PROCESS OF METHANE WITH CARBON DIOXIDE FOR
HYDROGEN PRODUCTION
G.W. BASSON
12897310
Dissertation submitted in partial fulfilment of the requirements for the degree
Master of Engineering
at the Potchefstroom Campus of the North-West University
Supervisor: PROF. P.W.E BLOM
2009
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TITLE: AUTHOR:
SUPERVI
Abstra
The world around the huge amou and save o This resea of synthes that is norm operates a occur stoic Plasma-arc hydrogen-t steam to th The variati total of 1 4 per GJ. T making us using a Pre stream. The annua sensitivity hydrogen g the produc also comp that Plasm NON-C CARBO GERTISOR:
ct
revolves a e world and unts of gree on valuable arch project is and hydr mally used at very high chiometrical c Reformin to-carbon m he inlet gas ion in the ra 435 million N The hydrog se of the w essure Swin al productio evaluation gas. It was ction cost a ared with th ma-arc Refor CATALYTIC ON DIOXID WILHELMPROF. P.
around ene provide sa enhouse ga fossil fuel. evaluates t rogen gas. in the Stea h temperatu lly in the un ng Units w monoxide ra stream. atio can be Nm3 synthe gen product water-gas-sh ng Absorpti n of hydrog was cond s observed and profitab he Non-cata rming comp C PLASMA DE FOR HY BASSON.W.E. BLO
ergy; it is n afety and co ases. New the Non-cat Carbon dio am Methane ures (2 000 nit. A 500 M with electric atio of 1:1, e achieved b esis gas ca tion by the hift reaction on system, gen is 1 120 ucted on th that natura bility of the alytic Plasm petes well w iii A-ARC REF YDROGEN POM
needed to p onvertibility f w technologi talytic Plasm oxide was u e Reforming 0-5 000°C) MWt Pebble cal power. which can by changing n be produ Plasma-ar n. Hydroge in order to 0 million Nm he process al gas and plants. Th ma-arc Refo with Steam M FORMING P PRODUCT power indu for everyon es are nee ma-arc Refo used as the g Process. and this e e Bed Modu Synthesis be varied g the steam ced annual rc Reformin en can be p separate th m3 at a prod s used for electrical co he Steam M rming Proc Methane Re PROCESS ION stry, move ne. Current eded to prod orming Proc oxidising a The Plasm nables the ular Reactor s gas can between 1 m to carbon lly at a prod ng Process produced w he hydrogen duction cos the produc osts have a Methane Re ess, from w eforming. OF METHA people an t technologi duce cleanecess for the agent instea ma-arc Refo reforming r can supply be produc :1 and 3:1, n dioxide fee duction cos can be inc with a purity n from the p t of $14.17 ction of syn a significant eforming Pr which it was ANE WITH nd products es produce er energies production ad of steam orming Unit reaction to y 21×8 MW ced with a , by adding ed ratio. A st of $10.43 creased by y of 99.0% product gas per GJ. A nthesis and t impact on rocess was s concluded H s e s n m t o W a g A 3 y % s A d n s d
TITEL: OUTEUR:
PROMOT
Opsom
Die wêreld produkte o wat tans kweekhuis waardevol Hierdie na vervaardig plaas van temperatur die nodige Reaktor (P Sintesegas verder gev te voeg. Die verand stoom tot teen ’n p hervorming Waterstof maak wat Die totale Sensitiwite winsgewen stoommeta en dit het g NON-C CARBO GERTTOR:
mming
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le fossielbra
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stoom wa re (2 000-5 energie so Pebble Bed s met ’n H2 varieer word dering in di koolstofdiok produksieko gsproses k met ’n suiw die waterst waterstofpr eitsanalise w ndheid van aan-hervorm getoon dat d CATALYTIC ON DIOXID WILHELM
PROF. P.
afhanklik van eld te vervo vervaardigin arom word n andstowwe rojek onder ntese- en at normaalw 000°C) wo odat die rea Modular R 2-tot-CO-ver d tussen 1:1 e H2-to-CO ksied te var oste van $ kan verhoo werheid vantof van die p
roduksie is wat uitgevoe die sintese mingsprose die prosess C PLASMA DE FOR HY BASSON
.W.E. BLO
n energie e oer en veili ng van en nuwe tegno in die prose rsoek die n waterstofga weg gebrui ord in die pl aksie stoigio Reactor) kan rhouding va 1 en 3:1 de O-verhouding rieer. Die p $10.43 per g word de 99.0% kan produk gass 1 120 miljo er is, het ge e- en wate s met die n se ekonomie A-ARC REF YDROGEN POM
en dit word b igheid en v nergie gebr ologieë ben es te bespa nie-katalitie as. Koolsto k word in lasmaboog-ometries kan n 21×8 MW an 1:1 kan eur ’n sekere g kan bewe produksie va GJ. Die eur van die n geproduse stroom ske oen Nm3 tee etoon dat a erstofgas pr nie-katalities es goed ver FORMING P PRODUCT benodig om verwisselbaa ruik word, odig om sk aar. ese plasma ofdioksied is die stoomm -hervorming n plaasvind W plasmaboo geproduse e hoeveelh erkstellig wo an sinteseg waterstofp e water-gas eer word de i. en ’n produ ardgas en e roduksie me se plasmabo rgelyk. PROCESS ION m industrieë arheid te ve produseer oner energ aboog-hervo s as oksida metaan-her gseenheid b d. ʼn 500 MW og-eenhede eer word. H eid stoom b ord deur di gas is 1 435 produksie v s-skuifreaks eur van ’n P uksiekoste v elektrisiteit erkbaar beï oog-hervorm OF METHA aan te dryf erseker. Di r groot ho ie te produs ormingspros asiemiddel rvormingspr bereik, en d Wt Korrelbed e elektrisite ierdie verh by die inlaa e voerverh 5 miljoen N van die pl sie gebruik PSA-sisteem van $14.17 die produks ïnvloed. Ve mingsprose ANE WITH f, mense en e prosesse oeveelhede seer en omses vir die gebruik in roses. Hoë dit voorsien d Modulêre eit voorsien. ouding kan tgas-stoom ouding van m3 per jaar asmaboog-k te maaasmaboog-k. m gebruik te 7 per GJ. ’n siekoste en erder is die es vergelyk, H n e e m e n ë n e n m n r -e n n e ,
Table o
Declaration Acknowled Abstract ... Opsommin Table of co List of table List of figu Publication List of abb List of sym List of units Chapter 1 1.1 1.2 1.3 1.4 1.5 Chapter 2 2.1 2.2 2.3 2.3.1 2.4 2.4.1 2.4.2 2.5 2.5.1 2.6 2.6.1 2.6.2of conte
n ... dgements ... ... ng ... ontents ... es ... res ... ns and pres reviations a mbols ... s ... - Introd Backgrou Problem Need an Objective Benefits - Litera Introduct Steam M Process Negative Dry Meth Process d Investigat Methane Non-cata Process d Plasma-a Hüls Plas Glidarc (Gents
... ... ... ... ... ... ... sentations .. and acronym ... ... uction ... und ... statement d importanc es of the res of the resea ture survey tion ... Methane Ref description aspects of hane Reform description tion into the e Process .. alytic Partia description arc Methan sma-arc Fur Gliding arc) ... ... ... ... ... ... ... ... ms ... ... ... ... ... ... ce ... search ... arch ... y ... ... forming ... n ... steam refo ming ... ... e different c ... l Oxidation ... e Reformin rnace/Torch ... v ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... rming of me ... ... catalysts tha ... of Methane ... g ... h ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ethane ... ... ... at can be us ... e ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... sed in the D ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... Dry Reformin ... ... ... ... ... ... ... i ... ii ... iii ... iv ... v ... viii ... xi ... xv ... xvi ... xvii ... xvii ... 1 ... 1 ... 2 ... 2 ... 3 ... 4 ... 5 ... 5 ... 5 ... 5 ... 7 ... 9 ... 9 ng of ... 10 ... 11 ... 11 ... 14 ... 15 ... 19 v v v 5 5 5 5 52.7 2.8 2.9 Chapter 3 3.1 3.2 3.2.1 3.3 3.4 3.5 Chapter 4 4.1 4.2 4.3 4.3.1 4.3.2 4.4 4.4.1 4.4.2 4.5 Chapter 5 5.1 5.2 5.3 5.3.1 5.3.2 5.3.3 5.4 5.4.1 Combine The wate Hydroge - Nucle Introduct Nuclear-Pebble B Nuclear S Thermo-Safety as - Proce Introduct Assumpt Synthesi Methane Methane gas ... Hydroge Methane energy s Methane thermal e Conclusio - Techn Introduct Assumpt Techno-e Techno-e agent .... Techno-e oxidising Conclusio Techno-e Techno-e energy fr ed methane er-gas-shift n economy ear energy fo tion ... type reacto ed Modular Steam Meth chemical w spects of co ess descript tion ... tions applie s gas produ Reforming reforming u ... n productio Reforming supplied by reforming w energy of a on ... no-economi tion ... tions on wh economic e economic ev ... economic ev g agent ... on ... economic e economic ev rom a Pebb e reforming . reaction .... ... or synthesis ... or ... r Reactor ... hane Refor water-splittin ombined Nu ion ... ... d for mater uction using using CO2 using a mixt ... on using Pla with CO2 fo a PBMR .... with CO2 for Pebble Bed ... c evaluatio ... ich the tech evaluation o valuation of ... valuation of ... ... evaluation fo valuation of ble Bed Mod
... ... ... s gas or hyd ... ... ... ming ... ng using nuc uclear Steam ... ... ial balance g Plasma-ar for the prod ture of CO2 ... asma-arc Te or the produ ... r the produc d Modular R ... n ... ... hno-econom of the proces f synthesis g ... f synthesis g ... ... or the produ f the hydrog dular Reacto ... ... ... drogen prod ... ... ... ... clear energy m Reformin ... ... calculations rc Technolo duction of sy and steam ... echnology .. uction of hyd ... ction of hyd Reactor ... ... ... ... mic evaluatio ss for the p gas product ... gas product ... ... uction hydro gen product or ... ... ... ... duction... ... ... ... ... y ... ng ... ... ... s ... ogy ... ynthesis ga for the pro ... ... drogen, util ... rogen, utilis ... ... ... ... on calculati roduction o tion using C ... tion using C ... ... ogen ... tion process ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... as ... duction of s ... ... ising the ele ... sing the ele ... ...
... ... ons are bas f synthesis CO2 as the o
... CO2 and ste
... ... ... s using the ... ... 21 ... 22 ... 23 ... 26 ... 26 ... 26 ... 28 ... 29 ... 34 ... 36 ... 37 ... 37 ... 37 ... 39 ... 39 synthesis ... 44 ... 53 ectrical ... 53 ctrical and ... 62 ... 70 ... 71 ... 71 sed ... 71 gas ... 72 oxidising ... 72 eam as the ... 80 ... 87 ... 87 electrical ... 87
5.4.2 Chapter 6 6.1 6.2 6.3 6.4 Chapter 7 7.1 7.2 Reference Appendix A A.1 A.2 Appendix B B.1.1 B.1.2 B.1.3 B.1.4 B.1.5 Appendix C C.1 C.2 C.3 C.4 Conclusio - Comp Refor Introduct Compari Process Compari Process Conclusi - Concl Conclusi Further i s ... A - Equat Equation Constant B - Equat Equipmen Heat exch Compres Pressure Reactor c C - HYSY Methane Methane gas ... Methane energy s Methane thermal e on ... parison of S ming ... tion ... son of the S
for the prod son of the S for the prod on ... usion of inv on of inves nvestigation ... tions and co ns for proce ts ... tions used f nt cost calc hanger cost sor cost .... Swing Abs cost ... YS simulatio e Reforming e Reforming ... e reforming supplied by e Reforming energy supp ... Steam Metha ... ... Steam Meth duction of s Steam Meth duction of h ... vestigation . tigation ... n ... ... onstants us ss calculati ... for techno-e culation ... t ... ... sorption cos ... ons of proce g using CO2 g using a mi ... with CO2 fo a Pebble B g with CO2 f plied by a P vii ... ane Reform ... ... hane Reform ynthesis ga hane Reform hydrogen .... ... ... ... ... ... ed for calcu ons ... ... economic ev ... ... ... st ... ... esses ... for the pro ixture of CO
... or the produ ed Modular for the produ Pebble Bed ... ming with No ... ... ming and P as ... ming and P ... ... ... ... ... ... ulations ... ... ... valuation ... ... ... ... ... ... ... duction of s O2 and steam ... uction of hyd r Reactor ... uction of hy Modular Re ... on-catalytic ... ... lasma-arc M ... lasma-arc M ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... synthesis ga m for the pr ... drogen utilis ... ydrogen utili eactor ... ... Plasma-arc ... ... Methane Re ... Methane Re ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... as ... roduction of ... sing the ele ... ising the ele ... ... 96 c ... 97 ... 97 eforming ... 97 eforming ... 98 ... 100 ... 101 ... 101 ... 105 ... 106 ... 109 ... 109 ... 110 ... 111 ... 111 ... 111 ... 111 ... 111 ... 112 ... 113 ... 113 f synthesis ... 115 ctrical ... 122 ectrical and ... 125 5 5 5
List of
Table 2.1: Table 2.2: Table 2.3: Table 2.4: Table 2.5: Table 2.6: Table 3.1: Table 3.2: Table 4.1: Table 4.2: Table 4.3: Table 4.4: Table 4.5: Table 4.6: Table 4.7: Table 4.8: Table 4.9: Table 4.10 Table 4.11 Table 4.12 Table 4.13tables
Gas co Plasma Test re Steam Hydrog Techni Design (Verfon Hybrid Comple oxidisin Mass a heat ex Mass a Mass a 1.6CO Mass a 1.33CO Mass a → 1.14 Mass a Mass a Produc Mass a Proces 0: Mass a Produc : Mass a Proces 2: Mass a Produc 3: Mass a Proces omposition o a processes esults of the , dry and m gen product cal and basn specificatio ndern, 2007 sulphur de ete mass a ng agent ... and energy xchanger ... and energy and energy + 2.4H2) ... and energy O + 2.67H2) and energy 4CO + 2.86 and energy and energy ction Proces and energy ss ... and energy ction Proces and energy ss ... and energy ction Proces and energy ss ... of the Partia s (Müller & e plasma ref ixed steam/ tion and CO se data for e ons of the s 7) ... sign param nd energy b ... balance for ... balance for balance for ... balance for ) ... balance for H2) ... balance for balance for ss ... balance for ... balance for ss ... balance for ... balance for ss ... balance for ... al Oxidation Kerker, 198 forming pilo /CO2 reform O2 mitigation economical steam reform ... eters (Sum balance of s ... r a single gr ... r a H2-to-CO r a H2-to-CO ... r a H2-to-CO ... r a H2-to-CO ... r a H2-to-CO r the Plasm ... r the compr ... r the water-... r the purifica ... r the Plasm ... r the compr ... n of Methan 84) ... ot plant (Mü ming of natu n costs (Mu analysis (M
mer for Hig ... mers et al., synthesis ga ... roup of thre ... O ratio of 1: O ratio of 1. ... O ratio of 2: ... O ratio of 2. ... O ratio of 3: a-arc Refor ... ression sect ... gas-shift re ... ation sectio ... a-arc Refor ... ression sect ... e (Sogge e ... ller & Kerke ural gas (Cz eller-Lange Meuller-Lan h Temperat ... , 2005) ... as productio ... ee Plasma-a ... 1 (CH4 + C 5:1 (CH4 + ... 1 (CH4 + 0. ... 5:1 (CH4 + ... 1 (CH4 + H2 rming sectio ... tion of the H ... eaction sect ... on of the Hy ... rming sectio ... tion of the H ... et al., 1994) ... er, 1984) .... zernichowsk er et al., 200 ger et al., 2 ture Test Re ... ... on, using C ... arc Reforme ... O2 → 2CO 0.6CO2 + 0 ... 33CO2 + 0. ... 0.14CO2 + ... 2O → CO + on of the Hy ... Hydrogen P ... ion of the H ... ydrogen Pro ... on of the Hy ... Hydrogen P ... ... 13 ... 14 ... 19 ki, 2001) 21 07) ... 24 2007) ... 25 eactor ... 33 ... 35 CO2 as the ... 40 ers per one ... 41 + 2H2) .. 46 0.4H2O → ... 47 .67H2O → ... 48 0.86H2O ... 49 + 3H2) .... 50 ydrogen ... 56 roduction ... 57 Hydrogen ... 58 oduction ... 59 ydrogen ... 64 roduction ... 65 5 5 5
Table 4.14 Table 4.15 Table 5.1: Table 5.2: Table 5.3: Table 5.4: Table 5.5: Table 5.6: Table 5.7: Table 5.8: Table 5.9: Table 5.10 Table 5.11 Table 5.12 Table 5.13 Table A.1: Table A.2: Table C.1: Table C.2: Table C.3: Table C.4: Table C.5: Table C.6: 4: Mass a Produc 5: Mass a Proces Techno Equipm Estima CO2 as Calcula agent . Effect o Equipm Estima CO2 as Produc the diff Effect o proces 0: Equipm Modula : Estima the ele 2: Calcula Pebble 3: Effect o proces Heat ca Values conditio HYSYS HYSYS HYSYS HYSYS HYSYS HYSYS and energy ction Proces and energy ss ... o-economic ment cost of ation of the t s the oxidisi ation of the ... of different ment cost of ation of the t s the oxidisi ction cost, p ferent H2 -to-of different ss ... ment cost of ar Reactor . ation of the t ectrical ener ation of the e Bed Modu of different ss ... apacities us s used for co ons ... S mass and S mass and S mass and S mass and S mass and S mass and balance for ss ... balance for ... c evaluation f synthesis total capital ing agent ... production ... electricity g f synthesis total capital ing agent ... payback per -CO ratios . electricity g ... f hydrogen ... total capital rgy of a Peb production ular Reactor electricity g ...
sed for ene onversion o ... d energy ba d energy ba d energy ba d energy ba d energy ba d energy ba ix r the water-... r the purifica ... assumptio gas produc investmen ... cost of syn ... generation c gas produc investmen ... riod, return ... generation c ... production ... investmen bble Bed Mo cost of the r ... generation c ... rgy balance of molar to m ... lance for th lance for a lance for a lance for a lance for a lance for a gas-shift re ... ation sectio ... ns ... ction utilising
t for the pro ... nthesis gas ... cycles ... ction utilising
t for the pro ... on investm ... cycles on th ... using the e ... t cost for th odular Reac hydrogen u ... cycles on th ... e calculation mass and vo ... e productio H2-to-CO ra H2-to-CO ra H2-to-CO ra H2-to-CO ra H2-to-CO ra eaction sect ... on of the Hy ... ... g CO2 as th oduction of s ... using CO2 a ... ... g CO2 as th oduction of s ... ent and inte ... e combined ... electrical ene ... e productio ctor ... using the el ... e combined ... ns... olumetric at ... on of synthe atio of 1:1 .. atio of 1.5:1 atio of 2:1 .. atio of 2.5:1 atio of 3:1 .. ion of the H ... ydrogen Pro ... ... he oxidising synthesis g ... as the oxidi ... ... he oxidising synthesis g ... ernal rate of ... d synthesis ... ergy of a Pe ... on of hydrog ... ectrical ene ... d synthesis ... ... t standard ...
esis gas usin ... 1 ... ... 1 ... ... Hydrogen ... 66 oduction ... 67 ... 71 agent ... 73 gas, using ... 73 ising ... 74 ... 80 agent ... 80 gas using ... 81 f return for ... 82 gas ... 87 ebble Bed ... 88 gen using ... 89 ergy of a ... 90 gas ... 95 ... 110 ... 110 ng CO2 114 ... 116 ... 117 ... 118 ... 119 ... 121 5
Table C.7: Table C.8: Table C.9: Table C.10 HYSYS electric HYSYS electric HYSYS electric 0: HYSYS electric S mass and cal energy o S Mass and cal energy o S mass and cal and ther S mass and cal and ther
d energy ba of the Pebb d energy ba of the Pebb d energy ba rmal energy d energy ba rmal energy lance for th le Bed Mod lance for th le Bed Mod lance for th y of the Peb lance for th y of the Peb e productio dular Reacto e productio dular Reacto e productio bble Bed Mo e productio bble Bed Mo on of hydrog or ... on of hydrog or (continue on of hydrog odular Reac on of hydrog odular Reac
gen gas usin ... gen gas usin ed) ... gen gas usin ctor ... gen gas usin ctor (continu ng the ... 123 ng the ... 124 ng the ... 126 ng the ued) .... 127
List of
Figure 1.1: Figure 2.1: Figure 2.2: Figure 2.3: Figure 2.4: Figure 2.5: Figure 2.6: Figure 2.7: Figure 2.8: Figure 2.9: Figure 2.10 Figure 3.1: Figure 3.2: Figure 3.3: Figure 3.4: Figure 3.5: Figure 3.6: Figure 4.1: Figure 4.2: Figure 4.3: Figure 4.4: Figure 4.5: Figure 4.6:figures
: Hydrog : Natura : Block f : Time-d (a) and : The pe temper : Hydrog synthe : Texaco : Hülls P : Plasma : A sche 0: The eff : Schem : Proces (Verfon : Flow s facilitie : High T Steam : New co : Schem : Methan : Simplif produc : A singl : The in-: Therma Unit .... : Synthe functios
gen product l gas-based flow diagram dependent c d reducible erformance rature ... gen productsis gas prod o POX Reac Plasma-arc a reforming ematic diagr fect of CO2/ matic diagram ss flow shee ndern, 2007 heet of the es EVA-II an emperature Methane R oncept of he matic block d ne conversi fied process ction using C e group of t -and-out flow al efficiency ... esis gas flow
ns of metha tion method d hydrogen m of Catalyt conversion o metal oxide if the 5 wt% ... tion plant m duction (Hig ctors with q Furnace (M pilot plant ram of the G /H2O ratio o m of the Pe et of High T 7) ... steam refor nd ADAM-II e Test Reac Reforming (V elium-heate diagram of t on as a fun s flow diagra CO2 as the three Plasm w of the the y as a funct ... w rate and o ane convers xi ds ... plant, typic tic Dry Refo of CH4 over es (b; Zhang % Ni/CaO-A
... making use o gman & Van quench cool Müller & Ker (Müller & K Glidarc-Ι (Cz on the conve ebble Bed M emperature ... rming test fa (right; Verf ctor coupled Verfondern, ed steam re the Hybrid S nction of ope am using P oxidising ag ma-arc Refo ermal energ ion of meth ... outlet tempe sion ... ... cal process orming of M r Rh catalys g et al., 199 l2O3 cataly ... of the Partia n der Burgt ing and syn rker, 1984) . erker, 1984 zernichows ersion of me Modular Rea e Gas Reac ... acility EVA-fondern, 200 d to a hydro , 2007) ... eformer (Ver Sulphur Cyc erating tem Plasma-arc T gent ... ormers per s gy for the pr ane conver ... erature of th ... ... layout (Dyb ethane ... st with irred 96) ... yst is plotted ... al Oxidation , 2003) ... nthesis gas ... 4) ... ski, 2001) .... ethane and actor... ctor with ste ... -II (left) and 07) ... ogen produc ... rfondern, 20 cle (Summe perature (La Technology ... single heat rocess ... rsion in Plas ... he Plasma-a ... ... bkjaer et al., ... ucible meta ... d against ... n Process fo ... cooler ... ... ... ... the H2/CO ... am reformin ... the combin ... ction plant b ... 007) ... ers et al., 20
ane & Spat y for synthes ... exchanger ... sma-arc Re ... arc Reform ... ... 2 , 1994) .... 6 ... 9 al oxides ... 10 ... 11 or ... 12 ... 13 ... 16 ... 18 ... 20 ratio ... 22 ... 29 ng ... 30 ned test ... 31 based on ... 32 ... 34 005) ... 35 th, 2001) 38 sis gas ... 39 ... 41 ... 42 eformer ... 43 er Unit as ... 43 5
Figure 4.7: Figure 4.8: Figure 4.9: Figure 4.10 Figure 4.11 Figure 4.12 Figure 4.13 Figure 4.14 Figure 4.15 Figure 4.16 Figure 4.17 Figure 4.18 Figure 5.1: Figure 5.2: Figure 5.3: Figure 5.4: Figure 5.5: Figure 5.6: Figure 5.7: : Combin : The tot : Synthe Plasma 0: Therma Plasma 1: Simplif Techno 2: Total th 3: Therma Units fo 4: Hydrog conver 5: Simplif Reform genera 6: The tot electric 7: Therma Units fo 8: Hydrog conver : Cash fl agent . : Sensiti oxidisin : Sensiti as the : Sensiti as the : Sensiti CO2 as : Sensiti as the : Sensiti methan ned steam tal thermal e esis gas out
a-arc Refor al efficiency a-arc Refor fied process ology, maki hermal ene al efficiency or the produ gen flow rat rsion in the fied process mer Techno ated by a Pe tal thermal e cal energy o al efficiency or the produ gen flow rat rsion in the low diagram ... vity evaluat ng agent ... vity evaluat oxidising ag vity evaluat oxidising ag vity evaluat s the oxidisi vity evaluat oxidising ag vity evaluat ne conversi and CO2 ox energy of th tlet tempera mer Units .. y of the proc mer Units .. s flow diagra ng use of th rgy for Hydr y as a funct uction of hy e and Plasm Plasma-arc s flow diagra logy making ebble Bed M energy for h of a Pebble y as a funct uction of hy e and Plasm Plasma-arc
m for the pro ... tion of the p ... tion of the p gent ... tion of the r gent ... tion of the in ing agent ... tion of the n gent ... tion of the p
ons for the
xidising age he process . ature as a fu ... cess as a fu ... am for the p he electrica rogen Prod ion of meth ydrogen ... ma-arc outle c Reformer am for the p g use of bot Modular Rea hydrogen p Bed Modul ion of meth ydrogen ... ma-arc outle c Reformer oduction of ... production c ... payback per ... return on int ... nternal rate ... net profit va ... production c production
ents for the ... unction of m ... unction of m ... production o l energy ge uction Proc ane conver ... et temperat Unit for the production o th the electr actor ... roduction u ar Reactor ane conver ... et temperat Units for the
synthesis g ... cost of synth ... riod of synth ... terest of syn ... e of return o ... lue of synth ... cost and tot of synthesi production ... methane con ... methane con ... of hydrogen enerated by cess ... rsion in the ... ture as func Production of hydrogen rical and the
... sing both th ... rsion in the ... ture as func e productio gas using C ... hesis gas u ... hesis gas p ... nthesis gas ... f synthesis ... hesis gas pr ... al capital co is gas ... of synthesis ... nversion in ... nversion in ... n using Plas a PBMR ... ... Plasma-arc ... ctions of me n of Hydroge n using Plas ermal energ ... he thermal a ... Plasma-arc ... ctions of me n of hydrog CO2 as the o ... sing CO2 a ... production u ... production ... gas produc ... roduction us ... ost at differe ... s gas .... 45 ... 51 the ... 52 the ... 52 sma-arc ... 55 ... 59 c Reformer ... 60 ethane en ... 61 sma-arc gy ... 63 and ... 67 c Reformer ... 68 ethane gen ... 69 oxidising ... 75 s the ... 76 using CO2 ... 76 n using CO2 ... 77 ction using ... 77 sing CO2 ... 78 ent ... 78 5 5 5
Figure 5.8: Figure 5.9: Figure 5.10 Figure 5.11 Figure 5.12 Figure 5.13 Figure 5.14 Figure 5.15 Figure 5.16 Figure 5.17 Figure 5.18 Figure 5.19 Figure 5.20 Figure 5.21 Figure 5.22 Figure 5.23 Figure 6.1: : Sensiti differen : Sensiti of 2.5:1 0: Sensiti of 2.5:1 1: Sensiti ratio of 2: Sensiti ratio of 3: Sensiti 2.5:1, u 4: Sensiti produc 5: Sensiti paybac with a 6: Cash fl genera 7: Sensiti genera 8: Sensiti genera 9: Sensiti energy 0: Sensiti energy 1: Sensiti genera 2: Sensiti differen 3: Sensiti paybac : Produc and $0 combin vity evaluat nt methane vity evaluat 1, using CO vity evaluat 1, using CO vity evaluat f 2.5:1, usin vity evaluat f 2.5:1, usin vity evaluat using CO2 a vity evaluat ction of synt vity evaluat ck period at H2-to-CO ra low diagram ated by a Pe vity evaluat ated by a Pe vity evaluat ated by a Pe vity evaluat y generated vity evaluat y generated vity evaluat ated by a Pe vity evaluat nt methane vity evaluat ck period at ction cost of 0.06/kWh (d ned cycle] (C tion of retur conversion tion on the O2 and H2O tion on the O2 and H2O tion on the ng CO2 and tion on the ng CO2 and tion of the n and H2O as tion of the p thesis gas w tion of the r t different m atio of 2.5:1 m for the pro
ebble Bed M tion of the p ebble Bed M tion of the p ebble Bed M tion of the r by a Pebbl tion of the in by a Pebbl tion of the n ebble Bed M tion of prod conversion tion of the r t different m f H2 versus otted line). Corradetti & xiii rn on invest ns during the production as the oxid payback pe as the oxid return on in H2O as the internal rate H2O as the net profit va the oxidisin production c with a H2 -to-return on inv methane con ... oduction of Modular Rea production c Modular Rea payback per Modular Rea return on inv le Bed Mod nternal rate le Bed Mod net profit va Modular Rea uction cost, ns for the pr return on inv methane con CH4 cost fo [SC – steam & Desideri, ment and th e productio cost of synt ising agents eriod of synt ising agents nvestment o e oxidising a e of return o e oxidising a lue of synth ng agents .. cost at diffe -CO ratio of vestment, in nversions fo ... hydrogen u actor ... cost of hydr actor ... riod of hydr actor ... vestment of ular Reacto e of return o ular Reacto lue of hydro actor ... , total capita roduction of vestment, in nversions fo or a electric m cycle, GT 2007) ... he internal r n of synthe thesis gas w s ... thesis gas w s ... of synthesis agents ... of synthesis agents ... hesis gas w ... rent methan f 2.5:1 ... nternal rate or the produ ... using the ele
... rogen using ... rogen using ... f hydrogen or ... f hydrogen or ... ogen using ... al cost and f hydrogen . nternal rate or the produ ity cost of $ T – gas turb ... rate of retur sis gas ... with a H2-to ... with a H2-to ... gas with a ... s gas with a ... ith a H2-to-C ... ne conversi ... of return an uction of syn ... ectrical ene ... the electric ... the electric ... using the e ... using the e ... the electric ... net profit va ... of return an uction of hyd $0.05/kWh ( bine cycle, C ... rn at ... 79 -CO ratio ... 83 -CO ratio ... 83 H2-to- .. CO ... 84 H2-to- . CO ... 84 CO ratio of ... 85 ions for the ... 85 nd nthesis gas ... 86 ergy ... 91 cal energy ... 91 cal energy ... 92 lectrical ... 92 electrical ... 93 cal energy ... 93 alue at ... 94 nd drogen .. 94 (solid line) CC – ... 99 O O f 5 5
Figure C.1 Figure C.2 Figure C.3 Figure C.4 : HYSYS produc 2: HYSYS steam 3: HYSYS electric hydrog 4: HYSYS electric produc S process fl ction of synt S process fl for the prod S process fl cal energy g gen gas ...
S process fl cal and ther ction of hydr low diagram thesis gas .. low diagram duction of sy low diagram generated b ... low diagram rmal energy rogen gas .. m of the Met ... m of the Met ynthesis ga m of the Met by a Pebble ... m of the Met y generated ... thane Refo ... thane Refo as ... thane Refo Bed Modu ... thane Refo by a Pebbl ... rming Proce ... rming Proce ... rming Proce lar Reactor ... rming Proce le Bed Mod ... ess using C ... ess using C ... ess using C
for the prod ... ess using C ular Reacto ... CO2 for the ... 113 CO2 and ... 115 CO2 and the duction of ... 122 CO2 and the or for the ... 125 5 e e 5
Publica
Basson, G carbon dio Internation Washingtoations a
G.W. & Blo oxide as th nal Topical on, D.C. USAand pres
om, P.W.E. e oxidising Meeting on A.sentatio
2008. Non g agent for n High Tem xvons
n-catalytic the produc mperature R Plasma-arc ction of syn Reactor Tec c Reforming nthesis gas chnology, 2 g of natura s or hydrog 28 Sept.–1 al gas with gen. Fourth Oct. 2008. h hList of
ACG BGL CCG CCG DMR FCI HHV HTGR HTS HTTR HYS IHX IRR LHV NGS NGS NPV PBM PBP POX PSA ROI SMR STPabbrev
LCC L LCC R R R RL RLCC R Rviations
− − − − − − − − − − − − − − − − − − – − − −and ac
Advanced Biomass G Convention Convention Dry Metha Fixed Cap High Heati High Temp High Temp High Temp Hybrid Sul Intermedia Internal Ra Low Heatin Natural Ga Natural Ga Net Profit V Pebble Be Payback P Partial Oxi Pressure S Return on Steam Met Standard Tronyms
Coal Gasifi Gasification nal Coal Ga nal Coal Ga ne Reformi ital Investm ng Value perature Ga perature Sh perature Te phur Cycle ate Heat Excate of Retur ng Value as Steam R as Steam R Value d Modular R Period dation Swing Adso Investment thane Refo Temperatur
s
ication Larg Large scale asification L asification L ng ment as Reactor ift st Reactor changer rn eforming La eforming La Reactor orption t rming re and Press ge scale wit e Large scale Large scale arge scale arge scale w sure h Carbon C with Carbo with Carbon Capture n Capture n CaptureList of
Cp,i ∆H0 i T Ni E ξ νiList of
Nm3 kg °C K barg GJ MWe MWt kWh ml wt%symbo
units
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− − − − − − − − − − − − − − − − − − Heat ca Enthalp Temper Number Energy Extent o Stoichio Normal Kilogram Degree Kelvin Absolut Gigajou Megawa Megawa Kilowatt Millilitre Weight xvii apacity of co py of compo rature r of moles o of reaction ometric coef cubic metre m Celsius te pressure ule att electrica att thermal t hour percentage omponent i onent of compone fficient of co es al e nt omponentChapte
1.1 Bac
The aro sup wor sup fue wor New imp pro var (DM Ele oth and Ene thu pro the and sou twoer 1 -
ckground
e world rota ound the gl pplied by fo rld’s growin pply the gro els, the pollrld. w energy so pacts and e ovide all ou rious proces MR), Auto ectrolytic Hy er methods d hydrogen. ergy input is s, energy i oduction of ese process d therefore urce, such a o hydrogen
Introdu
d
ates around obe and pr ossil fuels, ng populati owing popu ution gener olutions are energy secu ur energy s sses, such Thermal M ydrogen Pr s make use . s needed fo s needed t hydrogen, ses. High q it would b as nuclear p productionuction
d energy tha rovide safe such as co on more e lation with rated by th e needed to urity throug services, na as Steam Methane R roduction. e of natural or the produ to create en fossil fuels quantities of e beneficia power in ord methods ar at is used to ety and conoal, natural nergy is ne energy. Be e conversio o ensure eco gh diversity amely hydro Methane Reforming, Except for l gas as fee uction of hyd nergy. In o s are used f fossil fuels al if hydroge der to exten re displayed o power ind nvertibility fo l gas and p eeded; thus ecause of t on of these onomic gro . One sim ogen (H2). Reforming Partial Ox the last m edstock for drogen from order to pro to supply s are neede en could be nd the lifetim d in Figure dustry, move or everyone petroleum o s, more fos the increasi e fuels is a wth, a decr mple elemen Hydrogen (SMR), Dry idation (PO making use r the produc m methane oduce the e the energy ed for the p e produced me of the wo 1.1. e people an e. Today’s oil. But ow ssil fuels a ing use of t major con rease in env nt has the can be pr y Methane OX) of Me of water-s ction of syn (natural gas energy need y demand r production o d by a clea orld’s fossil nd products s energy is wing to the are used to these fossil cern to the vironmental potential to roduced by Reforming ethane and plitting, the nthesis gas s) or water; ded for the required by of hydrogen ner energy fuels. The s s e o l e l o y g d e s e y n y e
In t mo tod con eac
1.2 Pro
Thi Me (PB1.3 Nee
Hyd alte on imp the followin ore detail. S ay for the nditions und ch are invesoblem sta
s research ethane Refo BMR) to powed and im
drogen pro ernative pro the applica pact the proFigure ng chapter, Steam Meth production der which th stigated furt
atement
project see orming proce wer the Plasmportanc
duced by t ocess is the ation and gl ocess has o e 1.1: Hy SMR, DMR ane Reform of synthes hese proce ther. eks to eval ess using th sma-arc Syce
he above-m erefore nee obal deman n the enviro 2 ydrogen pro R and Plas mation is the sis gas or sses opera luate the fe he energy g ystem for thementioned p ded to prod nd. In addi onment is a oduction me sma Methan e most com hydrogen ate and the
easibility of generated b e productio processes duce hydrog ition to the a significant ethods ne Reforma mmon proces from natura positive an a Non-cata by a Pebble n of synthe makes use gen or synt global dem concern. ation are di ss used in t al gas. Th nd negative alytic, Carb e Bed Modu sis gas or h e of fossil e thesis gas, mand for hyd
iscussed in the industry he process aspects of bon Dioxide lar Reactor hydrogen. energy. An depending drogen, the n y s f e r n g e
The from rea cho syn gre
1.4 Obj
The e last two p m natural g actor to drive oice. The p nthesis gas eenhouse gajectives o
e objectives • determ powere PBMR • determ produc • determ gas ref monox • calcula conduc • compa arc Ga Reform • conduc parame co co ca va oints menti gas. Using e the hydro process also or hydroge ases.of the re
s of the rese mine the numed by a 500 is to be use
mine the vol ction cost th
mine the cap forming pla xide;
ate the hydr ct a
techno-are the prod as Reformi ming Proces ct a sensit eters on the ost of natura ost of electri apital cost (i arying the H oned form t g the proce gen proces o makes us en, thereby
esearch
earch projec mber of 8 M 0 MW PBM ed to gener ume of syn hereof; pacity of the ant for the progen produ -economic e duction cost ng Process ss; and ivity analys e production al gas ($2/G city ($0.02/ ncreases by 2/CO ratio b the driving f ess heat an ss makes Pl se of carbo y consuming ct are to: MW Plasma MR plant. T rate electric nthesis gas e water-gas production o uction outpu evaluation o t of hydroge s with that sis, in orde n of the syn GJ – $8/GJ); /kWh – $0.0 y 5.0%, 10. between 1:1 force of the nd the elec lasma-arc R n dioxide a g a greenh -arc Metha The high tem city needed that could s-shift plant of hydrogen ut of the pla of hydrogen en, making of the co er to determ nthesis gas/ ; 06/kWh); 0%, 15.0% 1 and 3:1 of e research in ctricity gene Reforming a s a reactan ouse gas r ne Reformi mperature h by the Plas be produce that is coup n, based on
ant and the n production use of the nventional mine the e hydrogen: and 20.0% f the synthe n hydrogen erated by t a very good nt for the pr rather than ng Units th helium gas sma-arc unit ed and the pled to the n the availa cost of prod n; Non-catalyt Catalytic S effect of th %); and esis gas. production the nuclear process of roduction of generating at could be exiting the ts; associated plasma-arc able carbon duction and tic Plasma-Steam Gas e following n r f f g e e d c n d -s g
1.5 Ben
The Sevnefits of
e findings veral of the • the hy Reform • the liqu use of • the me reducti alloys.the rese
of this rese industries t drogen ind ming Technouid fuels ind the WGS re etallurgical
on reaction
earch
earch proje that will ben dustry – cle ology; dustry – thro eaction redu industry – n of metal 4 ect will ben nefit from th eaner hydro ough the va uces the co – the synth oxides to m nefit many he results of ogen that i ariation of th ost of synthe esis gas t metallic iron areas of t f the investi is produced he synthesi esis gas; an hat is prod n for the pr he chemica gation are: d through P s gas ratio nd duced is u roduction o al industry. Plasma-arc without the sed in the f steel and . c e e d
Chapte
2.1 Intr
In t syn Ref gas2.2 Ste
On fue pro Ste rea exo Ow tem shif Beu2.3 Pro
A s tod rati pro Goer 2 -
roduction
this chapter nthesis gas forming Tec s or hydrogeam Meth
e of the m els, such as oduce synth eam Metha action is hig othermic (Va CH4 + CO + H wing to the mperature a ft in contras urden, 2004ocess des
steam to ca ay. The c o; more ste oduce the s l & DybkjaeLiteratu
n
r, the differe and hydrog chnology th en is also ehane Ref
most studied s natural ga esis gas (V ane Reform ghly endoth an Beurden H2O → CO H2O → CO2 steam refo and low presst is favour 4).
scription
arbon (meth onversion o eam means steam for th er, 1995).ure surv
ent reformat gen from na hat is used examined.forming
d technolog as, is SMR Van Beurden ming consis ermic and n, 2004): + 3H2 2 + H2 orming reac ssures bec ed by low tn
hane) ratio of methane s a higher c he reformingvey
tion techno atural gas ( in this resegies for the R. Steam i n, 2004; Dy sts of the the water-g ∆H ∆H ction being ause of vol temperature of betwee e in the refo conversion g process logies that methane) a earch projec e production is reacted ybkjaer et al following t gas shift re H0 298 = +206 H0298 = -41 k highly end ume increa e and unaff n 2.5 and 3 ormer is co of methane (Van Beurd can be use are investiga ct for the p n of hydrog with metha l., 1994). two reactio eaction that 6 kJ/mol kJ/mol dothermic, ase with rea
fected by pr 3.0 is main ontrolled by e, but more den, 2004; ed for the pr ated. The roduction o gen from fo ane over a ons: steam follows is (1) (2) it is favour action. The ressure cha ntained in t y the steam e energy is Dybkjaer e roduction of Plasma-arc of synthesis ossil based catalyst to m reforming moderately ed by high e water-gas anges (Van he industry m to carbon required to et al., 1994; f c s d o g y h s n y n o ;
The is u bec ste lea con 85. Stro The two onl shif the The rea as it e as des Figure 2 e feed gas used. The cause the re am and furt ves the refo nversion of 0% and the om & Sund e reformed o-step sectio y a one-ste ft reactor (D e medium an e carbon m actors. The 0.1% (Van enters the P high as 90. scribed proc 2.1: Nat to the refor e sulphur p eforming ca ther heated ormer at a methane in e thermal e set, 1994). gas is cool on, which c ep section, w Dybkjaer et nd low temp onoxide an e unreacted Beurden, 2 Pressure Sw 0% with a f cess can be ural gas-bas rmer is hea resent in th atalyst is se d to 535°C b temperatur n the steam efficiency of ed before it consists of a which is a al., 1994). perature sh d steam is carbon mo 2004). The wing Adsorp
feed gas pre e seen in Fi sed hydroge 6 ted in a wa he natural ensitive to s before it ent re of approx m reformer a f the proces t enters the a high temp high tempe The HTS r ift uses a co converted i onoxide con gas is then ption (PSA) essure of 3 gure 2.1 be en plant, typ aste heat se gas is rem sulphur. Th ters the refo ximately 82 at the oper ss is 66.7% e shift conve perature and erature shift reactor uses opper-base nto carbon ncentration cooled dow Init. The e 0 bar (Dybk elow. pical proces ection of the moved over e cleaned f ormer. The 0°C (Dybkj rating condi % (Simpson erters. The d low tempe (HTS) or a s an iron-ba d catalyst ( dioxide and in the prod wn to ambie efficiency of kjaer et al., ss layout (D e tubular re a zinc oxi feed gas is e reformed p aer et al., 1 itions is app n & Lutz, 20 e shift sectio erature shif a medium te ased catalys Dybkjaer et d hydrogen uct gas can ent tempera f the PSA U 1994). A la Dybkjaer et a eformer that de catalyst mixed with product gas 1994). The proximately 007; Sogge on can be a ft reactor or emperature st, whereas t al., 1994). in the shift n be as low ature before Unit can be ayout of the al., 1994) t t h s e y e a r e s t w e e e
2.3.1 Ne
The On refo The pro Sin Sin cat cat pro (Kir tak con con Beu Oxi Oxi act pro pha The SM kee Beuegative as
e negative a e of these orming procere are fou ocess, these sinterin oxidatio sulphu carbon ntering ntering is th alyst. This alysts, whic ocess, cryst rk-Othmer, es place d ntent, initial nditions un urden, 2004 idation of th idation of t ivities. The one to oxida ase, which i e nickel cat MR Process ep most of urden, 2004
spects of
aspect of C e negative cess. ur major c e causes ar ng; on; r poisoning n deposition he process agglomera ch then resu allites are a 2001; Van epends on l crystallite der which 4). he metal ca the catalyst e nickel cat ation. The is the active talyst is red s. At norm f the active 4).f steam re
Catalytic Ste aspects is auses of t re (Kirk-Oth ; and . of agglom ation of the ults in a dec also formed Beurden, 2 many fact size and the reform talyst t occurs at talysts used catalyst be e phase of t duced by a al SMR op e phase deforming
eam Reform the deact the deactiv mer, 2001; meration of crystallites crease in th d that are le 2004). The ors, namely distribution ming reacti t high stea d in the ind ecomes dea the catalysts a hydrogen-perating con uring the pof metha
ming of met ivation of t ation of th Van Beurde the crystal leads to the he activity o ess reactive e severity o y the meta n, the natur ion takes am-to-metha ustry today activated ow s (Kirk-Othm -rich gas b nditions, su process reane
hane is disc the catalys he catalyst en, 2004): llites of the e loss of the of the cataly e than the c of and rate l used in th re of the s place (Kirk ane ratios y for the ref wing to the mer, 2001; efore the c ufficient hyd duced (Kir cussed in t st that is u during the e active ph e active sur yst. Ideally, crystallites t at which th he catalyst support use k-Othmer, and with lo forming pro oxidation o Van Beurde catalyst is u drogen is p k-Othmer, his section. used in the e reforming hase of the rface of the during this hat are lost he sintering , the metal ed and the 2001; Van ow catalyst ocesses are of the metal en, 2004). used in the produced to 2001; Van . e g e e s t g l e n t e l e o nSul The ato Oth van Sul gas bec form oxid Car Car ope car tub 200 and Bec cat form cat 200 The stre the few cat but use lphur poison e poisoning omic structu hmer, 2001 nadium, lea lphur is the s to the ref comes pois m of H2S dation and rbon depos rbon depos eration temp rbon is depo bes where t 04). The de d the deacti cause Cata alyst leads mation of t alysts is fa 01). e conclusio eam needs The de e production w years owi alysts can b t these cata ed. ning of the of the cata ure of the ca 1; Van Be d, sulphur a e most seve former cont oned and t (hydrogen reduction o sition on the sition is a f perature for osited on th the methan eposition of vation of th alytic Steam s to low te the catalys r less than on regarding to be des eactivated c n cost of hy ng to the d be used ow alysts are m catalyst alyst blocks atalyst used urden, 200 and chlorine ere poison tains more he activity o sulphide). of the cataly e catalyst frequently e r the reform he catalyst; e concentra f the carbon e catalyst ( m Reforming emperature st (Kirk-Oth on the nic g the four m sulphirised a catalyst nee ydrogen from ecreases in wing to their ore expens 8 the active p d, which the 04). Som e. that affects than 5 ppm of the catal The sulph yst (Kirk-Oth experienced ming proces this is mai ations are s n on the ca Kirk-Othme g is a high e reaction hmer, 2001 ckel catalys major caus and a stea eds to be re m methane n the active r resistance sive, which w phase surfa en reduces e of these s the steam m of sulph ysts reduce hur can be hmer, 2001; d phenome s, some of inly observe still high (K talysts caus er, 2001). ly endother rates, thus ). Carbon sts used in ses of catal am to meth activated at . The cata e phases of e to sulphur
will then inc
ace area. It s the activity e poisons m reforming ur at a tem ed. The su e removed Van Beurd enon with c the methan ed in the fir Kirk-Othmer ses serious rmic reactio s increasing n formation the industr ytic deactiv ane ratio h t a cost and alyst must a the catalys r poisoning crease the c t may even y of the cat are arsen catalysts. mperature o lphur is pre from the den, 2004). catalytic SM ne is decom rst half of th r, 2001; Va s operationa
on, high act g the risk n on the n ry today (K vation is tha has to be m d this in turn also be cha sts used. N and carbon cost of hydr change the talyst (Kirk-ic, copper, If the feed of 800°C, it esent in the catalyst by MR. At the mposed and he reformer n Beurden, al problems tivity of the of carbon oble metal irk-Othmer, at the feed maintained. n increases nged every Noble metal n formation, rogen when e -, d t e y e d r s e n l d s y l , n
2.4 Dry
2.4.1 Pro
Cat of M syn dio the the Dry bec ste refo wid cat Sev refo hyd inc Methany Methan
ocess de
talytic Dry R Methane is nthesis gas xide is use e reformer is ermal energy CH4 + y reforming cause carbo am reform orming can dely in indu alyst surfac Figure 2 veral attem orming pro drogen to c rease the h nene Reform
escription
Reforming o an alternat or hydroge d as the ox s given by r y is needed CO2 ↔ 2CO is more att on dioxide ing (Van B also be us stry as ste ce. A proce 2.2: Bloc mpts have b cess, whic arbon mon hydrogen pming
n
of Methane tive to Cata en (Ullman xidising age reaction eq d for the refoO + 2H2 tractive than is consum Beurden, 2 sed in the d am reformi ess flow diag
ck flow diag been made h is discus oxide prese production o e or also kn lytic Steam n’s, 2006; ent instead uation (3) a orming proc ∆H n steam ref ed as a re 004). The dry reformin ng owing t gram is give ram of Cata e to improv ssed in the ent in the s or to vary t own as Cat Reforming Van Beurd of steam. and is more cess to take H0 298 = +247 forming from eactant and e same ca ng process. o the risk o en in Figure alytic Dry Re ve the cata e next sect synthesis ga he hydroge talytic Carb g of methan en, 2004). The reacti e endotherm e place. 7 kJ/mol m an enviro not produ atalysts tha But this p of high carb e 2.2 below. eforming of alyst’s perfo tion (Van B as has a ra en to carbo bon Dioxide e for the pr In this ca on that tak mic than (1) onmental po ced as is t at are used process is n bon deposi . Methane ormance us Beurden, 20 atio of 1:1. on monoxide Reforming roduction of ase, carbon es place in ) thus more (3) oint of view the case in d in steam not used as tion on the sed in this 004). The In order to e ratio, the g f n n e w n m s e s e o e
car gas
2.4.2 Inv
Re
Ext tha inve 199 The refo The 1 0 car 200 The me var me Figure 2.3 rbon monox s shift reactvestigatio
eforming
tensive rese at are used estigation a 96; Lemonid • Ni/θ-Al • Suppor • 5wt% N • FeO ca e catalysts orming of m e operating 00°C and f rbon dioxide 02; Gokon e e results of ethane with ried betwee entioned abo 3: Time-d xide can be ion.on into th
of Metha
earch has b in the Dry are (Roh, Ju dou & Vasa2O3; rted Rh; Ni/CaO-Al2O atalyst in mo were first p methane to s g temperatu flow rates b e is controll et al., 2002) f these inve carbon dio en 33.0% a ove. Sever dependent c and red converted i
he differen
ne Proce
been carried Reforming un, Baek & alos, 2002; GO3; and olten salt. pre-treated synthesis ga
ure for thes between 20 led at 1:1 ( ). estigations xide as the and 95.0% ral of these conversion ducible meta 10 into hydroge
nt catalys
ess
d out to att g of Methan Park, 2002 Gokon, Oku with hydrog as. se catalysts 0ml/min and Roh et al., seemed ve e oxidising a in the refo results are of CH4 over al oxides (b; en in shift csts that c
empt to imp ne Process 2; Zhang, T u, Kaneko & gen prior to s varied in d 200ml/min 2002; Zhan ery promisin agent. The ormer units given in Fig r Rh catalyst ; Zhang et a converters ban be use
prove the li . Several o Tsipouriari, & Tamaura, o loading in the range n. The fee ng et al., 19 ng for the e conversion s under the gure 2.3 and t with irredu al., 1996) by means ofed in the
fetime of th of the cata Efstathiou & 2002): to the reac e between ed ratio of m 996; Lemon industrial re ns that wer e operating d Figure 2.4 ucible metal f thewater-Dry
he catalysts lysts under & Verykios,ctors for the
600°C and methane to nidou et al., eforming of re achieved conditions 4 below. l oxides (a) -s r e d o , f d s
Figure 2.4 Fro spe
2.5 Non
The (Ull pro2.5.1 Pro
The ma car sho 4: The p om these in ent in the prn-catalyt
e gasificati lmann’s, 20 oduce synth CH4 +ocess de
e POX proc king use of rbon dioxide own in Figu performance (□ CH4:C vestigations resence of ttic Partia
on process 006). Dur esis gas, th 0.5O2 → COescription
cess can p f different t e to the reac re 2.5. e if the 5 wt% O2:H2O, ■ C s, it was als the catalystal Oxidati
s of heavy ring the PO his reaction O + 2H2n
produce a w types of fee ctor the rati% Ni/CaO-A CH4:CO2; Le so observed ts had a sig
ion of Me
y oils most OX Proces is shown in ∆H wide range edstock. A io can be va Al2O3 catalys monidou et d that the t nificant effeethane
t commonly ss the hydr n reaction e H0 298 = -37.5 of hydroge Also by the aried. A flo st is plotted t al., 2002) ime methan ect on the co y used in rocarbon re quation (4). 5 kJ/mol en-to-carbon addition of w diagram d against tem ne and carb onversion o the indust eacts with . (4) n monoxide steam or r of the POX mperature bon dioxide of methane. try is POX oxygen to e ratios, by recycling of X Process is e X o y f sFigure 2.5: The tem Hig tha the oxy The are ope stre the sch coo : Hydrog e complete mperatures
gman & Van at form in th ese two prod ygen in the e water that e not extens erating cond eam is give e reactor an hematic dia oler is given gen product gas pr combustio of 1350°C n der Burgt he reactor ducts, only reactor (Ull t is added to sive temper ditions is c en in Table nd needs to agram of th n in Figure 2 tion plant m roduction (H n of the hy to 1600°C t, 2003). H until all the will water a mann’s, 20 o the POX rature incre lose to 98.0 2.1 (Sogge o be remov he Texaco 2.6 following 12 making use o Higman & Va drocarbons and pressu Hydrogen a e hydrocar and carbon 06). process kee ases in the 0%. The c e et al., 199 ved before POX Reac g the table. of the Partia an der Burgt s, such as n ures as hig nd carbon bons have dioxide the
eps the tem reactor. T composition 94). Carbo the synthe tor with qu al Oxidation t, 2003) natural gas h as 80 ba monoxide a completely en be forme mperature lo The convers n of the fee n is produc esis gas ca uench coolin Process fo , takes plac ar (Sogge e are the ma y been con ed from the ow, ensuring sion of meth ed stream a ced as a by n be used ng and syn r synthesis ce between et al., 1994; in products nverted into e remaining g that there hane at the and product y-product in further. A nthesis gas n ; s o g e e t n A s
Table 2.1: Tem Pre Mo CH C2H C3H C4H CO CO H2O O2 H2 N2 CH Fi The and sat Gas co mperature ( essure (kPa olar flow rate H4 H6 H8 H10 O2 O O H3OH gure 2.6: e raw synth d pressure urated with omposition o (°C) a) e (kmol/h) Texaco P hesis gas le of 80 bar. water; app of the Partia F OX Reactor (Highman eaves the r The synt proximately al Oxidation eed gas co 331. 8537 2644 273. 121. 91.3 55.5 1.8 2651 2447 40.9 32.8 0.4 rs with quen & Van der B
reactor and thesis gas 2 kg H2O p of Methane mposition 7 7.0 4.4 2 9 3 5 8 .4 7.7 9 8 4 nch cooling Burgt, 2003) is cooled t enters the er Nm3 of s e (Sogge et a Prod and synthes to a tempe quench, w synthesis ga al., 1994) duct gas com
1204.8 8330.0 33.1 − − − 635.8 3310.4 3078.0 − 6601.6 32.8 −
sis gas coo
rature of ab where it is c as is added mposition 8 0 4 0 6 oler bout 250°C cooled and (Higman & C d &
Van for syn 200 The rem the gas rec Van
2.6 Plas
Hyd has pro can The bac nitr tec Ker 2.2 Table 2.2: Proces Nuclear fu Thermal pla Low press plasma n der Burgt the water-g nthesis gas 03). e cooled sy move any fi e gas is rem s is fed to th covered from n der Burgtsma-arc
drogen is m s already be oduction of n also be us e technical ck to the b rogen oxide hnology wa rker, 1984). below. Plasma ss usion asma sure a 1 0 t, 2003). Th gas-shift rea and is extr ynthesis ga nal traces o moved from he shift rea m the produ , 2003).Methane
mainly produ een discuss hydrogen f sed in Plasm application eginning of es from air as also used . Plasma p a processes Tempe (K > 1 00 1 000 – 100 – 1 0 000 – 100 0 his high wa action. The racted from s then ente of carbon fr the system ctors, wher uct gas of the Reform
uced from n sed in this c from natura ma-arc Refo of the Plas f the twent r, which fo d for the pro processes c s (Müller & K erature K) 00 000 – 10 000 000 (Gas) 000 (Electric 14 ter loading e quench re m the quenc ers a scrub rom the gas m. After the re more hyd he shift reaming
natural gas chapter. A al gas in the orming, dep sma-arc Re tieth centur orms the ba oduction of can be divid Kerker, 1984 El ach > 0.1 cal) 1 W makes the emoves the ch as black ber unit, w s before the e sulphur h drogen is pr actors with a using the c new proces e absence pending on t eformer Uni y, where it asis for theacetylene f ded into thr 4) lectrical hievement 100 MW – 10 MW W – 1 kW quenched e bulk of so water (Higm here it is s e sulphur th has been re roduced. F a final purity conventiona ss would be of a catalys the process its in the ch was used e productio from light h ree categor Energy p Chemica Heating Polymer Semicon corrode synthesis g olids (carbo man & Van
crubbed wi hat may be emoved, the Finally, the h y of 99.0% al SMR proc e advantage st, although s selection. hemical ind for the pro on of fertili ydrocarbon ies as show Applicatio production al reactions of gases risation, nductor tech (protective gas suitable n) from the n der Burgt, ith water to e present in e synthesis hydrogen is (Higman & cess, which eous for the h a catalyst ustry dates oduction of sers. The ns (Müller & wn in Table on s, hnology layers) e e o n s s & h e t s f e & e
The • • • Tem ele ind ma Hig dec pro A w of t The the al., Tw (co ope thro
2.6.1 Hü
2.6.1.1 O
In con rea syn ese plasma saving o necessa fossil fue achieve a soluti convent mperatures ctricity (Bro ependent o intained ov gh energy d creased, wh oducts (Brom wide range o the hydroca e plasma re e use of a c 2000). o types of ommercialise erating cond ough experüls Plasm
Operation o
1985, the nstructed th actors were nthesis gas a processes of high-qual ary for the cel basis; ment of hig on to the ional techno above 3 omberg et of chemical ver a wide ra density is c hich results mberg et al. of hydrocar arbons clos eformers ac atalyst or p f plasma re ed) and the ditions, the imental inve
ma-arc Fur
of the Plas
Union Ste he first 3×8 designed s was used have the fo lity fossil ra chemical re h temperatu technical ology. 000°C can al., 2000). l reaction ta ange of flow reated by t s in a short ., 2000). rbons can b se to 100.0 ccelerate the provide the eformers a e Glidarc (u general fun estigations.rnace/Tor
sma-arc F
eel Corpor MW Plasm to convert d as a redu ollowing adv w materials eaction canures and hig and ecolo n be gener The energ aking place w rates and the plasma t residence be used for 0% with the ermodynam energy nee are discuss nder develo nctioning of
rch
Furnace
ation of S a-arc Refor SASOL ga uctant to r vantages (M s: electricity be generat gh power d ogical probl rated in th gy that is g e, and optim d feed comp reformer a time for th the product e plasma re mically favou eded by end ed, namely opment) ref f the reform South Africa rming plant as (GASCO educe iron Müller & Ke y that is use ted by an in ensities; an lems that he Plasma-generated mal operati positions (B and the che he reactants tion of hydro eformer (Br urable chem dothermic re y the Hüls formers. At mers and thea and Che in South A OR gas) into oxide into rker, 1984) ed to produc nferior foss nd arise as a -arc Reform inside the ion conditio Bromberg et emical react s to be con ogen with c romberg et mical reactio eactions (B Plasma-ar ttention is g e conversio emische W Africa. The o synthesis o metallic ir : ce the heat il or a non-a result of mers using reformer is ons can be t al., 2000). tion time is nverted into conversions al., 2000). ons without Bromberg et rc Furnace given to the on achieved Werke Hülls plasma-arc s gas. The ron for the t -f g s e s o s . t t e e d s c e e
pro suc The arra Co Fig con Ge atta The ord con The The whe dist app oduction of ccessfully a e working angement, Figu re arrange ure 2.7 ab nversion of • the bur • the rota up con nerator ar ached slots e Plasma-a dinary carbo nnected to a e lower cylin e gas with ere the gas tributed ove proximately f direct red nd high che of the H generator a ure 2.7: ement: the bove. The the feed ga rning of the ation of the version. rc stabilisa form a gas arc Furnace on steel. T a direct cur ndrical pipe a pressure s whirl (vor er the entire 800 – 1 00 duced iron emical and t Hüls plasm arc stabilisa Hülls Plasm core arran e stabilisatio ases (Müller elbow in th elbow star ation: in the s eddy that e consists The upper c rrent potent e is the grou e of betwee rtex) is form e length of 00 hours for 16 . The Pl thermal effi ma-arc furn ation and eff
ma-arc Furn ngement of on of the r & Kerker, he pre-deter rting points e centrifuga stabilises th of a cylin cylindrical p tial of 7 to unded anod en 1 – 2 ba med, which the unit. T r a 1.2 kA a lasma-arc ciencies ha nace is di ficiency con ace (Müller the Hüls P arc in the 1984). Sta rmined area on the elec al chamber he arc (Müll ndrical wate pipe is the 8 kV (Mülle e of the furn arg enters t makes it a The lifetime and 8 MW P Reforming ave been ob iscussed, ntrol (Müller & Kerker, 1 Plasma-arc core is es bilisation is a; and ctrodes, to a r of the fur ler, 1982; M er-cooled p cathode, w er, 1982; M nace. the plasma almost poss of the ano Plasma-arc plant was btained. addressing r & Kerker, 1 984) Furnace is ssential for defined as achieve an rnace, the t Müller & Ker pipe constr which is ins Müller & Ker
a chamber t sible for the
de and the Furnace un s operated the core 1984). s shown in r maximum : even burn-tangentially rker, 1984). ucted from sulated and rker, 1984). tangentially e arc to be cathode is nit, owing to d e n m -y . m d . y e s o
the 198 sur Eff from cat of 2 cat cen
2.6.1.2 E
A P arc usi Fig refo (me Ker e hydrocarb 84). The m rface, which ficiency co m the arc to hode (Mülle 2 000°C and hode and a ntre of the axperimen
Plasma Refo c Furnaces ng steam. ure 2.8 pre orming of m ethane), an rker, 1984). on atmosp methane ga h extends th ontrol: App o the gas; t er & Kerker d 5 000°C ( anode. The arc in a fewtal investi
orming pilot were used The three esents a bl methane. T nd the oxid . here inside as that is cr he lifetime o roximately the remaini r, 1984). Th (Müller & Ke e temperatu millisecondigation of
t plant was d for the ex e types wer lock diagra The feed ga dising agen e the plasm racked dep of the cathod 80.0% to 9 ng energy he gas is h erker, 1984 ure in the f ds and the gthe Plasm
constructed xperimental re 6.2, 7.8 m of the p as to the ga nt could be ma chamber osits a thin de. 90.0% of th is lost owin eated in the ). Part of th furnace rea gas becomema-arc Fur
d in the 198 l investigati and 8 MW plasma refo as-mixing un either stea r (Müller, 1 n layer of c he energy ng to the wa e furnace to he gas form aches more es ionised (Mrnace
80s. Three ion of the W units (Mü rming plant nit consists am or carb 982; Müller arbon on th (power) is ater-cooled o a tempera ms the arc b than 15 00 Müller, 1982 types of Hü reforming o üller & Kert for the ex s mainly of bon dioxide r & Kerker, he cathode transferred anode and ature range between the 00°C in the 2). üls Plasma-of methane ker, 1984). xperimental natural gas e (Müller & e d d e e e -e l s &
By follo The cou liqu 22. gas The fina com Ker Figur making us owing test r e Union Ste uld be enlar uefaction of 0% CO, 3.0 s was mixe e reformed al composit mposition c rker, 1984). re 2.8: P se of the th results were eel Corpora rged to 8.5 f coal and w 0% CO2, 27 ed with stea gas left the ion of 70.0 consisted o . Plasma refor hree types o e obtained, ation used MW units. was used as 7.0% CH4 a am in a rati e Plasma-a % H2, 25.2 of more tha 18 rming pilot p of plasma g which are g three Plas The metha s feed gas w and 1.0% N2 o of 1:1 an arc Reforme 2% CO, 1.3 an 90.0% h plant (Mülle generator u given in Tab ma-arc Ref ane-rich ga with a comp 2 (Müller & K nd the mixe er Units at 3% CO2, 0.9 hydrogen a er & Kerker, units in the ble 2.3 on th former Unit s (SASOL g position (vo Kerker, 198 ed gas was a temperat 9% H2O an and carbon 1984) pilot plant he following ts of 7 MW gas) was p olume %) of 84). The m pre-heated ture of 1 10 nd 2.4% N2 n monoxide setup, the g page. W each that roduced by f 47.0% H2, ethane-rich d to 850°C. 00°C with a . The final e (Müller & e t y , h . a l &
Pla 198 Table 2.3: El P Ga Hy Exh CH4
-2.6.2 Gli
2.6.2.1 F
Exp con has stre asma-arc re 84; Kaske, K • The pr (close steam • In orde gas fro time of gas co • Desulp reformi Test re Measuring ectrical ach Plasma-arc s to plasma Thermal eff drogen/met haust gas te -content in eidarc (Gli
unctional
perimental nducted usi s at least tw eam (Czern eforming of Kerke & Mu rocess can to stoichiom in the produ er to achiev om the plas f the gas in mposition. phurisation ing process sults of the g range hievement Furnace a reforming fficiency thane ratio emperature exhaust gasiding arc)
working o
investigatio ng a bench wo divergin nichowski, 2 natural gas uller, 1986): be driven metric value uct gas, wh ve a high c sma genera n the reacto of natural s. plasma refo Un M Nm % mol/ ° s vo)
of the Glid
on of the c h-scale Glid ng knife-sha 2001). A sk s has the fo at very low es). This resich causes conversion ator must b or unit and t gas is unn orming pilot nit W m3/h % /mol C ol%
darc Plasm
conversion ing-arc Ref aped electro etch of the ollowing thr w ratios of sults in sma a high redu of methane be higher th the size of necessary w t plant (Müll 6.2 7 000 83 1.1 1 040 9.0ma Reform
of natural former (Cze odes and is Glidarc-Ι is ree advanta f oxidising a all amounts uction poten e in the rea han 1 000°Cthe unit are
when maki
ler & Kerker Results 7.8 6 300 85 1.26 1 160 3.6
mer
gas to syn ernichowski s immersed shown in F ages (Mülle agents to n of carbon d ntial of the g actor unit, t C. Both th e affected b ing use of r, 1984) s 8 0 6 1 0 1 3 nthesis gas , 2001). Th d in a fast-f Figure 2.9. r & Kerker, natural gas dioxide and gas. he exhaust he retention by the feed a plasma-8.0 300 92 .05 250 3.0 s has been he Glidarc-Ι flowing gas s d t n d -n Ι sA h arc (Cz pro (Cz pre 200
2.6.2.2 E
Dur the 1.1 exp Figure 2. high voltage c forms bet zernichowsk ocess, whic zernichowsk essure rang 01).xperimen
ring the exp e following c % propane perimental i .9: A sch e with a low tween the ki, 2001). ch means t ki, 2001). A ge for the s
