This article was downloaded by: 10.3.98.104 On: 26 Sep 2021 Access details: subscription number Publisher: CRC Press Informa Ltd Registered in England and Wales Registered Number: 1072954 Registered office: 5 Howick Place, London SW1P 1WG, UK

Handbook of Petrochemical Processes

James G. Speight

Other Feedstocks—Coal, Oil Shale, and Biomass

Publication details https://www.routledgehandbooks.com/doi/10.1201/9780429155611-3 James G. Speight Published online on: 03 Jul 2019

How to cite :- James G. Speight. 03 Jul 2019, Other Feedstocks—Coal, Oil Shale, and Biomass from: Handbook of Petrochemical Processes CRC Press Accessed on: 26 Sep 2021 https://www.routledgehandbooks.com/doi/10.1201/9780429155611-3

PLEASE SCROLL DOWN FOR DOCUMENT

Full terms and conditions of use: https://www.routledgehandbooks.com/legal-notices/terms

This Document PDF may be used for research, teaching and private study purposes. Any substantial or systematic reproductions, re-distribution, re-selling, loan or sub-licensing, systematic supply or distribution in any form to anyone is expressly forbidden.

The publisher does not give any warranty express or implied or make any representation that the contents will be complete or accurate or up to date. The publisher shall not be liable for an loss, actions, claims, proceedings, demand or costs or damages whatsoever or howsoever caused arising directly or indirectly in connection with or arising out of the use of this material. Downloaded By: 10.3.98.104 At: 13:40 26 Sep 2021; For: 9780429155611, chapter3, 10.1201/9780429155611-3 cesses ( improve competitiveness economic significantly to the pro concert, of bio-based in promise, that fact, over occurred of has advances In technological a series two past decades the important. become (such alternatives other biomass-derived synthesisand gas) and biomass-derived chemical as will C-1 to chemicals synthesis gas andconverting gasification coal-derived on coal chemistry, based costly to extract, socostly they have However, past. extract, to the touched in barely been resources, these through and Western (Chapter the hemisphere more difficult in 2). located are dominantly resources These (of reservoirs the heavy oil) deposits pre bitumen) (of and sand are that tar and heavy extra oil nonbiologicalwith steps. process of biological application of processes, new integration overcome to technology and limitations, past ( coal and gas of new introduction natural the production technologies from forand chemicals and fuels some to extent mitigated be by exploitation fossil the will challenging resources of more technically supply/demand situation advantage issues its over economic erode This feedstocks. alternative other as unsustainable become position will and dominant industry, its is finite for petrochemicals the 2016 Islam, (Chapter tight formations in oil, crude spite and gas in of discoveries are, oil of natural crude and gas derived from are that feedstocks petrochemical geopolitics, common addition the to the In geopolitics go such accompanying with that regions agreements. the political unstable with from agreement, under imported, feedstocks petroleum-based from chemicals producing to alternative (renewable resources suggested an frequently as been has feedstocks) manner asustainable in ­ from feedstocks 1970s, of chemical the idea essential of crises oil the deriving Since the 3.1 availability ofavailability such feedstock beyond next the 50 available be the well next will feedstocks the predicting into century, although hydrocarbon-based economy. industrial suggest the relatively in Some that estimates future cheap near the in continue role will their and important are liquids gas natural society. and gas force industrial Natural the to 2011b products has put more pressure on the search for alternate energy sources ( sources energy for alternate search on the put has more pressure products for oil-based demand and oil in rise ofavailability this conventional with combined oil crude the in decline This India. and by rapidly of China economies growing the demands of increased for grow to demand continues oil every the year, time, because same maturity. At into the already or reaching are and productionrates have most basins prolific reduced the to begun experience ible ( reserves - produc of total UnitedStates), terms the Ford Eagle in in formation the and which may limited be others. many and people use, pharmaceuticals, such that plastics,­products as paints, petroleum More specifically, as crude oil prices continue to fluctuate (typically in an upward direction), an in upward to continue fluctuate prices (typically Moreoil specifically,crude as In order to satisfy the demand for feedstocks for petrochemicals, it will be necessary to develop to necessary be it for will for demand feedstocks the petrochemicals, satisfy to order In Several authors have correctly stated that petroleum is and will continue to be amajor be to continue motivating will is and petroleum that Several have stated authors correctly In spite of the apparent plentiful supply plentiful spite tight apparent (such of formation ofIn in formation oil the Bakken the as INTRODUCTION Speight, 2008 Speight, , 3 2011c Speight, 2008 Speight,

2) and 2)

and natural gas as feedstocks to make intermediates, which are later converted to final final converted to later which are intermediates, make to feedstocks as gas natural and ). In fact, the reality is that the supply basicand the the feedstock oil, for is that of refineries crude reality ). fact, the In ). Wachtmeister et al., 2017 Oil Shale, and Biomass Feedstocks—Coal, Other

are depleting, such as petroleum and natural gas. The petrochemical industry uses uses industry petrochemical gas. The depleting, natural and suchare petroleum as , 2014 ). Evaluation of this window of opportunity focuses on the inherent attributes attributes focuses). inherent on the Evaluation window of of opportunity this ) ) the oil industry is planning for the future since some since of for future the is planning industry oil ) the years is risky ( is risky years Speight, 2011a Speight, Speight, 2008 Speight, , 2011b ; Speight and renewable renewable , natural ­natural 2011a 79 - - , Downloaded By: 10.3.98.104 At: 13:40 26 Sep 2021; For: 9780429155611, chapter3, 10.1201/9780429155611-3 vide chemicals and end products from biomass from ( end products and vide chemicals developed being is technology continually pro to chemical Existing for future. of the resources prove will a reliable be to chemicals supply petroleum-derived replace the which can chemicals production of the oil, bio-based crude and gas such depleting to natural feedstocks as contrast In of wastes.ety processing (biomass), lignocellulosic recovered a vari materials from starch, in or biomass rich crops material includes such agricultural as ahuge feedstocks of number materials renewable term The chemicals. formations),shale for production of the petro renewable materials and source the as feedstocks kerogen from (produced adoption shale in oil of the coal, later—to than rather sooner hopefully (as lead sure eventually—­ will andThese country-dependent) independence. yet of oil undefined - amea basis of on the obtaining resources bitumen sand tar heavyand extra heavy oil, oil, with it moving is worth ahead occurs, this As high. remains products oil for demand emerge crude the as acceleration- issues ( issues supply oil of of geopolitical crude due avariety to uncertainty and variability the fact, with In world the East. equivalent Middle of could have soon those to the almost sources oil to access 80 able biomass resources is a first step toward this goal. The realignment of the chemical industry industry the chemical of realignment The towardgoal. ablethis step is a first biomass resources Supplementing renew growth. consumption with economic petroleum continued and security term legislation. comply environmental products stringent and increasingly with its processes that ensure to but feedstocks, also hydrocarbon more advantaged utilizing global competitors with effectively not only compete to pressure increasing under coming are industries petrochemical and petroleum emissions.gas the a result, As is a viable greenhouse chemicals route reduce to fuels and generation basic of the as into inputs power, materials of these utilization widespread the and thesis photosyn via atmosphere the from carbon industry.feedstock for accumulate chemicals Plants the cost-effectively and resources petroleum chemicals. and fuels produce industry, new for for but chemicals field is essential the this priority if with high compete it to is biomass. for from cesses Developing chemicals for catalysts biomass is not special processing a design shape-selective of other pro molecules abetter to could lead catalysts and onated zeolite behavior The of oxygen market. to biomass-derived products bring to improve ability greatly the will biomass other fractions and lignin, carbohydrates, for selectively modifying and manipulating processes of new catalytic understanding Afundamental is needed. chemicals into derived materials industry. paper pulp and the into chemical of this penetration market would permit (iii) synthesis gas; the and of or ethanol) costs without reforming methanol the (through intermediate compositionunique of process possible available synthesis gas biomass, makes from and abalanced given match interesting the an be to appears From synthesis gas, aroute that produced. be can using fast pyrolysispared catalysts; (ii) followed acid acetic on zeolite-type upgrading by catalytic derivatives pre of be pentane can avariety and butadiene while lignin from prepared be can ate, awell-known intermedi examples, chemical pulping (i) catalyst and anthraquinone, further As inexpensive available sugars, clean biomass hemicellulose-derived cellulose from fractionation. and from prepared could be that materials acid are succinic and acid, sorbitol,acid, levulinic mannitol, glucose, gluconic tetrahydrofuran, such xylose, as butyl chemicals Also, butyrate. xylitol, furfural, application afeedstock for has as that such as products chemical amajorcould be commodity production bioprocessing of exists from is the which butanol that opportunity ­petrochemicals—one Khoo The general term biomass term general The to continue will bitumen sand tar of and heavy extra heavy oil, oil, Nevertheless, importance the Reducing dependence of any country on imported crude oil is of critical importance for long- importance is of oil critical crude on imported ofReducing dependence any country a rawConsequently, as of material plant-based matter utilization is a renewed the there in interest However, of for reactions selectively abasic understanding converting biomass biomass- and conversionFor bioprocesses—the such of and fuels products as biomass useful into peracetic acid is an oxidant that is a good non-chlorine-containing pulp agent bleaching which is non-chlorine-containing agood oxidant that acid is an ­peracetic et al., 2015 Speight, 2011b Speight, deceleration slope. ­deceleration ). ), investments in the more challenging reservoirs tend to be on a variable on avariable be to tend ), reservoirs more investments challenging the in refers to any material derived from living organisms, usually plants. usually organisms, living derived from refers any material to Bozell, 1999 Handbook of Processes Petrochemical Handbook ; Besson et al., 2014 al., et Besson ; Straathof, 2014 Straathof, ------; Downloaded By: 10.3.98.104 At: 13:40 26 Sep 2021; For: 9780429155611, chapter3, 10.1201/9780429155611-3 may involve direct and indirect coal conversion coal may involve coproduction well approach. as the strategies as indirect and direct coal from materials for and chemicals Anew chemistry chemicals. of coal these sources ditional - tra the diminished has industry tar coal of the decline The for coke making. carbonization coal from tars and for coal from developing chemicals organic opportunities or specialty value-added new created has chains, main their in polyaromatic units and aromatic incorporating materials, polymer advanced in progress Substantial materials. carbon-based and chemicals, specialty cals, and diesel) can produce synthetic petroleum and chemical products ( products chemical and petroleum diesel) synthetic produce and can liquefaction coal kerosene) (throughand gasification indirect coal of for and synthesis of gasoline hydrogenation coal liquefaction coal (high-pressure liquefactiondirect for production of naphtha for production of The the chemicals. raw fuel, liquid and such materials synthetic products as many of raw by gasificationthe material coal is produced gas Synthetic protections. environmental and of fuel. gas is conduciveIt and is a cleanous energy types improvement the to of standards living production of the vari in is used and industry chemical coal position the in important occupies an industry. gasification chemical of Coal the part important an it applications, and is still earliest of the powergenerated plants. have coal- of that emissions the reduction processes in nowoperation into placed installation been the significantly by reduced be can plants coal emissions from that go realization along the with for development. prospects broad must realize may This once again industry chemicals-from-coal world of (they the resources oil nonrenewable of decrease course, are, crude resources), and gas the industry. chemical However, the have they time that dominated since and raw natural as materials, were gas as used met could not by coke be natural plants. that the Petroleum and chemicals other 1920 which World 1940 to after War and for brought imperative toluene, demands II ammonia, from period the fromcoal was production the for frame of chemicals time significant The neering. engi acetylene and carbide chemical processing, liquefactionification, tar as coal as coal, well of and by coal hydrogenation in England and Germany ( by hydrogenationand coal Germany and England in processes low-temperature carbonization various some to extent have through cals obtained been chemi other and these Europe, and England In byproduct carbonization. high-temperature through exclusively almost were coal derived chemicals from these UnitedStates, pitch, coke. the and In tar, bases, tar toluene,difficult-to-define xylene acids, (benzene, and tar (BTX)), difficult-to-define 3.2 biomass. and such coal of as chemicals sources other ( achieving self-sufficiency a panacea in energy, than rather of use biofuels increased context, should viewed be the one as ( perspective in goal the keep to production is important chemical industrial in the use of biomass-derived increasing andfeedstocks of abiorefinery construction However, countries. of goal for oil-importing a national many necessary are clearly goals defined time,concept, givento a biorefinery feasibly become refining has one petrochemical offrom the term term industry, the days early the chemicals-from-coal of the In raw as material. coal with processing cal chemi refers conversion the to after industry chemicals solidcals gas, liquid, fuels, into and of coal Revolution chemi coal were the when coal Thus, everyday power from chemicals and occurrences. 21st the feedstock in of chemical organic source the century. as and source energy an as both more some important may emotional, of and become which are real which are boy bad considered of the issues which fossil some is currently Coal, of fuels due environmental to Coal, Oil Shale, and Biomass and Shale, Oil Coal, In fact, coal has several has positive fact, coal when chemi afeedstock for consideredIn as aromatic attributes In the production technology of coal processing and utilization, coking process technology is technology one process coking utilization, and production processing of technology the coal In - gas coking, were coal predominantly for from production of processes the chemicals the Thus, Thus, in any text (petrochemicals), production of in about the chemicals Thus, it omit to would aremiss be The chemicals-from-coal industry was born in the late 18th century at the time of the Industrial Industrial of the time atthe 18th late the in century was born industry chemicals-from-coal The COAL chemicals covered primarily ammonia, hydrocarbon gases, low-boiling gases, derivatives hydrocarbon aromatic ammonia, covered primarily Speight, 2013a Speight, Crocker and Crofcheck,Crocker and 2006 of of arange possible for measures Clark and Deswarte, 2008 Deswarte, and Clark ). Speight, 2013a ; Speight, 1981 Owen, ). ). In this ). this In ). 81 ------Downloaded By: 10.3.98.104 At: 13:40 26 Sep 2021; For: 9780429155611, chapter3, 10.1201/9780429155611-3 tion conditions, and there is also the option complete of the the is decomposition also tion (i.e., of there conditions, coal and gasification) is some leeway of choiceThere - coal. from reac of terms the in chemical produce to means the are longer and/or times). reaction more severe temperatures (higher conditions reaction become secondary the as coal original the in species carbon less the to related lower decomposition are of products) coal weight molecular thermal of but species the are primary (i.e., products by formed decomposition products secondary of skeletal the of The coal. carbon the some relation to bear that nature, in weight molecular high aromatic often species, are reactions 2013a Speight, 1945 (e.g., coal from arise that Lowry, see types of chemical well variety ofas indications the as coal from produced be extent of present to chapter indications can the which to of chemicals this works. It earlier is, however, these text repeat texts; to of this therefore, it purpose is not the goal the numerous in reported been has coal from production of fact, the chemicals text. In of scope this the indeed. real very be can amajor ofas chemicals source Therefore, upwards. fluctuate conceptthe position changeof using prices oil coal suddenly as can industry, over have the chemicals taken by petrochemical been for the tar coal markets traditional feedstock once more. many Although chemical apredominant becomes coal and feedstocks cal supply to petrochemi strained become resources gas natural and petroleum as future the expand in adsorbents. carbon-based and materials for carbon have been made from coal ( coal have from made been well others as many as medicine, and drugs, activated carbon, nylon, as fertilizers, rials styrene, liquefaction coal fuels. liquid is produce to liquefaction indirect coal and direct carbonization, role common byThe gasification. coal produced of be low-temperature of can gases fuel varieties industry.position andin chemical City gas important an ylbenzene,up gasificationtakes etc. Coal - meth gas, benzene, coal like products some secondary and cokes produce to forused metallurgy processing. catalytic and hot working through products chemical and fuels various into coal transform by can bonds bridged connected units core their as rings condensed with of coal structures chemical and matters organic gas. The natural and petroleum to coal from raw by changing materials industry by chemical coal War World industry. of chemical After part important an became industry chemical coal then and ucts, - prod forestry and agricultural former the from were coal into changed of chemicals organic als century, raw materi 20th entering was set up. completethe system After industry chemical of coal lignite. and coal, is mostly subbituminous change and most coal, carbon), chemical the subjected to been bituminous anthracite (which are has ranks coal anda low a content low Important carbon value. fixed heating contents. For carbon values fixed consideredwhich is example,peat, a and heating has coal, young considered have to content lower with are subjectedmore to severe those carbon been changes than fixed value high and heating ahigh with coals general, In period. prehistoric the in plant remains decomposition the of during occurred change of that chemical degree the to according ferent ranks dif is classifiedinto Coal compounds. of inorganic amounts variable with contaminated substance combustible heterogeneousBy organic of way rock composed an is anatural coal of introduction, c 3.2.1 In 82

addition, the needs for environmental-protection applications have for demand market expanded environmental-protection needs also the addition, In very general terms, it is these primary and secondary decomposition which of reactions coal secondary and it primary is these terms, general very In ( of coal chemistry basis thermal of the the On possible is beyond the products chemical all produce to A complete processes of the description Thus, for many years, chemicals that have been used for the manufacture of such diverse have for that mate manufacture used for the chemicals Thus, been years, many is mainly carbonization Coal method. most important and earliest is the carbonization Coal the late the century in in and century, 19th 18th appeared first industry chemical of coal birth The

II, the petrochemical industry saw rapid development, industry up petrochemical position which the the weakened taken II, oal F ). eedstocks Gibbs, 1961 ; Mills, 1977Mills, Speight, 2013a Speight, ; Pitt and Millward, 1979 Millward, and Pitt Handbook of Processes Petrochemical Handbook ), many primary products of coal of products coal ), primary many ). These products will will ). products These - - - - ; Downloaded By: 10.3.98.104 At: 13:40 26 Sep 2021; For: 9780429155611, chapter3, 10.1201/9780429155611-3 Coal, Oil Shale, and Biomass and Shale, Oil Coal, decreased. coal the amountin of the and matter volatile increased content coal the of carbon fixed the and of acoal’smeasure value of age. progressive process heating place, took the the As transformation (i.e., source decayed original the plants) from of is therefore transformation a and degree upon the classified most usually deposits are by rank worldwide. of coal types different The (shiny)vitreous lower and lower-rank content then moisture appearance coals. lower-rank content. amuch than have energy which They in results higher coals more carbon amore contain coals, anthracite and including bituminous coals, well. as does High-rank rank the increase, all pressure have (earthier) lighter and levels. moisture burial are higher They and heat, time, As and ( (v)carbon fixed content, matter mineral the of reflective is which bustion (i) are: and International) was for Society developed Testing (ASTM;Canada by American now Materials the and ASTM and United States the in used (ASTM coals D388). anthracite to oflignite ranking method This from series or progressive natural the in alteration, of metamorphism, degree the to according coals, relative coal to other classification which is the coal, of the of a particular rank the as to is referred maturation. ultimate reached has coal when is used the ­terminology At minous. is classifiedas bitu coal physical the and and more continues, chemical changes occur alteration and of burial process this As coal. subbituminous to maturity in increases lignite passing of time, effects) pressure and further (due With the lignite. to which is metamorphosed thermal to peat, to is closely that akin amaterial off as It starts is believed coal anthracite. that and bituminous, of fuel. importation tion and - for exporta the planning in country. of the Knowledge needs important energy is also of resources long-term short- and the for problems and water, meeting air, to degradation; related land and future solution the and growth; of and current planning industrial for planning; governmental is important resources several coal of in regions. the Knowledge quality occurs and and size, distribution, of the asolid material. create to occurred plant remains of physical the and chemical properties changes the processes, metamorphic anaerobic through which, of of abody bottom water after atthe accumulated layers as has that begins of plant matter Coal matrix. coal of the part as gases and matter mineral contain mayoxygen, also and sulfur and seams coal coalbeds in occurs rock that is acombustible brownCoal black to sedimentary dark organic 3.2.2 H hydrogen, monoxide, of carbon (a synthesis gas CO, the and from production of the chemicals mixture and combustion, carbonization, gasification, and liquefactionand gasification, combustion, carbonization, (Speight,2013). employed is be to that (conversion, for such utilization as processes treatment) the in of coal thermal for design of the equipment required are they as insofar of importance are that properties thermal property. However, thermal other (Chapter are 8) most important there the considered be to is often conversion For value processes. example,value) content or calorific heating heat (also the the called of avariety to of applicability coal the determining in important are of coal properties thermal The c 3.2.3 There are many compositional differences between the coals mined from the different coal coal different the from mined coals the between compositional many differences are There (such coal Low-rank lignite) as lower has have they content energy because low content. carbon anthracite to peat from matures acoal as of (or alteration occurs degree that The metamorphism) coal), (brown lignite subbituminous, of are order alteration, increasing in of coal, types The for used having several UnitedStates, been fossil centuries the most in fuel abundant is the Coal P ro onversion

. Coal is composed primarily of carbon with variable amounts of hydrogen, amounts variable with of nitrogen, carbon primarily is composed . Coal this point the coal is dark and hard. Anthracite is the last of the classifications, and this this classifications,last ofand is the the Anthracite hard. and is dark coal the point this 2 ) produced by gasification process the ) produced 5) ( (Chapter p erties

and

heating value, (ii) value, heating matter, (iii) volatile (iv) com by moisture, production ash C om p osition Speight, 2013a Speight, Speight, 2005 Speight, ). which depends which depends , 2013 or or 83 a ) - - . Downloaded By: 10.3.98.104 At: 13:40 26 Sep 2021; For: 9780429155611, chapter3, 10.1201/9780429155611-3 oxygen which typically occurs under pressure and at operating temperatures above 430 temperatures at operating and oxygen pressure under occurs which typically of absence the in atelevated temperatures decomposition material or organic ofmochemical coal 84 in use that have that use in helped significantly lowerdioxide emissions of (SOsulfur foundation for the laid has Technology effective that technologies now Program Demonstration Coal left Clean of by the by initiation such footprint the processes environmental the reduce industry. coal-to-gas-to-chemicals the in necessary be might as is use a water-gas or methanation intended whenticularly the shift use, par before compounds further sulfur and matter such particulate as any pollutants from freed must product gas first be the system the it that with employed. is emphasized varies Furthermore, composition the gas as insofar are gasification ofvaried products coal fact, the In properties. and of yields gas outcome on composition but gas process; of terms not on also the only the in a bearing having as recognized all conditions reaction are size, and particle matter, mineral of rank, teristics - development technology, and coal charac the aresult, research numerous to As leading programs. of avastly area been expanding has production coal of fact, the from gas commonplace. In became and hotcoal, the the use of water especially gas, aflammable concept of produce to usingthe coal that onwards, it 15th is not surprising the century from of use coal the in rapid increase With the sion of processes) any (by one of of coal avariety combustible produce to (Speight, gases 2013). oil. of crude net importers also who are coal of vast with resources for of countries independence well energy those someas offering measure as of aviable as fuels cited liquid concept option is shortages often forfact, projected the alleviating ever supplies oil are disrupted. crude case in heating, and for oil produce transportation to provide to future for gas liquefaction lighting. the Coal 19th indoor in century maythe used be 1970s).early liquefactionimplemented coal in is quite old, wasduring used technology first and The (during supply Worldsecure (since such Germany of as petroleum, South the Africa and War II) without a countries in used been liquefactionsuch gasoline. Coal diesel historically and as has of products. gaseous amounts stantial coke) desired (in addition the to produces and sub is quite severe coal of temperatures the atthese up 1,500 to achieved is more usually of by use and temperatures the carbonization as to referred more commonly is often scale decomposition on acommercial of coal thermal oldest, one most of represents and of popular, uses The the coal. combustion, carbonization (coke) production ofthe carbon Next products. production well gaseous of as the and liquid to as by accompanied of absence air the in of coal distillation destructive is the carbonization Thus, decomposition process. removaland of thermal liquids) volatile the and (gases products during refer formation but the to more correctly time to time from used also are distillation and tilization excess in of 500 at temperatures is heated coke coal when the residue). of achar—carbonized which involves a to process decomposition (with of coal production ensuing thermal the widespread climate thereby making environment waste the reduction of of into goal effect process emissions the on the and a direct 2013). for have technologies offer which amore clean of potential coal use will coal the Clean the older,efficient and and than conventionalcostlylessmore more cases many in cleaner and environmentally are technologies that utilization coal advanced refers technology clean coal anew to generation term of The particulates. (NOx), airborne and often may be used interchangeably. may used often be However, it applyto isterm more usual the The The In terms of coal use through conversion have through use to of efforts serious made coal processes, been terms In gasificationderivative or a The coal of fromcoal)(i.e., is,essentially, produced converthe char is not received new production has coal of considerable and from fuels liquid The In attention. liquefaction convert to asolidCoal asubstitute used fuel, into coal, for is aprocess fuels liquid carbonization term The

thermal decomposition thermal change. a positive resolution global the to contribution and of issues acid to relating rain is more correctly applied to the process for or production of process the char the to applied is more correctly pyrolysis processes pyrolysis includes (which Handbook of Processes Petrochemical Handbook C (930 °C coal-using (Speight, processes and carbonization and C (2,730 °C ° F). The ancillary terms vola- terms ancillary F). The ° F). The degradation degradation F). The 2 ), nitrogen oxides oxides nitrogen ), pyrolysis C (800 °C processes) (a ther ° F)) F)) - - - - Downloaded By: 10.3.98.104 At: 13:40 26 Sep 2021; For: 9780429155611, chapter3, 10.1201/9780429155611-3 naphtha ( of conveniently analog be petroleum an can as and regarded nature in aliphatic and aromatic both of compounds, a variety benzole), contains from liquor, fraction benzole gas. The and ammonia isolated be can (which benzole benzene although for crude benzene and tar, should mistaken not be like. pitch, the and descriptor, i.e., tar appropriate coal wood of by use clear tar, tar, an the made coal benzole) or as pitch to referred shouldoften anonvolatile be tar ofand the origin pitch. the addition, In yields an oil tar the (volatileof distillation products organic definition, By waymaterials. of further removal of simultaneous decomposition distillate), (thermal the with oforganic distillation various or destructive carbonization, volatile nonvolatile the and during soluble produced are that products the to applied is usually “tar” term caution. should with applied ambiguity, be The terms of use these (Chapter substance 16). occurring However, orproduct anaturally avoid to and correct be any to or pitch it whether amanufactured be tar is popularly, as incorrectly, often described material and 2014 wellas heteronuclear compounds. as polycycliccontains methyl derivatives polymethyl hydrocarbon and their and aromatic derivatives, pitch is The ashiny, tar. of coal brown black to distillation dark residue the that during produced pitch nonvolatile is the tar coal residue creosote, tar coal and tar coal the Unlike mixture. creosote of majority the the derivatives—constitute derivatives ring naphthalene condensed higher ring and derivatives.lene, phenanthrene Typically, and polycyclic derivatives—two- hydrocarbon aromatic - naphtha derivatives, consist hydrocarbon of creosotes aromatic anthracene, tar coal brown. The have They tar. of coal oily color to consistency liquid in yellowish-dark an range from and green product is adistillation creosote tar pitch. coal By tar available comparison, coal are and for tar, coal data limited although similar, of are each physical properties The chemical and lation tars. of coal flowsheavy oil theyeasily be heated. must heat. Before create to in order any boilers, fire used is for often composition tar flammable coal phenol derivatives, heterocyclic oxygen, derivatives. nitrogen compound and sulfur, of Because its ofbination polycyclic PNA (PAH, as well) hydrocarbon as represented often aromatic derivatives, odor. is acomplex Chemically, anaphthalene-like with tar or liquid semisolid viscous com coal ( (namely, carbonization byproducts during tar) produced liquor, benzole, and crude gas, ammonia or secondary the with deal to necessary) emerged (in fact, became industry but asecondary of coke producing (Chapter a means as initially was established industry carbonization coal The c 3.2.4 byproducts formed when coal is carbonized ( is carbonized when formed coal byproducts brown-colored is or liquid ahigh-viscosity black or which dark semisolid is one of tar the coal Coal, Oil Shale, and Biomass and Shale, Oil Coal, Table Thus, the eventual primary products of the carbonization process (Chapter process 16) coke, coal carbonization of are products the eventual primary the Thus, ( industry petroleum of the that industry, like tar coal aside, of nomenclature the the an As distil the from obtained mixtures similar very are creosote tar pitch, coal and tar coal tar, Coal Coal tar is a byproduct of the carbonization of coal to produce coke and/or natural gas. Physically, coke natural produce to and/or of coal is carbonization abyproduct of the tar Coal , 2017 3.1 Speight, 2014 Speight, ) ( oal ), needs refinement and clarification. Almost any black, undefined, semisolid-to-liquid Almost any undefined, black, and refinement), clarification. needs Speight, 2013a Speight, T ar C Gas Product %w/w (% Products w/w)Bulk Carbonization Coal from 3.1 TABLE Liquids Tar Coke hemicals ). ). Low-temperature Carbonization Speight, 2013a Speight, 15 10 70 5 ). Coal tar usually takes the form of form a the takes usually ). tar Coal High-temperature Carbonization 20 75 2 3 Speight, 16) 16) 85 - - Downloaded By: 10.3.98.104 At: 13:40 26 Sep 2021; For: 9780429155611, chapter3, 10.1201/9780429155611-3 86 the range 19.0–36.0 range the (60–75gallons is approximately 15.5–19.0 retort yield but the a continuous vertical from carbonized of coal and xylenols) into carbolic oil fractions. On the other hand, the objective the xylenols)and coke hand, with oven other is to the On fractions. oil tar carbolic into (phenol, acids cresols, objective tar the the is concentrate to retorts, continuous vertical from tar conditions. feedstock) processing For coal the of example, upon case the the and depends the in tar (which crude the of the nature by influenced of ranges which are boiling and amounts tions, the solvents insoluble ( for amounts certain the in limits ( additionin constituents paraffinic pitches contain retort vertical itand that is reasonable assume to Some rings. methyl six to hydroxyl and three substituent have observed, groups containing been also derivatives hydrocarbon of polynuclear condensed or heterocyclic aromatic dominantly compounds orproduct for production of asphalt. the road pitch as atachieving a medium-soft is aimed distillation (Chapter 17) binder, or electrode primary outlet the pitchmain as a briquetting for the is If point. residuesoftening desired the of refined-tar apitch or is obtain to distillation objective another of hand, primary other the On products. ticular par recovered these be from can by chemicals which means various the is often distillation and anthracene comparatively and Coke naphthalene oven are in rich tars. tars retort continuous vertical the and are phenolicreactions)from relative mightbe than expected lack (as secondary of paraffinic are more tars mayLow-temperature have compounds. tars up 6% to retort of paraffinic vertical the xylenols higher-boiling phenols. mainly and are tar retort vertical phenol,comprise methyl poly-methyl and phenols (e.g. xylenols) cresols and naphthols; and in those up 30% to phenolic Moreover, may compounds. contain tars phenols coke the oven in mainly tars of recovery method (Chapter the 16). and equipment, of carbonizing type the of coal, type due the to tars the present in proportions the in variations marked are but there facture, of manu method the to regard little with usually tars, the in occur classes compounds of chemical weight molecular high to Similar compounds. such polynuclearspecies, benzene, as aromatic corrosion resistance. ( of the to which both contribute resistance, dielectric high there and moisture to low permeability their extremely is coatings tar-based of refined quality outstanding acids. Another inorganic and oils under petroleum holdcoatings of tar-based exposures better Refined coatings. up asphalt than tance polycyclic derivatives source. hydrocarbon upon the depending aromatic of have amounts will varying that compounds of chemical hundreds contains tar Coal is desired. that product refined upon the depending tar coal w/wdensity 20–50% represent oils crude of the These low-density products. and medium- tar coal refined various produce to tar coal crude the from coke Company Koppers byproduct first completed the around ovens 1912. since UnitedStates the in have processed been tars coal Crude chemicals. specialty and coatings, plasticizers, rubber, concrete, production of the aluminum, components in essential as used oils and tars, refined products, carbon various produce to distilled is further that is araw material tar coal Crude operations. foundry in steel and manufacture to agent ablast smelting in furnace ore in iron areducing coke. as and afuel make to Coke of as is coal used carbonization the during collected McNeil, 1966 McNeil, The yield of byproduct tar from acoke yield oven from The of byproduct tar is, on average, 8.5–9.5 Primary distillation of crude tar produces pitch produces (nonvolatile tar of crude distillation residue)- frac several and distillate Primary of composition, positively compounds terms the In as pitch identified components consist pre derivatives, hydrocarbon of quantities non-aromatic whilst only minor Coke oven contain tars relativelyCoke oven contains low tar (ca. proportions 3%) (phenols), acids of tar retort vertical low-boiling, components from range the and low is a complex weight molecular tar mixture Coal resis have - coatings tar-based advantage chemical great Refined better that a overhas in it asphalt removed low-density are oil tar, coal medium-density of and oil crude distillation the During is abyproduct coke oven or simply tar crude as to coal referred tar sometimes tar coal Crude ). Pitches are often characterized by solvent quote specifications many analysis characterized and ). often Pitches are L) per ton of coal carbonized. In low-temperature retorts, the yield of tar varies over yield varies the of tar low-temperature retorts, In L) carbonized. ton of per coal U.S. (75–135 gallons Munger, 1984 Munger, ). L) ton of per coal. Hoiberg, 1966 Hoiberg, Handbook of Processes Petrochemical Handbook ). U.S. (32–36 gallons L) ton per U.S. - - - Downloaded By: 10.3.98.104 At: 13:40 26 Sep 2021; For: 9780429155611, chapter3, 10.1201/9780429155611-3 Coal, Oil Shale, and Biomass and Shale, Oil Coal, (C 2- ing fraction (170 fraction ing for hydrogen acid. astabilizer as which acid, is used peracetic peroxide and linic dipico converted to be (2,6-dimethylpyridine) can 2,6-Lutidine The drug. which is atuberculostatic acid hydrazide (Isoniazide) of isonicotinic manufacture the in 4-methylpyridine) intermediate is an γ diets. animal and human widelycomplex; fortify to are used products both (nicotinamide), form B amide which acid, belongs the with vitamin the to nicotinic to oxidized young coccidiosis in against poultry.is used (3-picoline; Beta-picoline be 3-methylpryridine) can (Amprolium) compound which for synthesis of cattle)mintic quaternary a2-picoline the in and automobile the nonpersistentthe herbicides paraquat. and diquat of manufacture the is in for market pyridine Another of antihistamines. preparation the in used are ­ 2- derivatives and The synthesis of 2-benzylpyridine drugs. the in agents and repellant line, and quinaldine. isoquino quinoline, mainly are these and higher-boiling range the in occur bases tar Other ­resins. coumarone and naphtha, bases, pyridine contain tar the from distillate of the fractions boiling solvents. specialty as Higher- marketed be can xylene isomers since pure mixtures individual the xylenes low-boiling not foams. The always the into present in are oil polyurethane separated and trinitrotoluene, of saccharin, preparation the in material toluene hand, is astarting other the On of including nylon, products numerous aniline. polystyrene, and phenol, gammexane, nitrobenzene, toluene, benzene, xylene(s). and yieldto containing afraction manufacture the in is used Benzene solvents. as used distilled be are can benzole To fractions naphtha the products, These pure obtain the 150the when obtained mixtures the are naphtha below high-boiling Low-boiling and naphtha benzene. (cyclicnaphthenes compounds), aliphatic nitrogen compounds. and phenols, well as sulfur as zene, toluene, xylene(s) and derivatives, hydrocarbon of quantities aromatic paraffins, minor with ben coke components are works oven atgas in gases and main plants. The carbonization the from recovered benzole composition crude chemical the to in low-boiling benzole, is similar or crude oil, blends. tar their Coal pitch, and creosote, which are products bulk and cessing fractions, of the respectively. oil, anthracene and oil naphthalene components into anthracene and naphthalene the concentrate vinylpyridine which, when copolymerized with 1,4-butadiene with (CH which,­vinylpyridine when copolymerized 6 The tar-acid free and tar-base free coke oven naphtha can be fractionated to give to boil coke oven anarrow fractionated free tar-base be and can naphtha tar-acid free The of 2- preparation the in are uses Other Alpha-picoline (CAlpha-picoline asolvent, water- textile as long used chemicals, has production of been the rubber ­ in Pyridine The first step in refining benzole is steam distillation is employed distillation benzolesteam is to remove refining in step boiling first compounds The pro further the made by products, refined into divided be can distillation of products tar The H 5 CH °C–200 = CH

tires. 2 ), produces a used as a latex adhesive which is used in the manufacture of a latex), as adhesive manufacture a used produces the which in is used C (300 °C °C–185 6 ° H C; 340 °C; F–390 7 N, 2-picoline; 2-methylpryridine) for production is used of the ° F) fraction, after removal of tar acids and tar bases, is fractionated. is fractionated. bases, tar removal and acids of after tar fraction, F) ° F–365 ° F) containing coumarone and indene. This is treated with with is treated indene. This and coumarone containing F) β 2-methylpyridine -methoxyethyl pyridine (known as Promintic, an anthel an -methoxyethyl Promintic, as (known pyridine 2,6-Lutidine 2 = CHCH -Picoline (4-picoline, (4-picoline, -Picoline = CH aminopyridine, 2 ) and ­ ) and styrene styrene 87 ------Downloaded By: 10.3.98.104 At: 13:40 26 Sep 2021; For: 9780429155611, chapter3, 10.1201/9780429155611-3 insecticide. (DNOC), herbicide/ ageneral acid (MCPB) butyric well the as 2,4-dinitro-o-cresol and as 4-chloro-2-methyl-phenoxyacetic acid (MCPA) propionic acid (MCPP) corresponding the and of 2,4-dichlorophenoxyacetic acid (2,4-D)manufacture which is aselective killer. weed the is use in important phenol, derived another from and all agents are tanning detergents, and certain pharmaceuticals, other many and Aspirin preservation. timber in and afungicide as used of pentachlorophenol which is phenols. manufacture ­p-t-butyl the Phenol p-octyl in and is used nylon,as of on bisphenol polycarbonates epoxy based and of resins oil-soluble Aand from resins plastic field the in uses include productionthe polyamides of such important other while resins, of byexceeded phenol. synthetic that Phenol for production is used of the phenol-formaldehyde recovery. for naphthalene taken then phenol-free which oils the are from iscresylate. separated extract The or sodium phenolate, carbolate, phenate, sodium sodium sodium variously crude known extract as aqueous an as hydroxide salts sodium sodium phenols the with giveThe to react corresponding the sufficientpreventto crystallizing. from atatemperature naphthalene caustic soda aqueous with phenol-depletedthe for oils recovery. naphthalene by Tar oils extraction of produced the are acids process thento and the oils from the phenolic compounds first to extract It tar. is necessary coal polishes. and in paints and tiles production of brown color. the flooring in in used dark to are amber They pale from vary obtained resins the off and is distilled oil Unreacted coumarone. of the part and indene acatalyst with (such is heated concentrate fluoride/phenol aboron as complex) the polymerize to The redistilled. washed and is then components and acid remove to unsaturated strong sulfuric 88 4-hydroxytoluene), an antioxidant. Paracresol (p-HOC Paracresol selective of the killers: weed for manufacture the predominantly used been has Orthocresol Phenol (C volatile from from oils extracted products important the are acids severalNaphthalene and tar 6 H 5 OH) is a key industrial chemical; however, chemical; is akeyOH) industrial is output of tar the phenol coal from 6 H 4 CH 3 ) has been used widely for the manufacture of widely BHT (2,6- used been for) has manufacture the 4-chloro-2-methyl-phenoxyacetic acid(MCPA) 2,4-Dichlorophenoxyacetic aci 2,4-dinitro-o-cresol (DNOC) Handbook of Processes Petrochemical Handbook d - ditertiarybutyl Downloaded By: 10.3.98.104 At: 13:40 26 Sep 2021; For: 9780429155611, chapter3, 10.1201/9780429155611-3 Coal, Oil Shale, and Biomass and Shale, Oil Coal, 200 is range distillation approximate The tars. coal of crude distillation by fractional the odor, obtained ( tions - frac have bases removed corresponding been tar the acids, and from tar anthracene, naphthalene, andanthraquinone. to oxidation purification after 480 glyptal resins and plasticizers for plasticizers plastics. polyvinyl and other resins and chloride glyptal and of alkyd manufacture the in which is used anhydride phthalic produce to oxidized be lene can - naphtha (75–90% majority w/w)oven separation, the contain naphthalene. After tar, total of the of case coke the which, oils in into naphthalene the concentrates tar crude of the fractionation mary disinfectants. nonionic detergents, oils, and cutting antioxidants, resins, wire-coating additives. petroleum and plasticizers into the surrounding environment have brought an awareness of the potential environmental and and have environment environmental awareness brought potential of an the surrounding the into of seepage processing. of such Issues the to products coal related complex mixtures chemical close preservative come recently under has scrutiny, atimber as have as ill-defined other many black. However, of carbon lampblack and manufacture the in and ofbitumen, use creosote the concentration. and type consistentrarely their in components are creosote the aresult, process; as distilling of the by nature also the and coal of the Coal tar creosote is the residual distillate oils obtained when the valuable when the components, such as obtained oils distillate residual is the creosote tar Coal The main chemical extracted on the commercial scale from the higher-boiling oils (b.p. higher-boiling oils the from scale 250 commercial on the extracted chemical main The pri The tars. coal Naphthalene is probably component high-temperature most in abundant the as solventsdegreasing, outlets agents for flotation, metal as for cresylicOther are froth acids for production of the phenoplasts, in tritolyl used phosphate are mixtures paracresol and Metacresol Major preservative,oils fluxing for havefor uses andpitch as a timber creosotes as been ° °C–400 F) is crude anthracene. The majority of the crude anthracene is used in the manufacture of dyes manufacture the in is used anthracene crude of majority the The anthracene. is crude F) Figure 3.1 Figure C (390 °C ). It is a brownish-black/yellowish-dark green oily liquid with a characteristic sharp sharp ). oily acharacteristic It with liquid is abrownish-black/yellowish-dark green ° F–750 ° F). The chemical composition of creosotes is influenced by the origin composition the origin by chemical is influenced ofF). The creosotes 2,6-ditertiarybutyl-4-hydroxytoluene Phthalic anhydride m-cresol p-cresol C, °C, 89 - Downloaded By: 10.3.98.104 At: 13:40 26 Sep 2021; For: 9780429155611, chapter3, 10.1201/9780429155611-3 90 shale. Oil shale must be heated to temperatures between 400 between temperatures to must shale heated be shale. Oil decomposition kerogen of the component of by thermal shale oil oil the from Shale is produced oil s 3.3.1 oxygen-, compounds. nitrogen-, sulfur-containing or by by of content concentrations also high heteroelements of and large range by and wide boiling 2008 Speight, (cracked) (shale product liquid the produce to oil) ( decomposed kerogen which the by in is thermally must aprocess produced be any oil—this contain kerogen is called shale the in contained (kerogen) material organic shale. matter The the organic of in the decomposition by thermal produced be to has awell pumping. Oil and by sinking resource the from directly produced be is considered shale unconventional oil cannot coal, oil and Canada) because ( sand tar Like resource. hydrocarbon mostly and untapped a large represents shale Oil 3.3 mention to only afew. construction wall cover, landfill cementing for stabilization, roadbed contentthe materials),(due to andpozzolanic of materials as ash of use the relates the to that and must addressed, content be that of coal mineral ( recovery of valuable materials inorganic for offer the potential and the matrix coal of the part important avery are minerals Coal processes. coal from ash a tendency-to-be-forgotten coal, mineral from is the item included. mustbe That also used. be can chemicals before such is now of use testing such Stringent the to required related chemicals. hazards health 3.1FIGURE position importance. is of great 2008 ( more hydrogen relatively decomposed produce can and when gas thermally and more oil hydrogen kerogen shale oil convertible coal, with content the contains in solid compared fuel. Thus, gases. Generally, solid with fossil on the yield fuels, the volatile of mainly the depends products kerogen to combustible and oil sediments convert to embedded the is necessary process heating As a corollary to this section, where the emphasis has been on the production of bulk chemicals chemicals production of on the bulk been emphasis where has section, the this to acorollary As I SHALE OIL , 2012 , a solid material intimately bound within the mineral matrix. However, matrix. not mineral does shale oil the within bound intimately , a solid material hale , 2013). com asubstitute of as for oil the shale products, standpoint petroleum From the

Representation of the production and composition of coal tar creosote. tar of composition coal and production of the Representation ). Compared to crude oil, shale oil obtained by retorting of oil shale is characterized of is characterized shale oil by retorting obtained oil shale oil, crude to ). Compared O il P roduction Speight, 2013a Speight, Scouten, 1990 Scouten, ). However, of the aspect is another there Handbook of Processes Petrochemical Handbook C and 500 °C and ; ; 1991 Lee, C (750 °C Lee et al., 2007 Lee ° F–930 oil sand oil ° Speight, Speight, F). This F). This in in - ; Downloaded By: 10.3.98.104 At: 13:40 26 Sep 2021; For: 9780429155611, chapter3, 10.1201/9780429155611-3 (ii) ­processing— decomposition kerogen shale: of the the (i) in thermal low-temperature the of accomplishing disposal of spent shale, use of water resources, and impacts on air and water quality. and on air of impacts spent shale, of and use disposal water resources, mental impacts of involve processing shale oil and of environ mining Both avariety is reclaimed. land mined the mine. the Eventually, intoit by backputting often disposed, the refinery,spent be mustshale and before processing sent a be to it can by further must oil upgraded which be the after for retorting afacility to is transported shale oil the mining, After or wall. (ii) by aheated conduction through by by which shale is provided by heat hot the to gas—(i) asolid manner carrier heat is the differ processes way retorting of various which heating. Another method the in the to according egorized cat further be can turn, in method, Each may used. be methods mining or underground mining depositional setting. natural situ in of true In situ technology. by situ in produced be can oil shale methods, high-valueand or deep-mining For deposits, chemicals. deeper, thicker amenable not surface to as kerogenof produce to (iii) kerogen shale feedstock oil processing and oil, refinery produce to oil (ii) ­ preparation, ore major and steps: consists (i)face of processing three mining shale oil (e.g., Generally, retorting ground. sur the the place and is left in shale in occurs shale of heating) the option second ( the In retort. a surface in shale oil have treat to used been pyrolysis Both retort. ­ shale oil and an in surface atthe processing thermal subjected to high yieldA high yield deposit ton of of of gallons 25 per will shale. oil shale oil oil decomposition ( well shale of situ in the as followed shale of as the processing technologies have including mining used by been thermal can vary in properties and composition and ( properties in vary can shale oil retorting from raw produced shale. oil oil shale (kerogen) The in matter organic contained pyrolysis is the and shale oil of product by the retorting produced oil crude Shale is asynthetic oil s 3.3.2 Coal, Oil Shale, and Biomass and Shale, Oil Coal, compounds ( compounds oxygen 0.5–1% w/w, 0.15–1% sulfur and metal-containing and particles w/w well as mineral as compounds). composition oil shale includes: Atypical sulfur-containing nitrogen 1.5–2% w/w, and compounds, oxygen-containing compounds, of (nitrogen-containing heteroatom compounds ofquantities derivatives olefin derivatives aromatic hydrocarbon as ­ and as well significant large contains oil. of Shale usually oil the properties using bulk derivatives, it and is characterized or evenconcentrate, values. compound pure group, range broad on functional based have products marketed of specialty number been nonfuel a also and industry chemicals specialty of the to interest structures molecular possess oils shale even have fuels liquid and beforevarious produced World exported been time, War same At the II. arelatively to so far used been extent. has Using chemicals small stepwise specialty cracking, and present. are iron and of arsenic quantities a relatively has Shale also compounds. oxygen-containing oil small and point pour high the order of 0.9–1.0gravity—on cific nitrogen-, high-boiling and presence the sulfur-,of to owing oxygen nitrogen and in is spe high oil shale ahigher and petroleum, with compounds Compared oil is less fluid than crude oil, which is reflected in the pour point that is in the order of 24 the order of in that is point pour the in reflected oil, which is crude is lessoil than fluid

Depending on the depth and other characteristics of the target oil shale deposits, either surface deposits, shale oil either surface target of the characteristics other and depth on the Depending In the mining-thermal processing option processing ( mining-thermal the In The thermal processing of oil shale to oil has quite a long history and various facilities and and facilities various and quite along of has oil to processing shale oil history thermal The Shale oil (produced from kerogen-containing shale rock) shale of hydrocarbon is acomplex kerogen-containing from Shale (produced oil mixture fuel liquid that from and oil shale produce to fuel retort of as shale oil potential chemical The high-temperature high-temperature hale Scouten, 1990 Scouten, semicoking or retorting—by heating the oil shale up shale about to oil 500 the heating or retorting—by ­semicoking , eliminate the need for mining and surface pyrolysis, its in surface resource and the by heating for need mining the , eliminate O , such as global warming and greenhouse gas emissions, disturbance of mined land, land, of mined emissions, gas disturbance greenhouse and , such global warming as il P ro processing—coking—heating up 1,000 to ­processing—coking—heating p erties ; ; 1991 Lee, ; 1991 Lee, Scouten, 1990 Scouten, production), oil shale is mined, crushed, and then then and production), crushed, situ ex is mined, shale oil Speight, 2008 Speight, Lee et al., 2007 Lee ; ; 1991 Lee, , 2012 processes minimize, or in the case case the or in minimize, processes ). In principle, there are two ways are ). principle, there In °C–1,200 Lee et al., 2007 Lee ; Speight, 2008 Speight, production), situ in the C (1,830 °C C (930 °C ; ). Generally, the Speight, 2008 Speight, ° F–2,190 combustion combustion quantities °C–27 pyrolysis pyrolysis ° F), and F), and ° F). F). °C 91 ). ). - - - - Downloaded By: 10.3.98.104 At: 13:40 26 Sep 2021; For: 9780429155611, chapter3, 10.1201/9780429155611-3 (75 92 occur as phenols carboxylic as acids. and occur 30% w/w consistswhich of The remaining compounds, disulfides. oxygen-containing and sulfides well as which thiophenes as exists compounds, in sulfur bound organically components contains 10% w/w components. 60% Another organic comprises heteroatomic w/w of the typically of these and well nitriles, as in e.g., pyrroles as ring, the nitrogen pyridines, with in compounds pyridines, oxygen. and ring in nitrogen, sulfur, nitrogen occurs which contain compounds, The organic atomic range. boiling in arise derivatives with alkene range,ing while decrease boil in derivatives slightly a rise with aromatic increase the and derivatives increase oil shale the in hydrocarbon Saturated product. oil shale of ranges the derivatives boiling different the aromatic in derivatives, hydrocarbon derivatives, alkene and of saturated distribution of the is avariation There monocyclic,are bicyclic, homologues. alkyl-substituted derivatives tricyclic their and aromatic and derivatives, cycloalkenealkene derivatives and components of aromatic derivatives, main the while atives, derivatives cycloalkane derivatives, alkene and consist the of and n 200 of n- concentrations 300 atlow times reaction temperature greater slower use that conditions, Processes with heating structures. weight aromatic lar multi-ring and oxygen compounds. and nitrogen 2008 Speight, by method which it ( was produced retorting on the as oil. However, well as which composition it from shale the was on the of obtained depends oil shale raw the shale throughout distributed are alkanes the and waxes alkanes consisting of long normal of quantities gives shale oil significant to in rise matter organic of the structure fundamental The Products Hydrocarbon 3.3.2.1 before oil shale itthe is blended aconventional with liquid. petroleum removed are cause such from incompatibility that functions the all that ensure to must taken be care ( products conventional petroleum and feedstocks petroleum issues worthyof also consideration) are incompatible compounds be to oil cause shale with can fur byproducts. as oil shale from produced cides. are fuels Some conventional distillate such various coke products as and diphenyl phenol-formaldehyde ketonepesti and and chemicals, modifiers, adhesive rubber resins, agents, adhesives, epoxy and resins tanning produce derivatives to high-value and intermediates resorcinol for alkyl other production 5-methylresorcinol of and pure crystallized and tionated Water-soluble product. specialty oil-derived selectively- phenols are frac oil, shale from extracted effective produce to used of for oil impregnation wood amajor are as the shale properties septic having Higher-boiling (mid-distillate)anti fractions oil shale produced. of are oil shale fractions tolueneand for production of well acid on as benzoic pyrolysis solvent as of lower- mixtures benzene, softeners, rubber oils, anticorrosion mastics, construction asphalt, road blending material, polycyclic contains derivatives.also hydrocarbon aromatic to ( anitrogen to content nitrogen of contenthigh 0.2–0.3% w/w compared petroleum for atypical olefin and diolefin content—constituents, which are not present in petroleum and which require whichrequire and petroleum in arepresent not diolefinwhich andolefin content—constituents, Scouten, 1990 Scouten, + Shale oil not only contains a large variety of hydrocarbon compounds ( of compounds hydrocarbon variety alarge Shale not oil only contains w/w 40% derivatives hydrocarbon River w/w 60% contains oil shale and Green hetero A typical Saturated hydrocarbon derivatives include oil shale hydrocarbon the n in Saturated Retorting processes, which use flash pyrolysis, produce more fragments containing high molecu which flash use processes, pyrolysis,containing fragments Retorting more produce However, oxygen nitrogen and (containing constituents polar of presence the sul the functions, asphalt- fraction, high-boiling the of in quantities on compounds oxygen-containing large Based ° °C–400 86 F–81 ° F), which affects the ability of shale oil to be transported using unheated pipelines. Shale pipelines. oil using unheated transported of be to oil shale ability the F), which affects ° F), while conventional crude oil has a pour point in the order of order − the in point apour conventionalF), has while oil crude C, 390 °C, ). As compared with petroleum crude, shale oil is high-boiling, viscous, and is high in in is high and viscous, is high-boiling, oil shale crude, petroleum with ). compared As ; ; 1991 Lee, ° alkanes. Naphthene-aromatic compounds of intermediate boiling range (such range boiling as of compounds intermediate Naphthene-aromatic alkanes. F–750 ° F) also tend to be formed with the slower the with formed be to tend processes. also heating F) Lee et al., 2007 Lee ; Speight, 2008 Speight, °C–400 Scouten, 1990 Scouten, C (570 °C Handbook of Processes Petrochemical Handbook ). In addition, shale oil also has a high ahigh has ). also oil shale addition, In Speight, 2014 Speight, -alkane derivatives, iso-alkane deriv ° F–750 ; ° ; 1991 Lee, F), tend to produce higher higher F), produce to tend ). As a result, particular ). particular aresult, As -alkene derivatives, iso- -alkene Table 3.2 Table 60 C to + °C to Lee et al., 2007 Lee ), has but also 30 °C ( boiling ­boiling − 76 ° F ------; Downloaded By: 10.3.98.104 At: 13:40 26 Sep 2021; For: 9780429155611, chapter3, 10.1201/9780429155611-3 Speight, 2008 Speight, Coal, Oil Shale, and Biomass and Shale, Oil Coal, are the nonbasic constituents. the are homologues amide and derivatives, nitrile the their and indole, and pyrrole, basic carbazole ones are derivatives, alkyl-substituted weakly the their and amine, acridine, quinoline, pyridine, are oils classifiedas be basic, basic,and can oils nonbasic. weakly in nitrogenThe shale basic compounds shale. oil the in species organo-nitrogen the providesprocesses regarding valuable information analysisretorting by that is the extracted of oil shale rock difficult, is very shale oil in compounds of of forms nitrogen-containing molecular determination analysis and deposits.shale Since direct of oil heavily geochemistry depend on the types and amount the and shale oil the from originated all are catalysts. nitrogenSuch compounds refining of poisoning the particular, of in oil, shale processing the downstream in difficulties technological render oil Nitrogen shale in compounds 3.3.2.2 of complexes.emulsification properties and metal of specific water explain the also solvents. nitrogen of polycyclic the weightmolecular polarity alkane The may constituents aromatic weight—for molecular high than example, hydroxy-pyridine the derivatives insoluble are low in rather fraction asphaltene an precipitation causes as content it oil, shale that heteroatomic is high since, in may oil unique shale be in constituents product—asphaltene a distillate being oil shale refinery. particular of economics the individual of the availability equipment and on the depend largely will selected process reforming. The and cracking, catalytic hydrotreating, hydrocracking, coking, distillation, are refining oil the in basic operations unit of The products. oil shale properties improve to the needed are processes of further oil, shale characteristics of the because Thus, als. (v) and retorting, vapor oil during the rock in of low-to-moderate the levels entrainment to of met present), are compounds (iv) sulfur shale, high solids suspended (finelydividedrock) due typically oil available world the mostwith in crudes of (though marine retorting for the some from oils shale (ii) diesel fractions, kerosene lowto and ratio, levels, (iii) hydrogen-to-carbon low sulfur compared refining. with nickel interfere and that iron, of arsenic, appreciable amounts contains also oil Crudeshale refining. in difficulty nitrogen content, which high with gives characteristic the oil shale deposits).line olefin of presence derivatives It these diolefin is the and derivatives, in conjunction (fuel sediments and gums form and tendency polymerize to due their to processing during attention ; 1991 Lee, Most of these compounds are useful chemicals ( chemicals useful Most are compounds of these ( oil crude is oil relatively shale natural nitrogen content the in in The than higher is low— oil shale in constituents content resin of and/or constituents the asphaltene Although of (i) are: oils shale levels properties high deleterious compounds, of characteristic aromatic Other irgnCnann Compounds Nitrogen-Containing Lee et al., 2007 Lee ), although some of them are believed to affect the stability of oil. shale Generally, stability believed), the some of are although affect to them ; chrysene phenanthrene biphenyl naphthalene tetralin indan Benzene Aromatic Olefin cycloparaffin paraffin Saturate Types Oil Compound in Shale Major 3.2 TABLE Speight, 2008 Speight, ). The nitrogen-containing compounds identified in shale in shale identified compounds ). nitrogen-containing The Scouten, 1990 Scouten, pyrrole ketone nitrile quinoline pyridine carbazole phenol dibenzothiophene benzothiophene Heteroatom systems ; ; 1991 Lee, Lee et al., 2007 Lee Scouten, 1990 Scouten, 93 - ; ; Downloaded By: 10.3.98.104 At: 13:40 26 Sep 2021; For: 9780429155611, chapter3, 10.1201/9780429155611-3 range of petroleum distillates, they are more concentrated in the residuum. the in more concentrated are they distillates, ofrange petroleum the throughout occur compounds these atom. Although forent, provides sulfur protection the steric - pres are groups on alkyl two if sides and, sulfur the attaches structure ring molecular the because prove that to compounds difficult hydrotreat thiophene-type multi-ring in is bound sulfur remaining new However, units. adding diesel to belowtreating 500 in may difficulty refineries face 500 current ( oil but oil shale others. is absent is in found some crude in sulfur Elemental compounds. sulfur miscellaneous and other thiophenes, include oils shale sulfides, the thiols, in compounds Sulfur 3.3.2.4 ( boiling low- the in compounds oxygen-containing Other 3-alkanones. and exist 2- as mainly oil shale the contents in shale oils are much higher and vary with different shale oil ( oil shale different with vary much and higher are oils shale contents in derivativesally of phenol, poly-methylated such cresol and as phenol derivatives. usu are low-boiling and oil shale the of in the fraction acidic compounds oxygen-containing main oxygen the phenolic Low present. are molecular compounds also such ketones compounds as are nonacidic and acids phenolic constituents—carboxylic oxygen mainly are oil shale in compounds weight Low molecular petroleum. oxygenThe natural in content of is muchoil shale than higher 3.3.2.3 of which emulsions oil, shale forms water. with colloidal nature and surface nitrogen content the to high of color could contribute oil shale The and product. oil odor shale of the give the viscosity to and the rise in increase which cause an processes, polymerization induce they storage since of problems products oil shale during stability to contribute also They processes. lytic 350 homologues its alkyl-substituted than and is higher of point benzoquinoline boiling the because homologues,substituted the lower-boilingin present could not significantly be fractions oil shale alkyl- and derivatives, acridine one principally nitrogen atom. Benzoquinoline contain majority the oil. shale of the fraction point boiling high- the in may occur Porphyrins fractions. oil shale of point the boiling the in arise with increases nitrogen Pyrrole-type but oil, shale fractions. point have tendency exist high-boiling to adecided in of ranges the boiling the throughout Nitrogen fractions. point occur compounds boiling different the is evenly in nitrogen, and total distributed of forbasic the nitrogen accounts about one-half 94 et ( feedstocks available or fuels chemical useful into plant energy subsequent devices the conversion with energy-capturing solar of activecally natural as plants (and been has photosyntheti attention is being) givenIncreasing possibility of utilizing the to 3.4 < the present in also are hydes, amides and esters, such ketones, group as alde acarbonyl with nonacidic functional compounds oxygen-containing fraction. point high-boiling the in concentrated most oxygen of and the increases, point boiling are atoms the as it general, increases oil.shale In et al., 2007 Lee

al., 2016 al., Generally, the sulfur content of oil-shale distillates is comparable in weight percentage to crude weight in is comparable crude to content percentage of oil-shale distillates Generally, sulfur the The oxygenThe of order 0.1–1.0% the in content ofis typically petroleum w/w, oxygen the whereas - cata different in catalysts poison oil shale the the in compounds nitrogen-containing Organic low-boiling the in ( compounds nitrogen-containing the Of Other oxygen-containing constituents of shale oil include small amounts of carboxylic of amounts and constituents acids oxygen-containing include oil shale small Other C (660 °C BIOMASS Scouten, 1990 Scouten, ufrCnann Compounds Sulfur-Containing xgnCnann Compounds Oxygen-Containing < 350 ; ° ppm requirement by increasing the existing capacity of their hydrotreatment units and and units hydrotreatment of capacity existing their the by increasing ppm requirement F). Wu et al., 2016 C, < °C, ). In addition, the oxygen content varies in different boiling point fractions of the of oxygen the ). fractions point the addition, In boiling different in content varies ; 660 ; 1991 Lee, ° F) fraction include fraction constituents. alcohols, ether naphthol,F) and ). Acquisition of follows biological for capture energy raw materials Lee et al., 2007 Lee ; Speight, 2008 Speight, 350 °C ( < Handbook of Processes Petrochemical Handbook 660 ). Refiners will be able to meet the ablebe ).to meet will Refiners ° < F) fraction of oil. shale Ketones fraction in F) 350 Table 3.3 Table °C < 660 Scouten, 1990 Scouten, ) ( Metzger, 2006 Metzger, ° F) shale oil fraction, fraction, oil shale F) ; ; 1991 Lee, ppm. The The ppm. ; Biddy Biddy - - - Downloaded By: 10.3.98.104 At: 13:40 26 Sep 2021; For: 9780429155611, chapter3, 10.1201/9780429155611-3 Coal, Oil Shale, and Biomass and Shale, Oil Coal, 1,3-Propanediol Lactic acid Isoprene Glycerin Furfural Fatty alcohols Ethyl lactate 1,4-Butanediol 1,3-Butadiene Chemical Bio-Sources from Produced of Chemicals Examples 3.3 TABLE A linearaliphaticdiol,whichmakes itausefulchemicalbuilding block;canbeused fora An alpha-hydroxy acidwithdual functionalgroups;mostfrequentlyoccurringcarboxylic The building blockforpolyisoprenerubber, styreneco-polymers,andbutyl rubber; A polyhydric alcoholandisamaincomponentoftriglyceridesfoundinanimalfats and A heterocyclic aldehyde, producedbythedehydration ofxylose,amonosaccharide often Also calleddetergent alcohols,arelinearalcoholsof12ormorecarbons,usedprimarily A biodegradable solvent producedbytheesterificationofethanolandlacticacid;primary A building blockfortheproductionofpolymers,solvents, andspecialtychemicals; The building blockfortheproductionofpolybutadiene andstyrene-rubberbutadiene are usedintextiles andfibers. lubricants; alsousedasacomponent inpolytrimethylene terephthalatepolymerswhich variety ofapplicationsincludingpolymers,personal careproducts,solvents, and tableware, shrinkwrap,and3-Dprinters. polymers; polylacticacidhasgained popularityforuseinfood packaging,disposable applications infood,pharmaceuticals,personalcareproducts,industrialuses, and acid innature;producedbymicrobialfermentationofcarbohydrates; usedfor produced byaerobicbioconversion ofcarbohydrates. and succinicacid;emerging usesincludeanimalfeedandmarinefuel. products; afeedstockforconversion tomorevaluable products,suchasepichlorohydrin therefore, theoverall supplyofglycerinisdriven primarilybythe demandforthese propyl; biodieselandsoapproductionaccountsformostcurrentglycerinproduction; in theoleochemicalindustryduringsoapproductionandisproducedsynthetically from formulation; glycerinisthemainbyproductofbiodieselproduction.It alsogenerated compound 1,2,3-propanetriolandtotheanhydrous contentinaglycerinproductor mostly glycerol;theword “glycerol”mostoftenrefersspecificallytothechemical vegetable oil. The word “glycerin”generallyappliestocommercialproductscontaining stocks. produced fromfossilfeedstocks;maybeforconversion tojetanddieselfuelblend pharmaceuticals, agrochemicalproducts,andnonpetroleum-derived chemicals;not piping; abroadspectrumofindustrialapplications,suchastheproductionplastics, of furfurylalcoholisusefulinthemanufacture offuranfiber-reinforced plasticsfor alcohol whichisusedfortheproductionoffoundryresins;anticorrosionproperties and xylose,canserve asaraw materialforfurfuralproduction;converted tofurfuryl material containingalarge amountofpentose(five-carbon) sugars, suchasarabinose found inlarge quantitiesinthehemicellulosefractionoflignocellulosicbiomass;any fermentation ofcarbohydrates. renewable sourcesbyautotrophicandheterotrophicalgae, orbythemicrobial tallow, vegetable oils,orpetroleum;also have thepotentialtobeproducedfrom derivatized byethoxylation,sulfation, orsulfonationbeforeuse;canbeproducedfrom to produceanionicandnonionicsurfactants forhouseholdcleaners,personalcare; lactic acid,andethanol,have ahighpotentialtobemadefromlignocellulosicsugars. pyrrolidone inmany applications;thestartingmaterialsusedtomake ethyl lactate, exceed thoseoftraditionalsolvents such astoluene,methyl ethyl ketone, andN-methyl- use forethyl lactateisasanindustrialproduct—thepropertiesandperformancemeetor sugars; canbeproducedbytheconversion ofsuccinicacidto1,4-butanediol. bio-derived butanediol isbeingproducedonacommercialscaleutilizingcommodity direct renewable butadiene replacement. can beproducedthroughmultiplebiomassconversion strategies fortheproductionofa rubber, currentlyproducedfrompetroleumasabyproductofethylene manufacturing; Comment (Continued 95 ) Downloaded By: 10.3.98.104 At: 13:40 26 Sep 2021; For: 9780429155611, chapter3, 10.1201/9780429155611-3 p-Xylene Succinic acid Propylene glycol Chemical Bio-Sources from Produced of Chemicals Examples 3.3 TABLE 96 ; 1981 (iii) ­ hulls; and or switch (ii) grass; mass bio context book, the of wastes. in this Thus, vegetation,ral (iii) collection of and agricultural natu clergy cultivation (ii) crops, approaches: harvesting (i) of main so-called purposeful three coal) but, like the fossil the fuels, biomasscoal) ( but, is like energy of aform solar stored conversion ( methods secondary and/or primary through products of petrochemical of for production feedstocks the avariety converted to be can that manure even and crops, animal agricultural grasses, such trees, as of biological recent including plant materials origin, ­material less to the environment if spilled. if environment less the to it relatively is that is thus biodegradable, and types fuel most to other biofuel harm comparison in of advantage of plants. growing photosynthesis One process in the through is captured sun of the Biomass is a renewable energy source, unlike the fossil fuel resources (natural gas, crude oil, and and oil, gas, crude Biomass fossil (natural the is fuel resources a renewable unlike source, energy Biomass Feedstock to Feedstocks Petrochemical Conversion for of the Biomass Methods 3.4 TABLE refers (i) to Vasudevan et al., 2005 ( Continued residues from forestry, construction, and other wood-processing industries ( wood-processing industries residues other forestry, and from construction, Biological conversion Thermochemical conversion energy crops grown specifically to be used as fuel,as suchas be used fast-growingto trees specifically grown crops energy agricultural residues such byproducts, straw, as and rice fiber, and sugarcane agricultural Conversion Type ) Used toproducebothterephthalicacidanddimethyl terephthalatewhichareraw A dicarboxylicacidthatcanbeproducedfrombiomassandusedasaprecursorforthe Also known as1,2-propanediol,propane-I,2-diol,andmono-propylene glycol;aviscous, catalytic upgradingofsugars. thermochemical pyrolysis routes,andhybrid thermochemical/biochemicalstrategies of the traditionalbiochemicalfermentationprocessfollowed byupgrading, materials fortheproductionofpolyethylene terephthalatebottles;canbeproducedvia commodity chemicals,polymers,surfactants, andsolvents. synthesis ofhigh-value productsderived fromrenewable resources,including hydrogenolysis ofglycerinover mixed-metal catalysts,orhydrocracking ofsorbitol. serves asasolvent, enzymestabilizer, clarifyingagent,anddiluent;canbeproducedby of ethylene glycol,andintheairlineindustryasanairplanerunway de-icingagent; vehicles, andconsumerappliances;alsousedasanenginecoolantantifreezeinplace use markets suchasresidentialandcommercialconstruction,marinevessels, passenger grade propylene glycolisusedintheproductionofunsaturatedpolyesterresinsforend lotions, eye drops,foodflavorings, and bulking agentinoral,andtopicaldrugs;industrial in water; usedintheproductionofconsumerproductssuchasantiperspirants,suntan colorless, odorlessliquidthatisnonvolatile atroomtemperatureandiscompletelysoluble ; Wright et al., 2006 Fermentation Hydrocarbonization Pyrolysis Primary Method ; Speight, 2008 Speight, Comment Handbook of Processes Petrochemical Handbook ). It is the term used to describe any describe to used ). term It is the Protein Sugar Methane Oil coke Gas Char Oil Gas Product Speight, 2008 Speight, Secondary Method Gasification Gasification Gasification Gasification Table 3.4 Table ). The energy ). energy The Detroy, Detroy, ).

- - - Downloaded By: 10.3.98.104 At: 13:40 26 Sep 2021; For: 9780429155611, chapter3, 10.1201/9780429155611-3 Coal, Oil Shale, and Biomass and Shale, Oil Coal, mean by processed. feedstock is be to whichmean the composition basis the chemical of on the feedstock ofand the the operated and constructed be ery However, heat. and/or abiorefin that biomass may various feedstocks dictate the in differences the fuels,power, chemicals, products:materials, final feed, food, and includingenergy intermediate biomassaquatic (algae,and seaweeds).products marketable of a spectrum produces A biorefinery waste, waste, and municipal plant- crops, animal-derived and agricultural dedicated wood and of biomass, kinds all use can theory, fuels. abiorefinery In petroleum-derived certain biofuels are products context other the current the ­products—in technologies have the ability to be coordinated in abiorefinery. in technologies coordinated have be to ability the These for future. is aprerequisite of use the biomass sustainable in impacts energy environmental negative minimize to in order basis on asite-specific Applying processes technologies and these fossil fuels. than environment the to properly, used which, if biomass-based less fuels harmful make Technologies environment. exist today natural processes the and convert it use and without harming biomass to produce to world’s of and be the proportion challenge will the future, the in needs energy biomass negative many is supply If to consequences. agreat with agreater environmental manner ( landfills waste in or organic manure animal ­ result such, from as includes that gases the categorized not usually although sources tertiary to residuals sources secondary to land the from directly residues and crops harvested/collected sources primary from includes waxes. everything and This terpenoids, terpenes, resins, alkaloids, usage. due its to current arise that by differences semantic diverted ( chemicals specialty and commodity to means or enzymatic chemical, by thermal, materials these derived from Bioprocesses focus on materials. microbiological conversion starting are of fermentable that sugars conventional from those to petrochemical conversionand similar chemicals to methodology leading minerals. and lipids, lignin, ­proteins, i.e., constituents, chemical carbohydrates, of composed several similar are rawtion, materials these or forage (iii) conventional addi and crops wheat. In and perennials foodas such crops corn as such crops energy woody which rotation or herbaceous feedstock crops crops includes short and simple categories: such (i)food wastes, as processing three (ii) into fall dedicated waste materials individually, renewable of overwhelming, number potential be the but can to tend they feedstocks considered of If sources. variety alarge from obtained be can chemicals producing in used rials biological processes. routes or either chemical through generated be Such can platform chemicals manipulations. further (e.g., features exploited be blocks retain can that or nucleophilic character) that in electrophilic converts building biomass chemical into approachstrategically complimentary and alternative an syngas, converted into be also biomass can alcohols. and While syngas production, alkanes form to down with complex case such the compounds, as breaking molecules desired up before the building from the field or forest where it is grown. Examples of primary biomass feedstocks currently being field biomasscurrently the from or feedstocks forest grown.where Examplesit is primary of is produced. feedstocks which the in manner feedstock or the or classified content plant the the specific More of generally,by recognized biomass are feedstocks 3.4.1 A biorefinery ( biorefinery A unsustainable a very outMost in present of use day production biomass and for is carried energy include ­ amounts, triglycerides, Biomass minor present in generally components, which are by accomplished novel is typically separation materials of processing these or chemical Thermal feedstock diversity A major of use biomass issue the is in one of feedstock available several rely currently chemicals, processes on entirely and fuels produce to order In are thus primary biomass that is harvested or collected or collected is harvested biomass that primary thus are feedstocks biomass For example, primary B iomass Detroy, 1981 Detroy, F Speight, 2011c Speight, eedstocks ). choosing not in afeedstock for be to Thus, agiven it product, is important of postconsumer residuals that often end up in landfills. A landfills. end up often in that residuals of postconsumer ) is the means by which biomass can be converted to other by other converted to which be biomass means ) is can the Wright et al., 2006 ; which replace have to potential the Speight, 2008 Speight, . Biomass-based feedstock mate anaerobic digestion of of digestion anaerobic ). such as sawmill such sawmill as fourth source including sterols, sterols, of of 97 - - - , Downloaded By: 10.3.98.104 At: 13:40 26 Sep 2021; For: 9780429155611, chapter3, 10.1201/9780429155611-3 makes the most sense to consider it to be part of the tertiary biomass stream. tertiary of the most consider to sense the it part makes be to (and environments statistics), included those in urban wastes from postconsumer along other with it awaste as stream biomass. handled However, is normally nition of material primary this because defithe fits which technically trees, urban from includes trimmings environment urban the from waste wood other Acategory gases. solid landfill wastes,well wastes, municipal and packaging as as environments, urban demolition waste the and wood other from wood debris, construction oils, resource. biomass asecondary also for are uses of various processing oilseeds the from derived directly are Vegetable biomass resources. collectable secondary for are used oils operations biodieseling that - feed whey animal (which processes). concentrated from is abyproduct of Manures cheese-making includes sawdust black liquor (which sawmills, from cheese and is abyproduct of making), paper biomass biomass. Specific examplessecondary limbs) of tops and classifiedsecondary as be to tree bychipping, was or photosynthesis pressing produced do not that (e.g., cause a biomass resource range of chemical products. This biorefinery concept is analogousconcept is conventionalto biorefinery and This refineries products. ofrange oil chemical efficient and production complexes integrated viable highly diverse in economically a producing be only production will significant of plant-based chemicals further that It is widely recognized fuel. converted to by be biomass which can the means chemical ofconstituents biomass, the and individual of the of some knowledge biomass, chemistry the biomass chemistry requires of the of processes. plant-based chemical of anumber commercialization the biotechnology rapid in facilitated has progress that last decade advantages overof compelling production; conventional however, petrochemicals it the is only in Bioprocessing targets. routes have of environmental national anumber attainment the to contribute competitive advantage and maintain to conversionof-the-art opportunity technologies an presents most fossil fuels. low, is generally feedstocks even densification,density about ofthe 40% bulk and after of 10% of range 2%–30%. the in However, density (and bulk density) the energy hence of most biomass varying of coals, characteristic 0%. important biomass an content is Moisture around is also dried aboutcontent 15%–20% has for moisture biomass the oven- whereas typically moisture, Air-dried ( Btu/lb 6,000–8,500 range the in much lower value heat falling for generally the petroleum, than ofvalue) content, value calorific heat (heat of biomass, which andis somewhat than coal for lesser composition the of biomass ( is variable Furthermore, ( both differentto would bitumen significantly sand be for tar ery example, somewhatdiffer would fromand a conventionalrefin a refinery aheavy oil refinery waste oils. and together fats, with greases, tracked be to for most used likely being bioenergy are amounts though biomass resource, would asecondary be for bioenergy (e.g., directly of used processing plant components and biodiesel) in used soybean oil Vegetable waste stream. apostconsumer become they derived oils from after bioenergy until use not available some are oils, and for most greases, since fats and biomass component into parts, mal byproducts; byproducts; biomass production of and physical primary of breakdown the is substantial or chemical there that By feedstocks. processing, abyproduct of primary of processing the are feedstocks for power used and heat currently production. are forest that operations nut and hulls) somesome residues residues crop and logging and (suchfrom trimmings orchard as fuel production, plus for used crops transportation oilseed and forused bioenergy include grains 98 Speight, 2008 Speight, Tertiary biomass includes residues wastes, postconsumer feedstock such and fats, greases, as biomass Tertiary Plants offer a unique and diverse feedstock for chemicals and the production of diverse offer the biofuels and Plants feedstock for and aunique chemicals renewable state- from production chemicals of and fuels The plant-based utilizing feedstocks composition the any is for the of arefinery Forfeedstocks designing of feedstocks. aspect One Secondary biomass feedstocks processors ). Moisture content is probably the most important determinant of heating value. of heating determinant ). content Moisture is probably most important the fats and greases includes often and fats may be factories or animals. Field processes such as harvesting, bundling, Field bundling, such harvesting, as processes may or animals. factories be in that the secondary secondary the that in feedstocks biomass primary from differ , which are byproducts of the reduction of of byproducts ani the , which are Speight, 2008 Speight, Handbook of Processes Petrochemical Handbook ) which is reflected in the rangethe in ) which is reflected Speight, 2008 Speight, , 2014 it is meant , 2017 from from ). ). - - - Downloaded By: 10.3.98.104 At: 13:40 26 Sep 2021; For: 9780429155611, chapter3, 10.1201/9780429155611-3 and chitin. By chitin. way and chitin of clarification, [(C β

cal structure of lignin is unknown and, at best, can only be represented by hypothetical formulas. by hypothetical represented only be can atbest, and, is unknown of lignin structure cal chemi of wall plants. cell The of the part integral is an woodis derived most and from commonly isa complexthat insulationproducts. Lignin in chemical andglass fibers textilematerials in fibers and polyester replacecan cotton andfrom flax suchas hempLignocellulosic plants fibers extracted 3.4.1.3 ( reaction up the speed to used onlystep whereby be can acidic catalysts in one alcohols occurs chain withacids short production ofof esterification biodieselfatty by direct of The catalyst used. type well as the as temperature cracking including variables the process the product(s) of the properties The by controlled unit. controlling be can cracking forstocks acatalytic polymer additives, solvents. and monomers, functional such diesel polyurethane new fuel, as lubricants, markets entering cessfully products) now care are suc - and personal and dispersants, (surfactants, industry oleo-chemicals the oil. Vegetable of vegetable is rapeseed source countries amajor many feedstock in for oils are oils sunflower, Vegetable such plants oil palm, as and soya. seed predominant The from is obtained oil Oils Vegetable 3.4.1.2 dibasic acid. such acids and acid, succinic lactic acid, as production citric ofthe ethanol, a valuable sugars, produce to feedstock for fermentation or enzymatically hydrolyzed, catalytically plasticsbe such polyethylene polystyrene as can polysaccharides and foams these addition, In film. of those to conventional similar of arange produce to biodegradable polymers properties with ulated manip readily be can polysaccharides of these wood pulp. from structures The cellulose is obtained grain. corn in starch the of derived fermentation from entirely sugars on the almost based biomassproduction from are hemicellulose accessibleand acid to hydrolysis. focused on ethanol efforts many reason, For this which must brokencellulose be down the render to of order composed lignin, in are lignocellulose the of Among walls intofactors, relatively other sugars. convertto this difficult material unreactive of forms biomass,lulose. most it abundant is lignocellulose one and cheapest of is Although the or cel starch than degraded is less readily and hypothetical is totally that groups aromatic taining ( constituent monomers by hydrolysis, conversion to chemicals or other preparatory ethanol to hemicellulose. (iii) and of macromolecules: polymeric (i) types (ii) ­ starch, three in stored are produced sugars The (CH sugars dioxide and convertedto is carbon which water during carbon fixed as energy solar capture Plants 3.4.1.1 materials. and pharmaceuticals, of arange produce valuable intermediates, monomers, chemical to utilized be can metabolites secondary and complexand molecules primary as organic known drive down to production costs. feedstock utilization and integration, complexes havepetrochemical that evolved synergies, energy process over maximize to years many Coal, Oil Shale, and Biomass and Shale, Oil Coal, Vasudevan et al., 2005 -glucose that forms a hard, semitransparent material found throughout the natural world. is Chitin natural the found throughout material semitransparent ahard, -glucose forms that Lignin (Latin: lignum (Latin: Lignin - feed as used be feedstocks, vegetable advocated that it been cases, similar many has and oil, In while potato, (starch, wheat and from Carbohydrates cellulose, sugars): obtained readily starch In general sugar polymers such as cellulose and starch can be readily broken down readily their to be can polymers sugar such starch cellulose general as and In components specific of suchas carbohydrates, vegetable plants the addition, In oils, plant fiber, Carbohydrates ln Fibers Plant 2 O) x : ; — Speight, 2008 Speight, wood ) is one of most abundant organic chemicals on earth after cellulose after on earth chemicals ) is one organic of most abundant CO 22 ). In contrast, lignin is an unknown complex structure con complex unknown structure is an lignin ). contrast, In +→ HO 8 H 13 O () 5 CH N) n 2 ] is of along-chain polysaccharide polymeric OO x + 2 .

Demirba ş , 2006 ). cellulose, cellulose, 99 - - - - Downloaded By: 10.3.98.104 At: 13:40 26 Sep 2021; For: 9780429155611, chapter3, 10.1201/9780429155611-3 and therefore the entire plant. entire therefore the and wall) cell mature (stabilizing the wall cell the to strength mechanical confers Lignin saccharides. plant poly different to covalent forms also which polysaccharides enables with bonds cross-linking hemicellulose. to (bonded) Lignin is covalently components and linked pectin hemicellulose, and cellulose,between cell the wall in the excessspaces in be to fills of 10,000. is Lignin estimated that hydrophobic, mass amolecular macromolecules with alarge, cross-linked sidered be to aromatic cephalopods of butterflies),(e.g.,beaks the and and octopuses).and squids (e.g., crustaceans such the as crab, lobster, (e.g., shrimp), insects and and arthropods, beetles, ants, amajor is also component and exoskeletons of ofthe component walls fungi cell of the main the of 100 of biomass (for ( distribution example,product the wood) influences used zene, toluene, xylene dioxide. monoxide the type well and carbon isomers The as carbon and as residence ethylene, time), short and are products ben the cracking pyrolysis (high-temperature ( products conversionfor sent arefinery to then processing) and fuelto salable (primary oil crude synthetic to a processed which is first sand tar of from processing bitumen the is in analogy The product. salable final the become to processing further requires that product convert biomass aprimary to units. refinery in various coprocessed be to streams blendedfeedstock be to refinery with or,unit asinglelikely, as feedstock aspecific to acceptable biomassmore be from might ucts as a - biomass prod from processing. or solids such products liquid, gases, These products as processing mightbe suitable forfor raw, refinery processing biomass. A typical processed, or even partially aslateto (salable) of useful unsuitable is configured refinery, Apetroleum products. as currently convertedbe can petroleum processes by unit which integrated of series is a refinery A petroleum 3.4.2 the feedstocks to fuels and chemicals ( chemicals and fuels to feedstocks the convert to used a divergence methods the biomass require in various feedstocks ferences the in dif refinery, analogousan the that oil conceptconcept of is of to abiorefinery the fuels. Although therefore fuels. suitable are for commercial and as use easily transportable, conversion solid which fuels and have liquid, gaseous, thermal produce to contents, are energy high which conversion include of use biochemical processes several the both distinct through plished and for. else used fossil conversion are fuels generation or anything electricity The heating, is accom fuels, suitable substitute to for for used commercial into be transportation, fossil can fuels. These Biomass converted be can for have to known practice millennia. activities in Many of are these been considered. are pretreatment activities such production of as vegetable requiring wine beer, oils, and feedstock. is product ethylene as gaseous used tion plastics of if this are - frac important An formed. are products more gaseous the temperature, the higher pressure—the and composition solids. on temperature The and of depends product liquid, of gaseous, the mixture yield to waste of constituents decompose the the a degrees, of several hundred At atemperature oxygen-free an in plastic waste is heated atmosphere. mixed the process, the In manufacture. ical petrochem for materials by flash pyrolysis treated be also produce starting to can biomass material) process. cracking naphtha the with much common in flashTheoretically,has the wideprocess pyrolysisThe range a use of can biomass sources. process produce fuels, power, and chemicals from biomass. In a manner similar to the petroleum refinery, petroleum the to similar fuels, power,produce biomass. amanner from In chemicals and biomassconversion integrates that equipmentand to refinery, be a to mayfacility processes need Lignin makes up about one-quarter to one-third of the dry mass of con is generally mass wood and dry of the one-third to up about one-quarter makes Lignin Analogous, in many cases, to the thermal decomposition of crude oil constituents, in the flash the in constituents, oil decomposition of crude thermal the to cases, many Analogous, in early the stages development,of in might, which abiorefinery processes unit Thus, of series be a Biorefining offers a method to accessing the integrated production of chemicals, materials, and materials, production of chemicals, integrated the Biorefiningaccessing to offers amethod is notproducts newif in of Biorefiningchemical which intobiomass a convertedis variety context the of in point flash Atpyrolysis, this that it is plastic of note worthy waste not a (while B Speight, 2008 Speight, iorefinin g , 2014 , 2017 ). Speight, 2014 Speight, , 2017 Handbook of Processes Petrochemical Handbook ). abiorefinery, petroleum Thus, a like Steinberg etSteinberg al., 1992 ). ). ------Downloaded By: 10.3.98.104 At: 13:40 26 Sep 2021; For: 9780429155611, chapter3, 10.1201/9780429155611-3 and upgrading biomass feedstocks in arefinery. biomass in feedstocks upgrading and biomass have feedstocks development focused the oftransforming efficient of chemically methods of limitations and content is even of mass characteristics abiomass unit per feed inherent less. These energy of physically up the 50% to moisture, by weight. drying, adsorbed without substantial Thus, Most burden petroleum. biomass, received, ahigh and as has coals, most bituminous of anthracite, (50%–100%) substantially of and alow-rank that or lignite, with comparable coal lower that than Btu/lb) content basis heat is atbest (7,000–9,000 of fuels. The leum-derived biomass, on adry example, density or petro energy of biomass the petroleum, liquid of is low coal, that to compared domestic availability, For renewable its it limitations. and has also time, same At character. the biomass feedstock due its universal to is anearly ­ synthesis gas. araw As and material, electricity, steam, well as heat, of fuels, liquid chemicals, including forms as energy process useful top before new broken build to being molecules. down used and have bottom-up, bio-feedstocks off the the some already valuable from built skim to products are where most chemicals petrochemicals in more complexas petroleum-derived Unlike compounds. well as plant, of the for growth essential the are that acids metabolites) amino and including sugars manufactures (called essential usually are by pathways.they specific cals produce The chemicals development. further requires products convert fiveto useful the ring sugars economically to technology enzyme lignocellulose, the the from fractions existstechnology effectively to sugar-containing the separate lignocellulosic of engineering the Although feedstock. hemicellulose cellulose fractions and the convert five-in andpresent and the six-memberedring access sugars economically can that ogy low-value including the utilized be components. lignin every oil, elementenergy, crude with By plant of feedstock chemicals. will analogy the fuels, and such products as marketable convert into components and these individual into rawmass materials efficientlycomplex will bio that separate integrated highly isa the biorefinery that in refinery oil of concept is analogous amodern that to This substitution markets. existing into their facilitate and productionreduce costs ofconceptcould biorefinery significantly plant-based chemicals The ized. real be can area of this potential exist before full still the barriers technical and economic that clear it is of anumber new Although bioprocessing bioprocesses have techniques. commercialized, been state-of-the-art and operations conventional thermochemical utilize components will individual the biorefinery. the of application tools in processing Processing of the awider variety require will economics. operation enhancing while needs energy national address high-volume both produce to high-valueandfuelsliquidto refineries in order products or chemicals idea is for The bio petrochemicals. from made be wouldof including products, ones that otherwise foster to conducted being convert to new biomass is currently industries awide into range Research they produce frommultiple biorefineries biomass. into since products categorized be can mills paper pulp and and processing Currently, products. it different wet-mill many into corn processes lignocellulosic suchas with major the andinput abiorefinery feedstocks biomassas products, would cellulose high content, with such straw, as rial waste. paper wood, and would raw use mate biorefinery lignocellulose the and or maize such cereals as rawuse materials For feedstock. of example, the biorefinery crop by character the have the differentiated be to However, intermediates. of useful biorefinery would type of arange into industrially the materials only two possible name to options. processes fermentation processes and biomass inclusion from such the as chemicals other such of motor and fuels as gasificationprocesses conversionof a a biorefinery integrate variety produce wouldmultipleto processes product streams Biomass and Shale, Oil Coal, As a feedstock, biomass can be converted by thermal or biological a wide routes to of range converted by be biomass thermal afeedstock, As can they produce chemi as insofar or refineries effective very mini-factories are chemical Plants to developrefinery the technol of ability the process is for biorefinery A key the requirement However, oil, crude to biomass of compared feedstock, the compositional different nature the different majorintomany the andinputprocesses it as petroleum uses refinery apetroleum As biologicaltechnologiestransform to rawessential the shouldcombine abiorefinery short, In versatility, would would 101 ------Downloaded By: 10.3.98.104 At: 13:40 26 Sep 2021; For: 9780429155611, chapter3, 10.1201/9780429155611-3 into a biorefinery are: abiorefinery (i)into pyrolysis, (ii) anaerobic gasification,(iii) digestion, and (iv)fermentation. power avoids the and emissions. and gas costs production reduces needs, energy greenhouse electricity. profitability, high-valuehigh-volume theThe enhance products fuel helps national meet for heat enough process its for perhaps own and and of use electricity sale generating fuel, while volume, but high-value, alow-value, and products chemical but high-volume transportation liquid might, biomass for Abiorefinery feedstock. the derivedexample, from one severalor produce low- value the maximize and biomass intermediates in components and advantage differences of the take can biorefinery the petrochemicals, jet oil, fuel, and of such heating gasoline, products, as realized. be concept can biorefinery the by renewable possible. becomes chemicals However,before remain challenges technical significant substitution petrochemicals production a that costs substantial of suchreduce significantly to means provides concept The biorefinery a term. the near in more significant become of will nonfood crops utilization atwhich bioscience pace the developedthe that both is being demonstrates applied and development. further requires products convert fiveto useful the ring sugars economically to technology cellulose, enzyme the ligno the from fractions exists technology effectively to sugar-containing the engineering separate lignocellulosic of the Although feedstock. hemicellulose cellulose fractions and the present in ars convert five-and and the six-memberedring access sug economically can that technology process processes. of biomass ahydrogen-rich awide of produce to range in chemical used be which synthesis gas can conversion is employ to alternative which pyrolysis use thermochemical processes or gasification acid lactic to showsexample, path fermentation aroute biodegradable to plastics. as the promise An one As processed. further be then can that content biomass sugars ferment into carbohydrate the Biotechnology-based materials. conversion fuels, to and used chemicals, be of can bulk processes employed be portfolios product different can techniques obtain to of methods addition avariety to such ethylene as alarge-volume be but afuel acid. orbe lactic In could also intermediate chemical of higher-value not necessarily need high-volume abiorefinery in The chemicals. streams product plants. biodiesel production of example is the glycerol of this Apertinent (glycerin)chemicals. abyproduct in as cost to valuablefor upgrading minimal and at large benefits scale volumes of streams byproduct high-volume complex existing biorefinery service economy-of-providing the in will markets, production of biofuels The bioprocessing techniques. state-of-the-art and operations mochemical conventional ther utilize biorefinery.componentswill individual the toolsthe in Processing of of application processing of the awider variety require will oil, crude to compared feedstock, low-valuethe components. However, lignin biomass of the compositional different nature the such energy, products as marketable chemicals. fuels, and intoand convert these components individual into efficientlybiomassraw materials will separate complex that integrated highly isa the biorefinery that in refinery oil ofanalogous amodern that to concept is This substitution markets. existing into their facilitate ofcosts and plant-based chemicals productionreduce considerablecould which biorefinery significantly is the momentum gaining concept One realized. be can area of this potential exist before full still the barriers technical and hydrogen. fuels, and oils, suchchangeable transportation as commodities existing with inter are that chemicals and fuels produce to biological raw upgraded be may fuels The then means. 102 The basic types of processes used to generate chemicals from biomass as might be incorporated incorporated be biomass might from as chemicals generate to used of processes basic types The series a into oilcrude separated is which in refinery analogous an oil to truly is biorefinery the If biofuel large of renewable both and construction coupled productionThe facilities with chemical to developrefinery the forof use and ability A keythe deliveryis requirement biorefinery of the for platform chemical conversion is apotential and Glycerol arange into functionality high has including oil; every element utilized crude be with By plant of analogy feedstock will the economic it that is clear of anumber newAlthough bioprocesses have commercialized, been sugar-baseThe involves of breakdown biomass raw into and component using chemical sugars Handbook of Processes Petrochemical Handbook - - - - Downloaded By: 10.3.98.104 At: 13:40 26 Sep 2021; For: 9780429155611, chapter3, 10.1201/9780429155611-3 Coal, Oil Shale, and Biomass and Shale, Oil Coal, can then be further processed into useful fuels or fuels feedstock ( useful into processed further be then can Pyrolysis 3.4.2.1 carbon dioxide, and hydrogen by reacting the feedstock at high temperatures ( dioxide, hydrogen temperatures and carbon feedstock athigh the by reacting hydrogen. for and production ofprocess the chemicals convert biomass hydrogen to efficient without products, combustion an represents other and and oxygen involving pathway technology and process acontrolled uses steam, that a mature heat, to followedgas conversion by catalytic fuels) liquid to ( gasification (by to Alternatively,syn indirectly chemicals and fuels converted into be biomass can Gasification 3.4.2.2 any venture. as supply muchover as risk as be short-term of long can feedstocks the term, may true be this inexhaustible. supplies the are While that it since is assumed underestimated often compounds. organic oxygen reduced with content soluble (about byproduct is water containing 10%) primary the and liquid organic is product an conversion. organic promote to may added be primary The Alkali for phase liquid up 30 to residence the in times water primarily the maintain to pressure biomass (300 water with the atelevated temperatures collection product efficiency.the conditions, and and type process the feedstock, on the depend bio-oil, product, liquid generated the of yields properties the several and and fast pyrolysis status near-commercial technologies reached 1990s, the fuels. In hydrocarbon high-quality to upgraded been and boilers, and turbines, engines, activelyis being developed in tested for successfully fuels. liquid Pyrolysis producing been has oil Fastchemicals. pyrolysis now has for success achieved and production of acommercial chemicals Pyrolysis for is used arenewable oil be production of also can and fuel liquid transported. and stored cyclonicbeds, and ablative reactors, reactors. transported and circulating fluidbeds, biomass weight. dry include They 75% bubbling as of high as product liquid starting on the based achieveandconditionto have zone. this Severalyields configurations shownbeen assure reactor to reaction the hot vapor in ashort residence and time biomass particles the to rate transfer heat high of hydrogen, dioxide. monoxide, carbon carbon a clean syngas and mixture derivatives hydrocarbon reform to these acatalyst yield with to must step extra taken be an typically when no true oxygen especially is result, As a this gasifier;is used. exiting the mixture gas the in compounds hydrocarbon it other and produces coal, easily as as biomass notgeneral, does gasify of absence oxygen. the in mass However, significantly. may of differ process each In chemistry the it be product gasification char, or gas. Pyrolysis liquid, the desired considered be to of is often bio output of the the maximize to components, and the all of conditions capture to out avariety under technologies, pyrolysis With more modern carried be charcoal. as can whatknown is commonly is char residual the feedstock, the wood char. as a residual is of used and If gases, liquids, ture sion fuel. of biomass commercial to conver thermochemical most common the is still dawn of civilization, the since charcoal produce such pyrolysis, process, as fuels. or Pyrolysis, gaseous solid, liquid, into to used thermochemical a waste, hulls) wood converted through peanut gin wastes, be wastes, and cotton can agricultural ( conversion which include thermochemical processes pyrolysis,direct liquefaction, solvolysis and Kavalov Peteves, and 2005 Gasification is a process that converts organic carbonaceous feedstocks into carbon monoxide,into carbon feedstocks carbonaceous converts that organic Gasificationprocess is a provisions of the for biomass supply other are the and crops importance of as feedstocks The liquefaction involves hydrothermal Direct oily converting biomass by liquid an to contacting Fast pyrolysis of readily pyrolysis be biomass product, aliquid produces can that or bio-oil oil a with temperatures atmoderate occurs Fast decomposition that pyrolysis process is athermal down a complex into breaks and pyrolysis, mix ofabsence air the in During biomass is heated cellulose (such and of lignin biomass as which contain types Wood similar other many and Pyrolysis is a medium temperature method which produces gas, oil, and char from crops which crops from char and gas, whichoil, produces method temperature is amedium ). Molino etMolino al., 2016 ° C–350 Boateng et al., 2007 ° C, 570 C, ° F–660 ). Biomass gasification is ° > F) with sufficient with F) ). Pyrolysis is the 700 C, 1,290 °C, min. min. ° 103 F), F), - - - - Downloaded By: 10.3.98.104 At: 13:40 26 Sep 2021; For: 9780429155611, chapter3, 10.1201/9780429155611-3 using gasoline engines or diesel engines (Chapter or diesel engines engines using 10) gasoline ( Fischer–Tropsch the converted via be can of arange into suitable fuels synthesis liquid process for synthesis gas feedstock because say, combustion than, original of source the energy direct of the an production of overall is synthesis gas amore The efficient cleaner process. an in results production and source energy an as more useful potentially gas—is of product focus—synthesis the is that hydrogen) and carbon feedstock (acarbon) or hydrocarbonaceous is employed feedstock containing wastes) potential. fullest carbonaceous other their resids, to and of feedstocks various biomass,petroleum the (coal, utilization permits Gasification tion processes. for coal is gasifica amove- there than other some feedstocks to areas in of coal shortage potential However, the and further. is pollutants not discussed issue on of the environmental concern the with gasified composition variable complexity highly has and mass cellulose with one major as component. bio for that scheme cellulose reaction glucose uses asurrogate but as itThis must recognized be ( without of combustion, oxygen amount mixture gas acontrolled resulting with The steam. and/or 104 dent upon the feedstock ( dent upon the (v) waste, such wood pulp. as pulp or paper industrial For processing, asimple of form biomass such residues,straw or slurry, (iv) like animal and and crop food commercial, domestic waste, and both applications,for energy specifically grown agricultural (iii) are such that crops, wheat, energy as (i)are: logs, wood, including bark, sawdust, (ii) yield high briquettes, wood chips, wood and pellets reaction is: simplified The hydrogen stream. gas this from the separate more hydrogenand can membranes awater-gas via or Adsorber special reaction. shift water with (steam) reacted dioxide be monoxide then a fossil carbon form to carbon can fuel. The (e.g., asource from of renewablea source are products gaseous the if energy biomass) than other gasification and feedstocks followedcombustion the by product the gas(es)of be consideredis to 2003 of conversion energy types technologies such biomass as gasification ( different suitable the for are forms all fuel but produce to not all used be can biomass materials the or by such coal feedstocks, itself. as blended However, traditional with electricity—either of each produce to used be Biomass forms. numerous also in and can of sources number a large different when any conversion designing ( process consideration of into widely biomass must varies taken types be content and heat different of the widelythe pollution. addition, In air wheat straw causes by and varying of open-field rice burning For residues example, concerns. have disposal environmental widespread caused agricultural these methods for disposal Current is available, energy used. potential due inefficient to of their burners percentage combustion, only asmall direct residues, fuel, through when as used Agricultural lized. worldwide vastly underuti are annually and plant produced residues are ofquantities agricultural residuesMany developing Large ample quantities. in have of agricultural countries awide variety stover, and renewable leaves, plant stalks potential green molassesseeds, resources. are energy and residues such straws, as shells, fruit nut food byproducts. Agricultural shells, processing fruit and sewage, material, manure, residues, municipal organic residues, agricultural industry paper and saw and dust), chips,scraps, biomassexample, (bark, wastes include typical pulp wood material synthesis gas The advantage of the gasification process when a carbonaceous feedstock (a feedstock containing feedstock advantage gasification ofwhen acarbonaceous process the The (a containing feedstock be also can feedstock for gasificationunits—coal primary the been for has, decades, Coal many Biomass includes a wide range of materials that produce a variety of products which are depen of which are products avariety produce Biomass that includes awide of range materials Raw materials that can be used to produce biomass fuels are widely available and arise from widely from biomass produce to fuels are used available be arise can and that Raw materials ; Dasappa etDasappa al., 2004 (in the underground seam) ( underground (in the situ in , syngas CH producer gas , or producer 61 CO Balat, 2011Balat, ; 26 Speight, 2011a Speight, OO +→ ++ HO 22 22 ; HO Demirba CO ) is itself a fuel. The power derived from carbonaceous power) is itself afuel. The carbonaceous derived from Jenkins and Ebeling, 1985 Ebeling, and Jenkins ; Speight, 2013a Speight, Basu, 2013 →+ + CO H( ş , 2011 , 2 wate CO ). The main basic sources of biomass material of basic biomass sources material ). main The ; Chadeesingh, 2011 Chadeesingh, r- Ramroop Singh, 2011Ramroop 22 ga ), text subject is not but and the of that this ++ ss Handbook of Processes Petrochemical Handbook Ho hi ft r eactio ther ). sp Rajvanshi, 1986 Rajvanshi, n) ecies ).

; Speight, 2011a Speight, ; Brigwater, ). For - - - Downloaded By: 10.3.98.104 At: 13:40 26 Sep 2021; For: 9780429155611, chapter3, 10.1201/9780429155611-3 ing Japanese cedar wood and coal ( coal wood and Japanese cedar ing scientificcommunity. the includcombinations of from interest Feedstock deal - agreat attracted has et al., 1992 gasification to up may take plant 150 For example, industrial footprint. alarge while environmental a smaller sive has and construct to supply fuel of the brought question. is often into such, As abiomass gasification is plant less expen sustainability industries—the power,andthe refining in gasification used plants fertilizer, chemical, gasificationreactions. biomass in Air-blown gasification used scales plants. theair theuse gasifiers oxygen for the in oxygen; provide to not gaseous/liquid cost-effectiveration unit is usually the smaller this atthe power and gasification industrial plants). sepa- air large-scale usethat an Gasifiers oxygenrequire of instead oxygenificationair systems use the gasificationreactions for in used typically (which is most biomass- gas Furthermore, products. downstream these to processes catalytic converted via gassynthetic the produce to biomass dieselgasified fuel. isgas), first The (synthesis then and synthetic and ethanol produce to used be can mills paper pulp and waste from and switch grass much as biomasspossible. ofas that is the gasified ensure to sistent and rate gasifiercon ata the into feed to or shape size auniform to systems, biomass must the processed be gasifier.many biomassIn range in a the into comeaddition, gasificationof In biomasssizes. can content feeding to prior moisture the reduce to biomass dried be the that tion technologies require gasifier,the the efficiency reduces thengasifier. the which of Therefore, many gasifica- biomass inside of levels(Chapter presence high temperature 3)—the biomass the reduces the in of moisture of a viability gasificationthe process of influence which can constituents—both sugars) mineral and ( of by availability oxygen (mainly controlled the allowed proceed to conversion and temperature) involved reactions the by the extentto chemical which principally are separated are ification basic of alternatives The combustion, form. pyrolysis, chemical torrefaction, another - gas and wood chips,for stoves. biomass and in use boilers may be into cut a wood of physicalnumber andincluding unfinished pellets and forms, untreated as improves H the but also environment, on the not alow only footprint produces process carbon some synergy—the et al., 2000 ( ( residue of biomasstypes suchas sugarcane gasification using of process the various performance 10 up less than take day and feedstock per stock (such oftons coke), or petroleum 25–200 coal as process biomass typically plants smaller the waste ( waste Coal, Oil Shale, and Biomass and Shale, Oil Coal, upstream processing. upstream during andpretreatment content important addition, gasification. In (torrefaction)moisture are very for optimum uniform be to biomass and is required coal of size the side, particle the upstream the On processes. and gasification,downstream present on upstream, problems are practical region-specific residues. and forwood coal processes the gasification the coal. However,of optimized and custom fittings require co-gasification processes et al., 1999 ( Gabra et al., 2001Gabra Speight, 2011a Speight, Pan et al.,Pan 2000 Rapagnà and Latif, 1997 Latif, and Rapagnà In general, biomass gasification plants are much smaller than the typical coal or petroleum coke petroleum or coal typical the than biomassare much general, gasification smaller In plants crops energy so-called Biomass, the wastes, crop and such and wood yard as pellets, (along of percentage moisture ahigh of and Many forms biomass carbohydrates contain with convert to biomass mechanism into conversion dominant the as heat use processes Thermal Biomass gasification has been the focus of research in recent years to estimate efficiency and estimate to recent in Biomassthe years focus been research gasificationof has While co-gasification of coal and biomass is advantageous from a chemical viewpoint, some and from a biomassadvantageous co-gasificationchemical is coal of While Ko et al., 2001 ; ; ) have been reported in gasification practice. Co-gasification of coal gasificationandhas Co-gasification in practice. biomass of coal ) have reported been Hanaoka et al., 2005 Hanaoka Kumabe et al., 2007 Kumabe 2 ). /CO ratio in the produced gas which is required for synthesis fuel ( liquid which gas is required produced the /CO in ratio ), coal and silver), and coal wood birch ( ), rice hulls ( ), hulls rice ), wood biomass and ( ; Rapagnà et al., 2000 Rapagnà Boateng et al., 1992 ). Recently,mixtures co-gasificationandcoal biomassof various ). In addition, the inorganic matter present in biomass catalyzes biomass present in catalyzes matter inorganic ). the addition, In Kumabe et al., 2007 Kumabe acres of land and process 2,500–15,000 tons per day of per tons - feed 2,500–15,000 process of and land acres acres. Pakdel and Roy,Pakdel and 1991 Collot et al., 1999 ), wheat straw ( ), sawdust pine ( ), coal and saw dust, coal and pine chips chips pine saw), and and dust, coal coal Ergudenler and Ghaly, and Ergudenler 1993 ), and coal and birch wood birch ( and ), coal and ; Bhattacharya et al., 1999 Bhattacharya Lv et al., 2004 ), shells almond Sjöström Sjöström such as as such ), food ; Brage Chen Chen 105 - - Downloaded By: 10.3.98.104 At: 13:40 26 Sep 2021; For: 9780429155611, chapter3, 10.1201/9780429155611-3 et al., 2012 (Speight, 2011 required are compatible feedstock mixture therefore reactors the to different compositiongas quality. and and coal Biomass atalower than decomposition occurs temperature and catalysts) agent,product the gasifying dictate of(temperature, gasifier parameters operation 106 content (dry basis) ( incomplete gasification.in residuesForest at point 30%–31% a or saturation has fiber wood moisture gasification achieved thusresulting zone, the in temperature content the reduces moisture tion. High areas. feeder the flowimproveand in pellets material and density densificationmayprepare to conducted be achieve to content suitable moisture foris required addition, In gasificationbiomass operations. sizes; however, particle appropriate fed agasifier.be into to obtain drying reduction is needed Size gasifier. the into feeding to prior sulfur remove to and coal process mercury would to cleaning gas be option alternative downstream to pipes. An downstream in temperatures problems cause corrosion also high biomass present in can Alkali for environment. the unhealthy and to use difficult synthesis gas make can coal present in mercury and such sulfur as impurities downstream. handled be to of impurities amount not composition gas product only the decide dictate but also parameters alternate fuels ( fuels alternate benefitsco-gasificationthe aboutastic supplying of with co-gasificationpower andrealize plants may practical. gas be eases notwhich cleaning, operation, oxygenPressurized gasificationpreferred. be should plant separation air use of a small-scale gasification large to plants—the challenges compared 800 range the in at temperatures and sure, gasificationoxideprocess. the in biomass. Torrefaction original of those to the yields higher of in results hydrogen mon carbon and amore reactiveproduces lower feedstock with oxygen-carbon hydrogen-carbon and atomic ratios molecules broken with 79%–95% hydrogen of but not feedstock energy only retains also and bonds cellulose ( decompose tially 250 gas. resulting the in concentration gasificationzone, the in favors steam hydrogenincreases that of a formation reaction water-gas shift more tightly. bind closer and other each to level Ahigh of form in injected of usually moisture, long-chain move molecule wall cell The of constituents the shrinkage. to leading wall cell the from In contentsuchpoint. a below moisture situation, removed is water fiber saturation the decreased cient, viable, relatively and (iv) and clean-burning, biomass is available on aworldwide basis. by effi biomass produced fuels (iii) are other alcohols and impact, environmental is minimal there pyrolysis—isof and fermentation combustion energy generate to as not used of plant mass—such (i) conversion inexhaustible (ii)advantages are source, fuel biomass when is atheoretically direct mustchange disadvantages considered carefully. issue, be advantages and the For example, the for the gasifiers when valuablehydrogen ( is particularly areopportunities plants petrochemical development fuel and and refineries In oil fact, refineries. in option of hydrogen offers technology biomass. afuture the addition, wastewith and In production supplied plant just be to alarger of from feegate allows biomass scale economies waste and that the involvingtechnologyco-gasification and includebiomass the use coal reliable of a supplycoal with While upstream processing is influential from a material handling point view,of handling the choice material from a is influential processing upstream While It is recommended that biomass moisture content should be less than 15% content biomass should moisture less that be than It w/w is recommended gasifica to prior - beforereduction and theyHowever,size can drying andand biomassrequire foremost,coal first and co-gasified is with biomass.Heavycoal if metal modified be to need processes Downstream Biomass fuel producers, coal producers, and, to a lesser extent, waste companies are enthusi alesser to extent, are and, waste companies Biomass producers, coal producers, fuel - pres atatmospheric blown,air are biomass/wasteoperated gasifiers medium-sized to Most small- of absence of oxygen, biomass the in treatment at usually is athermal process torrefaction The In addition, while biomass may seem to some observers to be the answer to the global climate global climate answer biomass the to while addition, the may some to be to observers seem In °C–300 ; C (480 °C Speight, 2013a Speight, Speight, 2008 Speight, ° Brar et al., 2012Brar F–570 ° , F) to drive off moisture, decompose hemicellulose completely, decompose driveto off moisture, F) par and Speight, 2011a Speight, 2013b , 2011a ). Furthermore, feedstock and gasifier type along with operating along with operating type gasifier feedstock and ). Furthermore, ; ). Compressive and shear strength of the wood increases with with ). wood of increases the Compressive strength shear and Lee and Shah, 2013 Shah, and Lee ). Torrefiedunstable reactivecellulose andbiomass has ° C–100 ° C (1,470 C Speight, 2011b Speight, ; Speight, 2013a Speight, Handbook of Processes Petrochemical Handbook ° F–2,190 ° F). They face very different F). face different very They , 2014 , 2013b ). ). benefits of a The c ; Brar Brar - - - - Downloaded By: 10.3.98.104 At: 13:40 26 Sep 2021; For: 9780429155611, chapter3, 10.1201/9780429155611-3 acidogenesis, methanogenesis): acetogenesis, and four (hydrolysis, steps methane) through biogas and usually (hydrogen, dioxide, ammonia, carbon digestion anaerobic in resulting fuels and liquid or fermentation, alcoholic produce to fermentation of absence oxygen. the in conversion methane biochemical The digestionAnaerobic 3.4.2.3 balance. biomass energy must the included the be in harvest grow to put and energy used of account the net loss scale—an ofis when apotential on energy asmall abiomass plant is operated (iii) and balance, energy process the affect water (ii) can content high feedstocks, that mass the (methane-forming) bacteria then convert these products into biogas. into convert products then these (methane-forming) bacteria of digest products hydrolysisther the hydrogen, acid, dioxide. acetic into carbon Methanogenic and hydrolysis is called stage This fides. liquefaction).(or Next,acetogenic fur (acid-forming) bacteria sul dioxide, and acids, alcohol, biomass hydrogen, carbon present fatty in feedstock into ammonia, and fats proteins, the carbohydrates, Hydrolytic breakdown first fermentativebacteria. and bacteria dioxide.carbon (iv)dioxide, and acetate; and biogas hydrogen, produce acid, acetic from bacteria methanogenic and acids; hydrogen, convert into acids organic into (iii) the products acidogenic carbon microorganisms acids; (ii) convert then complex those fermentative amino bacteria and wastes sugars into organic involved of microorganisms four basic types (i) are There process. hydrolytic breakdown bacteria digestate called digestion anaerobic is usually the process from resulting (e.g., stomach vents, animals of the various and cows). thermal ocean matter organic digested The water-logged including water hot environments, sediment, springs, anaerobic soils, natural natural of avariety in occurs stages and various action in bacterial decomposition by isThe caused natural Methanogenesis Acetogenesis Acidogenesis Coal, Oil Shale, and Biomass and Shale, Oil Coal, Hydrolysis On the other hand, the disadvantages include disadvantages the content (i) heat variable of bio highly hand, different other the the On The process of anaerobic digestion occurs in a sequence of asequence of stages involving in of digestion anaerobic process types occurs The distinct digestion stages of atdifferent the functions different Symbiotic perform of groups bacteria neoi Digestion Anaerobic A F mino S : : atty : uga : Car acids rs acids →+ bon is a natural process and is the microbiological is the conversion and process to of matter is anatural organic →+ car →+ acids car bon car bon A bon +→ acids cetic alcohols acids acids aci Car alcohols P dm ro alcohols F bohydr →+ alcohols tein at acetic sf sa → ethane ++ → ates hydr ++ atty acid ++ mino hydr hydr → ogen acids ++ car s oge acids car uga ogen, bon

bon n, rs car car

dioxide car bon dioxide bon bon of biomass is completed through dioxide dioxide dioxide

. hydr + ammoni oge ammoni ammoni n

a a

a

there there 107 - - - Downloaded By: 10.3.98.104 At: 13:40 26 Sep 2021; For: 9780429155611, chapter3, 10.1201/9780429155611-3 peratures, up 150 to peratures, of at least 68 atemperature activity, digesterbacterial must the maintain change. globalto climate a contributor as atmosphere the would in gas atmosphere. Scientists enter the have methane targeted otherwise that of methane amount the reduces manure the from methane capture and produce to digester’s may where aproblem. loading nutrient basin the addition, be In drainage of the ability sold be removes solids digester out can process the the and about 25% manure, from nutrients of the amajor of water source pollution. solids of during the Separation eliminating 99%, virtually than by more manure in bacteria coliform fecal digester reduce feedlots. Anaerobic systems can animal other and farms of dairy hazards environmental effectively they the because built being eliminate technology. renewed the in interest stimulated waste has New digesters now ofodor animal are of wet30% whereas 15% or greater, digestion refers or mixtures to less. of biogas produced. amount the in adecrease to leading remain, digest to materials hardest only the end reaction, of the Toward small. is still of number bacteria the the because is gas produced little reaction, stages of the In reaction. of the middle duction the of biogas it during is highest is not stream; asteady pro The source. energy friendly environmentally it an tions; is of considered be to this, because cycle, dioxide- carbon concentra carbon short atmospheric biogas increasing to not does contribute a with source organic dioxide an comes from carbon the and atmosphere the into directly released of levels hydrogen amount trace a small occasionally and of hydrogen the is sulfide.notgas Since digestate. (iii) methanogenic and fuel. transportation alternative an as used be digesterment. can Compressed gas stoves, cooking equipment, refrigeration equip or other heaters, space in or gas propane natural substitute or cells. fuel Digesterinclude for power can gas electric turbines gas production from a generator, with which, electricity.combined produce applications can of digester Future maygas combustion digester engine, fuel is internal suitablegas as drying, an and for filtering After steam. 108 temperatures (thermophilic bacteria). High-temperature digesters also are more upset to prone are digesters also bacteria). (thermophilic High-temperature temperatures athigher thrive that species are there design (mesophilic bacteria) than of range a standard ture - tempera However, the by in 25%–40%. thrive that of more bacteria species anaerobic are there Digestion either wet be can for sewers into batch reactors sequencing discharge in or for irrigation. treated sometimes is also by of ways, one of avariety separated of most be to Excess which common the is filtration. water has sweetened before sometimes sludge use. storage and The and liquor mixture is dried stream gas catchments. industrialized from sewage risktreating providedwhen of by use biogas. is gains the asignificant This environmental offset any can by such posed materials risks environmental the and costs disposal the extreme cases, properly.liquid of dispose this to order in In required be will treatment liquor. such further cases, In digesterchlorobiphenyls,the in effect of the digestionsuchmaterials concentrate is significantly to include low such levels pesticides or poly as materials organic of or synthetic toxic heavy metals materials digested the If digested. being material of the quality dependent on the excellent fertilizer low-grade such fiberboard. products as building compost or make to as used resembles be domestic can compost This present. and be maytic also cells; some plas- of bacterial dead amatrix components in of mineral avariety and chitin and lignin Controlled anaerobic digestion requires an airtight chamber, called adigester. chamber, called To airtight an promote digestion anaerobic Controlled requires and help disposal digesters can awareness anaerobic control the that increasing years, recent In byproduct ( second The Biogas of byproducts digestion: anaerobic (i) principal biogas, three (ii) are acidogenicThere digestate, combustion of form The hot of hot supply the water, air, digester in can gas energy useful or Nearly all digestion plants have ancillary processes to treat and manage all the byproducts. The byproducts. The the all manage and treat to processes digestion have plants Nearly all ancillary byproduct is ( aliquid third The is a gaseous mixture comprising mostly methane and carbon dioxide, and also containing containing dioxide, also and carbon and mostly comprising methane mixture is agaseous ° F, shortens processing time and reduces the required volume of the tank volume tank of the required the reduces and F, time processing shortens acidogenic digestate or dry or . Dry digestion refers to mixtures which have digestion a solid refers content. Dry mixtures to of methanogenic digestate ) is a stable organic material comprised largely of comprised ) is astable material organic Handbook of Processes Petrochemical Handbook ) that is rich in nutrients and can be an an be can and nutrients in is rich ) that ° F. Using tem higher the early early the - - - - Downloaded By: 10.3.98.104 At: 13:40 26 Sep 2021; For: 9780429155611, chapter3, 10.1201/9780429155611-3 Coal, Oil Shale, and Biomass and Shale, Oil Coal, late. The hot water heats the digester to keep the slurry at25 slurry digester the keep to hot the waterlate. heats The digester. the heat to digester, used pipesbe the Inside allow hot water heating suspended circu to generator set. engine- biogas digester an to the the from cover the beneath carry gas. Pipes the digester traps the digester.the flows through releases A biogasflexible, material the as impermeable slurry cover on digester) the in plug is 20–30 (the a manure remains time in aplug tank the flows through material the aresult, As digester tank. the in solids separation limiting digested, are they as material aviscous form manure ruminant solids in expandable cover. below-grade,built airtight, an with consistency. usually container, optimal the to digester is along, The slurry rectangular manure the of addition of pit, solids water the in proportion adjusts the digester mixing itself. the pit, the and In 11%–13%. design for Atypical aplug-flow systemmixing collection includes system, a manure a 20 less to than tion time reten digester reduces the in slurry the or warm boiler to Using engine the steam. waste from heat produce boiler to fuel or as electricity produce for fuel to engine-generator as biogas used an be can suspension. solids in the keep to Biogas digester. toptinuously of the atthe mixed accumulates The is con slurry manure digestion the the process, During container. concrete steel or poured circular volumes suitable forare manure having larger of solids concentration 3%–10%. is a reactor The digesters mix Complete plug-flow cost more than and maintain. and construct digesters to operate expensive suspension. solids in digesters are the keeps Complete or mixer gas mix to A mechanical water table exists. not suitable systems butcost, for are or locations these where cooler ahigh locations in climates Covered lagoon large climate. volumes lagoons awarm havedigesters require and low capital cover. the lagoon under collects the in for gas Asuction the use. pipe extracts Covered lagoon produced Methane seal. edge lagoon of alonging holds the the cover airtight the place an with in the lagoon. concrete of A foot cover floating covers or part fabric all impermeable industrial of of 3% digester, suitable lesstechnology with type than for solids. an For manure liquid this least expensive storageis the lagoon Covering is asimple amanure of form three. of digester the of digester type cover. This decomposition manure. of the cover during The produced gas traps (i) digest: solids can they of suitability, concentration manure the climate cost, and in differ they but bacteria, coliform fecal reduce and methane trap of can them basic digester all designs and a about 55% from content varies Methane it 80%. to contains. methane Typical digester gas, with of hydrogennitrogen, sulfide, hydrogen,and methyloxygen. mercaptans, amounts smaller Biogas contains total. of 90% the typically up more than dioxide making carbon diligent maintenance. diligent and close monitoring requires operation successful their and fluctuations of temperature because through anaerobic digestion into methane and carbon dioxide. This biogas dioxide. is carbon areasonably This and clean digestion anaerobic methane into through be ofbroken effluents, biomass, down can including sewage industrial wastes, and sludge, animal any form of almost fraction organic The India. developing many and in such China as countries aboiler. in digester directly gas burning digester with fueled or gas from engine-generator an from recovered come hot from water waste can heat The bacteria. suitablerange for methane-producing methane concentration of 65%, contains about 600 Btu of energy per cubic foot. There are three three cubic of of Btu concentration per 65%, energy are foot. about 600 methane There contains a­ A plug-flow digester requires minimal maintenance. Waste heat from the engine-generator can can the engine-generator from maintenance. heat Waste A plug-flowminimal digester requires opposite end. the to Coarse atone end pushes older material tank the to added New material A A A Methane is acombustible of contentMethane energy amount of gas. on the digester The depends gas The biogas adigester ( in The produced Anaerobic digestion of biomass has been practiced for almost a century, and is very popular popular is very for acentury, digestion and Anaerobic almost practiced of biomass been has covered lagoon digester, (ii) digester, acomplete mix (iii) aplug-flowdigester. converts organic waste to biogas in a heated tank above digester or below waste mix converts tank biogas to organic aheated ground. complete in is suitable for ruminant animal manure that has a solids concentration of asolids concentration has that manure animal digester plug-flow is suitable for ruminant covered digester lagoon days. , as the name suggests, storage name lagoon consists of a the with , as amanure digester gas digester ) is actually a mixture of gases, with methane and and of methane with gases, amixture ) is actually days. digestion Anaerobic manure of the °C–40 C (77 °C ° F–104 . Average retention time ° F), a temperature F), atemperature 109 - - - - Downloaded By: 10.3.98.104 At: 13:40 26 Sep 2021; For: 9780429155611, chapter3, 10.1201/9780429155611-3 ( apolymer of hexose which is actually recovered starch, be sugars from for also can fermentation hemicellulose fraction is principally apolymer of C is principally hemicellulose fraction hydrogen ( hydrogen or such fuels methane gaseous into as allow of biomassA number transformed processes be to 3.4.2.4 generation. electrical or heating, end such uses put cooking, different many to as and captured be can that fuel burning 110 ambient temperatures, e.g., 30 region around ambient mesophilic temperatures, the in only slightly above are processes for bacterial the temperatures Operating maintained. tion is be to 100%), feedstock compositions- the opera abruptly, not vary to optimal if it and is found important conversion high to for efficiencybeing near obtaining limit above theoretical (typically 60%,the away in composition suitable stabilize bacterial the offor makes some usually months aperiod responsible abiogas bacteria plant for formation. gas Operating methane the anaerobic strictly the solution, biomass dissolving aquatic in the to over bacteria and acidophilic plant the ing material, hydrolyz and decomposing microbes by of agents, the number accomplished alarge different from biomass conversion 64% The methane. output households, is gas typically from the is and process sewage residues, waste urban and agricultural manure, feedstock plants. use they As municipal possibility of solid abiofuel. using the byproduct as the is also hydrogen into gas, which may transformed by step. addition be biogas, to reaction asecond In there yields. gasification energy suppliescrude Finally, a maximum high-temperature lessimplies than only for produced energy on-site the but with for use use, often whichspread often waste treatment, wide in and is technology established This isolated. be can fuels biogasto desired which the from leading residues process afermentation in such pathway agricultural second as plant uses material conventionalthe of A instead produce to hydrogen modified biologicaldirectly carriers. energy carbon or “C carbon ahexose (a is sugar—traditionally fermentations ethanol for feed The all of corn. instead used et al., 2006 lower 30 temperatures, hydrolysis the acid in at used be detergents, can simplyin step. cellulase sulfuric The the replaces and stone to washlysis denim industry textile cellulase, now the of in cellulose. enzyme used The (iv) and acid, (iii) acid, nitric ric followed acid pretreatment hydrolysis. by enzymatic lignin. as known material organic complex framework of crystalline recovery, a together in bound biomass hemicellulose cellulose in of are fermentation and the and while the cellulose fraction of biomass is principally apolymer of of C cellulose biomass easily fermented fraction the is principally while polysaccharides. However, residues contain starch, agricultural wood and starch, unlike tion. Like - produc for such ethanol feeds. As itmaterial as a starch receives attention and sugar feed significant than quantities available greater far potentially It in is also starch. and sugar to cost feed alternative ring organisms. They can be converted to ethanol by genetically engineered yeasts that are currently currently are yeasts that by ethanol converted to genetically engineered be can They organisms. ring occur to by naturally ethanol are readily fermented not that from hemicellulose sugars five-carbon addition glucose, to In hydrolysisduce ethanol. cellulose from and sugars six-carbon other produces step. same the in convert fermentative ethanol to the them organisms produced, are sugars as so that combined, yeast fermenting are and cellulase process, fermentation tion and - and improvements fermentation the saccharifica (SSF).In now saccharification allow simultaneous polysaccharide The production of ethanol from corn is a mature technology that holds ( that technology much potential is amature corn production from of ethanol The large to farms from use, ranging routine Traditional biogas in producing plants fermentation are The greatest potential for biomass, production from however, ethanol potential greatest The hydro enzymatic in lies of hydrolysis: several methods different are (ii) acid, sulfu There dilute (i) sulfuric concentrated Biomass, in the form of wood and agricultural residues such wheat straw, as Biomass, of form agricultural wood the and in is viewed alow as Once the hydrolysis the Once pro to must cellulose fermented of sugars be is resulting achieved, the the Fermentation Sørensen et al., 2006 ). cost may reductions possible, be Substantial however, are feedstocks cellulose-based if 6 ” sugar) such as those present naturally in sugar cane, sugar beet, and molasses. and Sugar beet, sugar cane, sugar in ” sugar) present naturally such those as ). °C–50 C, which reduces the degradation of the sugar. In addition, process sugar. of process addition, the degradation In the which°C, reduces ). One pathway uses algae and bacteria that have). that pathway genetically One bacteria been and algae uses 5 sugars, with quite different characteristics for characteristics quite different with sugars, Handbook of Processes Petrochemical Handbook °C. 6 sugars, the the sugars, Nichols six------Downloaded By: 10.3.98.104 At: 13:40 26 Sep 2021; For: 9780429155611, chapter3, 10.1201/9780429155611-3 unsuitable for other animal species. unsuitable for animal ents other vegetable high and distiller’s constitu fibercontent make soluble characteristics with grains dried produce asolid into (wet to is separated dried (syrup) liquid and and grains) combined be can that phase followedanddehydration alcohol. residueThe the mash of by purification, concentration, (stillage) saccharification and fermentation).saccharification yeast (simultaneous fermenter fermenting the to and enzymes saccharifying adding simultaneously by hydrolysis This eliminated be starch. the can step breakdown to mash the cooking further, and, liquefying enzymes with treated withbe to mixed water is flour the bran). grinding, and After (including whole germ grains grinds milling Dry cellulose, proteins. of and oil, starch, separation which It it well-known uses is ground. allows after technologies and hulls, loosen the and kernels dioxide the soften to sulfur adding grain water-soaking the with rye, or maize). starts Wet milling (wheat, of grains distilling encompass and fermentation processes of end The products. a variety for planted. be to aneed more crops being there alcohol yield the raising butanol, ofinto without fuel crops made could be ethanol make to used waste fiber because left and overcrops ethanol, from sugar density energy than ahigher has butanol of 7%. would because useful be boundary This natural the than higher ism resistance abutanol with improve organ Weizmann scientists of may resistance, the yet its ethanol one daya strain produce up 16% to withstand can However, ethanol. to Saccharomyces modified yeast be can ordinary if yeast turbo tolerate concentrations—so-called even ethanol 14%. can greater strains Specialized 7%. to rises fermenting content yeast of ethanol when dies its For the feedstock hits comparison, content butanol when dies of the whatever also organism it plant. This afermentation is locating consideration into when and must designing extremely taken be duces an this smell, unpleasant and conversions these perform to used pro acetobutylicum currently execute,to Clostridium the and scale. a commercial enough for hardly production made on of be ethanol yeasts can the whether seen be to remains also attractive. It economically available,process the not yields sufficientmake ethanol butto are the can vary as a function of soil type and the timing of feedstock harvest. In contrast to their fairly their to contrast In of feedstock harvest. timing the and of soil type a function as vary can content combustion mineral for processing,precautions and that equipment. Note harvesting, also special may require contents—these metal or alkali silicon such high as properties, peculiar their ment help to removed replenish nutrients Afew by out harvest. for biomass stand feedstocks - amend asoil biomass as may ash used be contaminants, trace other and toxic metals contain content is much lower sulfur for which and ash, may fossil many coals, coal than fuels. Unlike higher-value or hydrogen. such fuels methanol as lower Ash content for is typically most than into thermochemically easier process to them makes also ignition stability. characteristic This more reactive higher with are they because coal than easier gasify to are Most biomass materials Products Gaseous 3.4.3.1 replace nonrenewable of energy. sources by atmosphere dioxide to using the them into of released away carbon as amount the reduce to earth’s dioxide the of in carbon by atmosphere. biofuels aresult, anet seen increase As many in are it not does result dioxide by carbon so plants, burning growing atmospheric from extracted recently biofuels in production biofuels gas of was and carbon liquid which The yield gain. net energy high sewage and (usually waste) of use matter cellulose, cheap organic efficientthe agricultural the in active is gas in development, production of biofuelsThe natural and replace oil to focusing on c 3.4.3 Coal, Oil Shale, and Biomass and Shale, Oil Coal, After fermentation, the mash (called mash beer the fermentation, After into processed are straw fractions and by which grain means the are milling dry and Wet milling fairly tricky cellulose from are butanol and propanol produce to processes fermentation The distiller’s constituents soluble with grains dried hemicals

from B iomass ) is sent through a multicolumn distillation system, amulticolumn distillation ) is sent through , to be used as cattle feed. Its nutritional Its feed. nutritional cattle as used be , to 111 - - - Downloaded By: 10.3.98.104 At: 13:40 26 Sep 2021; For: 9780429155611, chapter3, 10.1201/9780429155611-3 dioxide, hydrogen, carbon place forming methane: and take is when conditions, not reducing that enough under oxygenand is available, following the reactions (iv) and dioxide temperatures heat, athigher and carbon produce to occurs reduction that air the in 700 of order the in place attemperatures oxidation, which takes during decomposition and process the after gasifier the into is introduced solids, (iii) and oxidation liquids, which gases, into air in biomass withoutthe supplying any oxygen or separated biomass is the decomposed aresult, and, biomass pyrolysis undergoes the continues, heating as which involves decomposition of thermal 100 to is heated mass fuelscontain 10–35%biomassusually gasifier (i)drying—biomass and when biow/w moisture the solidfrom biomass which more efficientlythan it made.and was cleanly burns solid fuels. Syngas, more easilytherefore, than inherently mix turn liquid fuels, which in easily than oxygen of with oxygen mix fuels fuel. Gaseous hydrocarbon more mixture of the with the function monoxideand of carbon hydrogenitmixture gasifiesto a (synthesis gas, syngas). Combustion is a combustion (amount biomass if of gasifies oxygenor pyrolyzes), conditions determine other and atmosphere. shouldhouse allowed not the and gas into be escape to digestion.anaerobic green potentUnfortunately, is a occurring methane naturally through landfills is a gas less biologicalof clean systems.biogascal form in Landfill treatment produced which is elemental composition.cal chemi their to heterogeneous respect with rather biomass physical fuels are properties, uniform 112 ones at present. The key advantage of bioethanol and biodiesel is that they can be mixed with with key mixed be ones The atpresent. advantage biodiesel of can they and bioethanol is that most feasible biodiesel the be to and bioethanol biofuels, seem suitable for application transport, in amongst different Furthermore, biomass liquid fuels from resources. produce to used technology catalysis ethanol. to either or chemical fermentation conditions; anaerobic under (iii) gasificationethanol and lignocellulosic of biomass, followed by wood), followed convert to carbohydrates microorganisms by Here, ethanol. again to fermentation conditions;anaerobic (ii) hydrolysis of lignocellulosic biomass (e.g., waste, and wheat, agricultural under convert ethanol to carbohydrates which microorganisms in ethanol, to starch or maize beet, of fermentation biomass (i) biomass, sugar/starch-rich ethanol: into sugar such cane, sugar as direct well-known convert to methods three atleast 1908. since are such United States as There countries many the in fuel as used been has and crops from produced chemical predominant is the Ethanol 3.4.3.2 whichto solid limited. biomass fossil and are fuels boilers steam than amore efficienttechnologygeneration turbines, gas electrical in burned be also of industry, major paper biomass sources both pulpof and power. gas, syngas can the natural Like such facilities black as liquor recovery boilers for residues those specialized as forest and industry Biomassimprovethus gasificationthe efficiency can large-scale biomass of power suchfacilities Producing gas from biomass inside from gas consists a following of which reactions, the occur Producing main no with oxygen biomass oxygen is heated the When for efficient or only about needed one-third mechani digesters and anaerobic recovered industrial be in can and Biogas methane contains Currently, the production of ethanol by fermentation of corn-derived carbohydrates is the main main is the carbohydrates Currently, production by of of the ethanol fermentation corn-derived °C–1,400 iud Products Liquid C (1,290 °C C (212 °C ° F–2,550 ° F), the moisture is converted into steam, (ii) pyrolysis—after drying, drying, (ii) pyrolysis—after steam, is converted into moisture F), the ° F), charcoal, or the solid carbonized fuel, reacts with the oxygen the with fuel, reacts solid carbonized or the F), charcoal, CO CH CC +→ C2 +→ +→ +→ HO 22 22 OC HC O2 24 2 CO OH CO H + +

H Handbook of Processes Petrochemical Handbook

2

- - - - Downloaded By: 10.3.98.104 At: 13:40 26 Sep 2021; For: 9780429155611, chapter3, 10.1201/9780429155611-3 quenching takes only two seconds. only takes quenching injection to from reaction entire heating. The process maintain to reactor the to returned are gases receiver aproduct into condenses any non-condensable bio-oil and The process. the in made already from gas a cyclone vapors into pass resulting The The izes. extracted. char, where are solid particles, bed feedstock is fed afluidized into (at the cess, 450 suitable pro for for boilers are another generation. in use electricity In produced currently bio-oils 350 between ­temperatures (fast process production. The pyrolysis, flash pyrolysis) at heated are fuelswhen solid occurs for diesel engines. However,economical. excellent an thereby offering crops biodiesel from renewable is produced fuel process the derivatives tissueamountthe make the to plant of in hydrocarbon insufficient present derivatives. hydrocarbon produce also algae flower Somepetroplants. also Composiae),are Leguminosae) (family (family pinnata Hardwickia Similarly, petroplants. sun etc. are Dipterocarpaceae, Moraceae, Sapotaceae, Asclepiadaceae, Normally,engines. some latex-producing of the Euphorbiaceae, Apocynaceae, of plants families diesel in used be to petroleum for source alternative obtaining an be can plants petroleum Thus, derivatives. hydrocarbon from obtained one products of is gas also the Natural petrocrop. as crop their and or petroplants plants petroleum called are Therefore, plants hydrocarbon-producing (i.e., fuel petroleum). transportation derivatives high-grade converted into hydrocarbon be can derivatives hydrocarbon liquid weight of molecular such contains high plants (10,000). These latex. latex of into products photosynthetic of amount which The lies, convert asubstantial B100 diesel ( fuel in blend, the e.g.,in B20 is v/v 20% B100 5% v/v is v/v contains 80% Europe B5 of diesel, in and used acids) B100. is called of B100 amount the blended designation diesel with indicates the fuel When diesel well ( petroleum-based to pares have before is, or biodieselcan as general, added oils use. used combe In scented byproduct can asa produced that is the soap glycerin curing, the readyAfter filtration, biodiesel is use. for a final two biodiesel soap. products, and are reaction After of results this The reaction. achemical causes agents,with other which proportions specific in mixed then of by use and apress the is extracted coconut, sunflower,kernel, oil The crops. oil-producing other of safflower,hundreds and a corn, palm such canola, crops soybean, as oilseed of oil Biodiesel certain the from is fuel made afuel fats. of vegetableanimal transesterification or oils the from made biodiesel esters refers alkyl to vegetable or waste oils vegetable context, some diesel in fuels vehicles. as current used oils the In the straight fromdiesel engine vehicles.distinguished thus, unmodified It is, in used be which can cold in weather. engines ing butanol has a high flashpoint ahigh of has butanol 35 counterpart. its gasoline dioxide than carbon more completely burns but ethanol, much releases as or more like afuel. Methanol, as used is also and iscrops acolorless,Methanol from produced is also odorless, alcohol tasteless nearly and and fermentation. through enzymes and by action of microbes the produced are butanol and propanol necessary. are modifications mixed at low ( mixed concentrations biodiesel strongof point when and bioethanol are they is that important Another infrastructure. conventional diesel, respectively, and petrol distribution and which handling allows same using the Biomass and Shale, Oil Coal, Bio-oil is a product that is produced by a totally different process than that used for used biodiesel that than process different by atotally is produced Bio-oil is that aproduct However, being there crops, from derivatives, produced hydrocarbon not usually such, as are belonging plant species fami various different to derivatives from Hydrocarbon products are Biodiesel is adiesel-equivalent biological derived fuel from (such sources vegetable as oils) Propanol and butanol are considerably less toxic and less volatile than methanol. In particular, considerably are particular, butanol less and In toxic less methanol. Propanol volatile and than lessBiologically commonly and methanol, and alcohols, ethanol most produced commonly

the cyclonethe aquench enters tower quickly cooled using by bio-oil transfer where heat are they Pinto et al., 2005 Pinto C and 500 °C and ≤ 10% and petrol in bioethanol C, which°C, is abenefitsafety, fire for difficultstart but be for may ). Lotero et al., 2006 Lotero C (570 °C ° F–930 °C–500 ° F) for a very short period of time ( of time for period F) short avery ). Pure biodiesel). (100% fuel Pure of esters fatty C) and the feedstock flashes and feedstock flashes vapor the °C) and ≤ 20% biodiesel20% diesel), in no engine < s. The The 2 s. 113 ------Downloaded By: 10.3.98.104 At: 13:40 26 Sep 2021; For: 9780429155611, chapter3, 10.1201/9780429155611-3 plant is high. is plant lowerinvestigation produce to potential weight the since molecular for feedstocks apetrochemical of viability biofuels.the on influence stovesing adirect has of cook quality the fuel, thus more work put gathering that be to into it has means more importantly use), for land clear to but agricultural destruction (though is negligible deliberate to this compared stove. forup 40% to acustom-designed charcoal Inefficientfuel use of is acause deforestationof widely, may vary process 10% from for awell-made fire carefully)(even made is fire not the if less stove.in a special or The this fireplace efficiency open on an biofuel of heating. The may burned be cow dung. and of use dung, widespread such home One particularly cooking is fuels in dried and biomass include ofExamples from feedstocks solid wood-derived charcoal wood chemicals and 3.4.3.3 114 waste material that is not included under the general category of category biomass general is not ( included the that under waste material feedstock for production ofIt the chemicals— potential not would mention to remiss another be 3.5 Kaminsky, 2006 Kaminsky, units for steam cracking and in fluid catalytic cracking units ( units cracking fluid catalytic in and cracking forunits steam industrial which in production of may used atthe fractions, waxy be oil aimed is usually peratures 2000 Kaminsky, and atpresent ( scale industrial on an practiced is rarely recycling plastic of waste the stream pyrolysis for is poor, the hydrocarbons able feedstock ameans so that as gasoline-range process overall but yield the of requirements, out heat valu provide to process the burned be can generated compounds gaseous The temperatures. place athigh takes process waxyThis to products. methane material. or industrial is metallic table or scrap waste; and America) is kitchen junk and (North household food packaging; mixed waste waste including and or garbage Rubbish paper are or trash waste Domestic gases. and liquid but includes also waste not solid only solid materials, term The meanings. specific no longer purpose. can for used or that be its original discarded wasteviewpoint, is anything From cost ora regulatory whose technology of life the value itsin utilization. today is less than involved perspective, waste economic is a material From an consumed. component been has useful a after remains that Non-biomass it material waste civilization; is is the abyproduct of and life of 300 of are a classifierpyrolyzed the removefor chips to 1 which after beltingthe steel sources. energy on traditional forproduction is pressure essential reducing waste of for the and potential gasification fuelsubsequent the Knowing intermediates. chemical for production petro of and fuels harnessed be can and mostSuch countries in waste is abundant relatively gasification convert.because contains it which biological lignin, cannot more processes (v) hot well zone, as the feedstock in of residence the and time pressure, such temperature, eters, as (iv) and such (i) type, as param (ii) reactor catalyst, polymer (iii) process feedstocks, the the the the on parameters depending obtained be of can products avariety since versatile a very process, be zeolites ( over when cracked plastics are conversion isHigh obtained distribution product interesting and improveto yield pyrolysis the the of from naphtha of suitable plastic catalysts. waste is introduce to

Investigation of the products produced during thermal decomposition (pyrolysis) thermal Investigation during produced products of is worthyof the The thermal pyrolysis of from of thermal plastic hydrocarbons, distribution abroad wastesThe produces Waste Also, discarded tires can be reduced in size by grinding, chipping, pelletizing, and passed through through passed and chipping, pelletizing, by size grinding, in reduced be can tires discarded Also, waste (domestic considerable afeedstock for has as urban addition, promise In industrial) and as product removal from the hot removal product zone ( as the from WASTE °C–500 oi Products Solid is the general term; though the other terms are used loosely used synonyms, have they as are more terms other the though term; general is the Hernandez et al., 2007 Hernandez C (570 °C (also known as rubbish, garbage, trash, or junk) is unwanted or undesired material. material. or junk) is (also unwanted or undesired garbage, trash, rubbish, as known Marcilla et al., 2008 . Marcilla ; ° Kaminsky and Zorriqueta, 2007 Zorriqueta, and Kaminsky F–930 ° F) and then heated for heated 2 then and F) ). of proven Moreover, polymers has cracking itself to catalytic the Al-Salem et al.,; Al-Salem 2009 Aguado and Serrano, 1999 Serrano, and Aguado ). In contrast, thermal cracking atlow cracking tem thermal ). contrast, In h in a closed retort to yield to aclosed h in retort gas, distillable, Handbook of Processes Petrochemical Handbook Sarker et al.,; Sarker 2012 Aguado et al., 2002 Aguado ; Demirba John and Singh, 2011John and ş , 2004 ). h at a temperature h atatemperature ). alternative An ; Scheirs and and Scheirs Predel Predel ). ). - - - - - Downloaded By: 10.3.98.104 At: 13:40 26 Sep 2021; For: 9780429155611, chapter3, 10.1201/9780429155611-3 Demirba Dasappa Crocker Chadeesingh Collot Brigwater Brar ASTM D388 ASTM Balat Al-Salem Bhattacharya Aguado Brage Clark Coal, Oil Shale, and Biomass and Shale, Oil Coal, tal fuel source at the plant or sent off-site for petrochemical manufacture. plant or sent atthe off-site source fuel manufacture. tal for petrochemical asupplemen as directly used could be produced end of products the All is produced. oil distillable 750 Zeon process, crushed tire chips undergo fluidized thermal cracking (fluidized bed, 400 bed, cracking (fluidized thermal undergo chips fluidized tire crushed process, Zeon pyrolysis black asupplemental as (35% fuel) carbon reactor and w/w) Nippon the In is produced. aquench to is passed tower that (recycled gas and which and oil fuel from stream fluidized char to of hydrogen introduction without the yields occurs reaction lytic agaseous or using acatalyst. This tion flash for step pyrolysis occidental involves that pyrolysisflash Thepyro product and collection. and Basu Aguado REFERENCES Besson Bozell Chen Biddy Boateng Boateng °

, 25 to shredded be also can tires char. Discarded , F–1,110 , , J.S. , , , Journal of Analytical and Applied Pyrolysis Applied and of Analytical Journal The Royal of Chemistry Society The (Editor). Technology—A Needs Energy Route Meet to Reactors Bed Fluidized and Fixed-Bed Bench-Scale Biomass in Berkshire Journal of Forestry Research of Forestry Journal Hoboken, West PA Conshohocken, Chem. Rev Chem. Reactor Bed Spouted PolyConical in a ole fins Biomass and Coal Biomass and (PSW): A Review A (PSW): American Chemical Society Chemical American Industrial & Engineering Chemistry Research Chemistry Engineering & . Industrial Production for Bio-Oil of Switchgrass Reactor (Editor). Royal of Chemistry Society (Editor). Academic Press, Inc. Press, Academic Gasification on Low. Energy on Production Gasification Tar Hull with Near-Termwith Potential Golden, CO Golden, , P. G. , M. M.J. , C. J. A.G. , , J. , M.

, , J.J. , M. 2013 , ş , , and , and R. A.A. A.A. , , S.

, Singh , Sjöström Bioresource Technology. Bioresource 2011 , and Serrano , and Yu S.M. A. ,

, , A.V. , , and Crofcheck , and , Scarlata Paul 1999 . Olazar Gallezot , , . Zhuo

° Ind. Eng. Chem. Research Eng. Chem. . Ind. 2018 , , , 2004 R. F), which yields a gaseous stream that is passed to aquench to is passed tower that F), which which yields and gas from stream agaseous Biomass Gasification, Pyrolysis and Torrefaction Gasification, Biomass . S. Daugaard Q. Walawender Deswarte , NJ (Editor). 2003 (Editor). . , K. Chapter 3: Fuels from Biomass—An Overview 3: Biomass—An FuelsChapter from

, , 114 , Lettieri . 2011 , United States Department of Energy Department States United . Also, P.J. . , , . , Mizanur Rahman Siddique Rahman Mizanur Renewable Feedstocks for the Production of Chemicals Production forRenewable the Feedstocks Chen . , Standard Classification of Coal by Rank by Coal of Classification Standard K Y. Wang , M. Pyrolysis of Municipal Plastic Wastes for Recovery of Gasoline-Range Hydrocarbons Wastes Plastic for of Recovery Gasoline-Range of Municipal Pyrolysis , , C. ( . and Bjornbom . and , Mukunda . 3 P. Dugwell ): 1827 ): , , and , and . Waste Management , D. Chapter 5:Chapter Fischer-Tropsch The Process Biomass and Bioenergy and . Biomass , , and Pinel , and , San Jose San , , , G. P. D.E. J. F New York , New 1999 , C. , , and Baeyens , and . , and Kumar , and , and Sjöström , and Kinchin W.P. 2008 – . , 2006 . 1870 National Renewable No. National Energy NREL/TP-5100-65509. Report . Technical , Goldberg , Pyrolysis and Gasification of Biomass and and Waste Biomass of Gasification and Pyrolysis Feedstock Recycling of Plastic Wastes Plastic of Recycling . Feedstock H.S. D.R. , , , 44 Fan , 2012 . M.J. , , 40( . Introduction to Chemicals from Biomass Reducing national dependence on imported oil onimported dependence national . Reducing , , C. , ( , and Kandiyoti , and C. E Rajan . , 2 ,

): 204 ): . L.T. , 2014

3 2016 Gaisan 1992 ( , 31 S. , ): 235 ): , 2012 N.M. London, UK , London,

, 2012 , and Chee , and J. , ( , 29 K. . N.K.S. 12

. – . 2009 Conversion of Biomass into Chemicals over Metal Catalysts overConversion Metal of Chemicals Biomass into Chemicals from Biomass: A Market Assessment of Bioproducts Bioproducts of Assessment A Market Biomass: from Chemicals 209 Pyrolysis/Gasification of Wood in a Pressurized Fluidized Bed Bed Fluidized Pressurized of in a Pyrolysis/Gasification Wood ): 1 ): London, UK , London,

– , ): 2764 ): , and , and , 2000 ( . 239 , 18 10 B. A.H.M.M.R Cogasification of Coal and Biomass: A Review Coal of Cogasification , 72 , 24 – . . , and Bilbao , and Current Science . Current ): 2625 ): 10 , . ( Recycling and Recovery Routes of Plastic Solid Waste Routes of Recovery Plastic Recycling and Energy &Fuels . Energy Sridhar Hicks 1 . , ( . : 285 ): 87 ): 1 , – Tar Evolution Profiles Obtained from Gasification of Gasification from Tar EvolutionObtained Profiles R ): 97 ): C.S. 2768 . Part 1 . Part 1999 24 to ground and mm – – , – . 2643 91

– K.B. 296 , Annual Book of Book Standards Annual 1992 . Part 3 . Part 102 G. Washington, DC , Washington, , and , and . . , , and Sridhar , and . . Co-Pyrolysis and Cogasification of Coal and Coal of Cogasification and Co-Pyrolysis .

. . The Biofuels Handbook The . In: J. The Biofuels Handbook The . In: 2007 . . 2nd Edition

Fluidized-Bed Steam Gasification of Rice Rice of Gasification Steam Fluidized-Bed 2002 , pp. 476 Pham , 87 , 16 . Fuel . Bench-Scale Fluidized-Bed Pyrolysis Pyrolysis Fluidized-Bed Bench-Scale ( . of Chemistry . of 7 ( Wax Formation in the Pyrolysis of Pyrolysis the in Wax Formation 6 , ): 908 ): ): 1429 ): , 78 H.-L. , – H.V. . 517 : 667 Practical Design and Theory and Design Practical . Preprints. Div. Fuel Chem. Chem. Fuel Div. Preprints. . – .

916 2004 John Wiley Inc. & Sons John – - afeed-prepara mesh as 1999 1437 – . . Energeia . 679 CPL Press CPL Cambridge, UK , Cambridge, . . . . Biomass Gasification Biomass Gasification ASTM International ASTM . A Study in Wood in A Study , 46 . . . , 17 : 1891 International International °C–600 J.G. J.G. , ( Newbury, Newbury, 6

). – Speight Speight 1897 . 115 C, °C, . - - . , , . . ,

Downloaded By: 10.3.98.104 At: 13:40 26 Sep 2021; For: 9780429155611, chapter3, 10.1201/9780429155611-3 Lee Kumabe Ko Jenkins Hoiberg John Hernandez Kavalov Gabra Ergudenler Demirba Khoo Kaminsky Lowry Hanaoka Detroy Lee Lv Gibbs Demirba 116 Lee Lotero Nichols Munger Mills Molino Metzger Marcilla McNeil , , P.M. , S. , , S. M.K. , S. , G.A. , , F.W. and Coal with Air and Steam and Air with Coal and Fluidized Bed 95 from Various Lignocellulosic Feedstocks: Sustainability Assessment via LCA via Assessment Sustainability Feedstocks: Various Lignocellulosic from Interscience Publishers Inc. Publishers Interscience Reactor for Hydrocarbons of Recovery Fuel-Like Reactor Steam Gasification Steam 39 Analytical and Applied Pyrolysis Applied and Analytical Waste 272 Part A Part Biomass Elevated Temperatures Elevated (Editor). Royal of Chemistry Society (Editor). Energy Union 3 Part Biodiesel Synthesis Biodiesel for Gasification of Sugar Cane Residue—Part ofBagasse Gasification 1: Residue—Part Cane of forSugar Gasification Raton, FL Raton, Alcoholic Fuels Alcoholic 351 Overview E.J. Air-Steam Gasification in a Fluidized Bed Fluidized in a Gasification Air-Steam 696 47 in the Catalytic Pyrolysis of Polyethylene Pyrolysis over Catalytic the HUSY in , , H.H. , , , , and Shah , and 1991 H.H. , M. , D. , , , C.G. R.W. E. , , Speight , ( : 174 , , ( , A. B.M. ş ş , 18 N.N. 5 Xiong , – K. B. A. , and Singh , and – A.J. , , – , , T. J.O. , ): 14 ): 369 Lee , 281 , 1966 , A. Goodwin Pettersson ): 6896 ): A. 698 1977 1961 , and Peteves , and , , W. , pp. 333 , M.R. The Biofuels Handbook The . In: , Oil Shale Technology. Oil Shale . A. , 28 (Editor). 1945 (Editor). Chianese

Hanaoka . Petten, The Netherlands The , Petten, 1981 Beltran Inoue Wong 1984

, and Ebeling , and , European Commission. Directorate General Joint Research Centre (DG JRC). Institute for JRC). Institute (DG Centre Joint Research General Directorate Commission. European

. 2006 . , CRC Press . CRC , and Zoriquetta, and 2011 , and Ghaly , and – 1966 . Dien 2006 , Journal of Energy Chemistry of Energy . Journal , W.Y. 18 : 1181 . . Coal Carbonization Products Organic Chemistry Today Chemistry . Organic Chem. Tech . Chem. Z.H. J.G. , , Y.T. . Garcia . – Bioconversion of Agricultural Biomass to Organic Chemicals Biomass Organic to Bioconversion of Agricultural , Corrosion Prevention by Protective Coating Protective by Prevention . Corrosion . , . . 6903 , S. Korean Journal of Chemical Engineering of Chemical Journal . Korean , – , . , , and Loyalka , and Chapter 1: Production of Fuels from Crops of 1: Fuels from Chapter Production Current technologies for biomass conversion into chemicals and fuels and for conversion biomass technologies chemicals into Current L.L. , , B.S. Bituminous Materials: Asphalts, Tars, and Pitches Tars, and Asphalts, Materials: Bituminous , M.I. 376 . S. Kim J.G. , , – , Production of Liquid Hydrocarbons from Biomass from of Hydrocarbons Liquid Production Chang K. 2013 E. T. 1188 Uno S. . , , Biomass and Bioenergy and . Biomass Minteer

, , , , and Musmarra , and . . Catalysis

, 2011 , and Navarro , and Fujimoto Backman Jr. A.N. , , S.D. Boca Raton, FL Raton, , Boca Tan , Chemistry of Coal Utilization Coal of . Chemistry Bothast , A.E. S.B. . . Biofuels Bioenergy and J.M. , S. Bioresource Technology. Bioresource , Bruce . 7 J. . , ,

, and Marcilla , and , , Chapter 1: Production and Properties of Fuels from Domestic and Industrial Industrial and Domestic of Fuels from Properties and 1:Chapter Production 2005 Ogi , J.

(

Wu 1993 1985 Lee I.J.N. 7 New York , New CRC Press CRC (Editor). , ): 418 ): , , CRC Press . CRC , Isoni . Fuel , , S.K. , , 19 S. R.J. , R. . T. D.A. , C.Z. . . , Status and Perspectives of Biomass-to-Liquid Fuels in the European European the in Fuels Biomass-to-Liquid of Perspectives and Status K.W. .

, and Minowa , and , and Kjellström , and Agglomeration of Alumina Sand in a Fluidized Bed Straw Gasifier at Gasifier Straw Bed aFluidized in Sand of Alumina Agglomeration Thermochemical Properties of Biomass Fuels Properties Thermochemical Minowa , , 79 : 41 2007 .

, and Cotta, and , . R. 2007 , 86 J.G. , , V. ,

London, UK , London, Suwannakarn ( – D. 2008 , and Chun , and Chen 1–2 . , and Sharratt , and Pergamon Books Ltd. Books . Pergamon 83 . : 684 . ,

. Speight , 25 Catalytical and Thermal Pyrolysis of Polyolefins of Pyrolysis Thermal and Catalytical A. 2016 . Handbook of Alternative Fuel Technologies Fuel Alternative of Handbook Boca Raton, FL Raton, , Boca ): 368 ): , Pergamon Press . Pergamon . Bioresource Technology. Bioresource , T.

2007 Evolution with the Temperature of the Compounds Obtained Obtained Compounds Evolution of the Temperature the with ( Y. – , 28 1 , and Sakanishi, and . 689 ): 10 ): , , and Zhu , and , Biomass Gasification Technology: The State of the Art Art the of Biomass The Gasification State Technology: CRC Press . CRC M.A. – The Royal of Chemistry Society The (Editor). ( T. . Boca Raton, FL Raton, , Boca 1 , 374 , 43 . , ): 69 ): Catalytic Flash Pyrolysis of HDPE in a Fluidized Bed Bed aFluidized in of HDPE Pyrolysis Flash Catalytic H.S.

. – 2005 B. , Part 2 . Part 25 Journal of Analytical and Applied Pyrolysis Applied and of Analytical Journal . K. ( Vol. 3 , Vol.

,

3 2001 2006 . P. –

): 259 ): , . 2001 76 . , Liu Industrial & Engineering Chemistry Research Chemistry Engineering & Industrial

Effect of WoodyEffect onAir- Biomass Components J.X. 2015 , 18 ...... NACE International Handbook of Processes Petrochemical Handbook London, UK , London, , Boca Raton, FL Raton, , Boca Evaluation of Cyclone Gasifier Performance Evaluation of Cyclone Performance Gasifier The Biofuels Handbook The . In: John Wiley & Sons Inc. Wiley &Sons . John . , Chapter 4: The Corn Ethanol Industry Ethanol Corn 4: The Chapter – Y.

( K. Gasification of Food Waste with Steam in of Food with Steam Gasification Waste 2004 268 London, UK , London, 6 . , and Lopez , and ): 961 ): Synthesis of 2-Methyl Tetrahydrofuran of 2-Methyl Tetrahydrofuran Synthesis

2007 . . . An Experimental Study onBiomass Study Experimental An , 95 – . , 964 Cogasification of Cogasification Woody Biomass Vol. 3 Vol. . ( . 1 Biomass and Bioenergy and Biomass . Angew. Ed. Int. Chem. . ): 95 ): Organic Chemicals from from Chemicals Organic . In: , . D.E. . . – . . Coal Tars and Pitches Tars and Coal . 101 Resour. Conserv. Recy.

California Agriculture California Houston, TX , Houston, 2006 New York , New . . . CRC Press CRC The Catalysis of Catalysis The Energy Sources Sources Energy , . London, UK London, J.G. . Journal of Journal , p. 32

Speight . , , , 78 21 Boca Boca , . In: . In: ( ( 45 5 2 . ): ): ): ): : , . , . ,

Downloaded By: 10.3.98.104 At: 13:40 26 Sep 2021; For: 9780429155611, chapter3, 10.1201/9780429155611-3 Straathof US DOE US Speight Speight Speight Steinberg Speight Speight Speight. Speight Speight Speight Speight Speight Owen Biomass and Shale, Oil Coal, Pakdel Pan Sarker Pinto Scouten Scheirs Rapagnà Rajvanshi Ramroop Singh Ramroop Shah Predel Rapagnà Sjöström Pitt Sørensen Speight , , G.J. , Y.G. , , J. Chem. Rev. Chem. Nowak States Department of Energy Department States pdf Ethylene, Light Hydrocarbons, and Aromatics and Hydrocarbons, Light Ethylene, Methanol and of Ethylene, Benzene, (Wood) Production for the Salem, MA Salem, New New York New of Wood of . Fuel Blends for Production Coal Fuel Gas Biomass/Poor Plastic of Waste (PS) Polystyrene Degradation by Thermal Chemical Naphtha Hydrocarbons of Aromatic Bed of Olivine Particles of Olivine Bed Inc. CRC Press CRC (Editor). Dekker Inc. Dekker Pyro-GC/MS to Yield Aliphatic Waxes Yield to Aliphatic Pyro-GC/MS Press Inc. Press Chemistry of Biomass and Coal: Synergies in the Thermochemical Process Thermochemical the in Synergies Coal: of Biomass and . Distribution Yieldand Product on Size and Particle of Influence Temperature 12 system De Andrade De Energy Congress IX Congress Energy S. A.C. , , , , , J.G. , J.G. , J.G. , J.G. , J.G. , , J.G. , J.G. M. , , J.G. , H. M. , J.G. , and Gupta , and ( J. , and Millward , and 1981 J.G. , , , J.G. . , , 4 J.G. , accessed November 5,, accessed 2018. , , C. Chichester, UK , Chichester, , , and Kaminsky , and N.J. K. , and Roy , and N.J. ): 281 ): B.E. , 2018 York , and Kaminsky , and A.J.J. Velo, , M. A.K. Rashid

Guarieiro

, , and Islam , and 2013b 2013a 2012 (Editor). 2011c (Editor). 2014 2011a 2017 2005 American Journal of Climate Change of Climate Journal . American

Process Biochemistry . Process 2011b 1990 Marcel Dekker Inc. Dekker Marcel (Editors).

1990 , Chen . Conversion Coal Uses of Fuels from Liquid and , and, Kiennemann, and, , and Latif , and 2008 Energy &Fuels . Energy , Fallon . New York , New Njakou – . . Chapter 37.. Chapter

,

London, UK , London, E. Fossil Energy Research Benefits Research Fossil Energy . 288 1986 2014 , 114 . Handbook of. Handbook Petroleum Refining New York , New . The Chemistry and Technology and of Petroleum Chemistry . The Shale Oil Production Processes Production Oil . Shale N. Handbook of Coal Analysis Coal of . Handbook , J.B. , Fuel Science and Technology Handbook Technology and Science Fuel . In: . , The Refinery of the Future the of Refinery . The , The Chemistry and Technology of Coal of Technology and Chemistry . The Coal-Fired Power Generation Handbook Power Generation . Coal-Fired , . Fuel Science and Technology Handbook Technology and Science Fuel . In: Shale Oil M.M. An Introduction to Petroleum Technology, Economics, and Politics and Technology, Economics, Petroleum to Introduction An , Roca G. C.

Synthetic Fuels Handbook: Properties, Processes, and Performance and Processes, Properties, Handbook: Fuels Synthetic M.N. , 2011 , . . ( ,

L.N.N. 3 1991 P.T. , 2005 , Biomass Gasification Biomass , M.R. Transformation of Biomass into Commodity Chemicals Using Enzymes or Cells or Using Enzymes Chemicals of Commodity Biomass into Transformation Yu ): 1871 ): S. G.R. , , , , Boca Raton, FL Raton, , Boca , and Blumberga , and . WREN, London. . WREN, . Rahman

. X. , and Ssundaram, and A. , W. , 2007 . . The Biofuels Handbook . The Q. Biofuel W. Biodiesel: An Overview An . Biodiesel: Hydrocarbon Content of Liquid Products and Tar from Pyrolysis and Gasification Gasification and Tar Pyrolysis and from of Products Content Liquid Hydrocarbon ,

(Editors). 1979 (Editors). .

, 1997 2016 2006 Biomass and Bioenergy and . Biomass Manyà , Part 1 . Part – Rezende

Brage , 5 2000 . 1908 , Lipase catalyzed preparation of biodiesel from Jatropha oil in asolvent in oil Jatropha free of from biodiesel preparation catalyzed Lipase : 427 A. . , . Peak Energy—Myth orReality Energy—Myth . Peak The Biofuels Handbook The . In: , 42 M.S. , Steam Gasification of Almond Shells in a Fluidized Bed Reactor: The The Reactor: Bed Fluidized in a Shells Almond of Gasification Steam Feedstock Recycling and Pyrolysis of Waste Plastics Waste of Pyrolysis and Recycling Feedstock , Foscolo , and . . , , . Chapter 5. . Chapter Washington, DC Washington, Pyrolysis of Mixed Poly-olefins in a Fluidized-Bed Reactor and ona Reactor Fluidized-Bed Poly-olefinsin a of Mixed Pyrolysis J.J. C. – : 409 , 436 M.J.C. , and Molla , and , and Rosén , and , and Puigjaner , and , , pp. 83 New York , New D. , . . – Alternative Energy in Agriculture in Energy Alternative . In: M.S. Polymer Degradation and Stability and . Polymer Degradation . Introduction Processing: An Coal Modern and Coal 414

2006 Gulf Professional Publishing, Elsevier Publishing, Professional . Gulf , John Wiley & Sons Inc. Wiley &Sons . John Ribeiro . . Clean Coal Technology Demonstration Program. Program. Technology Coal Demonstration . Clean

– 1992 Gulf Professional Publishing, Elsevier Publishing, Professional . Gulf P.U. , 2012 102 . CRC Press . CRC , , . Gaseous Fuels Biomass Gaseous The Royal of Chemistry Society . The M. C. R.C. J. Braz. Chem. Soc. Chem. . J. Braz. . . , 19

. , .

2000 https://www.energy.gov/sites/prod/files/cct_factcard. 2012 1999 , N.M. The Flash Pyrolysis and Methanolysis of Methanolysis Biomass and Pyrolysis Flash The ( L.

1 ( von Herausgeg von 3 ): 145 ): CRC Press . CRC . 3rd Edition

): 187 ): 2000 . . . Scrivener Publishing . Scrivener , Steam-Gasification of Biomass in a Fluidized- in a of Biomass Steam-Gasification A New Kind of Renewable Energy: Production of RenewableA New Production Kind Energy: Promoted Reactivity of Char in Cogasification Cogasification in of Char Reactivity Promoted . Fuel , 79 Torres Boca Raton, FL Raton, , Boca CRC Press . CRC Edition . 5th . – – . 153 . J.G. : 1317 197 Fluidized-Bed Cogasification of Residual of Cogasification Residual Fluidized-Bed Scrivener Publishing . Scrivener J.G. , 60 . ,

. Fuel . E.A. Speight

Novel Production Methods for Methods Novel Production . In: Hoboken, NJ , Hoboken, ( – Speight 9 , 1326 ): 755 ): L.F. , 16 , , 78 . Lopes . Proceedings. World Renewable World Renewable Proceedings. : 1313 Marcel Dekker Inc. Dekker Marcel (Editor). . J.G.

: 1189 Albright – (Editor). Royal of Society (Editor). 761 . , 70 ,

Speight W.A. Salem, MA , Salem, . – Boca Raton, FL Raton, , Boca Biomass and Bioenergy and Biomass , ( – 1330 3 , Oxford, UK Vol. 2 Vol. . . London, UK , London, 1194 ): 373 ): Scrivener Publishing Scrivener , . Boca Raton, FL Raton, , Boca , B.L. Beverly, MA , Beverly, John Wiley & Sons Wiley &Sons John Pereira . , Oxford, UK (Editor). . . – . McGraw-Hill

385 D.Y. , and , and Crynes . , . P.A.P.

Academic Academic Goswami . . Marcel Marcel . United United . . , and , and 117 . S. . , , , ,

Downloaded By: 10.3.98.104 At: 13:40 26 Sep 2021; For: 9780429155611, chapter3, 10.1201/9780429155611-3 Wright Vasudevan 118 Wu Wachtmeister , L. Wells Ford Shale Eagle in Oak Ridge, TN Ridge, Oak Laboratory National Ridge Oak of No. Energy. DE-AC05-00OR22725. Contract Department States Edition Scientific & Industrial Research Industrial & Scientific New York. www.sciencedirect.com/science/article/pii/S2451929416300043. S2451-9294(16)30004-3 Beyond and Biomass: Reactions from Condensation , , Moteki L. , , Boundy P. . Office of Planning, Budget and Analysis, Energy Efficiency andRenewable Efficiency Energy, Energy Analysis,United and Budget of Planning, . Office , , H. , Sharma T. , Lund , Gokhale , . R. , , , L. S. Perlack , , and Kumar , and Aleklett , A.A. Natural Resources Research . Natural , , R. Flaherty , , K. , 64 Davis Mikael Höök Mikael , and , : 822 A. , ,

D.W. S. 2005 – , and Saulsbury , and 831 , and Toste1 , and . . Liquid Fuels from Biomass: Overview Fuels from Liquid An . , Chem M. , 26 ,

F.D. 2017 , Handbook of Processes Petrochemical Handbook , ( B. 3 1 ): 365 ):

:

2016 . 2006 32 Production Decline Curves of Tight Oil of Tight Oil Curves Decline Production – . 58 – . Production of Fuels and Chemicals Chemicals of Fuels and Production 377 , July 7, 2016 ª2016 Inc., Elsevier Biomass Energy Data Book Data Energy Biomass .

www.cell.com/chem/ . Journal of Journal ­fulltext/ . 1st 1st , ​