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Handbook of Hydrogen Energy

S.A. Sherif, D. Yogi Goswami, Elias K. Stefanakos, Aldo Steinfeld

Reformation of Hydrocarbon Fuels

Publication details https://www.routledgehandbooks.com/doi/10.1201/b17226-6 Paul A. Erickson, Hong-Yue (Ray) Tang, David R. Vernon Published online on: 29 Jul 2014

How to cite :- Paul A. Erickson, Hong-Yue (Ray) Tang, David R. Vernon. 29 Jul 2014, Reformation of Hydrocarbon Fuels from: Handbook of Hydrogen Energy CRC Press Accessed on: 27 Sep 2021 https://www.routledgehandbooks.com/doi/10.1201/b17226-6

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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: 11:22 27 Sep 2021; For: 9781420054507, chapter3, 10.1201/b17226-6 Paul A. Erickson Paul A. of Hydrocarbon Fuels Reformation 3 References 3.18 Summary 3.17 3.16 3.15 3.14 3.13 3.12 3.11 3.10 3.9 3.8 3.7 3.6 3.5 3.4 3.3 3.2 3.1 Introduction CONTENTS Humboldt University State VernonDavid R. Davis California, of University Hong-Yue Tang (Ray) Davis California, of University Reformer Control Issues Reactor Design High-Temperature in Reforming Internal Fuel Cells Fuel Selection Methods Reforming ofComparison the 3.12.5 Controls 3.12.4 3.12.3 3.12.2 3.12.1 Reformation Processes the in Mechanisms Limiting ATR Fuels of Different Autothermal Reforming Oxidation Partial ReformationSteam Types of Reformation Catalyst Selection 3.5.4 3.5.3 3.5.2 Stoichiometry 3.5.1 Reactor Parameters Performance and Quantifying TechnologicalModern Reformation: and State Barriers Art of the of Reformation History Reformation? Is What ...... Degradation Mechanisms Heat Transfer TransferMass Kinetics Chemical Reformer Characterization Analysis Output and Flow Rate ...... 44 44 44 34 34 54 30 30 48 46 25 45 38 53 53 28 47 27 49 29 29 26 37 32 24 51 51 41 23 Downloaded By: 10.3.98.104 At: 11:22 27 Sep 2021; For: 9781420054507, chapter3, 10.1201/b17226-6 thermochemical pathways. The mostcommonly used process to generatehydrogen isref from well-developedindustrial processes toemerging pathwaysinbothbiological and tion and distribution of hydrogen. There are manyhydrogen production methods ranging ronmental impactatthe point ofuse,there maybesignificantimpactsfrom theproduc converted from othersources ofenergy. Whilehydrogen asanenergy carrierhaslowenvi gen isnotaprimaryenergy source but,likeelectricity, isanenergy carrierandmustbe Hydrogen isnotreadily availableinnature intheunboundmolecularform. Thus,hydro 3.1 24 volume. Currently, diesel, gasoline, and LPG are common fuel for transportation application. transportation for fuel common are LPG and gasoline, volume. Currently, diesel, unit per lowest energy but weight the unit per energy highest the has Hydrogen fuels. of various A comparison FIGURE 3.1 storage energy total age, agiven capacity higher volume. in potentially and For stationary stor ambient pressure allows hydrocarbons liquid for fast refueling, high-energy-density madein recently been hydrogen has storage progress issues, reforming significant While liquid. higher-energy-density of a the storage transport and allowing storageby difficulties hydrogen applications avoiding hydrogen while of shows using potential technologies the power generation. hydrogen Producing mobile for reformation of fuel onboard aliquid via obstacle forenabling hydrogen-fueled present asignificant hydrogen ­ refueling for low The a fuel. such content volumetric energy of hydrogen of lack infrastructure the and to hold 3.1, for required that Figure tank not and the values itself fuel include the these only steam andautothermalreformation (ATR) processes. ormation offossilfuels.Thischapterwilldiscussthebasicprinciplesandstateart

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y - - - - - Downloaded By: 10.3.98.104 At: 11:22 27 Sep 2021; For: 9781420054507, chapter3, 10.1201/b17226-6 power systems,mobilegeneration(i.e.,auxiliaryunits,forkliftapplications), niche markets[1–6].Thesepotentialhydrogen applicationsincludestandbyandauxiliary cessors are notasestablishedandare foundintheresearch anddevelopmentfieldorin production, (GTL) gas-to-liquid and to methanol. plants, is, methane that converting forhydrogenation, as refinery such ammonia hydrogen processes viding for industrial emissions. gas to reduce systems sequestration dioxide and greenhouse carbon with capture combined be potentially can ofapplications, ahydrocarbon feedstock reforming catalytic of HydrocarbonReformation Fuels bring the H the bring followed be reactors that reformer can by water–gas shift numerous catalytic main The hydrocarbon ahydrogen-rich into reformation ofcatalyst the fuel the aids mixture. gas products toward desired (H the selectivity to shift of acatalyst catalyst or aseries bed reformation beds system uses temperature, typical the endothermic. being reaction total the with reaction water–gas shift the reassembly through thermic breakdown followed steam fuel by rate-limiting amoderately and endothermic exo ahighly reformation of one has hydrocarbon feedstocks, typical Thus,exothermic. with favored being as thermodynamically amounts, is added small in or externally mixture oxygen, with hydrocarbon elemental eitherthe constituents supplied fuel–water the with JP-8 as such fuel [15] jet and some examples of [5–7,12,16–18]. are the reassembly of The [10–12], ether, dimethyl propane, (natural gas), butane, methane [1,13,14], diesel isooctane, applications: [7,8], commercial and gasoline some prototypes in [4,9], ethanol ­ have and ­ reformation studies been in havehydrocarbon used fuels been A used. is when air nitrogen with purity output dilute the stream will typically fuel–water but the into this stream, oxidizer an by introducing used be also can sources heat system. Internal atypical to provide in burner, used energy is the external an as such bonds. Aheat source, H–C and C–C the break and hydrocarbons the toneeded volatilize is Thus, energy hydrocarbon or fuel–water the fuel mixture. state than energy a higher of fuels. characteristics the to change used be it can like cesses a desirable into reformed Equation are SR 3.1 shown in trait. The process pro other and fuel of acertain characteristics when the reformation (SR) steam in reaction is ofreformation definition, ahydrocarbon. apure In a compounded element to its form. elemental Equation overall 3.1 typical the represents hydrocarbon hydrogen into molecules breaks that process from achemical Reformation is 3.2 and stationarydistributedpowergeneration. While large-scale hydrogen production plantsare wellestablished,small-scalefuelpro For hydrogen about acentury, production large-scale plants have stationary pro been Although reformation can proceed unaided by using solely thermal processes at high at high processes solely by using thermal unaided proceed Although reformation can due reaction hydrogen endothermic to the an product typically Reformation having is What Is Reformation? Is What 2 concentrations up and minimize problematic compounds. conversion, The concentrations up minimize and CH nm +→ nn HO 2 C O +  nm + 2 2 and CO and HK 2 ∆ H 2 ). processor, fuel the Inside the () 298 > 0

successfully used used successfully variety of ­variety methanol methanol (3.1) 25 - - - - Downloaded By: 10.3.98.104 At: 11:22 27 Sep 2021; For: 9781420054507, chapter3, 10.1201/b17226-6 trading off reformate stream purity and results in product dilution when using air as the the as product air in dilution when results using and purity reformate off stream trading catalyst of by the bed improves transfer heat overall mass the and the process. This in POX reaction. ATR either and oxygen water–gas to shift produce use the or air can heat to produce consumed be water additional of hydrogen the part process, will then the via prior hydrocarbons to SR. water apart long-chain toformers If break added is or steam to processor. fuel of the control of the aspect catalyst operated;at the important is which an thus, is temperature efficiencies,are thecatalystsstrongly the dependent usable temperature cost,andof life on 26 more available mid-1900s. the in became electricity and gas before natural cooking and for lighting was used 1800s. This of reformation was deriving uses early commercial by POX fuels gaseous distributable the into fuel.One or coal gasificationsolidthe of and of wood as such solid fuels ways devising with of attributed changing Murdoch is William of systems London was developing. lighting the in depletion, resource acrisis with eting With price solid of transportability. skyrock the whale oil regarding traits of their because 1700s, were not biomass fuels systems applicable readily and coal lighting to distributed problems. lighting early street late the 1700s England’s adeliberate solving as in had its literature action roots in in known it independent not and combustion field, is an with alwaysas reformation has occurred that reformation argued While be can the it combustion gasification. field asin classified end products. to the burns then and oxidizer it the reaches until diffuses then fuel gaseous or This fuel. reformation of the lead gasification flames to a local most diffusion with vaporization seen and as heating mic phase. endother Thus, the gaseous but in only directly not does solid or burn fuel liquid atypical that combustion. It solid or fuel well liquid known is regarding especially bustion independentis andnot old of as com flame reformation is as itself speaking, Historically 3.3 oxidizer. For (or oxidation complex [POX]) reforming hydrocarbons, partial prere dry in used is Table 3.1thelate of reformation orIn gasification. uses shows the in early milestones usually is and process combustion of the short-circuiting effective an then Reformation is

History of Reformation of History Source: 1959 1816 1813 1804 1792–1794 Date of Gasification Early Milestones TABLE 3.1

http://www.netl.doe.gov/technologies/coalpower/gasification/basics/3.html. British GasCouncilstartedtoreplace coalgaswithliquidnaturalgas. Baltimore, Maryland,becomesthefirstUScityto lightstreets withtowngas. London andWestminster GasLightandCoke Company, Great PeterStreet, Coal gasfirstpatentedforlighting. Scottish scientist William Murdoch produced gasfrom heatingcoalforlighting. wooden pipes. illuminates Westminster Bridgewithtowngas lightsonNew Year’s Eveusing Milestone town gas town or or Handbook ofHydrogen Energy Handbook syngas from coal in the early the in coal from - - - - Downloaded By: 10.3.98.104 At: 11:22 27 Sep 2021; For: 9781420054507, chapter3, 10.1201/b17226-6 into a hydrogen gas with benefits in transportability and energy intensity. andenergy transportability ahydrogeninto in benefits with gas some biomass sources found with is usable as low-energy fuels to convertused marginally be also processing. Reformation can or allows chemical hydrogen in acteristics to used be hydrogen into point-of-use desirablesolid, fuels has that or char environmental gaseous converts liquid, Modern reformation also characteristics. had desirablethat transport asolid to form aform from of that afuel converting of was essentially gas town use The 3.4 of HydrocarbonReformation Fuels cooler regions of the tube from observation points within the furnace. Lifetimes on the on the Lifetimes furnace. the within points observation from tube ofcooler the regions the dark or be noted by observing also heat device. of high fluxcan multijunction Areas a with of tube each center down line temperature the monitorSome operators tube will at merged reformate the monitored exit. sensor by temperature asingle typically is stream tube. flows each in reformate entire the similar forTemperature to ensure entrance tube simple orifice aheader each with at an and mechanically is reformer tube standard The have plants might even of and small furnace. a72-tube asingle not array in unheard are of reformer tubes holding hundreds over Furnaces temperatures. wall 1000°C external negative gauge provide have pressure can heat that to arrays of reformer tubes steam high- due and high-temperature to the strength rupture creep high have and life long creep 10 from ranges must 100 from ranges to length 13 tubes to 150 the and m. These mm outer that an diameter with alloy tubes catalyst loadedcosts. The is high-strength into ratio, cost factorsthat other include operational reflect drop flow throughputand pressure (S/C) steam-to-carbon by the affected also is formation, which ratio. S/C the Along with avoidance and operational life with of (coke) solid carbon associated costs the in trade-off a catalysts but catalystas of typically generally more the is are expensive. selection The used catalyst be substrate. held pellet also on a ceramic Cobalt noble can other and metals aNi-based using bar at 450°C–800°C at typically catalyst temperature 30–45 the bed with now actively studied. hydrogen production [21].tralized for point-of-use processors fuel Smaller application are power applicationsfor dependent distributed is generation on decen transportation and gap hydrogen for decades, many to make current available readily the commercialized givesficationthat 99.9% hydrogen higher large-scale been purity. has productionor While (PSA) adsorption swing apressure into fed system reactors for is puri water–gas shift the hydrogen CO the the content. concentration of decrease output and increase The stream low-temperature and reactors to high-temperature into fed usually water–gas shift is to 500°C 950°C. from reformate,perature The product or the of hydrocarbon reformation, fuel. acombusted from heat endothermic, and supplied is tion is externally reforma steam; thus, input the and the fuel than energy more chemical carries typically The steps. purification various into lystproduct fed and gas bed. collected Product is gas methods. biological and sis, of heavier includefuels, andreforming gasification electroly used hydrocarbon methods productionOther producedhydrocarbons. refinery is light other and by gas SR of natural for hydrogenation hydrocarbons. Approximately of unsaturated 90% hydrogen of the used and for methanol, hydrotreatment refineries, and production for in gen is the of ammonia The dominant use of hydrogen is in the chemical industry [20]. of industry hydro use of chemical hydrogen the use primary in The is dominant The In commercial large-scale hydrogen production large-scale reformer operates steam systems, commercial the In atem requires typically process reformer, steam reforming methane the atypical In acata across fed and steam with reformation facility, amodern joined is In gas natural Modern Reformation: State of the Art and Technological and Art of State the Reformation: Barriers Modern pressure operation inside the reformer. Central external burners operating at operating slightly burners reformer. operation the ­pressure inside external Central 27 ------Downloaded By: 10.3.98.104 At: 11:22 27 Sep 2021; For: 9781420054507, chapter3, 10.1201/b17226-6 28 conversion, selectivity, yield. and (O oxygen-to-carbon as Typical parlance includes flow of space in terms rate velocity, such terms stoichiometric reformation industry. the in used is language and ofA somewhat terms set standard 3.5 Kolbs’Gunther book recent [28]. given in is vehicles cell fuel and for cells fuel processing fuel lent of review small-scale Toyota vehicle [FCEV]), (fuel electric cell Motors, General motors. excel Hyundai and An (NECAR 3), demonstrated by Daimler those by including vehicles early cell used fuel also (1994–2000). buses cell system earliest (1994) The 3.2. Figure Reformation was shown in is adaptedbeen to mobile applications several iterations including Georgetown fuel of the system. of Reformation the have systems performance and life apparatus the reducing operation.mal Frequent start-up shutdown and degrade catalyst of can the reformers and in nor transients significant to experience expected are reformers reformers, small-scale forreformers hydrogen production have published [15,25–27]. been large-scale Unlike of small-scale studies years, recent In detailed reformercatalyst design. and operation life [22–24], down shows scale challenges and unique processes industrial optimizing as such problematic. be also can species minor other formation and have at to Ni-based carbon tendency fuels form catalyst. hot on the the spots Ammonia as molecules suitable and longer-chain catalysts additional as prereforming with used be can heavy various hydrocarbon methane, feedstocks reformer than apparatus.and Other system catalysts commercial the with expected are order continuous use of with years 1994. April in demonstrated Georgetown’s First Test of Davis. Bus-1 at Bed University FIGURE 3.2 For small-scale hydrogen well-understoodFor from production, small-scale adopting technology Quantifying Reactor Performance and Parameters and Reactor Performance Quantifying 2 /C) ratio S/C and as such ratio, terms output and analysis and Handbook ofHydrogen Energy Handbook - - Downloaded By: 10.3.98.104 At: 11:22 27 Sep 2021; For: 9781420054507, chapter3, 10.1201/b17226-6 following: reactor volumetric the as flow therate dividedin thereactor is shown by volume.This applicable. if species uid Space velocity (sv) defined is that term aquasi-nondimensional is or equivalent liq species to indicate gaseous distinguished velocity, further be can which space as known parameter inverse residence to an time normalized Flow rate typically is 3.5.1 of HydrocarbonReformation Fuels than just O just than it to oxygen–alcohol note helpful is the ratio (i.e., oxygen [O to methanol its O oxygen bound counted in is ratio. Typically, O the not counted in be oxygen compounds will up bound in (i.e., alcohols). O the in S/C confused potentially be also can ratio stoichiometry and and/or oxidizer the as air oxygen therein when with using contained cially fuels using values should clearly reporting define O Those processes. O 3.5.2 values. of the mistranslation values of to avoid their description or to include afull ambiguity shouldity careful be flow in values space reporting thecatalyst. capacityThose with veloc full to its filled not reactor is housing research volume typical catalyst displaced by the the because include only the will typically academic reactor, by studies the in those required while volume and length it true as locations the indicates empty including tube cate entire the indi generally theprefer reactorindustry to definition of in the volume. is Those terms space velocity all with issue condition. Another given inlet or at another standard tants pressure, whereas reac and GHSV temperature at any or couldane all mean standard S/C. and conditions inlet GHSV-MSTP would hourly gas mean space velocity of meth flow as hourlygas tospace this represent used GHSV be velocity couldat specified also water.hourly and of methanol space or apremix velocity methanol be (LHSV) might LHSV-M would hourly a liquid represent space velocity whereas of liquid methanol, phase. liquid Adenotation in of not reacting certainly are and vaporized are reactants although the pressure, space liquid and used be temperature velocities can standard flowric andthe fuelratenot water the of or flow.steam under that liquids are fuels For space volumet dependence remove just the velocity by can stating steam-to-carbon the supplying reactant only energy, the often is the stream but fuel change, the often as S/C for normalization. used be also can pressure and ratio temperature can Standard used. often are conditions reactor; the reactorany location inlet thus, in nonreacted volumetric the flowvelocity, change rate can pressure at and temperature species the but unit hourly done any be time space For in used. can space velocitycommonly gas is spaceso flow as so does inverseincreases ratevelocity. time are units units The The where 2 V V /C ratio S/C and reformation in stoichiometry the to describe used ratio parameters are is the reactor volume the is is the volumetric the flow is rate Stoichiometry Flow Rate 2 /C to avoid mistranslation. 2 form and not as an oxygen radical. When using alcohols, oxygen using not an and radical. as form When SV = V V

2 /C ratio espe nomenclature 2 : CH : 2 /C ratio, and 3 OH]) rather (3.2) 2 /C /C 29 ------Downloaded By: 10.3.98.104 At: 11:22 27 Sep 2021; For: 9781420054507, chapter3, 10.1201/b17226-6 the following: the product. ora certain reactant toa certain and specific are most user the defined be by can ity, forsomeas a system outputs carefully outputs defined be yield. should and These also Typical species. or selected include all output includes conversion, nomenclature selectiv can output many and metrics ambiguous equally be ofOutputs reformation reactors can 3.5.3 30 in space velocity where the reactor begins to break away to break space 100%in velocity the where reactor from begins the or previously of point abreak speak space Many compared researchers velocity using ametric. often as thereactor. of the properties However to quantify inadequate, insufficient is are reactors volume capacity the and fuel-processing the reactorSpace of but the velocity describes 3.5.4 100%. to normalization allows ­factor SF would 1/3 be 3mol as of hydrogen H (CH product methanol desired hydrogen is is the reactant case, if the and this In following: to 100%. selectivity the factorwhere stoichiometric (SF) to normalize the used is and For example, complete complete implies combustion conversion but no hydrogen production. POX or with ATR employ reforming that nonexistent especially systems oxidation an step. what Thus, desired. even is conversion though hydrogen the may high, be output could be reformationhydrogen systems, the in because product typically is distinction important an progression. Ittant not does however give product of any indication the is produced. This reac Forsumed. and pathway asingle consumption fuel of give does the insight system, this Conversion is defined as the reactant consumed divided by the reactant fed as shown in as shown divided fed thereactant Conversionby consumed thereactant as defined is The yield shown in the following also uses a similar SF: asimilar uses following also the yield shown in The the shown in For equation is stoichiometric reformation, example, the methanol in the following: in are shown These definitions. at has least potential two selectivity The how indicates Conversion only percent was con and much given reactant in typically is

Reformer Characterization Reformer Output and Analysis and Output Sele Sele Yiel ct ct Conv ivit d ivit CH =× y y Desi ersion =× 32 = OH Desi Undesire re Desi +→ Reac dp = re Reac HO Reac 2 dp re is produced is 1mol per CH roduct tant dp tant roduct Reac dp tant roduct cons CO roduct fe produc tant cons d 22 produc umed + fe produc 3H umed produc d ed

ed Handbook ofHydrogen Energy Handbook SF ed

ed SF

3 OH reactant. This OH This reactant. 3 OH), the (3.7) (3.5) (3.3) (3.6) (3.4) - - - Downloaded By: 10.3.98.104 At: 11:22 27 Sep 2021; For: 9781420054507, chapter3, 10.1201/b17226-6 Reformation of HydrocarbonReformation Fuels conversion following: the theoretical shown in the is reactor’s the knowing RTD function, following: the shown in as ratebe expressed reaction the coefficientcan mechanism, example, Arrhenius the using conversion on fuel first-orderbased simplified to a be as SR reaction. can methanol Taking space velocity using (SV)descriptive [30]. than it more is kinetics, chemical and effect geometric the embodies time characteristic the Since characteristic. dependent heat are on the transfer performances their as reformers steam describing in important (RTD). especially distribution is residencethe time This rate byreaction in the coefficient captured indirectly are properties kinetic chemical the addition, residence In the time. from directly performance the condition describes and flow and characteristics, conditions, transfer geometric heatmation as such mass and by space velocity described be alone. clearly cannot shows reactor that performance This reactor radiusthe of configuration (i)is that0.635in.)cm of (iii).configuration(¼ than less that data is these between scheme, reactor volumes and difference identical. only are The space velocity.thecatalyst, figure, flow this In rate,reactortemperature,set point control 3.3 Figure [29], in seen greatlyforAs have reactors that vary same can the performance first-ordercharacterization. mance, the behavior by theis reactorsuch notcaptured of perforof limits knowthe to useful is percent defined conversionthis yield. While or 32(9), 1192, 2007.) P.A., D.D. Davieau, (From ratios. Erickson, and aspect different with reactors Two similar FIGURE 3.3 Following Fogler’s formulation of model asegregation for packed-bed reactors [31], by the a modification is of RTD. time The overallreformation process characteristic The factors additional which constant, infor time characteristic the to use is metric A better

Percent of methanol converted 100 50 55 60 65 70 75 80 85 90 95 0.0 Reactor config 0.5 1.0 uration (i XE E 1.5 =− ( kT t ), rate reaction from the Equation 3.8, coefficient and 1e () Pe )R ∫ ∞ lletize 0 = 2.0 LHSV eact A − kT () e d catalyst or config ER a -M t / 2.5 () T tt

d uration (iii)

3.0 3.5 4.0 Int. J. Energy Hydrogen 4.5 (3.8) (3.9) 31 - - , Downloaded By: 10.3.98.104 At: 11:22 27 Sep 2021; For: 9781420054507, chapter3, 10.1201/b17226-6 order systems after five time constants, thereactor should five constants, ordertime produce after systems near 100% conversion or producefuel reactor. first- 63.2% all Like possible of product aparticular the desired in Equation into stituted 3.9 following: the yields E 32 The porous structure of the catalyst allows fuel to diffuse into the catalyst. After the the catalyst. the into After catalyst of to the diffuse allows fuel porous structure The an active sitethecatalyst. find on can tomation long go continues as fuel forward as active, operation. catalyst highly refor the the is the If to sustain catalyst activity high process.Heat the added is in system temperature catalyst to to ensure fuel the the and heat it reassembles, reduces and bonds and and consumes chemical downit the breaks an active ahydrocarbonsite transfer. finds catalyst, on a When heat mass are and nisms mecha process; limiting endothermic thus, the an typically reformation is The ture. ahydrocarbon,reform provided catalyst active the is sufficient that tempera by having catalysts. of action of mode(PEMFC). degrade third catalyst, the the formation or also is coke Carbon which can of cell aproton membrane fuel electrode exchange the poison undesirable it because can reformation, CO output In of the is stream. purity or removal to needed ensure steps are undesirable by-product an creating reaction reduces that efficiencies. cleanup Additional of ideal asecondary because than less often is selectivity realistic The feedstock. of the overall the performance. and lyst activity one control another, catalyst of the helps improving the temperature and to improve cata coupled fully with are They alater section. in discussed are and kinetics chemical fer and heat and trans mass are mechanisms limiting factors. reformation, other the and In time, It species, residenceby temperature, influenced pressure, is chemical concentrationthe of selectivity, (or stability and degradation behavior). modes of of action catalyst [32]: three are There changes. physical chemical and activity, idealoccur. catalyst An would but not practice, consumed, be in catalysts do undergo new acatalyst reaction, pathwaysBy the into introducing acceleration and reaction of the 3.6 multiple reactor design. are the there ways to optimize geometry, time, catalyst, words, characteristic pressure, other etc. In required given the of temperature, regardless have performance, same the will time characteristic same the on conversion based is time or reactorswaves. with yield performance, characteristic As and size,acoustic as flowbaffles such particle and conditions, passiveother enhancements account into catalyst takes and performance descriptive actual of is the time characteristic behavior. SV, this Unlike captures characterization LHSV-M, this or yield and or GHSV, ( t The first-order characteristic time, first-ordercharacteristic The ideal plug an flowByfunction, assuming reactor Dirac (PFR)as a function RTD Catalysts help new introduce pathways to to reduce activation required the energy of desirable measure catalyst of the product the is quantity reacted to the selectivity The of how a measure reaction(s) is fast the Activity catalyst. of presence the the in proceeds ) = ∂( Catalyst Selection Catalyst t − t r ), identical residence an time with X =− τ , represents the time needed to needed convert time 63.2% the , represents of the 11 ee − kT () t t r r for every molecule in the reactor, the for every molecule in sub and =− − τ t r

Handbook ofHydrogen Energy Handbook (3.10) ------Downloaded By: 10.3.98.104 At: 11:22 27 Sep 2021; For: 9781420054507, chapter3, 10.1201/b17226-6 catalysts cannot operate toward but temperature atcatalysts hydrogen. cannot have high selectivity high it cheap,because is active at elevated temperature, stable. Cu-based hand, and other the On reformers high-temperature the in catalystor the bed. used ANi-based catalyst often is catalyst of the property poor heat of the because transfer temperature the controlling in must taken Care be liquids. most fossil-fuel-based with necessary often is Desulfurization reactor of [32]. operation the the life catalyst of the determine stability mechanical and mal, catalyst active to the allow site next reactant. to the reform out the from catalyst reform, products the into and to diffuse need diffuse reactants of HydrocarbonReformation Fuels examples of pelletized catalyst. (Courtesy University of California, Davis, CA.) Davis, of California, University (Courtesy catalyst. of pelletized examples are right the On catalysts. of monolith examples are left ATR. the and On steam for of catalysts Variations FIGURE 3.4 hydrogen to consume reaction reverse allows water–gas the shift temperature high The advantageAnother at low low the for is reforming level temperature of CO formation. compatible potentially is phosphoric with (PAFC) acid cell fuel or PEMFC applications. [10,34,43–46].est low-temperature The catalyst allowscomplex a less heat and exchanger have catalysts [33–42], proposed other been but Cu/ZnO/Al (Al byported alumina COgen and toward hydro selectivity high of their because industry reforming gas fornatural the catalysts water–gas shift as reformation have used ethanol been and for methanol used (MTS) [20] shift temperature medium copper-based catalysts.formulations Many of these using hydrocarbon reformed be reformation. Lighter can hydrocarbons, methanol, as such generally suitable to become active temperature are and for high higher-order require area. surface of internal amounts high and catalystto poisoning over resistance monolithtage of the catalyst their pelletized is sites open with forcatalyst. advan the The structures porous alumina usually Pellets are washcoatedcatalyst is material onto a monolith substrate monolithic catalyst. to the form of amount do Asmall general, pellets. monolith catalysts produce than drop pressure less development. more in hydrocarbon many lyst and are fuels, for formulations reforming In 3.4. Figure shown in monolith and of structures catalyst pellets substrates are types general two formation. The carbon where appropriate, should to controlled be minimize catalyst. of the Additionally,integrity S:C as such conditions O operating and other the to ensure reaction aCu-based exothermic when catalyst using an with taken is Care Catalyst degradation is an important issue in catalytic reformation. The chemical, ther chemical, reformation. The catalytic in issue Catalyst important degradation an is The reforming catalyst is usually based on nickel/nickel based catalyst usually is oxide reforming orThe cobalt composite. They of cata wide selections are There used. choice ofThe catalyst feedstock on the depends 2 . The catalyst. The system of copper (Cu) oxide of presence zinc (ZnO) the in sup 2 O 3 ), catalysts, most popular. the is derived There industrial from 2 O 3 remains the primary inter primary the remains 2 :C, :C, 33 ------Downloaded By: 10.3.98.104 At: 11:22 27 Sep 2021; For: 9781420054507, chapter3, 10.1201/b17226-6 34 another. Higher temperature typically speeds up the rate-limiting steps breakdown of fuel rate-limiting up the speeds another. typically temperature Higher catalysts to promote different separated reactors or with be individual into one reaction 3.13. physical happenthrough at same can the may location, reactions or these of these All 3.11 Equations followed shown in as sometimes by are methanation and reaction shift water–gas the breakdown and fuel as general SR described The steps are feedstock. bon the on hydrocar depending used preheaters. and heatare catalysts Specific exchangers cleanupand as as coupled be complexdevices well significantly with shift water–gas given in is reformer schematic duction plants. Atypical hydrogen pro large-scale in to hydrocarbons most reform widelySR method the is used 3.8 hydrogen ahydrocarbon from fuel. of process.Today,tion each plants, to obtain most method common SR the is large-scale in SR, are ATR. POX and gas. These 3.5rich Figure shows reforming, representa agraphical hydrogen- into hydrocarbon fuels for major reforming methods three currently are There 3.7 fabrication [50–53]. in techniques micromachining well as to degradation oxides various compounds [49], by and resistance incorporating and as [47,48].temperature Current catalyst development ways to improve targeting is selectivity active at highly elevated are structures spinel alumina or magnesium by porous alumina Ru, reformers. Rh, steam Pt, high-temperature Pd, in used catalysts are Re supported and for CO selectivity high catalysteven the has if of (a) SR, (b) representation Graphic POX, (c) and ATR. FIGURE 3.5

Types of Reformation Steam Reformation Steam (a) He at H ydr ri oc H ch pro ydrogen arb ga s on-stea duc t m He at (b Fu ) el anddef ri hy ch pro Burning CO and zone drogen ga s icient ai duc t 2 over CO. expensive precious metal Other r (c) generate internally ox throug He idatio at h Figure 3.6 Figure n Hy d Handbook ofHydrogen Energy Handbook dr and ox ri oc Hy ch pr arb drogen ga on-steam idizer od s . This system would . This uc t ox refo zone idatio Co Ho zone rm oler t atio n n - - - Downloaded By: 10.3.98.104 At: 11:22 27 Sep 2021; For: 9781420054507, chapter3, 10.1201/b17226-6 Reformation of HydrocarbonReformation Fuels 3.4 Equations 3.6: shown in are through These reaction. shift gas decomposition water– of the methanol and overall consisting the reaction as for methanol tivity. However complex application,be expressed in can reformation asimplified process selec favor as promote pathwaysformulations in reaction the of manifested certain is that debated of [10,56,57]. SR still is mechanism catalyst understood, commonly different As on aCu-basedics [10,36,54,55]. of catalyst available literature methanol the are in exact The examples. here SR as The kinet described be will ethanol and SR, in methanol parameters difficulties: formation have potentially or produced coke carbon are these often and radicals and mediate species plant. the With heavy hydrocarbons, through inter progresses gas hydrogen the as purity increasing have with temperature at operating multiple each adifferent series reactors in promotes CO CH typically but and temperature higher reformer. steam of atypical Schematic FIGURE 3.6 Many hydrocarbons have been used as feedstock for SR. To feedstock as Many have hydrocarbons used been some key of illustrate the Clean- CH CO CH up/pre-reformer CO CH CO 32 nm OH +→ 3H 32 +↔ +↔ OH HO HO +→ +→ 24 HO nn 22 22 H →+ CH 22 CO O Va CO CO CO po St += 2H ea rizer HO += += 22 m+f CO 2 += H H ( 3H 2 2 ue + ∆ ( l ∆ nm H ∆ ∆ H + H H 2 ( 298 ∆ () () 298 H 298 298 H K9 298 K2 ( ). K4 K4 ). =+ ∆ 4 K4 H production. It is thus typical to production. It typical thus is − ) − − 0 0 298 refor 1 k T 1k 1k burne 62 + ubular + J/ J/ 9k J/ K mer kJ mo mo mo r ) /m J/ Reformate > mo l l l 0 ol

l

(3.15) (3.12) (3.13) (3.16) (3.14) (3.11) 35 - - - Downloaded By: 10.3.98.104 At: 11:22 27 Sep 2021; For: 9781420054507, chapter3, 10.1201/b17226-6 following: the shown in hydrogen produced be concentration on 100% can based as dioxide carbon selectivity SR, For exothermic. is 75% methanol reaction dry faster water–gas shift the and thermic 36 reactions: simplified show SR. following equations the The to methanol quite similar is process ethanol the for vaporization needed fuel [58]. energy added the respect, water in atrade-off has this In or low S/C.ture S/C an that reported It been has ratio >1.5 reduces formation but carbon more is pronounced at of low fouling effect tempera The site catalyst the structure. inside active the contacting from catalyst fuel the by fouls blocking Solid carbon performance. degrade catalyst favor will can reactor potentially that the formation inside ethanol carbon of use The fuel. the bond in carbon–carbon the to needed break is temperature higher hydrogen yield at reformer outlet. the S/C an that dry higher 1.3 in ratio results 1.6 between and reforming steam for methanol found work has of coking. by Experimental by researchers many means alyst performance and degradedformation catcarbon in results Cu-basedsinter steam catalysts. Insufficient without fuel hydrogen adding to the the with product. may steam High-temperature also because it reduce efficiencies formation.be Excessive must energy vaporized will steam conversionfull andto suppressachieve and solid carbon required is CO Sufficient steam thereactor. of life and efficiencies, methanol) [54]. utilization, fuel impacts parameter This breakdown. fuel considering reaction fuel conversion high the forward andassist to sufficienthand, heat is to obtain needed undesirable by-productan other operation the when system. considering On cell of afuel to produce COmay typically high. too consumed is be is reactor CO temperature the if hydrogen reaction, reverse products. water–gas the shift desired COform In the from It should Equation noted be that 3.16 componentbackward thatcan asignificant has also hydrocracking. high-pressure as such or end use either feedstock with ter integration nificant [30].throughputallowsandbet higher fortypically Higher-pressure operation ata reformer operating than less catalyst of For the used. selectivity and activity dependent hence the and on temperature While the overall reaction is endothermic, the methanol decomposition endo is methanol reaction endothermic, overall the is the reaction While Ethanol SR can be carried out a Ni-based catalyst with at carried be SR Ethanol about can 550°C–650°C. Relatively S/C SR the is methanol in key parameter Another ratio (H practice, 75%. hydrogenIn conversion dry The than concentration less is strongly is %H CH 2 CH selectivity 32 CH 32 CH CO OH OH +↔ HO +→ = 22 +→ 3H mole o HO 22 22 O2 ∼ CO 250 PSI, the pressure effect has been found as less sig less found as been has effect 250 PSI, pressure the f 2C Hm mole H += CO 22 H O4 + 2 += += ole ofC 6H ( H ∆ 2 H 2  298 ∆ ∆ H O H K4 () 298 () ) = 298 3 mol+ − K K Handbook ofHydrogen Energy Handbook 1k 3 mol 2 298 J/ O/CH 347 mo 1mol kJ l kJ /m

3 /m OH, in the case of OH, case the in % = ol ol 75

(3.20) (3.17) (3.18) (3.19) - - - - - Downloaded By: 10.3.98.104 At: 11:22 27 Sep 2021; For: 9781420054507, chapter3, 10.1201/b17226-6 chemical reaction shown in the following: the shown in reaction chemical a catalyst allows for alower by the POX temperature. described The reaction is of methane outried or POX without temperatures. at with performed acatalyst, be high can but using to­compactness. coke Unfortunately, susceptible must is formation and car process be this ­ ­process oxygenpure available is [59]. With alower product concentration of hydrogen, this POX alternative generally employed to an SR is is and or hydrocarbons if higher with 3.9 of HydrocarbonReformation Fuels [60].Cheekatamarla ATR. on CPOX Experiments haveby of hydrocarbon liquid various reported fuels been fuel, but to vaporize the it relativelyand is required SR than efficient energy less the ers low and reaction tively the compact to it sustain heating because doesn’t external require reduce hydrogen the POX. will yield in pressure APOX or CPOX compara reformer is sure, O and conditions.the process by influenced is product present. The if stream Temperature, pres overheat hot can spots reformate catalyst composition. and sinter the and Localized ture the catalyst to itcontrol catalyst tempera the difficult make within limitation transfer heat the and reaction of the nature exothermic the hand, other the On reaction. of the SR, CPOX advantage the nature has fast exothermic of the of because short start-up time out at carried 1300°C–1500°Ctypically complete to ensure conversion. compared As to With catalyst, out CPOX at carried be lower can temperature. Without catalyst, POX is levelsplace POX high of up CO the the to from clean result that reformer. put cleanup systems other and in water–gas shift necessary potentially of the because time hydrogen alagging implies CO response concentration high levels and result. This that (orrapidly; air the oxidant)-to-fuel achieved by is increasing that ratio. Therefore, temperature the it possible is to reduce by increasing reformer start-up times flowfuel. additional air rateand the combusting is, that reaction, increasing oxygen the in −36 from to −319 increased quickly be kJ/molcan of amount the by simply increasing how of amount illustrate heat the equations generated POXThese the from of methane following: the shown in as A general equation for POX following: the shown in is oxidationPOX (CPO partial catalytic to process. acombustion and or CPOX) similar is low by the hydrogen inhibited POX of the time typically reformer is fast response The even becomes reaction more the exothermic then oxygen-to-fuel the If ratio increased, is

Partial Oxidation Partial sacrifices some efficiency relativesome efficiency sacrifices toand SR response offersbut rapiddynamic 2 /C variables. ratio some process of For are the reformer example, increasing CH nm CH CH +→ 42 42 nn +→ +→ OC OC 2 1 22 OC OH OH 22 OH +< += += m 2 2 23 2 () ∆ ∆ () ∆ H H H () 298 − − 319 Kk 6 kJ kJ /m /m 0 ol ol J/ mo

l

(3.22) (3.23) (3.21) 37 - - - - - Downloaded By: 10.3.98.104 At: 11:22 27 Sep 2021; For: 9781420054507, chapter3, 10.1201/b17226-6 oxidation: 3.24Equations 3.25 and show POX the Equation and 3.26 of ethanol, shows complete the O eral, than other thereformer of by efficiency the loweringoutput hydrogen stream concentration.In gen POX the reduceHowever, in the can process nitrogen as such gases of inert effect the systems. these in oxidizer as have oxygen catalysts. used air Pure been metal and cious catalyst cause that deactivation coke nonpre precious and for precursors potentially both also are output They of the stream. purity the decrease that radicals and mediate species 38 from waste, it was found that small amounts of pinenes existed in the methanol fuel used. used. fuel methanol the in waste, existed offrom pinenes amounts it small was found that hydrocarbons. For example, investigation under for at hydrogen apulp mill production produced or higher biomass may coal methanol from contain like reformed. Liquid fuels are alternative hydrocarbon if feedstocks characteristic multipleing anecessary fuels, temperature. on reaction based catalysts, output ATR the gas metal–based concentrations in generally follows equilibrium ideal products the form of hydrogen dioxide. carbon and on noble found that It been has and step. ignite same the reactants reactor The in the into fed all are air fuel, and steam, the at operation. reactor is temperature, the operating SR during Once reaction endothermic POX for rapidexothermic used is reaction start-up supplying and heat the for needed the loads. Ideally, adequatecentration to dynamic and response heat the generated the from advantages hydrogen SR of POXhigh both and it product potentially that has con in reactor. mostof transfer.heat efficient the reactor is means catalytic single The has ATR contact catalytic or asingle into by placing them thermal close into reactions reforming two the SR done CPOX. is and by between acombination bringing ATR This essentially is 3.10 used. oxygen is pure oxidizer; thus, to as use air economical typically power for cell combination a good fuel system integration. It should noted it be that not is POX makes SOFC POX and temperature. This typical reformate stream the is 800°C, which Moreover, it sensitive less to and impurities. is source SOFC operation near is temperature CO solid cells, oxide (SOFC) afuel fuel cell as fuel high-temperature with hand, utilize can tor, oxidation or preferential (PROX) for CO used be removal. other reactor can the On additional CO An electrode. oxidation the poison reactor,CO reac will water–gas shift problematic for low-temperature concentration of applications high cell the fuel because POX CPOX and have complex produces reaction systems. The inter various reaction With a higher temperature due temperature With oxidation ahigher to the step, ATR capable also is of reform POXIn especially is or CPOX, This reformate CO stream. the one products of is the in Autothermal Reforming Autothermal CH CH CH 32 CH 32 2 CH /C POX ratio, in no species control or is CPOX. over there chemical the 32 CH OH OH OH +→ +→ OC +→ 15 .( 22 0. O2 5O 22 22 OC CO ++ 2C O3 O3 += += 3H H H 2 2 †( ∆ ∆ ∆ H H H () 298 298 298 K5 K K5 Handbook ofHydrogen Energy Handbook ) ) =− − 7k 226 0 9k J/ kJ J/ mo /m mo l ol

l

(3.25) (3.26) (3.24) ------Downloaded By: 10.3.98.104 At: 11:22 27 Sep 2021; For: 9781420054507, chapter3, 10.1201/b17226-6 the resulting heat can be used to sustain the SR the steps; thus, to ATR sustain used heat be termed is can resulting the acceptably ATR dealt in with [63]. SR [61,62] in effects derived had similar coal methanol from found with as but could be traceamounts thatof heavier found oils studies Similar significant. be catalyston the can (about quantity in fuel), of one-tenth effect small apercent for volumetrically this their relatively levels are trace of pinenes hydrocarbons. the treatment of Although the higher oxidation ATR and temperatures found in higher reacted. may The are faster allow they compounds tend to other overwhelm SR and any pinenes systems, catalystIn the site until of HydrocarbonReformation Fuels O O The additionalallow oxygen heat to following: account lost, the for shown in this as However, reactor, atypical heat in lost due to conduction unavoidable. is to It necessary is following: the operation shown in as condition: aself-sustaining athermoneutral in result it used, is will mixture fuel proper the stoichiometry If fuel. the related available to the oxygen of amount directly heat is The in reaction generated the in previousSR section: the steps from 3.31 Equations steps 3.33 in identical are through Equation 3.30.shown in remaining The ide oxidation Equation 3.29, step in steps: these in consumed be much CO of the will 3.33.through Equation 3.28 shows CPOX the monox carbon the steps, with combined and 3.28 Equations shown in are feedstock as ATR an methanol steps of in process using The ATR following: typical equation the neutral. of The ahydrocarbon shown in is thermal 2 ATR is similar to SR with an additional CPOX to SR an with ATR fast, steps are step. and exothermic similar is These Another CPOXAnother combustion/methanol by formulation is substituting oxidation steps CH /C = 0.2–0.3 to be optimum using aCu-based catalyst using [54,64]. to optimum be /C = 0.2–0.3 O Higher 32 CH OH 2 /C ratio, or O nm ++ 00 ++ CH .. 27O 00 CH .. 5O 32 CH mm OH CH 32 OH CO 32 22 15 ++ CH OH CO 32 2 OH 00 /C, ATR. have in parameter found Researchers important an is +→ HO .. +↔ 1O 32 15 5H +→ OH +→ 22 HO .† +→ 0 0. OC 22 .† HO 5O →+ 5O →+ OC CO 22 8H CO →+ CO 22 O2 CO OC mm CO CO 22 2 2H →+ += += .. O5 46H 22 += H += 2H HO 2 3H O2 ∆ () 22 H 00 ∆ 2 += .. ∆ H () 14 H 298 ∆ () ∆ .( 298 ∆ + () H 8H H 298 H HO 5 K () () 298 2 298 () K9 298 K4 =− nH ∆ = K K H H 283 †( K5 ∆ 0 − 2 H . 298 1k − 1k − kJ ∆ 298 192 675 /m J/ 0 Kk J/ mo kJ () mo ) . K8 ol kJ 4k 298 /m = ) l /m 0

l

J/ ol

Kk − mo ol J/

1k mo =

l 0

2 J/ /C ratios will autothermal l mo

J/ mo l (3.35) l

(3.27) (3.30) (3.34) (3.33) (3.28) (3.29) (3.32) (3.31) or or 39 - Downloaded By: 10.3.98.104 At: 11:22 27 Sep 2021; For: 9781420054507, chapter3, 10.1201/b17226-6 following: the 3.18 3.20, through 3.24, 3.25. and of complete in case The described oxidation is of ethanol reactor,the lower while O inside temperature the reduce of amount increase hydrogen and the output the stream in 40 Schematic of a typical autothermal reformer. autothermal of atypical Schematic FIGURE 3.7 light-off the as known transition rate asharp reaction catalystthe has and temperature H high maintaining while overall of the SR reformer of reduces size the step. the limitation heat This the transfer However, ATR advantage awell-designed to overcome take reaction can exothermic of the degrades of catalyst sintering. often the by and combustion means catalytic in common is catalyst. of the This limitations ahot heat created by and spot is the transfer localized, [66,70–72], reaction endothermic the orders faster than of magnitude heat the generated is on Cu-based catalyst, methanol at rate is of the least reaction two reforming of exothermic away to and transfer active rate from catalyst mass the sites of reactants [68,69]. case the In catalyst dependent is on the surface on ner. occurring rate reaction The exothermic of the [65,66] studied been has start-up vehicle [67]. cell feature on fuel use potential for the and concentration efficiency Theof the reformatefast in hydrogenoutput thermal stream. reduce the reformer; autothermal dilutionthe into will thus, to feed nitrogen used cally catalyst;the reactor. of the thus, help warm-up they the time shorten However, typi is air ATR 3.7. Figure found in reactor is place of surface take on the reactions exothermic The power the efficiencies when reformerreactor. compared of schematic to a steam typical A In a small fuel processor design, an ATR design, an processor heat fuel compact higher reactor and is has asmall and In by Equations described are feedstock as ATR an ethanol steps of in process using The ATR also suffers from mass and heat transfer limitations as in SR but in a different man SR but adifferent in as in limitations heat and transfer mass from ATR suffers also CH 32 CH OH +→ 2 Oxidizer/air 2 /C low in result conversion ratios will dueheat. to insufficient concentration. In addition, the nonlinear relationship between between relationship concentration. addition, In nonlinear the 3O 22 2C O3 += St Reformate HO ea m+f 2 ue ∆ l H () A 298 TR catalyst K Handbook ofHydrogen Energy Handbook − 1368 kJ /m ol

(3.36) - - Downloaded By: 10.3.98.104 At: 11:22 27 Sep 2021; For: 9781420054507, chapter3, 10.1201/b17226-6 Poor heat transfer of the catalyst will create large temperature gradients, thus degrading gradients, degrading createtemperature large thus Poor catalyst of the will heat transfer catalyst the sinter by overheating potentially away will reaction heatthe the sink. from difficult be [65].can Second,if heat isexcessive sustain significant, lost to oxygen required S/C between reactor Balancing design. the O and but reaction, the it must have toneeded sustain to account excess oxidizer for heat lost by O [31]. reaction the it unableto sustain because is process combustion the in extinction in result below light-off will temperature. temperature the Operating of HydrocarbonReformation Fuels versions of greater than 90% are possible 90% are at just aboveversions temperatures of than greater 250°C, [79]. Based on atreformed relatively low 250°C. temperatures, around According to one ATR study, con be can to reformed. be more Methanol and energy temperatures higher require therefore (two alcohols have higher and Ethanol or more atoms) longer carbon chains carbon and oxygenated loweran for fuel, reformation it [75]. effective temperatures requires operating it gas. Because is natural but and it produced resources be coal may abundant from also producedbe multiple Ideally, from feedstocks. would methanol produced be renewably, S/C coke order formation. in to inhibit much higher applications practical ratio typically in is Note (2 that heat dependent The fuel. is of O the reaction on the atoms ofnumber carbon in ratio. ratio O and air-to-fuel air-to-fuel the The represents where (2 following: the shown in is reactants, the complete oxidizer, conversion the as ATR assuming air alcohol of of using an reaction fuel produced of general form alcohols the process. The of provides the a basic understanding for automotive optimal applications. than less them make hydrocarbons higher for ATR other and required of temperatures gasoline high reformer systems. The scale longer for and automotive start-up expensive materials times require temperatures High excess of 800°C. at in temperatures conversiona fuel obtained 97% be can of than greater [76,77].600°C–800°C have used been Saitoh, From Oyama’s and Sandakane, [78], research [75]. 400°C around However, ATR, diesel and of of temperatures gasoline studies other in hydrogen into to gasoline reform temperature is optimal the calculations, For theoretical not solve products long-term will petroleum the sil problem dependence. fuel of fossil (32.3 density energy high MJ/L, on LHV). based However, fos or other gasoline using and infrastructure fuel advantages its existing The are gen for cells. of fuel gasoline considered for ATR typically heavy are hydrocarbons and to produceGasoline hydro 3.11 have [73,74]. studied been (and possibly catalyst. reactors the Various destroying) reforming methanol autothermal 2 The light-off temperature has the following implications. of First, aproper the selection light-off has temperature The Methanol is a very attractive fuel for avery attractive fuel hydrogen is Methanol production. hydrogen, Like can methanol Although most work done is on on renewably ATR hydrocarbons, higher focusing with /C reactor Not design. and sufficient only is stoichiometry oxygen on both ratio based is CH nmp ATR Fuels of Different OH n −2 +− n () −2 x 22 − nx p x ) represents the minimum amount of water required in the reaction, and and reaction, the in of amount water required minimum the ) represents − p −+ ) is the minimum amount of water required for the reaction and the the and reaction for of amount water the required minimum the ) is px 22 OO () + 37 .( 62 NH 22 →− 2 /C ratioscatalyst forselection aspecific nx 22 2 /C related by are afactor of −+ pm /) ++ n CO 2 2 /C and S/C. S/C. and /C 37 . 6 xN n (3.37) , the the , 2 41

x - - -

Downloaded By: 10.3.98.104 At: 11:22 27 Sep 2021; For: 9781420054507, chapter3, 10.1201/b17226-6 in different methanol purities. For purities. example, methanol may different coal-derived include methanol in higher result of methanol feedstocks different The gasificationresources. from of coal biomass or costs. reduces manufacturing potentially that of materials variety larger made a be from reformer can the that possible. are shorter means start-up Itso times also system temperature, to operating to heat reforming the required is energy less that mean complicatedfore, less and lower system. The asmaller fuel-processing also temperatures achieved [80]. be reformate less cleanup into centration can and, that there translates This lower the temperature, lower reaction the the equilibrium, CO the con thermodynamic 42 Oxygen-to-carbon ratio and reaction progression, Master thesis, University of California, Davis, CA, 2004.) Davis, of California, University thesis, Master progression, reaction and ratio ­Oxygen-to-carbon vs. O of heat reaction ATR of methanol, FIGURE 3.8 produced divided lower by Equation the 3.38: shown in as value heating consumed of fuel at occurs point that neutral butreaction rather produced aproduct as of thermo combustion. It to the pinpoint easy is O an simply is reaction of 3.8. the ideal Figure yields reaction, stoichiometry an The assuming of afunction as fortion methanol heat produces ofthe point that of zero. reacthermoneutral a net Plotting enthalpy change of O By heat evaluating afunction the as of reaction nol ATRin Equation as shown simplified 3.38: is zero, heat hydrogen products all the and and for ofnitrogen, are reaction metha reactants heat heat the Since of the of formation oxygen, for reactants. formation of the the minus the heatas energy) defined the of is formation productsof and (requiring endothermic [62]. feedstock on the of fuel, depending purities should and hydrocarbons able be higher varying to cope with [61]. impurity an as hydrocarbons Fortunately, ATR a proven is of reforming method In addition to the ease of reformation, methanol can be produced be can addition renewably of reformation,In ease methanol to the through The efficiency of a reforming process is defined as the as is lowerdefined value heating process of reforming of a efficiency The hydrogen (releasing exothermic energy) heat is The whether areaction indicates or of reaction 2 /C = x and S/C and =1−2

–1000 Heat of reaction (kJ/gmol) –750 –500 –250 250 0 0 ∆∆ HH x , until , until x xo = .230 rf 0.25 0 =− = 0.230. = x x ,C >0.5. point, water At the no in longer this is consumed , from , from Of η= ΔH 22 0.5 2 /C. (From Dorr, J.L., Methanol autothermal reformation: reformation: /C. autothermal Dorr, (From J.L., Methanol r () vs LH LH 12 A −− . ox x TR ofmethanol O =0(SR) to Vf VH 2 ygen to /C xH uel H ∆∆ 0.75 2o 3 OH, x ut in pu ,H pu fu t el ratio, t O(l)

2 x /C, /C, =1.5 (complete combustion), and 1 x H x Handbook ofHydrogen Energy Handbook , it possible is to find f,fu el (l )

1.25 1.5 x 0 (3.38) (3.39) , the , the - - - - - Downloaded By: 10.3.98.104 At: 11:22 27 Sep 2021; For: 9781420054507, chapter3, 10.1201/b17226-6 Reformation of HydrocarbonReformation Fuels from ­ from Hydrogen infrastructure. near-established alternative with fuel an as mobile industries auto by the residue,dustries, forestry solid recognized waste. municipal is and Bioethanol agroin from fermentation of wasteproduced the biomass or materials organic through be can fuel, ethanol of the neutrality carbon Although actual much debate the surrounds [87–90]. neutral to carbon be on its candidate potential based fuel promising another is extensive SRoperation of was An review done methanol life. by Palo [86]. al et Ethanol active, less for formation is carbon helps which to prolong mechanism catalyst reaction the at reformed be relatively can Methanol low compared and fuels, to as other temperatures United for the States. supplying across exist fuel stations racing refueling methanol slight only modification with technology [4,9]. and Indeed presently,­infrastructure some energy existing the using form aliquid in transported stored be it and as can cells gen fuel complexity [62,82–85]. for hydro considered one possible of as It the been feedstocks has start-up operation of and biorenewable energies, availability overall sources, and ­ of basis carbon-to-hydrogen the ratio, including choice for reasons processor many fuel attractive renewables. from an is to sourced be Methanol potential the gas, has natural derived renewable although not Methanol, from currently butfeedstock. sources from atciency lower O effi the would which cell, waste fuel heat effectively increase the possible from to utilize It also reactants. of is temperature the the to increase of amount heat the role required in efficiency.amount The this not thereaction of excess includeddoes playgreat in in water a is to heat reactants the required of amount additional Also, energy fuel. the combusting to provided heat be aheat input assumed input. by is This requires thus and thermic is a desirablepriority. possible efficiency point as if to operatethermoneutral to the close as efficiencies of theoretical fuels ATR of various hydrocarbon [80].Therefore, most seems it point at thermoneutral of the methanol 3.9. Figure in point, seen at as thermoneutral the of nol efficiency peak occurs The ATR simpleof efficiency evaluation peak model the that ofFurther reveals this ATR of metha CA, 2004.) Davis, of California, University thesis, Master progression, reaction and ratio vs. O efficiency ATR of methanol, FIGURE 3.9 To maximize the overall the benefitTo of as hydrogen, are renewable desired maximize sources energy point ( to note belowIt that thermoneutral important the is ethanol is likewise considered potentially beneficial. considered potentially likewise is ethanol

Efficiency, % 100 20 40 60 80 0 0 2 /C toward SR ratios, reaction. balance an the moving Efficien 0.25 xo=.230 cy 0.5 A 2 /C. (From Dorr, J.L., Methanol autothermal reformation: Oxygen-to-carbon Oxygen-to-carbon reformation: /C. autothermal Dorr, (From J.L., Methanol vs TR ofmethanol O 2 /C ox ygen to H 0.75 3 OH, x 96.3% fu 1 el ratio, x o =0.230 96.3%, is one highest of is the which 1.25 x 1.5 800 1200 1600 2000 0 400

LHV (kJ/gmol) x < x o ), endo is reaction the LHV fu LHV Efficienc H 2 el y system 43 ------Downloaded By: 10.3.98.104 At: 11:22 27 Sep 2021; For: 9781420054507, chapter3, 10.1201/b17226-6 have significant cost and flow through through improvements.and have cost flow significant can mechanisms catalyst to improve the bed. Efforts inside gradients reactors limiting the concentration and Aconventional temperature reformer has steam following sections. the in individually discussed is mechanisms of these effect reformation. The in nisms mecha major limiting the are kinetics chemical and transfer Heat mass and mechanisms. conversionThe physical of yield presence by of the and of hydrogen the fuel limited are 3.12 44 Reaction rate versus temperature. FIGURE 3.10 and heat in transfer limitations increases typically practicelysts acommon although is this catalyst and/or the loading increase cata can catalyst Using crushed pellets. smaller use To diffusion. one improvecatalyst pore internal onto active as diffusion, site an known is the inside Diffusion diffusion. external the catalyst as ontothe bed acatalyst known is through diffusion Reactant diffusions. internal and external includes both transfer Mass [91]; heat and by transfer mass limited SR typically is thus, low-cost used. catalysts are 3.12.2 improve potentially overalllyst the can performance. temperature bed 5%, able being than less to cata control the factor typically catalyst is effectiveness tional active are at they Cu-based attractive about because catalysts are 260°C. conven the Since implement to difficult bed therequired. for longof mobile because times start-updevices aNi-based catalyst makes requirement most active high-temperature above 800°C. This low catalystsrugged may For desired. be activity example, typically Ni-based catalysts are transfer.heat ofindication insufficient an is limits of presence activity endothermic, the are reformation systems typical As ture. Figure 3.10 catalystCatalyst the activity. impacts temperature behavior shown in as Arrhenius 3.12.1 Increasing activity through increased temperature can also damage the catalyst; the damage thus, also can temperature increased through activity Increasing Limiting Mechanisms in the Reformation Processes Reformation the in Mechanisms Limiting

Chemical Kinetics Chemical Mass Transfer Mass

Reaction rate (mol/s kgcat) tempera with exponential is SRfor catalyst activity amethanol that indicates 0.00 0.05 0.10 0.15 0.20 0.25 0.30 180 200 refo Reaction ratevs rma tion overCu 220 . temp Te mp /Z erature (° nO/Al erature formethanolsteam 240 2 O C) 3 /g raphite catalyst 260 Handbook ofHydrogen Energy Handbook 280 300 - - - - - Downloaded By: 10.3.98.104 At: 11:22 27 Sep 2021; For: 9781420054507, chapter3, 10.1201/b17226-6 Reformation of HydrocarbonReformation Fuels rience fouling due to fouling relatively atrience centerline. the forming cold species condensed acatalyst yet that degraded atimplies be simultaneously wall expe might by the sintering 100°C/cmthat result This wall. the near encountered frequently are gradients temperature nol [93]. shows figure, experimentation Although conductionevident this are errors in 3.12 Figure reactor inefficient design. rendering increases drop pressure the and ratio increases, centerline.fer to the However, reactor-to-catalyst reactor weight the radius as decreases, improve radius active reactor can sites Usingblocking fouling. asmall causing heat trans deactivate catalystsion. may on the catalystpores fuel also Unreacted the by accumulating thefuel flow centerreducing converregion in overall potentially past can fuel Unreacted reactor wall. the near region the in exist gradients aconsequence, temperature As large reactor. the mode other. within each ofwith heat Convection dominating transfer the is packed randomly point-to-point are with catalyst contact particles or crushed pelletized reactor, the Inside by endothermic. overall SR is the process as heat required is External 3.12.3 flowresistance. increase will catalyst pellets smaller using while weight the reactor, of the increase catalyst will drop. loading pressure Increased increases 2002.) FL, Gainesville, of Florida, University dissertation, PhD applications, vehicle cell fuel for investigation An acoustics: with ­ steam-reformation P., the Erickson, (From reformer. Enhancing steam atypical in steps transfer Mass FIGURE 3.11 Typical mass transfer steps are given in Figure 3.11. Figure givenTypical in steps are transfer mass chemicalkineticsonthecatalyst St bulkstrea St po St St catalyst St St St Heat Transfer ep 1—Reacta ep 7—Pr ep 6—Pr ep 5—Pr ep 2—Reacta ep 4—Reactiontimegovernedby ep 3—Reacta streamtocatalystsurface shows experimental temperature gradients encountered with SR with encountered of gradients metha temperature shows experimental Reactant o o o re duc duc duc s tosurface nt nt nt ts ts ts s po s dif s dif s absorbontocatalyst dif dif desorbfromcatalyst m re fuse fuse s toop fuse fuse fromsurfaceto throughcatalyst throughbulk throug en reactionsite St h ep 1 St ep 2 St ep 7 Pr od St uc ep ts 6 St eps 3–5 process process 45 - - - - Downloaded By: 10.3.98.104 At: 11:22 27 Sep 2021; For: 9781420054507, chapter3, 10.1201/b17226-6 46 may have a temperature effect with higher temperatures inhibiting the poisoning of the of the poisoning the inhibiting temperatures may higher have with effect a temperature either be reversible can Poisoning reactants. site orreaction nonreversible the from and over drop pressure alarge time. in catalyst resulting apelletized crushes housing the displacement andresultant of coefficient of expansion where thermal housings the metal in cycling temperature phenomenon frequent with common reactor is system. the This in reactor. lead the tofrom physical also Catalyst can substrate flow and attrition restrictions and sintering. fouling, poisoning, as fied attrition, by catalyst classi degradation. limited be typically Degradation also is Reformation can 3.12.4 rate. reaction on the temperature and size CA, 2006.) Davis, of California, University thesis, Master reactors. production hydrogen steam-reforming in profiles temperature through scaling and geometry reactor of effects the Vernon, a 17.5 (From D., is which distance. Understanding centerline, to mm wall interior from 46.4°C is differences temperature The reformer. steam amethanol in gradients temperature of large Example FIGURE 3.12 Poisoning occurs in reformation when a species binds to the reaction site blocking the site the reaction to the blocking binds reformation when aspecies in occurs Poisoning broken removed substrate is catalyst when of off is the the and material occurs Attrition Table of velocity particle effect the and 3.2 of shows limitation each overall the effects Distance from top of catalyst bed (mm) 150 140 130 120 110 100

90 80 70 60 50 Degradation Mechanisms 01 lar Distance fromlef ge radiusreactorMLHSV 0 Te Source: Surface reaction Internal diffusion External diffusion Type of Limitation Rate Reaction on Effect Their and Mechanisms Limiting TABLE 3.2 mp erature profile 20

Fogler, H.S., 4th edn., PearsonEducation,Inc,2006. t wall(mm) 30 1 Independent Independent U Elements ofChemicalReactionEngineering ½ Velocity Variation ofReactionRate with: 220 230 240 250 260 270 280 290 180 190 200 210

Independent (dp) (dp) Particle Size Distance from top of catalyst bed (mm) 150 140 130 120 110 100 90 80 60 50 70 −1 −3/2 01 lar Distance fromlef ge radiusreactorMLHSV Handbook ofHydrogen Energy Handbook Te ∼ 02 Temperature Linear Exponential Exponential mp erature profil 03 t wall(mm) , e 0 4 18 19 20 21 22 23 24 25 26 27 28 29 0 0 0 0 0 0 0 0 0 0 0 0 - Downloaded By: 10.3.98.104 At: 11:22 27 Sep 2021; For: 9781420054507, chapter3, 10.1201/b17226-6 Reformation of HydrocarbonReformation Fuels ous literature and have also proposed control algorithms [23,100,101] have control proposed and algorithms literature ous also control the to better have modeledResearchers SR [13,83,95,96] the process reformer [82,97–99] the and vari in 3.12.5 heat high flux. and temperatures high withstand catalyst’s by the to heavy limited have be complex to with can ability fast reactions fuels 3.13. Figure shown in as cases sintering need extreme The in compromised be also can up to 1/3 used be can metal integrity certain of point temperature. its Structural melting a that is of catalyst. of thumb the rule Acommon selectivity and activity the change can transformation phase this and metal point of below far the melting the occur can changes and transformation phase to note substrate. metallic of that the melting important It also is catalyst of the through absorption lead and to pore can blocking temperatures thus, high catalyst Typical the melt material. as at a washcoated acting will with 1450°C; ceria metal substrate used aceria is reformation processes, substrate many catalyst or In the material. above temperature point of the either melting the the driving due reactions to exothermic surface. reaction the reaching from reactants gas or liquid solid the blocks the as fouling induce can transformations phase or gas–solid Any gas–liquid limitations. transfer mass m 1600 as high as be can area internal the Because limitation. duecantly transfer induced to mass the signifi drop can or cokeblocked by species formation, reformer performance condensed become exit pores and entrance catalyst. the of surface the When or internal external on the reformers. in effect slow poisoning down the to manner sacrificial in a used be can andrelated flow species following the Zinc pattern. reformer the active through endothermic zone of catalyst the as progresses seen be ically typ agents. can Deactivation catalyst of poisoning reformer catalysts the by and poisoning problematic for especially typical compounds are sulfur-containing and catalyst. Sulfur image. grayscale this in right the on shown is catalyst cut-away sintered a similar and left the on shown is ATR catalyst New monolithic FIGURE 3.13 Sintering can occur when the catalyst or the substrate changes form. Sintering is typically typically is form. Sintering catalyst when substrate the or the changes occur can Sintering of active when acatalyst the physically area is occurs forming blocked byFouling species Controls 2 /g of the catalyst in pelletized catalyst, it is important to keep pore areas clear to/g avoid clear catalyst, pore areas to keep it important is pelletized catalyst of the in 47 - - - Downloaded By: 10.3.98.104 At: 11:22 27 Sep 2021; For: 9781420054507, chapter3, 10.1201/b17226-6 sients due to changes of demand. Optimizing reactor geometry is one approach to enhance one approach is to reactor enhance geometry sients of due demand. Optimizing to changes ously for over rate fuel frequent tran 12,000 h[20], experience will reformers small-scale continu run reformers large-scale most current hurdle for alarge SR. is While response or flowstart-up large thereactor.changes with encountered of transients Slow transient steady-state the with dealing do control and not reformer temperature of address the the reformer. of design by the only the are lyst It limited concerns is should these noted be that heater heater power the power for agiven cata of to reformer, the getting means the and inputs to controlflowA high-level fuel manipulated sends rateand control algorithm fully addressed. not catalyst been temperature, has temperature but of issue controlling the 48 tion oftion hydrogen scale. on alarge produc choice agood for centralized on-site It reforming. still is or small-scale reforming choice for onboard coupled optimal This, along SR with than start-up aless makes time, irreversible membrane causing electrolyte damage. the protons from extracts cell fuel the supply hydrogen stack; consequently, cell fuel reformer cannot to required the the the catalyst. the sinter Alternatively, potentially can and load suddenly the is if increased, the flowreformer heats reactant up the ratesare and suddenlydecreased, is decreased may that lead to system degradation. responses slow load the has If and dynamic nally slow SR most heated inherently reactor process. An commonly is exter an therefore and SR method. endothermic is areforming should considered be when selecting this and SR However, the reaction. theprocess transfer heatof efficiency to the limitations are there fuel, 1− ing used, fuel total ofTherefore, the afraction only most conveniently is reaction providedthermic fuel. of by the simply aportion combusting heat reformer,reactor steam temperature. forendo For needed onboard the external an the (solid of coking leads deposits) towhich alow carbon instance the without to raise having applications. advantage desirable the is has for It S/C transportation of ahigh also ratio, high,mum hydrogen which also very is concentration 75%. the is process of efficiency The For bycell. afuel example, utilization leads for towhich better SR maxi the of methanol, specifications. reformer’s impact the cantly technical compounds (VOCs) forapplication aproper aspecific cell signifi fuel can Selecting fuel. as CO some volatile use and and tolerance. organic capable are reforming They of internal molten (MCFC) as such cell stacks fuel carbonate SOFC cell and fuel have impurity higher for issue PEMFC. important High-temperature an is over anode cell CO time. poisoning slowly hydrogen will fuel the the in poison stream Impurity have requirements. stricter fuel forpurity.usually requirements Lowerfuelstacks cell nificant temperature operating problematic, applications, not typically cell are unconverted sig fuel fuel yet are in there mation systems. For example, applications, combustion in concentrations of CO high and of refor types when considering hydrogen of aspect the End use perhaps important is the 3.13 parallel. reformer in the and control algorithm the both approach to design A better design. is control the algorithm heat impacting transfer, thus [102].reformer dynamics However, of the characteristic impact the can reformer geometry In an ideal reactor, an In would there to 100% reaction be combustion the from heat transfer advantage the SR has of arelatively hydrogen high product the concentration gas, in Comparison of the Reforming Methods Reforming of the Comparison Y , is fully combusted to provide the energy required for the desired SR desired reaction. for the to combusted provide required energy fully the , is Y , actually enters the reformer. enters the remain , actually The Handbook ofHydrogen Energy Handbook ------Downloaded By: 10.3.98.104 At: 11:22 27 Sep 2021; For: 9781420054507, chapter3, 10.1201/b17226-6 for 2,2,4- (an S/C ratio of zero), reactors musthigher operate temperatures (1180°C at significantly above of absence wateroperates usually an 1000°C. temperatures at is there high Because that reaction exothermic system. an POX fuel-processing is of the mass and reforming size the fore accompanied by be increases additional cleanup product of the gas. This made be compact. can reformers and However, POX produces excess CO must and there loads. much reactor smaller is The transient it wellto extremely handle reason, equipped is afast start-up. in results For same fuel; the this incoming of combustion the the increase of HydrocarbonReformation Fuels Insulation and heat recirculation are important for these reformers to maintain high high to reformers maintain for these important are heat and recirculation Insulation shown competitive advantage implementation, in flexibility,and efficiencies [105–108]. [3,4,7,11]. for hydrocarbon various processors fuel feedstocks haveers small built have They choice of the Many fuel. research deciding factors in are reasons environmental Cost and 3.14 reformer. of asmall-scale aspects most critical system, one of the reforming of would the start-up time decrease turn in reformer. This and prove reduce weightthe the size of to to beneficial further be mixing tant ATR, will it ATR Should reactor reac enhance performance. may also schemes mixing reactant Other tohave believeto it beneficial reason that be results mayThese also ATR. be tested.yet to proven been has to improveAcoustic a enhancement capabilities of is SR, the there and acoustic enhancement. and of bluff use include bodies, swirling, the schemes mixing fuel flexibility. a rapid to hydrogenand efficiencies, short start-up high response with demand times, ATR therefore and applications. should considered be for ATR transportation provide can the fitof intotheautomotive needs industry, or on-siteforwhether onboard reforming, a lightweight, compact reactor capable multiple [103]. of reforming fuels criteria These for applications catalyst potential ATR sintering. in require the that potential great has byPOX caused the is reduces thereby that and fuel potential of the rise temperature the lowers integration thermal This reaction. reforming addition of the the because of in steam Hot reduced are spots surroundings. heat the from transferring catalyst rather bed than multiple Rapid fuels. to produce the start-up possible ability of is the because heat within to accommodate flexibility SR the and than response dynamic abetter time, at same the energy. gives ATRand POX efficiency hydrogen This ahigher than and,concentration ATR external nor operates releasing ideally point, at neither athermoneutral consuming for automotive undesirable characteristic cially applications. the overall system efficiency,thus anddecreases espe the fuel an cell of efficiency PEM the of source oxygen), the (when as air using compared to 75% for SR [104]. affects directly This concentration of hydrogen theoretical 41% only highest is the to methanol, reform used is For nitrogen. product example, with dilutes the reaction gases the into whenof POX air drawback of POX low the is concentration of hydrogen product the addition gas. The in catalyst cause Most sintering. can importantly, and major the mixing ofresult nonuniform Hot may spots develop excess heat surroundings. to the a transfers heat as that exchanger A POX flow heat the reactorby can up simplyrate quickly increasing of oxygen to It should be noted that reactant mixing is an important consideration important for an ATR. is PossibleIt mixing should reactant noted be that solution potential drawbacksOne to of the SR POX and ATR. into two the to combine is Fuel Selection ­trimethylpentane) to avoid [103]. coking include systema must design The also 49 - - - - Downloaded By: 10.3.98.104 At: 11:22 27 Sep 2021; For: 9781420054507, chapter3, 10.1201/b17226-6 the hydrogen stream must be regulated [23,24,101,117]. hydrogen mustthe regulated be stream PEMFC; of the of humidity performance and and temperature thus, the life to the critical Waterment to overcome limitation. [4,105,112] management this also are temperature and develop under operation also cell are fuel high-temperature CO-tolerant and electrodes hydrogen reformed [3,113–116]. the stream to purify system, PSA, as such necessary is High example, PEMFCs generally have low CO tolerance at <50 ppm [110–112]; thus, a cleanup to addressed. For be arange of issues solutions are there to hydrocarbon reform feedstock, [3,106,109] onboard and power cell fuel have systems. Although they workable presented efficiencies. Coupled with PEMFC,stationary [4,107]theyhave functional demonstrated 50 reformers are used to ensure high-purity fuel is fed into the fuel processor. Gasoline and processor. and fuel the into fed Gasoline is fuel high-purity to ensure used are reformers pre and additional Desulfurization cleanup and priortemperature reforming. to or after Typically, feedstock. as used have been fuel higher also require heavier will hydrocarbons Table shown in catalysts are and 3.4. low-temperature with compatibility applications. cell fuel Typical reformer temperatures complex allows less reformation process reformer design, lower CO selectivity, good and at relatively made renewable be from low low-temperature can The and temperature fuels. However,clearly diesel. and not competitive gasoline with reformed be alcohols both can Other fuels such as diesel, gasoline, propane, and logistic fuels such as kerosene and jet jet and kerosene as such propane, gasoline, fuels diesel, as such logistic and fuels Other weight the Comparing of hydrogen are produced ethanol and liter per of fuel, methanol Table hydrogen of the hydrocarbons. various estimate yield 3.3 by an reforming is Kerosene/ Methane Propane/ JP-8 Dodecane Ethanol Methanol Natural gas Hexadecane/diesel Isooctane/gasoline Glycerol Fuel TemperatureTypical of Various Reforming Hydrocarbons TABLE 3.4 Source: Diesel fuel Gasoline Methane (LNG) Ethanol Methanol Fuel VariousHydrogen Yield Hydrocarbons by Reforming TABLE 3.3

Spiegel, C., n n -butane -octane C C CH C CH Formula 14 8 2 Designing andBuildingFuelCells H H H 4 3 15.4 5 OH 25.5 OH Reformation Temperature (°C) Wt.% H 42% 43% 52% 26% 19% 2 >500 >500 >520 600–800 450–550 200–300 200–300 650–800 700–800 650–800 650–900 SR g H 2 perL 357 301 205 209 150 , 1stedn.,McGraw-Hill,2007. fuel Wt.% H Handbook ofHydrogen Energy Handbook 28% 28% 38% 22% 13% 2 POX g H Catalyst Ni Ni Pd, Cu,Ni Mn, Ni Ni, Rh,Ce Cu, Zn,Cr Cu, Zn,Cr Ru, Ni Ru, Ni Ru, Ni Pt 2 perL 231 200 151 168 100 fuel - - Downloaded By: 10.3.98.104 At: 11:22 27 Sep 2021; For: 9781420054507, chapter3, 10.1201/b17226-6 mobile reformer systems. for fuel apotential also (LPG), gas is buses, leum and widely for cars been used has which Liquefiedpetro infrastructure. existing using transported convertedbe and to methanol It also can for settings. hydrogenworld feedstock as industrial production used is in and of the parts many in 50 ppm abundant CO is 60 s[7]. in than orless gas methane Natural deliver and 90% rated started be hydrogen reformer can gen. Agasoline capacity with storage energy for higher density hydro and havediesel infrastructure awell-established of HydrocarbonReformation Fuels eration. Employing a porous membrane within the catalyst bed to distribute air inside the the inside air catalyst to distribute eration. the bed Employing aporous membrane within of flow presence oxygen; the the alyst in thus,of control controlling oxygenheatcan gen heat the distribution. to enhance used be can disturbance employed catalysts have been also [125].Structured heat transferenhance insidetageous. reactor Passivethe [124]. to used be can flow baffles is advan configuration tubular catalyst; diameter to the reactor wall the thus,from a small one possible solution [121–123]. is limitation reactor to improve design the transfer heat mass the and lyst bed. Modifying cata by the inside convection; exist gradients limited thus, is high-temperature tribution achieve. totheis reactor inside profile difficult temperature ideal but is dis Heat uniform a reformer. cost of operating ahigh-temperature and material Maintaining the with off [35,42,120].ing Ni-based catalyst stable atrade- becomes is at temperatures, but higher this degrade catalyst and the unstable by sinter make copper, generally will 300°C exceeding For catalysts reformation processes. containing MTS proper in temperature maintaining deactivate thefor catalyst, need to the important efficiencies. address reducing is thus It catalyst,the will sufficient heat temperature be must Insufficient available thereaction. for order reformation process. In to activate the controlling in aspect important the becomes catalyst by the activating kinetics reaction SR,In CPOX, chemical ATR, and maintaining 3.16 oxidation cell fuel by reaction. the hydrogen the as produced pressures consumed and by immediately reformation is tures Chatelier’sLe toward reaction product principle drives the that side tempera at high favored are systems by reforming internal The cells. fuel of anode these high-temperature must the oxidation able be catalyze the hydrocarbon in and reaction to the fuel reform anodecatalyst The minimized. and heatis loss required is efficientsteam less since not necessary. are heat aseparated more reformer and since It energy exchangers also is [119].hydrocarbons advantage the has complexity of cost and reducing reforming Internal With SOFC MCFC, and sufficient reform to is low–molecular temperature stack the weight place cell. fuel of at anode the the or near to refers reformation taking reforming Internal 3.15 Inside the autothermal reformer, an exothermic reaction occurs on the surface of the cat of surface the on the reformer, autothermal occurs the reaction Inside exothermic an heat to transfer means reformer catalyst steam bed, the Inside primary convection the is

Reactor Design Reactor Internal Reforming in High-Temperature in Reforming FuelInternal Cells Figure 3.14Figure shows how passive flow 51 ------Downloaded By: 10.3.98.104 At: 11:22 27 Sep 2021; For: 9781420054507, chapter3, 10.1201/b17226-6 52 reactor enhancement. reactor of approach combination best active the The control control passive is algorithm. the and porated However, acontrol into algorithm. in designing reduce flexibility efforts the these incor be operation various The can region. conditions reaction endothermic to the exhaust region or reaction the exothermic efficiencies by fromheat moving energy to optimize reactor of [128] the regions intend passive all proposed. These have methods been also multiple [67], zones heating dual catalysts [127], to coupling endothermic and exothermic investigated [25] been byreactor has Lattner Liu [126]. and al. et of using variations Other CA, 2009.) Davis, of California, University dissertation, PhD applications, cell fuel for reforming autothermal and steam for design controller Tang, (From H.-Y., properties. heattransfer Reactor better velocity, dramatically space has but same one the have tworeactors These right. the on is applied flux heat and domain side of the left the on is of symmetry axis The baffles. without and with reactor cylindrical radius alarge inside heattransfer convective of the Simulation FIGURE 3.14 –0.005 0.005 0.015 0.025 0.035 0.045 0.055 0.065 0.075 0.085 0.095 0.105 0.115 0.125 0.01 0.06 0.07 0.08 0.09 0.11 0.12 0.13 0.02 0.03 0.04 0.05 0.1 –0.01 0 Su 0 rfac e: Te 0.01 mp erature (K) 0.02 0.03 Ma Min: 298.141M x: 314.436 300 302 304 306 308 310 312 314 –0.005 0.005 0.015 0.025 0.035 0.045 0.055 0.065 0.075 0.085 0.095 0.105 0.115 0.125 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09 0.11 0.12 0.13 0.1 –0.010 0 Su rfac Handbook ofHydrogen Energy Handbook e: Te 0.01 mp erature (K 0.02 0.03 ) Ma in: 293.886 x: 300 350 400 450 500 550 556.635 - Downloaded By: 10.3.98.104 At: 11:22 27 Sep 2021; For: 9781420054507, chapter3, 10.1201/b17226-6 mic reaction typically takes place top catalyst of the the bed. near takes To typically reaction mic catalyst control the placement sensor locationthe control not and variables obvious. ATR, are In exother the may catalyst. control, feedback or implementing fuel the foul or feedback poison In the heatcatalyst, meltis and sinter catalyst. SR,available, the insufficient it In unreacted if will in as shown catalyst difficult bed out heat and of in the transferring catalyst of the make properties poor heatThe transfer Temperaturefuel conversion control reformer influences ofand the catalyst degradation. 3.17 of HydrocarbonReformation Fuels fuel processor.fuel hence the and hydrogen of reformate the tration. End requirements use the may change lower present, is gas, nitrogen, it as such hydrogenapplications. will the inert an concen If hydrogena pure purity thus, for additional needed cleanup stringent stream; steps are not reformate is resultant the practiced reformation techniques, and known the cations. In generation appli mobile distributed and in required reformers small-scale for the earnest in presently of studied that POX. are methods of to the but All not attaining similar time, of that SR, afast response with outputa higher to not purity, though gas attaining similar low-quality hydrogen. with but demand associated is ATRtransient generally combines hydrogen reformate.ating POX produces to and highest-quality quickly respond the can of most of generranges widely SR method possible the is hydrocarbon used feedstocks. wide are there fuels; and gaseous recharging than intuitive and muchand more familiar faster well developed; is hydrocarbon is fuel liquid fuel refueling for transporting ture infrastruc production several advantages applications: has existing for the transportation may a viable be for solution.use hydrocarbon near-term liquid hydrogen fuels Reforming storage and of hydrogen transport costly. is Direct Hydrogen production at point of the 3.18 [129]. ramps transient range during temperature acertain catalyst of the in concept allows maintenance heater temperature. This rate external to feed adjust the reformation process fuel and the of the kinetics chemical the reactor of and the properties heat incorporate the transfer will input. controller The burner rate feed external to fuel control and the ability the combining reformer theto heatsteam in avoid to regulate flux is is tion done by such problems.This degraded be catalyst bythe can cycles. multiple Apossible solu high-amplitude thermal and could reduce overallas heat the is gradient.efficiencies not effectively This utilized, temperature a large creating may temperature a much temperature tor reach higher wall reac the increased, has temperature centerline the By time the transients. lematic during burner. more situation is The prob by reactor excessive external wall the the from heating catalyst of lead the near control to temperature sintering can Using strictly response. ture a long creates tempera catalyst of lag potentially the in bed resistance thermal high The reformer. the inside temperature in produce location feedback can the as oscillations line center. to the reactor wall the mode from of heatHowever,mary transfer center the using lowest the pri convection with region the because the is temperature is usually centerline SR, In the stream. fuel the to available control the in temperature, oxidizer it necessary is Summary Reformer Issues Control Figure 3.14 Figure . In ATR,. In excess heat produced if is on the 53 ------Downloaded By: 10.3.98.104 At: 11:22 27 Sep 2021; For: 9781420054507, chapter3, 10.1201/b17226-6 References 54 21. 20. 18. 17. 15. 13. 12. 10. 19. 14. 16. 11. Breen, J.P. andRoss,J.R.H.:Methanol reforming forfuel-cellapplications:Developmentof 6. 3. 2. 1. 9. 7. 5. 4. 8. Simulation ofa250kWdieselfuelprocessor/PEM fuelcellsystem, Holmen Center-Tryk, Holbæk, Denmark,2004,p.76. (Eds), Technical UniversityofDenmark, RisøNationalLaboratoryforSustainableEnergy, Risø Energy Report3—Hydrogen andItsCompetitors 2002, 6(4),150–159. December 7,2013. http://www.netl.doe.gov/technologies/coalpower/gasification/basics/3.html. with propane ATR reforming, 2003, 93(1),55–60. 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