The use of reversed diffusion flames for the production of acetylene and ethylene from paraffin hydrocarbons

The use of reversed diffusion flames for the production of acetylene and ethylene from paraffin hydrocarbons

7he Use oj' Reversed Di/.lhsion FI.ames ./'or the lh'o&;ction oF Acett,[ene and Elhytene fi'om Pa;'a/]in .' + ,; ¢ ' " ;' , h' '+. ," " " .~...

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7he Use oj' Reversed Di/.lhsion FI.ames ./'or the lh'o&;ction oF Acett,[ene and Elhytene fi'om

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Experimental V.',tS arT;iD~od &£ .,..;hov..'~ It/, [ ~:::tr,: / . Air o r +,xv'RLql..,.'l~richutt ;.LIE ~.Va~ fed. int~, ;by D , r t :\ a n d hv, h',~carL.~or~ w a s intro+ d~,.:vd :tt f, m r ink:t~ p l a c v d s y m m e t r i c a l l y arottr~d A in lhc has,: <.}f t h e fl;Llllc tllt)e D. T h e gak+es w,,rc i:.:mted t<~ f o r m ;t r e v e r s e d flame by vh.ctricalLy he;.tti:k~ the plat{r, u m s p i r a l E . w h i c h wax slll,..~cqulmilv withdr~twll f r o m t h e flame. E,~.CL's.', hvk,s of t h e products leaving ltit" tlitlllO [II[)P w c r c w h h d r a w n a t low r a t e s it~to u::~ .~amph. tubt,s+ [,i F i ! , . ' t r c t thc di&lut,tcrs rd t h e lta.."ne r o b e a.tM [~,rt a r e s]t,,wR :t'::. 2 R ;Hld 2~ +vspectiveb,. I.,~.I. '[}te 1.'lllllIllt ~ tIfP, V r a t e s ~,f h w l r ( ~ c a r b o n a.tqd ,dr 1,,, I.' a,ul r, rc.4pcetiv~qv. Terms u s e d in rids p : q . ' r m a y t i l t h I., ,!,ql/.kd as f o l l o w s : Flu,

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work r{,porwtl bel.',s-, TILL'dilm'nl ratio of the "air' stream is dgiinc, d as lhc' rat[(~ . f / h e v~-:hmw t,f {:lib/era l<, t{lat t,i the ¢~x],,'~:,,i~ ilitl'tit]llC~.'(_l

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~eclion a~ XX

Figure" 1. I¢~.'cv.,'<,i .tl<~*m. ,ff, paratrt~. Wh~,n studying the effec)s ,,f tt:t,.s¢, variai,los, file ,"estfles may i,c expressed is} several ways: e,g. as ~he percentage of ;.tct,tyl
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of tim perctmt.a-t. C u l l _, hi t h . ntw ~as xxitll diluet~t ratio is shown i~l l"i~trrs .l and ft. T h e ;.t.lll"ltiltls/jet r:l~.Jo x','6ls 1'>'7 ',ll'l(] lhl. v c l o c k v rat;o abuut 22. Tl,t. III.+LxirIIuIII ]ll ]"i.~HYC 4

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d[luc~-H :trc .uivvn in Tafi5: 7. F o r compar+.~tb,,e [~m+'t~,-c.S, t h i s tai+lt: al.s+) (.rOtlt;I, ill~' det:ail~ of -,.ttnpl,,~ Iw.vin~ :he h i g h e s t :tcctylc'nc c o n t e n t iN,,',. ,';S :tt++'l 122) a n d thc,sc h.W,'iI+.g t h e h i g h e s t

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gases.

tilt. ;tl.'~.tvlon, ~ t , n t e n t t;) he e x p e c t e d w h e n a n ,,~si!v rvm~:,+,qble. H~H'l-Foar:titlg di[1.1enl: IF, Ilscd, ,~II~.YfL V:,!tl~'S rrl:W i)(' ttt~/ltl'~:~tre(.[ d i r e c t l y w i t h tl,<,~.' <,t,l:~it,.d from ,'xperirnents in which ,tx3'gt.ll.".;O';~.Itl tlliXtllr~'s We:To ll.%ed, : t n d w i t h

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these result~ expressed o:~ a lu<'l-frce ba~.i~. Sirnph~ calculation sl+tuws til~t w h ( : l l s t e ; l . i l l i s used, ;fie act:tyltme coatent of tlw F~rodl.lcl: g;~st:s .~h¢:uld be up t<:) ~t[+i~,llt 4 ' ~ p e r UC'Itt f,,r ltl+.'l.i'lillli ' and for propane up to n~'arly 8 F~'r o::z~t. "i'h,~ actual contents obtained (see Table 7) ar[,' I+.+~,+,'l+r than these: sanlples I!~ and l-ll a r ~ : C+.K;lll~.plt'> of high acetyler~e contents from m e t h a n e al~d propane flames respectively, and samples 120 and I42 repr<~sent high conversi-,ns ~for rri,athane and propane flames. For .;ainph: i~,,5, consid,.rable preheat was used. The use of steam as it diluent h:~..+ thu Iollowing effects : {i) carbon dioxide is increased (ii) acetylene is increased but not to ~,',e exCr:nt

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A I',. rticuLartv ,;lir~,ct e x a m p l e ,:~ the iatur. ;c('lh)ll ()~ the CO{ll])llSl}e);I :illd I;)yr~dylic rcaclio|T~ :, p r . v i d v d hy thv ,,qu;1E>ria w h i c h (:az~ be Set ill) !)cDvtc~l I)I()dllCtS try)ill I)I[: tWO pCOCL'SSLS, V i i I':iLf hq;llil)gellwkHlS %%~llL)r..~:19 r,J:lCIi{))l £[I%'O1VilI,K

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o.~titila.tt'd

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HlillJIIg +It,' pn+duct .~<'is,+ and wul~llhi,t: them. Nitro~ett 'Wa.~ IJ~,t'd ;.t.~ the t +el Itl,qt"~] rt,ft,rvllt'~' ~a.S I;OlllWCtili~ irq'lti{ tinalltilk'- b+ pcr('eFil;i~+' cot~lpti.aiticlll +,f tht' p r o d u c t .~ s{,s. 'J'h+' Vxlllv:~ O.t" the t,qtIilibrium Cnii.'.lltllt~ il'Dh~71h'tt (',)r;c... p,.md,'d wd~ [<> vahk,.4 vxpcci<.rl l<,r l l w ~'xp,'ri. +i:t.'nta] t,,:;tlpt,ratur,...~ f'{~r tlle~e I]arm,+ rt..[if:rtt,tt if]. OU£ pl*.;'~.']titi7 p:.ipi'r, l){,tail~ i,f lW,~ - i lil,,~-c cxp'rillltqit,~ arc given ill T a b l e <','. T,+DI+'

x.

,',.~l'l+#,'/.

];'quUiLhum

rl'ai-~l".h'

ill ll'7'+

/,.'P

Y'+ (I" + /,',%','e +,'+

]. ~ ,, t,',,

.tll,f I'

31. ',,l~

V,,I.

ll,ilii~'-, Ill II1~' llr.~l , ,~:'.r , ~ ,liq!liltll;lll i~ dl~i.ltied enil~hh' lilt' llalii,' c~l'~,'],,lu ~ l l i lh~, r~],LtiVely t~i~[i t'~dh','lllld~i, ql , 'r lit, llI,t~h' ,,C,:llrriiJD4 there, whih, iI~ lh,, .,,,,h,t c,t.,, I~l~ Ih,,llC ~,uly <~ccur~ ill

I,P,~.

~',,l~i'~'lill',lli,

,ll

,4 ..... :~l

pr,.Ie~
i,I

Pli~'

h,rl~,,.+l

.~la.l.llt,

I i ,'h'vat.d

I IHt %

lit lh, ~ ~a-~' ,,I l>lhrr;lry i L v l , , h l f l

i~r~,l,,~!l,

t{:, ~,

.il,

!~,~." 1~liliIL

ll,ilr:,~;i.

t'.ll

.

"~

II,

til

.[s]

~'.li

+ -¢'

It,.

I1

.[.<~]

.+

7',;+/l;.'..

]'l

N lt'l'jll{NI

'-1~1

.ll

',t ;q<'

it, ll ', ,13.tilt ,

.;' llllV

('.

IIH'

;,f; i*i ~

h'~llrr,l'iLrb+qJ< ~r,+,,l,l,I, i~, ,Hi'l r:J, lh~.l ,uTl,lylt.ile!

Jh'l

IH ,' ~t

UII~II1

.,

fact. ;~ c':iI~ph'h' ;~Ii.~]~."-7.: ,,I ,~ ;:h-, ',,uliplt' fFUIll tl rl'vtq>t'¢t i)r+it~,lllt, ~1, all! 2il'f[ ri~t,'-:l'li liAltlt' Wli.4 !H.i,h.' Jhll lh,, ~lnat] ,lii.!lililt' ,,P I.,il~ C,, hydroc;/rb+m7 iu
c. It

N iL~a

..

L

"2~'2

17
l l),'~

1 ~;

3,

365

1 ,'.i,~

1;4"1

1"II5

35

I



I ;q;7

P~ .

1 +I.17

I+ I

*,JI'i'J',lll<' l" /"~,d,[~ • !~ i,

The ('X['lerilnC, lll %;'i!.ti the highv,~t (Ig)'~l.'I'l Pal(' gave the highur tenl[wr~,ture and the hi~zh~-r acetylene content in the p r o d u c t .qa.~c'>. Othc'r equilibrla, which m a y Iw it:wdv,.d h~ the tlames includ+,~ the followir,.q:

C H , 7~,.~ .£ Ci, H ,I'

--I "

CO..+ CH, C+CO,

~

;L: .+. l i ,

+: i

,--'--I "If 1~

.... ....

[4] {s]

2C•) .+-.[I . . . . .

[6]

2C()

[+7]

....

For reaction 4, th,' c+mstar,t calculated ,fr¢mi ttic gas comj.~sltinns from b+nh lllcttlalU.. ~uid propane flames cnrresponds Io tezrqx'raturvs lit the range I 20rl ~ to 1 Of)0°C. I;or reaction 5, the value o[ the equitlbriuni crmsmnt obi~tinod ¢:orrestxmds to a temperature range' of 900" If, I800°C, white that for reactl/m 7 corresportds to a temperature range of 820 ~ to 9 {-)0+e C.~ TJw reason for the pronounced reduetio, iu flu, values ot the latter range is not known, but b~,th m a y corre,~pond to a reaction shift during coollng from the peak temperaturu, The value of the equilibrium constant for reaction 6 corresponds to a temp0rature range of 680 ° to 8SO°C Ior reversed methane flames and to 850" to 105O°C f~r reversed propane

)~t' t'Xll,

i ll'+l

ill ~}h' I,,lr

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/ ~ r t ' ; ~ , ~,

I

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ll',ll l.[++r!

, ', '- *,

9

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:17 7

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I

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II

15 fi.;t

t

I °, ~..,,inr~ hl
(<;ei.

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f 4i

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I(

Ibm ..,~ l.u ;~ the

I'~,'l'+ pl %'1.ir •

lt'~l~ lil HI,.~ aft' ~ q iMc~'rlli, rd. r,':~ctiHh 8 w]]i l 1', |IH' IIJ,~JH ILrilH;IQ,' ~WLRh,!S.~, t . i~.. fldi,,v,',,
r.:cnrri:l;: in I!ll'[fl;lll,' ~llIJ +'lhvlel.' I>)'F,4)'SiS, I'+W !+,'lh 11il'l~lltllt' a~M ]'~!'~q'a'l" ruw,l'..~'ci llarne% II!1t~111"111

tiVltl'I+l';Irtl,~H~,

I'lo-4"

l~i I I~i' illt~lll'

fl"lJll|

hf,I rJlLJt' !,~." Vii'Ill,' +,t thl.ir 131.lq'l llil,rljl::[ +.:l[,achv Imi .~],,, i,c" illtqJi'l'-(,>ill~ ~'ri@dlu'r~rjit: <]('c+,ll~pH~,il{,,iL Thi' ~'llltHrhi'l'l'Ili(; ¢Ii.'C+IPNflH:qliiIII i-~ [Jarlli'lllrill.v ililt>l>r.t;Hi[ for pr'+lp;um ~,~hh:h IllulvrTnq,~, i>yr, 4ysl~ af H4i~l.Jw;ly id~>.~l'l)

lOW

ht';ll

i<~lrlf)l.r;i.lllr+,s

lr-lh,,7 liri,h.al

' ;ill~j

il

i~:; +d+vi
~h;i.l,

con-

<~I Ihl. [irulianc will Pllh;lllO.b tim

(m,' r,f' It., raCist <,bviolas ditYvrenees between tiw revt,rsPd d i f f u s h m Ilamc, s u,~ed her(: and p n ' I n i x e d flame Sy.'4leHis L'4 tl'W large dlfferenee irt [he lilic/.:llt:.,4,qt:s r~f lhe rc';~ctkm zone.~ and

TII~' ~,-i~l~l[!l', ' l]II~ {l', ;{t

hiul, {,,t,q,,,~;,

]~l

,I

ll+ ~

I'.t ~h,' l,r, .~ IJl t'X]~,,[iIll,,lll-. [hi, liIIh' ;il, + l , l r ! 111 . ' c c,,tttpim',l ~xiltl IO ~ ~,,

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~t

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p.~. :, ",

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ll;ttm'

[I[ "~IILI t ] ] I]]t I ]+l,';lliX!'t]

,,T,I,'r

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.+<',.evl~.ll,. +"l;ll

tile]

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Tilt

ilat

;,;,, ill, I :'.t ...... , Th,' [+'~t~,'-J~,ll ,:rl.lla;3 rgit Iiq 1:~ I lit :[I,' ;ll,t',lI41]II': I,[,~.i,+l:-lV lid[

t: I l :::I

!l: .... 11,,'I Ir+ ~],'ltlr;mnht.l,: I], I q u a l i l v rd 11:, 'v, ,1','. ~t. lh, ['] ~]ltt~ k ~q':[ ~;~!'{{1 i" , , ! < . < b, d~,, ',mm,hl~. j,.1 r,d[,, whki~ p,tltlT,' l., ' . . . .

[ I '1[l'1" I[IU q]llallllllk" t+i ]IVIJF4,C;LFI~Iql ]hI:.4]ll.~ air ]:Pl,I l } [{ I iJitll)4 l` l'h," ~[i-;ll[~.[kHll+t{( • i,t ;, ~lt Ilk', l

I,:~ :', .~'.muhl', is I<+ !.qt.',. ;e ]ti:.'!tl',,' .libra
;ITlrtl:!tl-

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]", Ill;, :,Ill;ilL

[ ] ~ l tD''~'ll'rJ('iLil)+q[ fl'dil. 'trL. l/ll.:t, H<.H,.yllIIy

I P] ~

,i l'e+.t l'-~,'d ilalll<' C;Ill

I , .qld~i}L'<',[. .i llarllu h,~m l:,.In:.' il~ ?h~. t'+~l'tl+ ,d all h l v c r l v : l C, ml:, !~;I .... g [}JltllllLl]l ";tml;l]':illl..;,

IIIC

[lib{

[]~L[?I l"

"+i/C Ill

|11''

II.,rl:l i:- ,'<,tllr,,llcd I,v ; h r li?t
l]~t I II;I11]" at]{+,'+'<

i~ .-I:+,i,, ~:,, ~h+l+. :~ +],., rii..+I i~ ,',,:+r~,,':b,l+ wi+h :IIIIIII1114 '}I'I rat[,+. ,t [I+ v,']'iPl{] t [,~ r : t [ - [ ~ + i~ ~ ]'+[I,~"F +,i,l,da-~L I h , ' ~,lh,.I Illql,~rlarH v.~r'i.ttdc i-. 1he lLiillt.lll ralil~ irl tll~, 'air' >lr,,aIH. .\: tiff- P~ti~, i~ re,lu,'~,,l lhr I]l~Jl,' It,[}ll,,iT';Lllll{, WIH ~~[<'~']';['1~ I . kt.]lil.']l i~ ia','~mr:lldt, b~ : t o ' l y ] l l l , l ~'+ItlP,'nl[,,~i, l]'h[-, i}ir~v{l~k~III }Ill'rt'[l~.('~ flal qIIt'}i
l,)' I]1,. [[u.'l tidal a pl,,t ol ac,,.ty]en,.. <,.f ]~q'['t:{?['lt~L~..{dl. ,2(}I']VtpFS[()]L ~.Lg~tillS[

,][h>nl r'ath~ ha=q a lDaXirlltlltl w h i c h dr+(.,s rme '~C+'~If al 2'[.i"~,. "['hlls w]litc w h e n pIzre o x y g e n i~ ia,,H thv ira,duel: ~a~(.s ar~. not diluted a n d

Ih,,

Ilam, ' tvml~'raUrtrt'

i< hi;It~'r,

ttm

los~

of

:ltNdV]q I1,' ,,ri~iuaLty ['oFIIX..i IDII~-I ;|lso ]K' gngrttcr.

'lh~' ( ' m w . s f.;i~"ta in [.zqe~.re:e 4 am] 5 i]R:;~trate lid. l>.d.+. 'fh,. . D'rl' r"tlISi{.[I .O'11 h'!f[' ;Llad tha.L it is !hb, ,'xpr,,ssi,m r,f ;It:'U,'[t'Hq" crmtet,t {i,c. h~,b'D'~-Ic;l~ ,;~ ,'[iluvml l h a t rist.., as :t]t;m[ng.;jet [',l[h a Ill q fH; ~:'.~':':.

iu4i,';!t,.-Ih,' llll[

[

';]a''~'~t

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' [~

ill

1.1|~ ' ('ll ~'V US

II('L:t':-.I':.3FV. [l{'l~,'~l('t'l| dihllh)l'l JflXlll ci,~';l! prtl.'.;iTllil:y 'b.,

I } ' ~l a ; ~ r ] { . ' . I,'rn,4.'itl

Ill, I [[alHc.

V;du,., ,,i t~v.x,, var'i;.dd,.~ alf,., t tht. prudttcLimt ,< vthyl,.lu., carb~,l~ trl~m,~xi~h, arid. h y d r o R c n . [,IH {lit' IlXglC{ I{I!I{?]KL1]i.~FII ~'d the c[fects is .... [Itll'+{t?[ll d,,ut,thtI. "[4P~ l c++r,'ur, tratic)ns ,,f ,,xitl,.s +.[ ~'::ir?',+~ri fit the p r a d u c t ~ will d e p e n d htr::t,!y ,,u ,,,all,l:sfi,,t, >..au'tkm,..;, a n d t h e y will :t,[+~I~
rc~u::ti.:~ ;d ~.ttcce~.Hv(..ly i+)wcr l , ' m p e r a t u r e s . 'J'htl tlt}~vl~,qtl. , . /tIld +'LilZLDL' I,'(tallelltS h;tvt! 'b(fcll -.hu.v,-'la. f,,r ,,'v..rsed m.cth;.nrl,+ llames., to del-~,nd t'f~.,rl the' ,,,luilil,rhar!'~ {'Zlll;

+l'

<.Jail+,. If;

,~t the highv.,.t lc+Jqv..'raltlr..,~, ill tiRP tl,J.lrw. For l+r<,pan, , tiara:,.,:, flu.. ~'thvh.nc c
dvp,,ll,! tm ll;.t+l,., tcl'tt[:,.'r.ttllrc {~1{'l d i h l c n t ratio) itll([ I. ID' ~lIFtl t't'tlll'tll. Will lit' lillkcd tt, the ratc ,,1 c,,dir/~ ;l! l; P2eD,'HI'III'il ]IV ;'t.loEiy rittio a n d tl:~tqlt:- i~'t r~ti~. C o ncl ~ksion 1 h,, im~ i~k~.i,' vaLu.:, ai: d w rcsuh,,, r,..portud abc~vt. ]i,,~. Jr. lhc f~u~t that d w y ~h0w th;.Lt the rcvvr'scd IJicfllq'S

~Jl

]'qII",LT]]IF

hy[.[F<~t'.:LF~ItITLS

C;IT!.

bO

Coil.

tr,,Iled t<) ali~,w the i.~ot:ttion of a p p r e c i a b l u q u : m t i t i e s uf tmsaturat~.d h y d r o c : t r b o n s . I"rom tla" cx;m~i~t:tti~,tt of these results infcreltces r n a y i,c +lra.wfl :t.'; discussed a b o v e . ()witl~ 1o t]te c o m p l e x i t y ~ po:~sil.~h~ to {~nnul.'tte a c o m p l e t e /'~';l(.:li~')lt HICCt'I~LrLi.'z.I[I fOF {~lt.! [>recesses o c c u r r i n g

2N

J. h'. \=tim~ .m,l I) ;I. X,l.~,:

in reversed flamc.~. H,wcver, it ha~ bv~,n sh(:)wll that p vrr@si.~ ,.,rod eonll:mstir,m !)coo)me intimatch' linked m this process or p:~rikd c)mlbu~tiun ::,~M ca|lnOt })Lrst~pitr.'ttedJilts,h{';tl-pth)dHcin~ ;~Hd h(tat-.'~bs<.~rb[ag ,~y,.qc m$. This cot:clusf,,rx is .qiiZliJ;J,r to r.hat rc;tc]a.d l)v tht' ~tu.thot's c(mccrn g carl)on f,~rmat.ion i;t flames when .-.tress was 1,id <,n the r~,I,, {)) <,xygL'n and the preset~cc ,)f oxvgt.natcd inlet. mediates. The com~.)sition ()f tt)c gas irt[xttH't,% ~,i)tai~ed cannot I.)e related t~.~ tha~ predicted ])y a simpk, pymiyfic rcactkm sch,,~nIt.,:: invt.dvin~ acc).ylene as intermediate and carl)on as ondproduct. This is not unexpected, slncc in ~.l diffusion lit.tin(? (:olnl.)usti(~n rt'acii<:m~; dcpc'ndcnl upon a tarRe ,xygc)~ supply -c<',r Sillll.llt;rtll(> ously with carbot~ formation.

V,,I. 4

-rah'jtf//v ,.:/,'~mr./~'dCcd.

,,j ,]..~I.

ll~,r.~],,,,,! ,,f //u." I:.(.L'.[('...].

",,:4,o

dnd c~O'ri~',~" ~)ul lit:"
Rel'er~nt'(:~ I

~,(;I)P h.,l,!:

#:~'lirt~

J.:..[.

i'~

t+,] Y.Xml:l:.

",,".~ Y , , r k ,

,:*,

l+i,=,'I

)~)~,~

I~. l ] . f'Jti:

",vm/'.,.',im+t