by",editors:[{id:"528",title:"Dr.",name:"Kresimir",surname:"Delac",slug:"kresimir-delac",fullName:"Kresimir Delac"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}}]},chapter:{item:{type:"chapter",id:"71636",title:"An Overview of Carbon-Based Materials for the Removal of Pharmaceutical Active Compounds",doi:"10.5772/intechopen.91934",slug:"an-overview-of-carbon-based-materials-for-the-removal-of-pharmaceutical-active-compounds",body:'\nIn recent years, there is great concern about the occurrence and the impact of the pharmaceutical active compounds in water, in addition, development of efficient and cost-effective technologies for the removal of these compounds and treatment of industrial effluent, surface water and ground water. Pharmaceutical active compounds are natural or synthetic chemicals that can be found in over-the-counter therapeutic drugs and veterinary drugs. They induce pharmacological effect and give significant benefits to human beings. A continuous release of these chemical compounds into aquatic environment has been increased due to the increase of general use of pharmaceutical compounds in human and veterinary medicines. Figure 1 illustrates the routes of releasing the pharmaceutical compounds into water. These routes include wastewater effluents, human and animal excreta, sewage sludge, medical and industrial waste and land fill leaching [1].
\nRoutes of releasing the pharmaceutical compounds into the environment.
Depending on the biodegradability and hydrophobicity of these pharmaceutical active compounds, they are naturally reduced by dilution, degradation and adsorption in the environment. Thus, these compounds in water exist in a trace concentration level [2].
\nSome of the pharmaceutical active compounds used for birth control, heart medication and painkilling were detected in wastewater in the United State of America (USA) since more than 40 years ago [3, 4, 5]. Literature shows that the pharmaceutical active compounds enter the surface water through different sources such as excretion, bathing, effluent discharging, improper disposal of these compounds and veterinary facilities [1, 6, 7, 8]. In addition, a study conducted in the United Kingdom by Drinking Water Inspectorate reported that many classes of pharmaceutical active compounds are present in wastewater influent [9]. Table 1 represents several pharmaceutical active compounds that were detected in the aquatic environment of United Kingdom (UK) and other European countries [10, 11].
\nPharmaceutical active compounds | \nMaximum detected concentration (ng/L) | \nAquatic environment type | \n
---|---|---|
Bleomycin | \n19 (United Kingdom) | \nSewage | \n
Clotrimazole | \n34 (United Kingdom) | \nStream or river water | \n
Diclofenac | \n1200 (Germany) 41 (France) 40 (Finland) 64 (Austria) | \nSurface water | \n
Carbamazepine | \n110 (Germany) 800 (France) 370 (Finland) 64 (Austria) | \nSurface water | \n
Iopromide | \n910 (Germany) 17 (France) 211 (Austria) | \nSurface water | \n
Roxithromycin | \n560 (Germany) 37 (France) | \nSurface water | \n
Ibuprofen | \n530 (Germany) 120 (France) 65 (Finland) | \nSurface water | \n
Erythromycin | \n80 (United Kingdom) | \nRiver water | \n
Fluoxetine | \n290 (United Kingdom) | \nSewage | \n
Mefenamic acid | \n1440 (United Kingdom) | \nSewage | \n
Paracetamol | \n< 20 (United Kingdom) | \nSewage | \n
Propranolol | \n215 (United Kingdom) | \nRiver water | \n
Tamoxifen | \n42 (United Kingdom) | \nSewage | \n
Tetracycline | \n1000 (United Kingdom) | \nRiver water | \n
Trimethoprim | \n1288 (United Kingdom) | \nSewage | \n
The measured concentration of some pharmaceutical active compounds in some of the aquatic environment in European countries.
Pharmaceutical active compound | \nCarbon-based adsorbent | \nAdsorption capacity (mg/g) | \nReference | \n
---|---|---|---|
Clofibric acid | \nMesoporous silica SBA-15 | \n70 | \n[70] | \n
Ofloxacin | \nNonporous SiO2\n | \n2.1 | \n[71] | \n
Tetracycline | \nMesoporous silica | \n44.4 | \n[27] | \n
Cephalexin | \nAmberlite XAD-16 polymer | \n116 | \n[36] | \n
Nalidixic acid | \nPolystyrene-divinylbenzene, X16 | \n800 | \n[31] | \n
Penicillin | \nPolymer Amberlite XAD-16 | \n1401 | \n[34] | \n
Amoxicillin | \nBentonite clay | \n53.9 | \n[38] | \n
Flurbiprofen | \nOrganophilic montmorillonite clay | \n240 | \n[39] | \n
Tetracycline | \nNa-kaolinite | \n29 | \n[40] | \n
Kaolinite | \n3.8 | \n[72] | \n|
Rectorite clay | \n40 | \n[46] | \n|
Tetracycline | \nNaOH-activated carbon produced from macadamia nut shells | \n455.33 | \n[48] | \n
H3PO4-activated carbon produced from apricot nut shells | \n308.3 | \n[49] | \n|
Activated carbons produced by KOH activation of tyre pyrolysis char | \n312 | \n[50] | \n|
Commercial activated carbon | \n471 | \n[51] | \n|
Sulfamethoxazole | \nAC | \n185 | \n[53] | \n
Metronidazole | \nAC | \n93.21 | \n[53] | \n
CAC | \n328 | \n[52] | \n|
Amoxicillin | \nAC | \n221.8 | \n[73] | \n
Dimetridazole | \nCAC | \n186 | \n[52] | \n
Ronidazole | \nCAC | \n394 | \n[52] | \n
Tinidazole | \nCAC | \n385 | \n[52] | \n
Penicillin G | \nAC | \n315 | \n[56] | \n
Oxytetracycline | \nMWNT10 | \n190.2 | \n[54] | \n
Tetracycline | \nMWNTs | \n148 | \n[58] | \n
SWNTs | \n370 | \n||
Tylosin | \nK-MWNTs | \n270 | \n[58] | \n
K-SWNTs | \n466 | \n||
Carbamazepine | \nMWNT100 | \n41.4 | \n[58] | \n
Cephalexin | \nCellulose oxide | \n79 | \n[59] | \n
Fluoroquinolone | \nGoethite | \n49.6 | \n[61] | \n
Ciprofloxacin | \nHydrous oxides of Al (HAO) | \n13.6 | \n[64] | \n
Different adsorbents and their adsorption capacities for removal of pharmaceutical active compounds.
There is no international standard method for drinking water sampling and method of analysis for pharmaceutical active compounds. In addition, a few systematic monitoring studies on measuring the pharmaceutical active compounds in surface water, drinking water and ground water were conducted. Therefore, limited data are available on their occurrence in these aquatic environments to be used in assessing the potential health risk due to the exposure to a trace concentration level of pharmaceutical compounds. However, literature showed that the surface water and ground water sources affected by wastewater discharges have pharmaceutical active compound concentrations less than 100 ng/L, while these compounds were found in the drinking water with a concentration less than 50 ng/L [2].
\nThe presence of these compounds at trace concentration levels (nanogram to sub microgram per liter) in the aquatic environment has raised a question concerning the efficiency of wastewater treatment techniques in removing of the pharmaceutical active compounds. Many removal techniques such as chlorination, photocatalysis, adsorption, biodegradation and advanced oxidation or ozonation have been investigated for the removal of pharmaceutical active compounds from the aquatic environment [12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25]. Some of these techniques have different disadvantages such as their high cost, high energy consumption and formation of toxic by-products. Adsorption technique has many advantages over these techniques such as it works at mild operation conditions, requires low energy and is efficient and cost-effective. Therefore, it is a promising technique for the removal of pharmaceutical active compounds.
\nThe removal of pharmaceutical active compounds from water by adsorption is considered as one of the easiest and safest techniques since it is easy to design and operate and this technique does not produce any toxic wastes as a by-product and is capable of removing most forms of organic material. The adsorption process includes the accumulation of pharmaceutical compounds on the adsorbent’s surface. Hence, the selection of adsorbent must be precious. The adsorbent must have a capability to accumulate the pollutant from water with high surface area and high hydrophobicity. The efficiency of this technique is mainly depending on the functional group composition, surface area, pore size and the ash content. It also depends on the chemical parameters like temperature, polarity, pH, concentration of the adsorbate and the availability of other competing solutes. The adsorption process also depends on the mobility of the adsorbate molecules toward the external boundary layer of the adsorbent, active surface sites and surface pore size. Many researchers have studied the adsorption of pharmaceutical active compounds from wastewater using different types of adsorbents. Several materials as an adsorbent have been reported in the literature and listed in Table 2 and were tested and investigated for the pharmaceutical active compounds’ removal from aquatic environment, such as silica-based adsorbents [26, 27, 28, 29, 30], polymeric materials [31, 32, 33, 34, 35, 36, 37], clay [38, 39, 40, 41, 42, 43, 44, 45, 46, 47], carbonaceous materials [48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58] and other materials [59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71]. The next sections focus on carbonaceous materials as adsorbents, namely activated carbon and carbon nanotubes.
\nActivated carbon is a pure carbon graphite form with amorphous and highly porous structure. It contains different range of pore sizes starting from cracks to slits of molecular dimensions [73]. The first produced commercially activated carbon was in early nineteenth century from wood as a raw material. It has been used for water odor and taste control in 1930 [74]. Nowadays, activated carbon is produced from a wide range of raw organic materials and sources, such as sugar, shells, refinery coke, rice hulls and different types of wood. The main features of activated carbon that make it good as an adsorbent in the adsorption process are the following: (i) its high surface area, (ii) its porosity and (iii) its surface reactivity.
\nActivated carbon can be classified based on its activation process or its properties. Based on the activation process, the following are the main two categories based on the activation process:
Physically or thermally activated carbon: the activation process involves carbonization of organic raw materials at temperature ranging from 500°C to 600°C [75].
Chemically activated carbon: the activation process involves addition of some inorganic salts such as metallic chloride to activate the surface of carbon [76].
Mattson et al. [77] suggested another classification, which categorizes activated carbon to acidic or basic activated carbon:
Carbon activated at low temperature range from 200°C to 400°C: this develops an acidic surface that lowers the pH value of the solution. This activated carbon exhibits negative zeta potential and usually adsorbs basic and hydrophilic compounds.
Carbon activated at a high temperature range from 800°C to 1000°C: this develops basic surface that increases the pH value of the solution. Therefore, this type of activated carbon has a positive zeta potential and is usually used for adsorbing acidic organic compounds.
Commercially, activated carbon can be classified as three main types [78], and they are the following:
Powdered activated carbon (PAC): it has fine granules or powder with particle size less than 1.0 mm and average diameters ranging between 0.15 and 0.25 mm.
Granular activated carbon (GAC): it combines powdered activated carbon with a binder and forms cylindrical shape activated carbon particles with diameters from 0.8 to 130 mm. The main application for this form is for gas purification.
Impregnated activated carbon (IAC): it is impregnated with different inorganic ions.
Polymeric coated activated carbon, which is used in medical field applications.
The properties of activated carbon are influenced by the used raw materials and activation method in its preparation process. The porous graphite and graphene sheets that form the activated carbon are connected together and have π-orbitals in the benzene rings, which enable several modifications to be carried out on activated carbon. For example, cooling the activated carbon in the presence of oxygen can produce activated carbon rich with oxides and acidic functional groups, as a result, alter the positive zeta potential of basic activated carbon to negative to be used for different applications. In addition, the surface chemistry, pore structure (volume and diameter) and surface area of activated carbon depend significantly on the employed temperature in the preparation process [75, 79].
\nA wide range of raw materials can be used as a starting material for producing activated carbon as stated in Section 2.1.1. The following activation methods are used in activated carbon production:
Thermal activation: this physical process may involve two main steps: the first one to eliminate the volatile matters in the raw materials by carbonizing them thermally at a temperature ranging from 500°C to 600°C and in the second step the porosity and surface are improved by the gasification process. In the gasification process, a carbon dioxide CO2, methane or steam as an oxidizing gas is used at a high temperature of 800–1000°C [75].
Chemical activation: in this process, inorganic salts such as metallic chloride are added before the carbonization step to improve the micro-porosity as well as the surface area of the activated carbon [76].
Activated carbon (AC) is widely used in adsorption processes as filtration and purification materials. For instance, in water treatment, activated carbon is used to control taste and odor and to adsorb undesired suspended metals and pollutants [74]. Due to the high surface area and commercial availability of AC, it was studied for removal of different pharmaceutical active compounds. Table 3 summarizes some of these pharmaceuticals. For example, different types of activated carbon were used for removal of tetracycline (antibiotic drug) from aqueous media. Martins et al. [48] prepared activated carbon from macadamia shells as precursors, the yield was 19.79% and the prepared activated carbon’s surface area was 1524 m2/g. They used it for the tetracycline removal and it had 455.33 mg/g adsorption capacity. Muthanna et al. [80] reported that the activated carbon was used for removal of three pharmaceutical active compounds (i.e., tetracycline, penicillins and quinolones) and the used activated carbon has 1340.8 mg/g adsorption capacity for tetracycline. Chen et al. [81] studied the effect of the adsorption parameters (i.e., pH, contact time, initial concentration and temperature) on the removal of tetracycline from aqueous solution using rice husk ash (RHA). They found the adsorption capacity increased from 1.51 to 3.41 mg/g when the initial tetracycline concentration in the solution increased from 5 to 20 mg/l. Another study showed that activated carbon prepared via a chemical activation of apricot shells using phosphoric acid heated in air at 100 °C for 24 hours has 307.6 m2/g surface area and 308.3 mg/g adsorption capacity [49]. In 2016, an activated carbon (TPC-AC) was prepared from tires waste by their pyrolysis and then activated using potassium hydroxide [50]. The prepared adsorbent was tested for tetracycline removal and it has been found that the adsorption process was spontaneous and has adsorption capacity (312 mg/g) higher than the commercial activated carbon. Carl et al. [51] reported that the adsorption capacity of the commercial activated carbon for tetracycline is directly related to the density of π electrons in the graphene layers on activated carbon and the aromatic ring in the tetracycline.
\nSingle and multiwall carbon nanotube (CNT) materials are graphene sheets rolled-up tubular individually or more than one inside each other. CNTs were discovered by Sumio Ijima in 1991 at NEC Laboratory in Japan using the Arc discharge production method and then characterized using a transmission electron microscope [82]. CNTs have two different structures based on the rolling direction of graphene sheets: (i) armchair nanotube and (ii) zigzag nanotube structure [83] as shown in Figure 2.
\nArmchair and zigzag structural forms of CNTs
The cylindrical shape of CNT nanostructure can have a length to diameter ration up to 132,000,000:1, which is significantly higher than any other materials [83]. This property was explained by the sp2 hybridization in the carbon atoms that CNTs are composed of in addition to the natural alignment of CNT into ropes attracted together by Van der Waals interaction [84].
\nCNTs form bundles of a highly complex network [85]. They have electrical conductivity that depends on the arrangement of the hexagonal rings along the tubular surface. Due to their extraordinary properties, such as large geometric aspect ratio, nanocavities and electrical conductivity, CNTs are considered as attractive candidates in many nanotechnological applications, including the removal of pharmaceutical compounds in water treatment processes. One of the main drawbacks of carbon nanotubes is that they do not have good suspension properties in aqueous and organic solvents that in turn has made CNTs’ use in industry limited [86]. This disadvantage can be overridden by modifying CNTs chemically with some hydrophilic functional groups that in turn increase CNTs’ suspension in water.
\nThe main distinct properties of the carbon nanotubes are categorized into the following:
Mechanical properties: due to the covalent sp2 bonds formed between the individual carbon atoms, CNTs have high strength and stiffness. According to the reported results, CNTs have elasticity higher than steel by 10–100 times with an elastic modulus 1Tpa [87]. A comparison between some materials, which have good mechanical properties, with CNTs is shown in Table 3.
Physical property | \nMaterial name | \n||||
---|---|---|---|---|---|
\n | MWCNTs | \nSWCNTs | \nWood | \nSteel | \nEpoxy | \n
Density (g/cm3) | \n2.6 | \n2.6 | \n0.6 | \n7.8 | \n1.25 | \n
Tensile strength (Gpa) | \n150 | \n150 | \n0.008 | \n0.4 | \n0.005 | \n
Young’s modulus (Gpa) | \n1200 | \n1054 | \n0.6 | \n208 | \n3.5 | \n
Comparison between CNTs and other materials.
Thermal conductivity: CNTs have thermal conductivity ranging from 2800 up to 6000 W/m K [88].
Electrical properties: CNT carbon-based material exhibits extraordinary electrical properties and it can be conducting or semiconducting material. The conductive CNTs are found to carry electrical current thousand times higher than copper material [89].
Chemical reactivity: CNTs can chemically be modified to make them highly soluble in aqueous and organic solutions as well as more efficient for certain applications. Their reactivity is related to the mismatching of π-orbitals, which are caused by the curvatures in CNTs’ structure. In general, smaller nanotube diameters result in increasing their reactivity. Moreover, the reported results showed that chemical modification of sidewalls or end caps of CNTs are also possible [90].
Based on the CNTs’ properties that have been discussed above, CNT materials and their modified structures are promising for different applications such as water treatment, environmental protection and pharmaceutical active compound removal, material science, medicinal chemistry and others.
\nCNTs are produced using different techniques, and the most common and widely used techniques are:
\nArc discharge technique. Arc discharge technique is the most common and simplest technique for CNT production. As mentioned earlier, CNTs were firstly discovered using this technique. In arc discharge technique, CNTs are produced at low pressure of helium inert gas or any other neutral gas [91]. They are produced through arc vaporization of two separated carbon rods in an enclosed system filled with inert gas [92]. One of the major disadvantages of CNT production using this technique is that the produced CNTs are not pure containing some of the catalytic metals; therefore, they require purification to remove these metals and get clean CNTs.
Laser ablation technique. In 1995, carbon nanotubes were synthesized using a laser beam to vaporize graphite at 1200°C [93]. The pulsed and continuous laser methods are the main two types of laser ablations. Much higher light intensity (100 kW/cm2) is used in the pulsed laser, compared to 12 kW/cm2 in case of the continuous laser type, which is the main difference between these two laser ablation technique types. In the laser ablation method, CNTs are produced and collected on a cooler surface in the reactor system as the vaporized carbon is condensed. In this technique, SWCNTs can be produced from graphite electrodes by adding metal-based catalysts such as Co, Fe and Ni to the system. However, MWCNTs are the main product when a pure graphite electrode is used [94].
Chemical vapor deposition (CVD) technique. Chemical vapor deposition technique is a simple process and it is believed to be the easiest technique for industrial production of CNTs. In this method, the desired CNT type and quality can be produced by controlling the system production parameters such as temperature, type of catalyst and type of carbon source gases. CVD technique consists of two main steps (catalyst preparation step and then CNT synthesis). In general, to produce CNTs, methane and carbon monoxide gases are dissociated into reactive carbon atoms using an energy source, and then these reactive atoms diffuse over a substrate that is coated by transition metals as a catalyst and heated at a temperature range from 500 to 1000°C [95].
A comparison between the previously discussed methods for CNT production is summarized in Table 4.
\nMethod | \nYield (%) | \nSENT | \nMINT | \nConcerns | \n
---|---|---|---|---|
Chemical vapor deposition | \n20–100% | \nLong tubes with diameters 0.6–4 nm | \nLong tubes with diameters 10–240 nm | \nNets are usually mints and often riddled with defects | \n
Arc discharge | \n30–90% | \nShort tubes with diameters 0.6–1.4 nm | \nShort tubes with inner diameter 1–3 nm | \nShort tubes with random sizes and directions and required purification | \n
Laser ablation (Vaporization) | \nUp to 70% | \nLong bundles of tubes with diameters 1–2 nm | \nNot suitable and too expensive | \nCostly and required high power | \n
Comparison between the three methods in terms of CNT production efficiency, type of CNTs produced, and the current drawback of each technology.
Carbon nanotubes with their excellent properties show considerable adsorption capability for removal of pharmaceutical active compounds. A study in 2009 found that the single wall carbon nanotubes (SWNTs) are more efficient for removal of tetracycline from aqueous solutions than multiwall carbon nanotubes (MWNTs), graphite and activated carbon [58]. This finding was explained through the molecular sieving effect, whereas the tetracycline is bulky molecules failed to seep through inner pores, which indicates the important role of molecules’ size and their accessibility into pores in the adsorbent materials. In 2016, Yu et al. [96] studied the adsorption performance of MWNTs for removal of ciprofloxacin and found the maximum adsorption capacity is 20 mg/g, which was obtained at pH 4 and 240 min that was attributed by the π-π interaction rather than hydrogen bonding and interaction with oxygenated functional groups on MWNTs. Another study by Yu et al. [97] showed that the maximum adsorption capacity of MWNTs for tetracycline was 269.54 mg/g, which achieved at 25°C and pH 5 within 80 min.
\nIn order to improve the performance and adsorption capacity of CNTs, different types of modifications can be performed such as graphitization, hydrolyzation, carboxylation and etching with potassium hydroxide (KOH). For example, Ji et al. [98, 99] modified the SWNTs and MWNTs by etching using KOH and tested the etched CNTs for three pharmaceutical active compounds (i.e., sulfamethoxazole, tetracycline and tylosin). They found the adsorption performance of the KOH modified SWNTs (K-SWNTs) and KOH modified MWNTs (K-MWNTs) for sulfamethoxazole and tetracycline was enhanced by around 56% and 84% compared to the unetched SWNTs and MWNTs, respectively. This has been explained by increasing the surface area of the etched CNTs.
\nGraphene is a two-dimensional carbonaceous nanomaterial formed from a layer of sp2 hybridized carbon atoms. The graphene nanomaterial has exceptional properties such as high specific surface area [98, 99], high electrocatalytic activity [100], great thermal conductivity [101], high stiffness and strength [102] and high speed electron mobility [103]. These unique physical properties attracted great interest of scientist and introduced it for different potential applications. Among these applications is the adsorptive removal of emerging pollutants such as pharmaceutical active compounds.
\nThe following are the common types of graphene:
Single layer graphene (SLG): it is one thick hexagonally arranged sp2 hybridized bonded carbon atoms. The dimensions of SLG vary from nano- to microscale. It can be suspended in an aqueous solution or adhered on a substrate.
Multilayer graphene (MLG): it consists of few flaks of single layer graphene and it is useful in the preparation of nanomaterial composites.
Graphene oxide: it is a single layer or multilayer graphene that has high oxygenated surface and prepared by exfoliation and chemical oxidation of graphite.
Reduced graphene oxide: it is that same as graphene oxide; however, the oxygenated functional groups are reduced chemically, thermally or biologically.
The graphene nanomaterials and their modified forms have extraordinary surface area and catalytic activity, and as a result, they can be used in several applications such as adsorptive removal of pharmaceutical active compounds [104, 105, 106, 107, 108, 109, 110, 111]. Gao et al. [106] investigated the adsorption performance of graphene oxide for tetracycline antibiotic from aqueous solution. They found that the adsorption of tetracycline achieved mainly through a π-π and cation-π interactions with a maximum monolayer adsorption capacity is 313 mg/g and it decreased with an increase in the solution pH or the sodium ions concentration. In 2017, Danna et al. [107] modified a graphene oxide with decafluorobiphenyl and then investigated the prepared adsorbent for removal of six pharmaceutical active compounds from water namely, carbamazepine, sulfamethoxazole, sulfadiazine, ibuprofen, paracetamol and phenacetin. They found that the adsorption capacities for these compounds are 340.5 μmol/g, 428.3 μmol/g, 214.7 μmol/g, 224.3 μmol/g, 350.6 μmol/g and 316.1 μmol/g, respectively. A study in 2014 showed that the adsorptive removal of acetaminophen, aspirin and caffeine from aqueous solution using graphene nanoplates (GNPs) was thermodynamically spontaneous and exothermic with adsorption capacities of 18.07 mg/g, 12.98 mg/g and 19.72 mg/g for acetaminophen, aspirin and caffeine, respectively [105].
\nThe surface area of graphene reduces significantly in solutions due to its aggregation, and as a result, the adsorption capacity of graphene is reduced, which is one of the main disadvantages associated with using graphene as adsorbents. Functionalization or modification of the graphene with certain functional group or metals can be the best solution to overcome that disadvantage as well as increase the adsorption capacity of graphene. Lin et al. [108] functionalized a graphene oxide with magnetic nanoparticles and then studied its adsorptive removal for four tetracycline (TC) pharmaceutical active compounds (i.e., tetracycline, oxytetracycline, chlortetracycline and doxycycline) from aqueous solution. They found that the solution pH and ionic strength had insignificant effect on the TC adsorption and the maximum adsorption capacity is 39.1 mg/g.
\nPharmaceutical active compounds are continuously released into aquatic environment via different routes (i.e., human and animal excreta, medical industry’s waste, wastewater effluent, sewage and landfill leaching). That release increases due to the increase of general use of pharmaceutical compounds in human and veterinary medicines. Therefore, these compounds should be removed from the contaminated water to prevent their accumulation, reduce the environmental pollution and provide an additional source of clean water. Removal of pharmaceutical active compounds from aquatic media can be achieved by either conventional or advanced methods. Among them, the adsorption technique has many advantages over the others. Several materials as adsorbents have been reported and discussed in the literature such as silica-based adsorbents, polymeric materials, clay, carbonaceous materials and other materials. Activated carbon, carbon nanotube and graphene oxide among carbonaceous materials show excellent performance and high adsorption capacity for pharmaceutical active compounds. As discussed in this chapter, the activated carbon can be activated using different methods (i.e., physical or chemical activation), while the carbon nanotube can be produced through using one of the following methods: (i) arc discharge, (ii) laser ablation and (iii) chemical vapor deposition. The physical (surface area and porosity) and chemical (functional groups) properties are significantly affected by the followed production method for these carbonaceous materials. Using freely available raw materials for the activated carbon and carbon nanotubes production and their modification with different nanoparticles and functional groups is the future prospect for the adsorptive removal of pharmaceutical active compounds from the aquatic environment.
\nThe support of the Center for Environment and Water in the research institute of King Fahd University of Petroleum and Minerals is highly acknowledged.
\nThe author declares that there are no conflicts of interest.
The need to slow down and eventually stop global warming has driven commercial production of the bioethanol in the past two decades because the use of renewable fuel is one of the few ways to mitigate climate change as it helps reduce GHG emissions. Multiple independently produced datasets confirm that between 1880 and 2012, the global average land and ocean surface temperature increased by 0.85 [0.65–1.06]°C [1]. Since 1979 the rate of warming has approximately doubled (0.13°C/decade, against 0.07°C/decade) [2, 3]. The scientific consensus as of 2013 stated in the intergovernmental panel on climate change (IPCC) Fifth Assessment Report is that it “is extremely likely that human influence has been the dominant cause of the observed warming since the mid-20th century.” In 2018 the IPCC published a Special Report on Global Warming of 1.5°C which warned that, if the current rate of greenhouse gas (GHG) emissions is not mitigated, global warming is likely to reach 1.5°C between 2030 and 2052 causing major crises. The report said that preventing such crises will require a swift transformation of the global economy that has “no documented historic precedent” [4].
\nA mandate required developed countries to take the lead in reducing their emissions and was sustained in the Kyoto Protocol to the United Nations Framework Convention on Climate Change (UNFCCC), which entered into legal effect in 2005. In ratifying the Kyoto Protocol, most developed countries accepted legally binding commitments to limit their emissions. Biofuel mandates are set in more than 60 nations and incentives are provided by the governments to boost bioethanol production [5].
\nIn the U.S., production, transportation and fermentation of the corn was adapted quickly by industry for fuel ethanol production, primarily because corn was the only crop that had the existing infrastructure to easily modify for this purpose, especially when initially incentivized with tax credits, subsidies and import tariffs. Figure 1 shows total U.S. corn use from 1986 to 2018. The amount of corn used for ethanol production increased substantially between 2001 and 2010, as nearly all gasoline was transitioned to 10% ethanol. From 2013, the trend remains consistent with production and usage remaining relatively constant.
\nThe U.S. corn for fuel ethanol, feed, and other use. Source: the United States Department of Agriculture Economic Research Service Feed Grain Yearbook.
There is still some debate on whether biofuel production from food feedstock can truly reduce GHG emissions. The United Nations Intergovernmental Panel on Climate Change released two of its Working Group reports state that “Biofuels have direct, fuel-cycle GHG emissions that are typically 30–90% lower than those for gasoline or diesel fuels. However, since for some biofuels indirect emissions—including from land use change—can lead to greater total emissions than when using petroleum products, policy support needs to be considered on a case by case basis” (IPCC 2014 Chapter 8). The report lists many potential negative risks of ethanol production from food feedstock, such as direct conflicts between land for fuels and land for food, other land-use changes, water scarcity, loss of biodiversity and nitrogen pollution through the excessive use of fertilizers.
\nAlso, the potential of using bioethanol from food feedstock to replace petroleum fuels is limited. The United States will use over 130 billion gallons of gasoline in 2014, and over 50 billion gallons of diesel. On average, one bushel of corn can be used to produce just 2.8 gallons of ethanol. If all of the production of corn in the U.S. were converted into ethanol, it would only displace 25% of that 130 billion.
\nOn the other hand, there is less controversy over GHG reduction from production of lignocellulosic ethanol production as cellulosic materials are mostly the wastes of the agriculture and forest industry. The shift from food crop feedstocks to waste residues and native grasses offers significant opportunities for a range of players, from farmers to biotechnology firms, and from project developers to investors [6]. However, the process to convert lignocellulosic materials to ethanol is much more complex than that used to covert starch and sugars into ethanol.
\nCellulosic ethanol industry is still in its infancy. In the U.S., as of 2013, the first commercial-scale plants to produce cellulosic biofuels have begun operating. In the following 5 years, cellulosic ethanol production grown from 0 to 10 million gallons [7], and most likely topping 15 million in 2018. However, that is far from the Renewable Fuel Standard’s original target of 7 billion gallons of cellulosic biofuel by 2018 and 16 billion by 2022. Of all five commercial cellulosic ethanol plants that were built/to be built in the U.S. from 2010 to 2016, only POET’s Emmetsburg, Iowa facility is still in operation in 2019 (Table 1). In 2017, the total cellulosic ethanol produced was less than half the nameplate capacity (25 million gallons year−1) of this single plant [13].
\nCompany | \nLocation | \nFeedstock | \nCapacity (mg year−1) | \nStatus | \n
---|---|---|---|---|
Abengoa Bioenergy | \nHugoton, KS | \nWheat straw | \n25–30 | \n2013–2016 Bankrupt [8] | \n
BlueFire Ethanol | \nFulton, MS | \nMultiple sources 19 | \n20 | \nConstruction halted 2011 [9] | \n
DuPont | \nNevada, Iowa | \n\n | 30 | \nSold to Verbio in Nov. 2018 [10] | \n
Mascoma | \nKinross, MI | \nWood waste | \n20 | \nConstruction halted in 2013 [11] | \n
POET LLC | \nEmmetsburg, IA | \nCorn stover | \n20–25 | \nOperational in Sep. 2014 [12] | \n
The status of the U.S. commercial lignocellulosic ethanol facilities.
The future of bioethanol generation from lignocellulosic materials is not clear at this point of time. The sustainability of this renewable fuel business will depend on the success of development of cost-cutting technologies for every stage of lignocellulosic ethanol production.
\nFirst-generation biofuel includes biodiesel produced from vegetable oils through transesterification and bioethanol generated from food feedstock, mainly starchy materials (e.g., corn, wheat, barley, cassava, potato) and sucrose-containing feedstock (e.g., sugarcane, sugar beet, sweet sorghum) [14]. First-generation bioethanol is produced from fermentation of these starchy and sucrose-containing materials in four basic steps: enzymatic saccharification or hydrolysis of starch into sugars, microbial (yeast) fermentation of sugars, distillation, and dehydration.
\n\nFigure 2 shows global ethanol production by country or region, from 2007 to 2017. Together, the U.S. and Brazil produce 85% of the world’s ethanol. The vast majority of Brazil ethanol is produced from sugarcane.
\nGlobal ethanol production by country or region, from 2007 to 2017. Source: Renewable Fuels Association. Last updated October 2018.
The United States is the world’s leading producer of ethanol, with nearly 16 billion gallons in 2017 alone, mainly produced from corn. The annual U.S. production of ethanol from 1981 to 2018 is shown in Figure 3.
\nThe U.S. annual production of ethanol from 1981 to 2018 [15].
Second and subsequent generations of biofuels including bioethanol are produced from non-food raw materials [16]. Second-generation bioethanol is typically produced from sugars derived from lignocellulosic biomass. Various types of biomass have been studied for production of biofuels including agricultural wastes (e.g., corn stover, wheat straw, corn cob, rice husk, and sugar cane bagasse), energy crops which grow on low-quality soil (perennial grasses such as Miscanthus sinensis and M. giganteus and switchgrass), forest-based woody wastes (bark, sawdust, softwood trimmings and hardwood chips), waste from parks and gardens (leaves, grasses, and branches), municipal solid wastes such as food waste, kraft paper and paper sludge, the whey-a byproduct of the cheese industry, and crude glycerol from the biodiesel industry.
\nThe amount of available lignocellulosic biomass far exceeds the amount of food feedstock that can be used for biofuel production. However, the production of lignocellulosic bioethanol requires feedstock preparation prior to fermentation and finding/developing microbes that are able to hydrolyze polysaccharides and ferment sugars from cellulose and hemicellulose breakdown.
\nThe term third generation biofuel refers to biofuel derived from algae and has only recently enter the mainstream. Previously, algae were grouped with other non-food biomass types as feedstock for second generation biofuels. However, the uniqueness in algae’s production methods and potential of much higher yields of biofuel production warrants its separation from other types of non-food biomass to form their own category.
\nWhen it comes to the potential to produce fuel, algae is unique in several ways. First, algae produce an oil that can easily be refined into diesel or even certain components of gasoline [17]. Second, it can be genetically manipulated to produce a wide list of fuels including biodiesel, butanol, gasoline, methane, ethanol, vegetable oil, and jet fuel [18]. Third, it is also capable of producing outstanding yields. In fact, algae have been used to produce up to 9000 gallons of biofuel per acre, which is 10-fold what the best traditional feedstock have been able to generate. Yields as high as 20,000 gallons per acre are believed to be attainable. According to the US Department of Energy, yields of 10-fold high mean that only 0.42% of the U.S. land area would be needed to generate enough biofuel to meet all the U.S. needs.
\nAlgae do have a down side: they require large amounts of water, nitrogen and phosphorus to grow. So much that the production of fertilizer to meet the needs of algae used to produce biofuel would produce more greenhouse gas emissions than were saved by using algae-based biofuel. It also means the cost of algae-base biofuel is much higher than fuel from other sources. This single disadvantage means that the large-scale implementation of algae to produce biofuel will not occur for a long time, if at all. In fact, after investing more than $600 million USD into research and development of algae, Exxon Mobil came to the conclusion in 2013 that algae-based biofuels will not be viable for at least 25 years which was calculated on strictly economical term without considering the environmental impacts that have yet to be solved [19].
\nDry plant materials are mainly comprised of three types of biopolymers: cellulose, hemicellulose, and lignin. Cellulose and hemicellulose account for more than half of the entire dry biomass (see Table 2) [28]. Ethanol yield and conversion efficiency depend on the type of biomass, and benefit from a high content of cellulose and hemicellulose and low lignin content [29]. The domains of the three polymers in plant cell walls are connected strongly through covalent and hydrogen bonds. These bonds make lignocellulosic material resistant to degradation [30] and different methods of pretreatment [31].
\nBiomass | \nCellulose % | \nHemicellulose % | \nLignin % | \n
---|---|---|---|
Corn stover | \n37.5 | \n30 | \n10.3 [20] | \n
Corn cobs | \n33.6 | \n37.2 | \n19.3 [21] | \n
Sugarcane bagasse | \n45 | \n20 | \n30 [22] | \n
Grasses | \n25–40 | \n35–50 | \n10–30 [23] | \n
Switchgrass | \n31.98 | \n25.19 | \n18.13 [24] | \n
Wheat straw | \n35.9 | \n23.9 | \n19.3 [25] | \n
Oat straw | \n39.4 | \n27.1 | \n20.7 [23] | \n
Rice straw | \n44.3 | \n35.5 | \n20.4 [26] | \n
Rice husk | \n34.4 | \n29.3 | \n19.2 [27] | \n
Hardwood | \n\n | \n | \n |
Black locust | \n41.61 | \n17.66 | \n26.70 [24] | \n
Hybrid poplar | \n44.70 | \n18.55 | \n26.44 [24] | \n
Eucalyptus | \n49.50 | \n13.07 | \n27.71 [24] | \n
Hardwood stems | \n40–55 | \n24–40 | \n18–25 [23] | \n
Softwood-pine | \n44.55 | \n21.90 | \n27.67 [24] | \n
Nut shells | \n25–30 | \n25–30 | \n30–40 [23] | \n
Newspaper | \n40–55 | \n24–40 | \n18–25 [23] | \n
Biomass composition.
Cellulose is a β-glucan linear polymer of 500–14,000
Hemicellulose is a branched heteropolymer of different monosaccharides including pentoses (
C5 sugars such as xylose and arabinose are mostly found in xyloglucan, xylan, arabinan and arabinogalactan (substructures of pectin), which are components of polysaccharides in the plant cell wall [38]. Xylan is the largest hemicellulose component, consisted of β-1,4-linked xylose residues with side branches of α-arabinofuranose and α-glucuronic acids and contribute to cross-linking of cellulose microfibrils and lignin through ferulic acid residues [39].
\nLignin is a natural three-dimensional polymer (600–15,000 kda) bio-synthesized from phenylpropanoid units via radical reactions [40]. Lignin accounts for 20–35 wt% in woody biomass (40–50 wt% in bark) and 10–20 wt% in agricultural stems [41]. In lignin, phenolic units are connected by more than eight different linkages, among them arylglycerol β-aryl ether (β-O-4) is the dominant linkage in both softwood and hardwood in most plants, consisting of ~50% of spruce linkages and 60% of birch and eucalyptus linkage [42]. It has long been recognized as the major renewable source of aromatic chemicals such as phenols and aromatic hydrocarbons.
\nDue to the complex polymer structure and heterogeneity in the ways monomeric units are linked, lignin is particularly difficult to biodegrade, making it an undesirable component in plant cell walls for bioethanol production. In plant cell wall, lignin functions like a glue to hold all components together [43]. As such, its recalcitrant character makes this three-dimensional polymer molecule a physical barrier to the enzymes that act on cellulose and hemicellulose.
\nIn biorefinery, around 62 million tonnes of lignin is obtained in the commercial production of lignocellulosic ethanol. A large amount of lignin is also being generated in the pulp industry as lignin has also to be separated from cellulose for a different reason: the aromatic components in lignin can turn yellow as it is oxidized slowly in air. Despite that lignin has mainly been burned to supply heat and to generate electricity, it has long been recognized as the major renewable source of aromatic polymer and chemicals [44].
\nDue to the lower oxygen content in lignin as compared to that in cellulose, the energy value of lignin could be as high as cellulose despite of its lower weight percentage in lignocellulosic biomass. This has generated a lot of interest in converting lignin into liquid fuels using thermochemical and biological methods including pyrolysis, hydrothermal liquefaction, and enzymatic decomposition [45]. Among these methods, hydrothermal liquefaction has been more investigated recently and appears to be a promising way to decompose lignin into bio oil which could be further processed into liquid transportation fuels.
\nSecond-generation bioethanol is produced using a process involving the four primary steps of (i) pre-treatment, (ii) hydrolysis to sugars, (iii) fermentation, and (iv) product/coproduct recovery [46]. During pre-treatment, the feedstock is subjected to physical (heat, steam) or chemical (acid or base) conditions that disrupt the fibrous matrix of the material, resulting in the separation of the hemicelluloses from the cellulose chains and the lignin that binds them together. Hydrolysis follows pre-treatment, releasing individual glucose from cellulose and hexose and pentose from hemicellulose. These monomers can then be fermented to ethanol by yeasts that have been modified to ferment both hexose and pentose sugars and adapted to deal with the inhibitors that are produced during pre-treatment and unavoidably associated with the hexose and pentose sugars [34]. Distillation and dehydration of the aqueous ethanol solution produces ethanol of 99.9% purity. Coproduct recovery will depend upon the feedstock and pre-treatment process used and can include a range of products such as extractives, lignin, and unhydrolyzed cellulose [47].
\nIn the following three sections (Sections 4–7), each of the four primary steps will be reviewed. Current topics of research, which are concentrated on recombinant fermentative microbes development and a consolidated process of hydrolysis and co-fermentation of hexoses and pentoses, will be covered in Section 8. A review on cost analysis is given in Section 9 to present opportunities for cost reduction for second-generation bioethanol production.
\nWithout pretreatment before the enzymatic saccharification stage, the non-biodegradable lignin in lignocellulosic material presents as a major obstacle to the enzymatic hydrolysis of crystalline cellulose and hemicellulose which themselves already have low digestibility [48]. Pretreatment removes or decomposes the lignin (delignification) [49] and thus makes cellulose and hemicellulose more readily available to cellulases and hemicellulose’s.
\nIn principle, there are three methods for pretreatment: biological, chemical and physical processes. Some processes, where chemical and physical actions are inherently inseparable, are termed physiochemical. Two or all of these basic methods can be used in combination to gain benefits from each method. Various pretreatment methods have been described and compared critically in a recent review [50].
\nBiological treatment uses microorganisms such as white, brown or soft rot fungi which break up the structure of lignin via the action of extracellular lignolytic enzymes released by the fungi [51]. Further research is needed to overcome the issues of selectivity, cost, retention time and effectiveness to make it a practical choice [50].
\nChemical treatments include treatment with bases, diluted acids, and oxygen as an oxidizer. These reagents react with lignin and cause the polymer to breakdown into smaller and more soluble fragments. Physical pretreatment is usually performed before chemical or biological treatment to reduces cell wall crystallinity and particle size by physical milling or grinding [50]. In some treatment methods, both physical action and chemical reaction play important roles in lignin removal. Such physicochemical pretreatment can involve steam explosion, liquid hot water, ammonia fiber explosion, ammonia recycle percolation or a supercritical carbon dioxide.
\nPretreatment contributes a vital role in the cost evaluation process of whole technology, because they contribute about 30–35% of overall production cost [52]. There are many issues that arise from this process [50] including loss of sugars (mainly pentose sugars derived from hemicellulose degradation), and generation of toxic substances that inhibits the downstream fermentation process. Both need to be minimized to make ethanol production more efficient.
\nSteam explosion has become one of the most adopted pretreatment processes, where hydrolysis of hemicellulose also happens which improves cellulose digestibility. It is a physiochemical method that uses both physical changes caused by sudden pressure reduction and heat- and catalyst-induced chemical changes. An impregnation agent is sometimes used before the pretreatment step. Upon steam explosion after 1–5 min soaking in 160–270°C and 20–50 bar steam, fibers loose up and sugar polymers (mainly hemicellulose) partially degrade into sugars via hydrolysis of glycoside bonds in polysaccharides and lignin into soluble fragments including some inhibitors and phenolic products [50]. The process allows for subsequent solubilization of hemicellulose in water and lignin in organic or alkaline solvent. Cellulose undergoes some degree of polymerization but is still insoluble in water or organic solvents and remains in the solid phase. Acid (sulfuric acid and sulfur dioxide) impregnation before steam explosion reduce the time and temperature necessary for proper depolymerization of the feedstock, increases the efficiency of enzymatic hydrolysis of polysaccharides to glucose and xylose and reduce enzyme consumption [53]. Compared to other methods of biomass fractionation, steam explosion uses less dangerous chemicals, less demanding on investment and energy consumption [54]. Steam explosion is not recommended for agricultural and hardwood wastes with high contents of pentoses and low levels of lignin, due to the susceptibility of pentoses to thermal degradation. Steam explosion is recommended for processing straw and bagasse.
\nOne of the lasting issues in the second-generation bioethanol production is the formation of inhibitors during the pretreatment. The inhibitors create unfriendly environments for fermentative microbes, increases the length of lag phase, causes loss of cell density and lower growth rates of fermenting microbes, and consequently decreases ethanol yields [55]. The commonly observed inhibitors are aldehydes such as 5-hydroxymethyl-2-furaldehyde and 2-furaldehyde (furfural), weak organic acids (formic, acetic and levulinic acids) and phenolic compounds [56]. Acetic acid is the major organic acid found in hydrolysates coming from the hydrolysis of acetyl side-chain groups in hemicellulose [57]. Cell growth of fermentative microbes is inhibited by the intracellular process of anions of weak acids. Furan aldehydes are poisonous for microbes and phenolic compounds interfere with the function and integrity of cell membranes [58].
\nThere are several methods used for the removal of inhibitors [59]. The detoxification of lignocellulosic hydrolysates can be performed using inhibitor sorbents such as excess of lime, active carbon or lignite (brown coal).
\nAfter pretreatment to partially remove lignin and loose up polysaccharide structures, polysaccharides need to be hydrolyzed into sugar molecules which will be converted into ethanol by fermentation [38]. The hydrolysis can be accomplished chemically via acid-catalyzed cleavage of glycosidic bonds or by enzymes produced by microbes. Enzymatic method is more popular due to less impact on the environment and higher selectivity in the hydrolysis. Glucose and xylose are the main products in hydrolysates from the enzymatic breakdown of polysaccharides.
\nEnzymes produced by the filamentous fungi such as Aspergillus nidulans, Aspergillus niger, Penicillium spp. and Trichoderma reesei are dominant in commercial biorefinery [38]. Among different types of cellulases, endoglucanases attack the internal glycosidic bonds in the amorphous cellulose regions, causing fragmentation of the cellulose structure, and exoglucanase works of the termini of β-glucan molecules to release glucose molecules one at a time, while β-glucosidase attacks catalyzes the hydrolysis of the glycosidic bonds to terminal non-reducing residues in beta-
Various strains of yeasts and bacteria are being investigated with the goal of developing a consolidated process of hydrolysis and co-fermentation of glucose and xylose, without the need for adding exogenous cellulases [63].
\nSugars in the hydrolysate are converted into ethanol by fermentation using microorganisms such as yeasts. Ethanol-producing ability of yeasts depends on lignocellulosic hydrolysate, their strain and fermentation conditions (temperature, pH, aeration and nutrient supplementation). For use in industrial bioethanol production, microorganisms (mainly yeasts) must show thermotolerance and high fermentative activity for simple carbohydrates such as glucose and xylose. They should also be resistant to environmental stressors, including inhibitors mentioned in Section 4.3, acidic pH, high sugar level at the beginning of fermentation (causing hyperosmotic stress), and higher temperatures which prevents microbiological contamination, and are able to grow on various lignocellulosic substrates at a fast growth rate [58, 64].
\nSaccharomyces cerevisiae JRC6 and Candida tropicalis JRC1 are recommended for hydrolysates after alkali pretreatment and acid pretreatment, respectively [41]. Saccharomyces sp. yeasts are used in biorefineries to ferment glucose released during starch hydrolysis. Apart from glucose, they are capable of fermenting galactose and mannose.
\nZymomonas mobilis is a Gram negative, facultative anaerobic, non-sporulating, polarly-flagellated, rod-shaped bacterium. It has notable bioethanol-producing capabilities, which surpass yeast in some respects. However, it only ferments glucose, fructose and sucrose [65]. This prevents them from being used in industrial production of bioethanol. The Z. mobilis strains are tolerant to ethanol concentration up to 120 g/L, and have low nutritional requirements for growth [58]. However, its tolerance to acetic acid is low: as little as 2.5 g/L of HOAc. Its recombinant strain AX101 also has low tolerance to acetic acid.
\nAfter fermentation, the mash is heated so that the ethanol evaporates. This process, known as distillation, separates the ethanol, but its purity is limited to 95–96% due to the formation of a water-ethanol azeotrope with maximum 96.5% v/v) ethanol. This hydrous ethanol can be used as a fuel alone, but is not miscible in all ratios with gasoline, so the water fraction is typically removed before ethanol is added to gasoline.
\nWater can be removed by passing hydrous ethanol vapor through a bed of molecular sieve beads. The bead’s pores are sized to allow adsorption of water while excluding ethanol. Two beds are often used so that one is available to adsorb water while the other is being regenerated. This dehydration technology can save 3000 BTUs/gallon over the azeotropic distillation and has been adopted by most modern ethanol plants.
\nRecent research has demonstrated that complete dehydration prior to blending with gasoline is unnecessary. When the azeotropic mixture is blended directly with gasoline, water separates from the gasoline/ethanol phase and can be removed in a two-stage counter-current setup of mixer-settler tanks with minimal energy consumption [66].
\nNumerous life cycle analyses (LCAs) of lignocellulosic ethanol have been published over the last 15 years and several reviews of these LCA studies have been completed and are cited in a more recent review [67]. These studies show a clear reduction in GHG emissions for lignocellulosic ethanol compared to gasoline. However, accurate quantification of GHG emission reduction is hard to obtain as gaps remain in understanding life cycle performance due to insufficient data, and model and methodological issues. Critical unresolved issues that are expected to impact its energy/GHG emissions performance include feedstock-related emissions, consequential versus attributional life cycle aspects, choice of system boundaries, and allocation methods.
\nDecisions regarding feedstock, process technology and co-products can significantly impact GHG emissions calculations. Predicted life cycle GHG emissions vary widely depending on how the following key parameters are considered: nitrogen-related emissions due to supplemental fertilizer requirements and the N content of feedstock, cellulase requirements, farming energy, ethanol yield, and how the value of co-products such as lignin are realized, among others.
\nGovernment support (i.e., Ethanol mandate, tax credit, etc.) is not expected to last forever. To be sustainable, lignocellulosic biofuels production must meet or exceed the economic performance of their first-generation counterparts. The growth in the capacity of commercial lignocellulosic ethanol production has been slow in the past decade, despite significantly better predicted performance on various environmental and energy security criteria than corn-based ethanol in the various techno-economic evaluations published before 2010 [68]. The slow growth has been due to both large technological risk, large capital cost, and the poor predicted economic performance of biorefineries in the short term.
\nAn LCA of US softwood cellulosic ethanol was reported in 2012 by Stephen et al. [68]. In the paper, the base case (capacity: 50 mL ethanol year−1) softwood ethanol production cost was compared with costs of ethanol produced from corn and sugarcane found in the literature. Softwood lignocellulosic ethanol was predicted to have a production cost of $0.90 L−1, 250–300% higher than US corn and Brazilian sugarcane ethanol production costs, which were in the range of $0.30–$0.40 L−1. The lignocellulosic base case scale of 50 mL year−1, compared to 150 mL year−1 of US corn and 365 mL year−1 of and Brazilian sugarcane, is much smaller as it was chosen based both on the projects funded under the US Department of Energy’s commercial biorefinery program and those operating in other places such as Denmark. Production costs of sugar- or starch-based ethanol are expected to continue to decline to $0.22–$0.25 L−1 by 2020. Thus, second-generation ethanol is not going to catch up with first-generation ethanol on production cost soon.
\nAnother very recent techno-economic evaluation was performed on production cost of ethanol produced from corn stover using either biochemical or thermochemical methods. For heat integrated biochemical route, the predicted bioethanol product costs at $2.00 for a production capacity of 43,300,000 gallon year−1 [69]. This result was clearly an underestimation of lignocellulosic ethanol as a major cost item, capital investment cost, was not included. Furthermore, the corn stover price of 46.8 $/ton was an underestimation, and feedstock transportation cost was not included in LCA. Feedstock cost can impact total cost by 40 percent according to a Lux Research report of 2016 [70]. The Brazilian birefinery company Raizen has the lowest projected minimum ethanol selling price of $2.17 per gallon while Abengoa’s capital-intensive $500 million Hugoton facility has the highest price of $4.55 with feedstock cost emerging as the most critical variable. The low cost of Raizen’s cellulosic ethanol is largely attributed to its access to low cost sugarcane straw and sugarcane bagasse ($40 and $38 per dry metric ton), respectively, compared with corn stover ($90) used by Abengoa and POET-DSM and wheat straw ($75) used by Beta Renewables [71].
\nIt is apparent that second-generation ethanol is currently much more costly to produce than first-generation ethanol. It is hard to predict when the cost of lignocellulosic ethanol will be reduced to the level of corn/sugar cane ethanol. Dramatic reductions in the capital and operational costs must occur before the potential superior environmental benefits from cellulosic ethanol relative to corn ethanol can be realized. Pretreatment, enzymatic hydrolysis and distillation are responsible for much of the cost of producing bioethanol. Currently, intensive research is being conducted to improve each of the processes to make them more economical.
\nAn effective pretreatment increases specific surface area of biomass, making cellulose better available for the action of hydrolytic enzymes obtained from fungi and bacteria, minimizing reductions in enzyme activity, and thus improving the rate of biomass hydrolysis and providing the highest possible concentration of fermentable sugars. Effective pretreatment also reduces the degradation of monosugars [72]. In selecting pretreatment methods, factors such as their environmental impact and recycling of chemical compounds (for example ammonia in the ammonia fiber explosion process [73, 74]) must be considered. Different pretreatment methods and their combinations are being explored for different types of biomass [50].
\nBetter results, e.g., improved ethanol yield, have been obtained from combination of two or more pretreatment methods, but have resulted often at the cost of more energy consumption compared to single method of pretreatment. Among single treatment methods, dilute acid pretreatment is more suitable for various types of biomass as it solubilizes most of hemicellulose and partially remove lignin [50].
\nIt is vital to analyze the pros and cons of each pretreatment technology before scaling up for industrial application. However, technoeconomic assessment will only give a rough estimate on capital cost and the final fuel cost in commercial scale production when many research findings are still in pilot scale level and demonstration plant level [52].
\nEfficient fermentation of pentoses helps reduce ethanol production cost since pentoses can be 25.8 wt% as in sugarcane bagasse [75, 76] 22.3–74.9 wt% in corn stover (Table 3). Wild microorganisms are incapable of producing ethanol in high yields, as they are unable to utilize both pentoses and hexoses. Pentose-specific transporter proteins and enzymatic reactions determining the metabolism of pentoses such as
Biomass | \nLignin | \nHexoses | \nPentoses | \nCarbohydrate | \n|||
---|---|---|---|---|---|---|---|
Glucan | \nMannan | \nGalactan | \nXylan | \nArabinan | \n|||
Corn stover | \n18.2 | \n30.6 | \n0.5 | \n0.7 | \n16.0 | \n1.9 | \n49.7 [76] | \n
\n | 20.2 | \n38.1 | \n0.4 | \n0.7 | \n20.3 | \n2.0 | \n61.5 [76] | \n
\n | 17.2 | \n36.1 | \nN/A | \n2.5 | \n21.4 | \n3.5 | \n65.3 [77] | \n
Corn leaf | \nN/A | \n34.2 | \n1.8 | \n2.5 | \n22.1 | \n3.5 | \n64.1 [68] | \n
Corn stalk | \nN/A | \n36.5 | \n1.7 | \n2.4 | \n21.6 | \n3.2 | \n65.4 [68] | \n
Corn fiber | \n6.9 | \n36.5 | \nN/A | \n2.9 | \n18.4 | \n13.3 | \n71.1 [77] | \n
DDG | \n3.1 | \n22.0 | \nN/A | \n0.3 | \n9.5 | \n5.5 | \n37.3 [77] | \n
Wheat straw | \n14.5 | \n36.6 | \n0.8 | \n2.4 | \n19.2 | \n2.4 | \n61.4 [77] | \n
\n | 16.9 | \n32.6 | \n0.3 | \n0.8 | \n19.2 | \n2.4 | \n55.3 [76] | \n
Switchgrass | \n23.2 | \n32.2 | \n0.4 | \n0.0 | \n20.3 | \n3.7 | \n56.6 [77] | \n
\n | 23.1 | \n35.9 | \n0.4 | \n0.5 | \n19.6 | \n1.5 | \n57.9 [76] | \n
\n | 27.6 | \n31.9 | \n0.3 | \n0.3 | \n10.6 | \n1.1 | \n44.2 [76] | \n
\n | 24.1 | \n42.6 | \n0.3 | \n0.5 | \n23.1 | \n1.5 | \n68.0 [76] | \n
S. bagasse | \n18.4 | \n38.1 | \n0.4 | \n0.0 | \n23.3 | \n2.5 | \n65.0 [77] | \n
Softwood | \n\n | \n | \n | \n | \n | \n | \n |
Spruce | \n28.3 | \n43.2 | \n11.5 | \n2.7 | \n5.7 | \n1.4 | \n64.5 [76] | \n
Red pine | \n29.0 | \n42.0 | \n7.4 | \n1.8 | \n9.3 | \n2.4 | \n62.9 [76] | \n
Lodgepole pine | \n27.9 | \n42.5 | \n11.6 | \n2.1 | \n5.5 | \n1.6 | \n63.3 [76] | \n
Ponderosa pine | \n26.9 | \n41.7 | \n10.8 | \n3.9 | \n6.3 | \n1.8 | \n64.5 [76] | \n
Loblolly pine | \n28.0 | \n45.0 | \n11.0 | \n2.3 | \n6.8 | \n1.7 | \n66.8 [76] | \n
Douglas-fir | \n32.0 | \n44.0 | \n11.0 | \n4.7 | \n2.8 | \n2.7 | \n65.2 [76] | \n
Hardwood | \n\n | \n | \n | \n | \n | \n | \n |
Red maple | \n24.0 | \n46.0 | \n2.4 | \n0.6 | \n19.0 | \n0.5 | \n68.5 [76] | \n
Aspen | \n23.0 | \n45.9 | \n1.2 | \n0.0 | \n16.7 | \n0.0 | \n63.8 [76] | \n
Yellow poplar | \n23.3 | \n42.1 | \n2.4 | \n1.0 | \n15.1 | \n0.5 | \n61.1 [76] | \n
Poplar | \nN/A | \n39.8 | \n2.4 | \n0.0 | \n14.8 | \n1.2 | \n58.2 [77] | \n
Poplar stem | \nN/A | \n40.3 | \n3.1 | \n0.7 | \n17.6 | \n0.6 | \n62.3 [68] | \n
Poplar DN34 | \n23.9 | \n43.7 | \n2.9 | \n0.6 | \n17.4 | \n0.6 | \n65.2 [76] | \n
Euclyptus saligna | \n26.9 | \n48.1 | \n1.3 | \n0.7 | \n10.4 | \n0.3 | \n60.8 [76] | \n
Salix | \n26.4 | \n41.4 | \n3.2 | \n2.3 | \n15.0 | \n1.2 | \n63.1 [76] | \n
Hexose, pentose and lignin contents in different types of biomass.
S. bagasse = sugarcane bagasse.
Owing to large microbial biodiversity, fermentation of pentoses can be achieved either by finding a potent naturally occurring pentose utilizing microorganism or by a genetically engineered C5 utilizing strain [78, 79]. One effective strategy is to create recombinant strain with genes for xylose metabolism [80]. Genetic engineering has been conducted mainly on Saccharomyces cerevisiae yeast, [81] the Gram-positive bacteria Clostridium cellulolyticum and Lactobacillus casei and the Gram-negative bacteria Zymomonas mobilis, Escherichia coli and Klebsiella oxytoca [43]. Recombinant yeasts consume xylose much slower than glucose, thus requiring prolonged fermentation time due to a lack of reaction intermediates and efficient pentose transporters [82].
\nA common problem of xylose-fermenting strains is the production of xylitol or the reabsorption of ethanol, which lead to low ethanol yield. One grand challenge is glucose repression, which results in di-auxic fermentation of a mixture of glucose and pentoses since glucose prevents the catabolism and/or utilization of other non-glucose sugars, leading reduced volumetric ethanol yield [83]. Approaches and conditions sought to improve glucose and xylose fermentation to ethanol are reviewed in a recent paper with emphasis on microbial systems used to maximize biomass resource efficiency, ethanol yield, and productivity [64].
\nSeparate processes have been established for enzymatic hydrolysis of cellulose and hemicellulose and fermentation (SHF) of sugars in hydrolysate. In the SHF processes, saccharification and fermentation take place in separate vessels, so the two processes can be optimized separately. One drawback of SHF is that accumulation of simple carbohydrates (such as cellobiose) causes end-product inhibition of hydrolytic enzymes, for example cellulases or cellobioses. To prevent end-product inhibition, extra doses of β-glucosidase are needed together with the commercial cellulase preparations [84].
\nThere is a strong incentive to develop a process to perform simultaneous saccharification and fermentation (SSF) as it reduces investment costs by reducing the number of vessels and has the potential to become the preferred approach. In SSF, the problem of end-product feedback inhibition is largely eliminated because glucose molecules are fermented immediately by the fermentative microbes as it is produced from hydrolysis of cellulose [85]. However, the benefits come with a major downside which is an inherent mismatch between the optimal temperatures for the enzymes (fungal cellulases and hemicellulose’s) on the one hand, and yeast biocatalysts on the other. The temperature optima for saccharifying enzymes (50–55°C for cellulase) are higher than those for fermenting mesophilic culture. The optimal temperature for yeasts is below 35°C. Mesophilic yeasts (that thrive best in a moderate temperature) exhibit slower growth rates at higher temperatures. Currently, SSF must run at temperatures between the optimum temperature for cellulase and the optimum temperature for fermentative organisms. The compromise results in higher cellulase loading and an increase in enzyme costs. Efficient bioethanol production by SSF requires the use of thermotolerant ethanologenic yeast. It is a hot topic for research to genetically modify microorganisms with the ability to ferment at higher temperatures [43]. Some isolated yeasts, including Pichia, Candida, Saccharomyces and Wickerhamomyces, are found to grow at temperatures of 40°C and ferment sugars at higher temperatures [41]. To make SSF process highly efficient in ethanol production, the pentose metabolic pathway is been engineered into microorganisms to enables the use of C5 sugars by microbes that do not ferment them earlier [86].
\nReduction in enzyme cost is been sought by searching for new organisms with cellulolytic and hemicellulytic activities [87], lowering the enzyme dosage through protein engineering [86, 88], and improving cellulase thermostability for performing hydrolysis at elevated temperatures to increase the efficiency of cellulose hydrolysis [89]. Cellulase enzyme cost reductions are challenging as cellulase costs need to be significantly lower than those of amylase enzymes on a unit-of-protein basis. The high price of the enzymes encouraged research into solutions to the problem of glucose inhibition and to the deactivation caused by lignin by-products [90].
\nFurther integration of enzyme production with SSF leads to a new technology of consolidated bioprocessing (CBP). One area of research is aimed at engineering all three capabilities (saccharification, hexose fermentation and pentose fermentation) into a single strain for the CBP process [91, 92]. Cellulase-encoding genes may be introduced into specific species during recombination [63] to eliminate the need for exogenous cellulases in the process of SSF and decrease the capital costs of processing. CBP technology promises to eliminate costs associated with enzyme production and additional infrastructure/vessels [93].
\nWorking with a high dry matter (DM) concentration is also potentially an effective way to reduce the hydrolytic enzyme costs. However, high DM content causes an increase in viscosity, inadequate mass and heat transfer within the bioreactor, and, consequently, a strong reduction in the conversion of cellulose/hemicellulose to fermentable sugars. This problem could be overcome by adopting various fed-batch strategies or coprocessing substrates with different degrees of porosity [94].
\nA variation of SSF, simultaneous saccharification and co-fermentation (SSCF), in which a starch material is co-fermented, has been adopted to address low ethanol concentration issue in lignocellulosic ethanol production. SSCF can reduce ethanol production cost by increasing ethanol concentration and thus reducing distillation cost [95].
\nRecycling yeasts and enzymes is also an effective way to reduce the cost of ethanol production. The remaining unhydrolyzed solids with some enzymes adsorbed are collected by filtration or centrifuge and are recycled to the next cycle for further hydrolysis. In one study, the enzyme loading was reduced from 36 to 22.3 and 25.8 mg protein per gram glucan, respectively, for separate hydrolysis and fermentation (SHF) and for SSCF on AFEX™ pretreated corn stover [96]. Enzyme adsorption to the residual solids is probably inhibited at high sugar concentrations in the fast SHF process [97] and hence affected enzyme recycling. The fast SSCF process removed most of the sugars by fermentation but produced ethanol whose effect on enzyme adsorption is unclear.
\nCost effect renewable fuel generation from lignocellulosic materials is one of the few options the human beings have to slow down/eliminate global warming and achieve energy independence from fossil fuels. Second generation bioethanol is a promising path in the roadmap to the future world of renewable energy. The cellulosic ethanol industry is still in its infancy and its survival is relying on heavy policy support. Major technological advances at every stage of the cellulosic ethanol production are critically needed to lower the ethanol production cost to a level comparable to the corn ethanol. The key problems that remain to be solved include: (1) Effective and low-cost biomass pretreatment method that exposes polysaccharides to enzymes for efficient saccharification, (2) efficient fermentation of all sugars (pentoses and hexoses) released during the pretreatment and hydrolysis steps into ethanol, (3) development of enzymes that tolerate various inhibitors including monosaccharides (mainly glucose), and ethanol accumulation, and (4) heat-tolerant fermentation microbes and enzymes for efficient simultaneous saccharification and fermentation.
\nThe support of the South Dakota NSF EPSCoR Program (Grant No. IIA-1330842) is greatly appreciated.
\nThere is no conflict of interest involved in this work.
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