REACTOARE CHIMICE. cu curgere piston (ideala) (Plug Flow Reactor PFR) cu amestecare completa (Mixed Flow Reactor MFR) de tip batch (autoclava)
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1 RETORE HIMIE cu curgere pisto (idel (Plug Flow Rector PFR cu mestecre complet (Mied Flow Rector MFR de tip btch (utoclv Rectorul cu curgere idel Tote prticulele se deplsez itr-o directie de- lugul rectorului, precum u pisto, fr se mestec cu cele cre le preced su cre urmez i flu. Tote prticulele se crcterizez pri celsi timp de rezidet: τ = /Q = H/w i cre = volumul rectorului (m 3 ; Q = debitul volumic de limetre (m 3 /s; H = iltime rectorului (m; w = vitez liir de curgere mestecului de rectie (m/s. ocetrtiile recttilor si, deci, vitez de rectie scd de- lugul rectorului. Grdul de coversie creste pe lugime rectorului. Tempertur se modific de- lugul rectorului: operez fie i regim dibtic fie i regim politermic. The plug-flow rector my be operted i the differetil or the itegrl mode. Differetil flow rectors re typiclly used for the determitio of the kietics of ctlytic rectios. rector is operted s differetil rector if it is rector with very smll volume d low coversio. The differetil rector is ssumed to be grdietless, tht is, hvig uiform cocetrtio throughout the rector, d hece the observed rte is tht correspodig to the cocetrtio. I the differetil mode (smll coversio the whole ctlyst c be cosidered to be eposed to the sme cocetrtio of rectts. The ifluece of products is geerlly wek, ecept whe the ctlyst is etremely sesitive to oe prticulr product. The plug-flow rector opertig i the differetil mode is the simplest d most relible wy of determiig the order of rectio with respect to rectts d products. This my be chieved by systemtic vritio i the iitil cocetrtio of the rectts. I the differetil mode further mjor dvtges re: (i it provides good kietic dt becuse of the short holdup (ii the low coversio helps miimize het d mss trsfer problems (iii the ifluece of prmeters such s temperture, pressure d cocetrtio c be studied seprtely. The mjor disdvtges of usig plug-flow rector i the differetil mode re: (i t the smll coversios required lrge errors i lysis c occur (ii the techique is time-cosumig i kietic mesuremets (iii high gs velocities my be required to keep coversios low. The itegrl plug-flow rector hs the dvtge tht lrge coversios fcilitte lysis d provide more ccurte kietic dt. Disdvtges of the itegrl mode re problems i mitiig isotherml opertio, the eistece of cocetrtio grdiets, d possible het d mss trsfer limittios. Furthermore, ccurte kietic lysis of itegrl dt is geerlly more difficult th for differetil oes.
2 I geerl i lbortory rector, i cotrst to idustril rector, the depth of the ctlyst bed is smll, so tht the rector hs behvior itermedite betwee tht of plug-flow d bck-mied flow rector. Ecuti crcteristic PFR Fie u elemet de volum d di rectorul cu curgere idel i cre re loc recti D.
3 Iltime corespuztore este dh, ir timpul de rezidet este dτ. Dc l itrre i elemetul de volum d grdul de coversie este, ctitte de produs D i mestecul de rectie, G, cocetrti produsului D, D, ir cocetrti recttului,, l iesire ceste vor fi + d, G + dg, D + d D si, respectiv, d. itez procesului pote fi descris de oricre ditre rportele: dg ; d d d ; ; d d d ; etc. d osiderd procesul di elemetul de volum d cre re loc i timpul dτ, ctitte de rectt itrt este: Gi Q ( titte de rectt iesit di elemetul de volum (dimiure ctittii de rectt este dt de ecuti: Gout Gdec Q [ ( ] d I celsi timp, ctitte de rectt iitil cosumt i rectie se scrie: G r ud Ecuti biltului de mterile pe elemetul de volum d v fi: Gi Gout G r dic Q ( Q [ ( d] ud cre se reduce l Q d ud Pri itegrre cestei ecutii se obtie biltul de mterile pe itreg rectorul: d d Q u dic d Q u Ultim reltie reprezit ecuti crcteristic rectorului cu curgere idel. Dc cietic rectiei este cuoscut, utilizd ecuti crcteristic se pote determi timpul de rezidet si poi volumul rectorului petru u debit de limetre si u grd de coversie dte, su cpcitte de productie rectorului, Q /τ, petru u volum l recorului si u grd de coversie dte etc. Petru recti ireversibil D, ecuti crcteristic se scrie: d d d Q k k ( k ( Dc recti este de ordiul, i.e. =, ecuti crcteristic devie: k k Dc recti este de ordiul, i.e. =, tuci
4 k d k l P ici s- cosidert c recti u re loc cu modificre de volum. Dc recti este isotit de o modificre de volum, volumul corespuztor uui grd de coversie este ( ude β = modificre reltiv volumului sistemului cd coversi se modific de l l. This prmeter tkes ito ccout the presece of ierts, the use of ostoichiometric qutities of rectts, d the presece of oe or more of the rectio products i the origil system. Dt fiid c P RT, ude = r. totl de moli di sistem, tuci I ceste coditii, cocetrti corespuztore uui grd de coversie se scrie si, tid sem c ( tuci ( ( ir ecuti crcteristic devie: d k k d k d Q ( ( ( ( Petru o rectie de ordi zero k ir petru o rectie de ordiul = ] l( [( k I czul geerl corespuztor uei rectii de form: ( ( ( g g g dd b d b dc este recttul limittiv, tuci sut vlbile urmtorele ecutii: b
5 b Petru recttul si produsul D: b D D d Dc recti se relizez i prezet uui iert I: I I Dc se modific tt tempertur ct si presiue i timpul rectiei: PT P T PT PT su P T PT P T PT b P T PT d D D U rector rel operez itotdeu i coditii de mestecre icomplet, is i uele rectore idustrile grdul de mestecre este tt de sczut ict se pote folosi petru clculele tehice modelul cu curgere idel. Eemple: Rectore ctlitice tubulre similre schimbtorelor de cldur de tip tev i tev, cu ctliztorul i tevi su i sptiul itertubulr, petru rectii i fz gz.
6 Rectore tubulre petru rectii i fz lichid cu rport mre H/d, utilizte i sitez orgic idustril. oloe cu umplutur Sobe de sitez i fz omoge (E. Hl Rectorul cu mestecre complet Recttii sut supusi uei gitri itese. Prticulele de rectti itroduse i rector sut imedit mestecte cu prticulele dej eistete => distributie uiform i volumul prtului. ribilele procesului: cocetrtii, grd de coversie, vitez de rectie tig imedit vlore fil, costt de- lugul rectorului. Operez itotdeu i coditii izoterme. Timpul mediu de rezidet l prticulelor di mestecul de rectie este: τ = /Q = H/w Timpul de rezidet petru o prticul idividul pote vri itre si ifiit.
7 Ecuti crcteristic se deduce di biltul de mterile pe itreg rectorul (itruct cocetrti recttului este costt pe itreg volumul rectorului. stfel, petru recttul se pote scrie: titte itrt Gi Q titte iesit Gout Q ( titte cosumt i rectie G r u ir Gi Gout G r dic Q Q ( u su Q u ce coduce l Q u
8 ce reprezit ecuti crcteristic rectorului cu mestecre perfect. Tid sem c grdul de coversie petru rectii fr modificre de volum se scrie: tuci u Eemple: Rectore cu sisteme de mestecre folosite i procese omogee lichide su procese eterogee lichid-solid (suspesii, lichid-lichid (emulsii si gz-lichid. Rectore cu strt fluidizt.
9 Rectore ctlitice cu strt fi, de dimesiui mici. Rectore ciclo (rdere sulfului su prjire piritelor. Petru rectorele cu mestecre complet precum si petru rectorele cu curgere idel, dimesiuile rectorului, vitez de curgere recttilor, cocetrtiile iitile si file su grdul de coversie pot fi determite dor dc cietic rectiei este cuoscut. scd de rectore cu mestecre complet itez de rectie i rectorul cu mestecre complet este mic => petru obtie coversii mri trebuie utilizte rectore de dimesiui mri. => Se impue utilizre uui lt de rectore cu mestecre complet: compoziti mestecului de rectie se modific pri trecere de l u rector l ltul. U umr suficiet de mre de rectore i cscd => ceesi coversie c i rectorul cu curgere idel.
10 Petru determi umrul teoretic de rectore ditr-o cscd se utilizez fie metod lgebric fie metod grfic. Metod lgebric, prezett i cele ce urmez, se bzez pe itocmire biltului de mterile petru fiecre rector di cscd. stfel, petru o rectie ireversibil de ordiul iti ecuti de bilt pe primul rector v fi: Q Q k ( Q k cre coduce l Q Q Q k Q k k ( Q Ecuti de bilt pe l doile rector se scrie: Q Q k 2 2 si, c urmre 2 2 k ( k Petru o cscd cu m rectore cu volume egle, l tempertur costt, se obtie: m m ( k cest ecutie pote fi folosit petru clculul cocetrtiei l iesire di fiecre rector l cscdei precum si umrului de rectore ditr-o cscd ecesre petru obtie u umit grd de coversie: log m m log( k Rectorul de tip btch (discotiuu I rector este icrct o ctitte defiit de rectti. Recttii rm i rector p se tige grdul de coversie dorit. Modificre cocetrtiei recttilor i timp este similr cu ce di rectorul cu curgere idel: oditiile de regim se modific i timp: idepedet de grdul de mestecre, u dor cocetrtiile recttilor, dr si tempertur, presiue si, deci, costt cietic rectiei se modific i timp. Uzul, tempertur si presiue cresc l iceput poi scd spre sfrsitul
11 procesului; cocetrtiile recttilor scd cotiuu, dr vitez scderii cestor u este costt. Este politermic i fuctie de timp. Ecuti crcteristic rectorului de tip btch se deduce di biltul de mterile: G r Gc Gc G r ude, petru speci di sistem, d d[ ( ] d Gc d d d G r u deci d u d Seprd vribilele se obtie d d u ir dup itegrre d u cest reprezit ecuti crcteristic rectorului de tip btch cu mestecre complet fiid similr cu ce corespuztore rectorului cu curgere idel. Este utilizt petru determi timpul ecesr petru tigere uui grd de coversie dt. Fuctiore rectorului implic u ciclu de opertii: icrcre coversi chimic descrcre. Dezvtje: - rectotul este oprit i timpul opertiilor de icrcre si descrcre - i period p l tigere coditiilor optime producti este mi mic - timpul ecesr petru relizre uui proces btch este itotdeu mi mre dect timpul ecesr petru procesul cotiuu corespuztor - procesele btch sut dificil de cotrolt, ir clitte produsului depide dese de coditiile de operre ceste dezvtje justific tedit de ilocuire proceselor btch cu procese cotiue.
12 Utilizre rectorelor de tip btch Se recomd i procese l scr mic: Fbricre rectivilor chimici Fbricre uor ctliztori Fbricre produselor frmceutice Fbricre vopselurilor Rectore semicotiue (semibtch Sut itermedire itre rectorul de tip btch si rectorul cotiuu MFR: I the semibtch mode the tk is prtilly filled with rectt(s, d dditiol rectts re dded progressively util the desired ed compositio is chieved. ltertively, oe my chrge the rectts ll t oce d cotiuously remove products s they re formed.
13 Rectore chimice rezumt
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