Methanation on Nickel-Alumina Catalyst Anchal Jatale Abstract

Although all the Group VIII metals are catalytically active in the hydrogenation of carbon oxides to form methane ("methanation"), nic el remains the favored catalyst for the reaction by virtue of its life, high activity, selectivity to!ards methane formation in preference to other hydrocarbons, and it"s comparatively lo! cost# $upported nic el catalysts are preferred on account of their thermal and mechanical stability# In this paper, %i&Al'() catalyst is discussed at length and subse*uently its effect on methanation reaction along !ith the mechanism is also explained# +,- of %i&alumina catalysts gives evidence that they have ' sites for reaction, surface %i( and a form of %iAl'(.#/ethanation of 0( proceeds via dissociation on nic el catalyst and the surface carbon species thus formed are hydrogenated to methane# 0( ' methanation proceeds via conversion of 0(' to 0( via the reverse !ater gas shift reaction follo!ed by 0( methanation#

Introduction:
-eaction bet!een hydrogen and carbon monoxide can lead to a variety of useful products depending on reaction conditions, ratio of the gases in the feed and the type of catalyst# Among the reactions of greatest interest are those producing methane, paraffins, alcohols, especially methanol, and olefins# /ethane from hydrogen and carbon monoxide ("methanation") is receiving particular attention because it is an essential step in one process for the manufacture of substitute natural gas ($%G) gas from coal# /ethanation is practiced also for another purpose# In the manufacture of ammonia by the catalytic reaction of hydrogen and nitrogen the content of oxides of carbon in the synthesis gas must be reduced to a very lo! level to prevent catalyst poisoning# +o effect this, after conversion of carbon monoxide to carbon dioxide by !ater gas shift and absorption of the latter, residual oxides of carbon are removed by methanation, a simple and relatively inexpensive process# +he methane produced is inert to ammonia synthesis catalysts#

+he reaction bet!een carbon monoxide and hydrogen over a nic el catalyst to produce methane !as first reported by $abatier and $enderens (123', 1234) in the early part of this century, and since then, despite much research, nic el had continued as the ma5or catalyst for the reaction because of its high activity, selectivity for methane formation and lo! cost#

Catalyst Preparation
$upported nic el catalysts are !idely used in a number of industrial processes such as hydrogenation, methanation# +he activity of the supported catalysts is strongly dependent on the preparation method used and on the choice of reagents and support# +here are many methods !hich can be used to prepare the catalyst depending upon the re*uirements# +here are various methods of preparation of %i&Al '() catalyst# +!o most important methods !ill be discussed in brief6 Wet Impregnation method6 +he ,retreated 78alumina is added to the solution of %i(%())' #9:'( in deminerali;ed !ater and the mixture is dried in desiccator for 9 hours# +hen through a programmed increase in temperature from 113 o0 to 433 o0 , the mixture is calcined at 433o0 for 9 hours# Instead of using %ic el nitrate, %ic el acetate can also be used# Coprecipitation method: +he coprecipitated %i&A1'() catalysts !ere prepared by co8precipitation of %i (%())' #9:'( and Al (%())) in an a*ueous solution !ith %a(: at ambient temperature# +he precipitates, matured for '. hrs, !ere vacuum filtered and subse*uently !ashed until free of nitrate# +he air dried samples (134<0, .= h) !ere ground in an agate mortar and the po!ders obtained !ere air dried again (134<0, 9 h) >1?# Co-crystallization Method: %ic el (II) nitrate hexahydrate in de8ioni;ed !ater !as added, !ith stirring, to a gelatinous solution of alumina in nitric acid previously prepared by the slo! dissolution of alumina in concentrated nitric acid# +he resultant solution !as neutrali;ed (@inal p: A), !ith continuous stirring, by the careful drop8 !ise addition of ammonia# After standing overnight !ater !as slo!ly removed (.= h) on a rotary evaporator and the resulting solid dried in a vacuum oven >'?#

Atomic Layer pita!y Method: Vapori;ed %ic el acetylacetonate !as chemisorbed on a porous alumina support, and the produced surface complex !as then air treated to remove the ligand residues >)?# %i8alumina catalysts are also synthesi;ed by one-step sol-gel method using micelle complex comprising lauric acid and nic el ion as a template !ith metal source and using aluminum sec8butoxide as an aluminum source >.?#

Mathematical Modeling o" Impregnation Process #$%: -ecent studies have tried to *uantify the impregnation method for preparation of %i&Al'()# +he hypotheses adopted to solve the mathematical model !ere based on the one8dimensional single8pore model !ith cylindrical geometry, concentration gradient only in the axial direction of the pore (i#e# radial gradients inside the pellet) and time8 dependent plug8flo! velocity of the penetrating li*uid# +he partial differential e*uation corresponding to mass balance is6
c c 'c + vp = D ' BBBBBBBBBBBBBB# (1) t z z

+he effect of the concentration gradient close to the pore !all is explained by the mechanisms of impregnant removal of the solution# +hus, a term describing the impregnating removal rate of system V(c, ) is added to C*# (1)6
c c 'c + vp = D ' + V (c, ) BBBBBB## (') t z z

+o non dimensionali;e C*# ('), the follo!ing definitions are used6

= z , L

c t v pt Dt ,= ,= ' , u= co tL L L

t +u = L V (co , ) (@irst term of -:$ is neglected since D EE1) cO

Fith6 G (3, H) I 1 and G(3,3) I 1 After some algebraic steps, !e arrive at follo!ing t!o e*uations6
1 + 1& ' = K ' K L (1 )

 K = K L (1 )

!here J I ' mtK&r,

L I 'cs&rMco,

JK I JK" co

+hese three variables describe the impregnation process is observed6 K, reduced mass transfer coefficientN , relative capacity of adsorption of the pore !all and KL, adsorption e*uilibrium constant# +able 1 sho!s the values of these constants obtained experimentally# Catalyst Characterization: Wet chemical analysis: +he amount of nic el in the oxide form is determined by acidic extraction of nic el from the sample, follo!ed by dimethylglyoxime precipitation >9?# Total surface area: +he surface area is determined by dynamic lo! temperature nitrogen adsorption in helium as a carrier# +he data !ere interpreted using the OC+ e*uation and an effective %' cross8sectional area of 19#' nm' >9?# Porosity: +he total porosity (P) !as calculated from apparent (a) and true (d) densities, P (Q) I &' -a(d) 133, determined pycnometrically using mercury and ben;ene vapors as !or ing fluids >9?# Pore size distribution: ,ore si;e distribution is determined by mercury porosimetry, pressure range up to 1433 bars >9?# X-ray diffraction: Identification of crystalline compounds and determination of average crystallite si;e are carried out by R8ray diffraction (R-S) using a G#C# diffractometer !ith %i filter and 0uJD radiation# +he mean crystallite si;e (S) is related to the pure R8ray broadening (T) by the $cherrer formula S I JU&T cosV +he si;e (S) is defined as (volume) 1&) leading to a value J I 3#24 !hen T is defined as the half8maximum line!idth# +he half8maximum line!idth from %i( (''3) reflecting plane is employed for the alumina8supported #+he instrumental line broadening is determined from the half8maximum line!idth of a single silicon crystal >9?#

In Fig. 1 R-S diffractograms of catalysts and y8A1'3) are sho!n# +he diffractogram of the 14Q catalyst sho!s strong %i( lines at 'V values of )A#), .)#) and 9'#2W) confirming a presence of XfreeW nic el oxide# @or both catalysts no distinct nic el aluminate lines are observed# (n the diffractogram of the reduced 4Q catalyst one can observe lines characteristic for nic el crystallites at '=I ..#4 and 41#=W >A?# SE studies: +he catalysts are examined in a scanning electron microscope !ith

resolution of about 4338 1333 A# +he samples are coated !ith gold to about 1338'33 A thic ness prior to observation(@ig ',),.,4 ) >9? # *emperature Programmed +eduction &*P+): +,- determines the number of reducible species present in the catalyst and reveals the temperature at !hich the reduction occurs# +,- analysis begins by flo!ing analysis gas (typically hydrogen in an inert carrier gas such as nitrogen or argon#) over the sample, usually at ambient temperature# Fhile the gas is flo!ingN the temperature of the sample is increased linearly !ith time >=?# (T J min81) +he -ate of reaction is monitored6 1# Oy measuring concentration or pressure changes in the gas phase (reactants or products)# '# Oy observing !eight changes of the solid through a micrometer microscope# +,- had advantages over other characteri;ation techni*ues, such as6 It is highly sensitive and does not depend on any specific property of the solid other than its reducibility# %on destructive, as solid does not have to be dissolved# Cven the condition that the solid must be reducible is not mandatory# (better than spectroscopic and R8ray techni*ues)# +he apparatus is inexpensive !hen compared to R ray and spectroscopic techni*ues# -obust and minimal maintenance re*uired# @ig 9 , sho!s +,- of %i&Al'() made from three different precursors %ic el nitrate, %ic el 0hloride and acetone solution of %ic el8acetylacetonate (%iAA)# %i (%())'

catalyst is easily reduced and sho!s the first pea in the '43Y)43o0 range, !hereas for %i0l and %iAA catalysts the first pea occurs at ca# .330# +he three catalysts also demonstrate t!o other pea s of :' upta e at ca# 9330 and A430# +he first +,- pea corresponds to the reduction of %i(# +he t!o latter pea s are due to the reduction of nic el aluminate# $o it is confirmed from the +,- profiles that %i&alumina catalysts have ' sites for reaction, surface %i( and a form of %iAl'(.#(n reduction of surface %i( !ill form nic el crystallites, but reduction of %i'Z ions in octahedral sites in the alumina lattice !ill form %i atoms surrounded by oxygens of he alumina lattice# +hus there appear t!o forms of reduced nic el on %i&Al'() catalysts >2?# (Fig 7) ,ispersion o" Ni- on .-Al/-0: Sispersion of %i(& 78Al'() system has been extensively investigated and the state of the dispersed nic el oxide has been proposed# %i'Z ions preferentially incorporated into the tetrahedral surface vacancies at lo! %i( loadings, and both the tetrahedral and octahedral nic el oxide species !ere present at the high %i( loadings# $o, t!o inds of surface vacant sites e#g# octahedral and tetrahedral sites exist on the exposed plane of 78Al'() >13?# (@ig = ) Methanation :ydrogenation of 0( and 0(' to methane on nic el catalysts are important reaction occurring in purification of ammonia feeds and methanation of coal derived gas# Ooth reactions are also of interest in the production of process heat or po!er from reclaimable !aste streams containing dilute carbon oxides or from nuclear reactor steam reformed 0(8:' streams as part of a so called Xheat pipelinesW# +he reactions involved are 0( Z ):' 0:. Z :'( 0(' Z .:' 0:. Z :'( [:I 8.2 cal&mol [:I 8)2 cal&mol

/ethanation of 0( and 0(' occurs effectively on various transition metal catalysts# It !as observed that 0( is dissociated on nic el catalyst in methanation of 0( and the surface carbon species thus formed are hydrogenated to methane# 0(' methanation mechanism could be categori;ed into t!o (i) conversion of 0(' to 0( via the reverse !ater gas shift reaction follo!ed by 0( methanation and (ii) direct hydrogenation of

0(' to methane by a mechanism distinct from 0( methanation# Out various studies sho!ed that the first mechanism may be correct and that 0(' methanation may proceed via 0o' dissociation to 0( and atomic oxygen follo!ed by further dissociation to 0( to carbon intermediate !hich is hydrogenated to methane >11?# C- Methanation Mechanism :'(g) Z' $ ' :8$ 0((g) Z $ 0(8$ (') 0(8$ Z$ 08$ Z (8$ 08$ Z :8$ 0:8$ Z $ 0:8$ Z :8$ 0:'8$ Z $ 0:'8$ Z:8$ 0:)8$ Z $ 0:)8$ Z:8$ 0:.8$ Z $ 0:.8$ 0:.(g) Z$ (8$ Z:8$ (:8$ Z$ (:8$ Z :8$ :'(8$ Z$ :'(8$ :'((g) Z$ C-/ Methanation Mechanism (1) :'(g) Z' $ ' :8$ 0(' Z ' $ 0(8$ Z(8$ 0(8$ 0((g) Z $ ()) 0(8$ Z$ 08$ Z (8$ (.) 08$ Z :8$ 0:8$ Z $ (4) 0:8$ Z :8$ 0:'8$ Z $ (9) (A) (=) (2) (13) (11) 0:'8$ Z:8$ 0:)8$ Z $ 0:)8$ Z:8$ 0:.8$ Z $ 0:.8$ 0:.(g) Z$ (8$ Z:8$ (:8$ Z$ (:8$ Z :8$ :'(8$ Z$ :'(8$ :'((g) Z$

(1) (') ()) (.) (4) (9) (A) (=) (2) (13) (11) (1')

%o! based on this mechanism given above !e can derive many different langmuir8 :insel!!ood expressions# @or example consider mechanism of 0(' methanation 1) Assuming 0(' adsorption to be the rate determining step !e get 6

r=

k ' L' PCO ' (1 + K 1 H ' ) ' k1 L' PH ' (1 + K 1 PCO '
1& ' 1& ' ' 1& ' 1& '

') Assuming :' adsorption to be rate determining step !e get6

r=
:ere, rIrate

KItotal concentration of surface sites# ,:'Ipartial pressure of hydrogen ,0('Ipartial pressure of 0arbon di8oxide

$imilarly one can get lots of rate expressions considering other steps as rate determining steps# -ecent studies sho! that there exist mechanisms in !hich both the sites present on %i&Al'() play different role# Ket this t!o sites be site 1 (M) and site ' (\)# (i) 0( /ethanation6

0(M 3#4 :' Z M :M

0( Z M 0(M Z \ (M Z 0\ 0\ Z ' :' 0:. Z \ (M Z :' :'( Z M

(1) (') ()) (rate determining step) (.) (fast) (4) (fast)

In this mechanism 0( molecules compete !ith hydrogen atoms for type 1 sites (M) at the nic el surface and 0( dissociates to a type ' site (\), !hich are al!ays free at the conditions used during the study# -eaction ) is the rate determining step, reactions 1 and ' are so fast that 0(M and :M are in e*uilibrium !ith the gas8phase species 0( and :', and reactions . and 4 are so fast that the coverages of 0\ and (M are negligible >1'?# (ii) 0(' methanation 6 :' Z 'M ':M 0(' Z '\ (0\ Z (\ ':M Z (0\ :'( Z 'A" Z 0A ':M Z (\ :'( Z'M Z \ :' Z 0\ :'0\ :' Z :'0\ 0:. Z\ (1) (') ()) (.) (4) (9)

+he rate expression is derived using some assumption li e steps(1) and (') are much slo!er than steps())8(9) #+hus !e can say that the reaction is on18half order in both reactants, provided N(i)the coverage is relatively lo! and (ii) slo! dissociation follo!s rapid adsorption# ""ect o" addition o" promoters on Ni( Al/-0 "or methanation reaction #'0% -ecent studies have characteri;ed the effect of cerium, lanthanum and ;irconium on nic el&alumina catalysts !ith respect to 0( and 0( ' hydrogenation# +he

examinations of (' and 0( adsorption demonstrate that the promoters decrease rate of adsorption but do not affect *uantity of the adsorption# (n the other side, the promoters do not affect +, desorption of hydrogen and +, hydrogenation of pre8 adsorbed oxygen !hich indicates that the promoters do not modify the state of hydrogen and oxygen adsorbed on nic el# @ig 2, sho!s that in contrary to ;irconium, cerium and lanthanum considerably increase conversion of 0( and 0(' to methane 1ighly selecti2e methanation #'3%: In the present, selective methanation became attractive in order to reduce the 0( content to less than 133 ppm in hydrogen8rich reforming gases for fuel cell applications# (ne !ay to do highly selective methanation is to use micro channel reactors4 $tudies sho!ed that a -u&Al'() and -u&$i(' catalyst !ere successfully applied to micro reactors to reduce the 0( content by methanation in a model gas mixture that contains the ma5or product components of a natural gas reformer or of a partial oxidi;er used for hydrogen production# -ther catalysts "or methanation: As methanation is one of the very important reactions there are various other catalysts !hich can be used for hydrogenation of 0o and 0(' in effective manner# @e! of them are6 ': Ni(5i-/ : +he catalyst !as obtained by contacting silica !ith a solution of nic el nitrate hexamine# +he solid !as dried, then crushed to po!der, and reduced at 943 ]0 for 14 h at ']0&min heating rate in flo!ing hydrogen (4 liters &h) >14?# /: 6ltra"ine Ni &II) 7errite Catalysts6 prepared by %i'Z substitution for @e'Z in magnetite# %i (II) ferrites !ere prepared by t!o different methods >19?6 (i) 0oprecipitation of %i', @e', and @e)Z at 930 follo!ed by heating to )330 (ii) (xidation of a*ueous suspension of @e'Z and %i'Z hydroxides at 940 0: Ni( +1A-Al/-0: -ice hus ash and aluminum nitrate !ere used in preparation of rice hus ash8alumina support# +hen %ic el nitrate is used and the catalyst !ith desired loading is prepared using !et impregnation >1A?#

3: Ni-Ca aluminate on 8-A'/90 hydrate: A blend of po!dered nic el oxide, calcium aluminate and alumina hydrate !as !ater8sprayed and 0atalyst and rolled to form pellets, !hich !ere calcined to a highly active catalyst# +here exist a !ide range of catalysts for methanation# /any transition metals li e %ic el, Iron, and 0obalt are also active catalysts but %i catalysts are more selective and efficient >14?#

+e"erences: 1# :aber^ J#, Oloc ,J#:#, Selmon, O#, ,ure _ Appl# 0hem#, Vol# 9A, %os =&2, 1224 1'4A8 1)39 '# Savid Jac son , $#, Fillis Janice, Jelly Gordon J#, /cKellan Gavin S#, Febb Geo#, /ather $ue, /oyes, -# O, $ydney $impson, Fells, ,# O#, Fhyman -obin#, ,hys# 0hem# 0hem# ,hys#, 1222, 1, '4A)8'4=3 )# Kindblad /arina, ,eter Kindfors Kars, $untola +uomo, 0atalysis Ketters 'A (122.) )')8))9 .# Jrompiec, $#, /ro!iec8Oia`o, J#, $ util , J#, Su o!ic; , A#, ,a5a; , K#, Jar;e;bs i , A#O#, Journal of %on80rystalline $olids )14 ,('33)) '2Aa)3) 5. Assaf,C#/#, Jesus K#0# Assaf,J#/. 0hemical Cngineering Journal 2., ('33)) 2)a2= 9# Gavalas, G# -#, ,hichit ul, 0#, Voec s, G# C#, Journal of 0atalysis ==, (12=.), 4.89. A# -yn o!s i J#/, ,ary5c;a , +#, Keni /#, Applied 0atalysis A6 General, 139 (122)) A)8=' =# Jones, A#, /c%icol, O# S#, +emperature ,rogrammed reduction for solid materials 0haracteri;ation,Se er,12=9 2# Oecerra, A# /#, 0astro8Kuna, A# C#, J# 0hil# 0hem# $oc#, 43, % ' ('334), .948.92 13# Fang Jun, Song Kin, buhai :u, cheng Guishan, cheng :u, bi 0hen Journal of $olid $tate 0hemistry 14A, ('331) 'A.8'=' 11# Featherbee,G#S# ,Oartholome!,0#:#,J# 0atal# AA, (12='), .938.A' 1'# $ehested, Jens, Sahl $dren, Jacobsen Joachim, -ostrup8%ielsen Jens -#, J# ,hys# 0hem# O ('334), 132, '.)'8'.)= 1)# cna ,K#, $to`ec i, J#, cielines i, J# , 0atalysis +oday 131, ('334) 94aA1 1.# Gofr e ,(#, ,feifer,,#, $chubert, J#, 0atalysis +oday 113 ,('334) 1)'a1)2 14# :andboo of methanation catalyst, G# :# Fatson, @ebruary 12=3, lCA 0oal -esearch, Kondon 19# +su5i, /#, Jodama, + #,boshida, +#, Jitayama, b#, +amaura,b#, Journal of 0atalysis 19., (1229)# )14a)'1 1A# 0hang,@#F#, Juo,/#$#, +say,/#+#, :sieh,/#0#, Applied 0atalysis A6 General '.A ('33)) )32a)'3

APP N,I: *able ':

7ig4 ': :+, patterns "or &a) Ni-; &b) '$< Ni-( .-Al/-0 &c) $< Ni-( .-Al/-0; &d) $< Ni-(-Al/-0 catalyst reduced in the *P+ process &b=; c=; d=: subtracted :+, patterns)> &?) .-Al/-0

7ig4 /4 5canning electron micrograph o" @A'/90 at ! /9;9994

7ig4 04 5canning electron micrograph o" Ni-(A&-A'/90-B$9 at !$9994

7ig4 34 5canning electron micrograph o" Ni-(@A'/90-?$9 at !$9994

7ig $4 5canning electron micrograph o" Ni-(a-A'/90-'9$9 at C/9;9994

7ig D: *P+ pro"iles4 a) NiAl/-3; b) Ni-; c) Ni-(Al/-0 catalyst precursor&'940< Ni)

7ig B: *P+ pro"iles o" Ni catalyst "rom di""erent precursors4&Ni B4B<)

7ig ?: *entati2e model o" the sur"ace-dispersed nickel o!ide species "ormed on the &''9) plane o" .-Al/-0 support @ith a Ni/E ion incorporating in a tetrahedral 2acant site4

7ig4 F4 Acti2ity o" un-promoted and Ce-; La- and Gr-promoted catalysts: &A) C- hydrogenation and &H) C-/ hydrogenation4