Title of Invention	SHELL-AND-TUBE TYPE REACTOR AND A PROCESS FOR OPERATING THE SAME
Abstract	Shell-and-tube type reactor for carrying out catalytic gaseous phase reactions, comprising a contact tube bundle (8) through which the relevant reaction gas mixture flows and which contains a catalytic filling, extends between a gas intake-side tube sheet (4) and a gas output-side tube sheet (148) and is flushed by a heat transfer medium inside a surrounding reactor shell (6), further comprising a gas intake and a gas output hood (2; 60) spanning the two tube sheets for administering the relevant process gas to the contact tubes or evacuating the reacted process gas to the contact tubes or evacuating the reacted process gas from the contact tubes and comprising a process gas main pipe (172) for feeding the process gas into the gas intake hood (2) characterized in that the process gas main pipe (172) comprises a first section, in which the process gas is in a non-explosive range, and in process gas flow direction behind it a second section, in which the process gas is in an explosive range; the process gas main pipe (172) comprises in its first section a check valve arrangement (180), the check valve arrangement (180) comprising at least two paralleled check valves; a pressure reduction space is disposed in the first section downstream of the check valve arrangement (180), the pressure reduction space being formed at least partially by a chamber (190)housing the check valve arrangement (180), and the check valve arrangement (180) and the gas intake-side tube sheet (4) and all parts therebetween, which bear the process gas pressure under normal operation conditions, are also designed for stability for the maximum pressure caused by a deflagration or detonation.

Title of Invention

SHELL-AND-TUBE TYPE REACTOR AND A PROCESS FOR OPERATING THE SAME

Abstract

Shell-and-tube type reactor for carrying out catalytic gaseous phase reactions, comprising a contact tube bundle (8) through which the relevant reaction gas mixture flows and which contains a catalytic filling, extends between a gas intake-side tube sheet (4) and a gas output-side tube sheet (148) and is flushed by a heat transfer medium inside a surrounding reactor shell (6), further comprising a gas intake and a gas output hood (2; 60) spanning the two tube sheets for administering the relevant process gas to the contact tubes or evacuating the reacted process gas to the contact tubes or evacuating the reacted process gas from the contact tubes and comprising a process gas main pipe (172) for feeding the process gas into the gas intake hood (2) characterized in that the process gas main pipe (172) comprises a first section, in which the process gas is in a non-explosive range, and in process gas flow direction behind it a second section, in which the process gas is in an explosive range; the process gas main pipe (172) comprises in its first section a check valve arrangement (180), the check valve arrangement (180) comprising at least two paralleled check valves; a pressure reduction space is disposed in the first section downstream of the check valve arrangement (180), the pressure reduction space being formed at least partially by a chamber (190)housing the check valve arrangement (180), and the check valve arrangement (180) and the gas intake-side tube sheet (4) and all parts therebetween, which bear the process gas pressure under normal operation conditions, are also designed for stability for the maximum pressure caused by a deflagration or detonation.

Full Text	Shell-ar.'Ci-t ube type reactxr for carrying . ut cata y gaseous pnas-r reactions and a procedure for operitinq r n same I The invention relates to a shell-and-tube typ~ rea-'t'-r j according to t le generic terms -of patonfe-Ji;4r^-3L-m—i a.:' '.vel . is , \ pirocedure for ,'perating such a reactor. S'^uch a she! I-and-tube type reactor is app'roximatei / Know, from DE 100 21 986.1. In that specific case hr-v/eve: tne endeavour tc- rr^duce the risk of deflagration -^las l-rd thf inventor, zo s )me extent, to feed a criticall/ exp lo::^ iv>:. component of tne process gas brought to reaction j-'i : he reactor only immediately before or even in tne rea-t;or, tubes. Moreover, the volume available to that component is until then fitting inserted into an otherwise cc'nventional more jr less spheri::al cap-shaped gas intake hood. These mea.rui^. - -.t based on the t-llowing insights: 1) In order tr. attain the greatest possible \|;roduc-:i.n capacity m r-^Lation to the size of the react 3r s-,'-5t';m ¦ is desirable t i he able to maximise the process gas r'large .¦- t h the criticall\ explosive components sucn as ixyger: acd liydrogen. 2) The risk c-t a deflagration increases, besides i \ ie.i.;t i in to the charge, with the amount of time m whiih tf-- ^ wc components are ooth resident in the same space. i'nere have pre- lously been attempts to guard ngairi.--t exf r. - sive damages t • >jm any eventually occurring de : lagr it „ oii-- ; y installing lup' jre disks in reactor systems. ;-ut i' * ne i .m is to further increase the charge and thus th- output ai .vel. then the use c-: rupture disks is inadequate lu viev/ .-,: r t ,- heightened risr;s of deflagration. Replacement of tne rup' ire cisks, expensi .'e enough in themselves, m the case ot a :¦- flagration req_iires relatively protracteci rep^air v,'_;rK an: concomitantly ..rotracted down times. The rupt are or" rupt .. i ^ disks is conne ~ted with a blast wave which ca:'i be leard i liie. away as a bang and simply for that reason is maccep:: at . ; - !¦ siddition noxious gases can escape into the encironiaer t. Moreover, after a deflagration and the concomitantly ne^ ^ssi - tated replacenvsnt of the rupture disks the re-starlirig - i idi- reactor required in each case is difficult ani time-'.; or.-..- ming, especially since during the build-up tc^ a great ei charge in operating mode care must be taken tnat p^ssir;-: through the deflagration range of the gas mixture :ui; re: ' iv being fed mte the reactor is avoided. Such a deflagration range can be illustrated ^n a tw. three-componen: diagram like the one shown ir. Hanciburh .•- - Explosionsschut zes by Henrikus Steen {Verlag Wiley-V/H, ed, 2000, page 332) where the third component, is an ne.' uo- added for dilution such as nitrogen. It has keen snown ¦ ' it the danger of a deflagration only obtains v;itnin a w:nci> .-. like range thfit is moreover dependent upon pressure, temperature aii:: geomietry. According t,o C'E 198 06 810 Al the temperature of t .te ti;i r sheet on the gas intake side can be reduced cy a tea^ ; ¦ .- > lat ion layer ^applied to it in order to prever.t; hazardou. lateral reactions including ignition and def1^gration. "tP I 180 50c Al i^riows how to avoid the defiagr^cior cauq^^ thcouqh oonstarit measurement and modificatLcn ;t th- p-o- . :- gas composition luring startup of a reactor, i: v;hi-ri ;a;- initially an in-rt gas is added that is then s.ccessivrl: replaced by ali-ady reacted process gas after me irdc:! sets in. Or this basis, me present invention is based _n th-- :ir^" instance on the problem of being able to increase ir-ie :h.-i r j-r of process gas lo be moved forward to reactiC'O in -i risk ,---.' and additional!/ economic manner. This problem is solved by the invention with t ne feat:.rt'. f Claim 1 to which those of the subclaims then make a furt.'>-M. contribution. I Secondly the ircv-ention is based on the problen of :pe-a; -i'J ' shell-and-tube type reactor according to the -nventioi t , taking corrunerc lal advantage of its spsscial pr'.^.-pert : es . [¦ .- ¦i pproblem is sol\-ed by each of the two process :laim.. - :) .^ ^ i 40. The reactor or the invention miay for one thin;] eve.-: te ¦ (. - r ated with a critically explosive charge of the pr^o -e^s .i-: ' be moved forward to reaction, for another thi ig h\- g-ir,; through an igriitable range during startup, scmethiig the significantly tacilitates and accelerates the pro.-^s- - ¦ startup. For the follo-/:ing considerations a distincti'n mius^ be :'i-o^ oetween a deflagration and a detonation (or ^xplo;icn>, distinction that nonetheless was not made in rhe ^le 'a ¦ .. i/ cited EP 1 18' 508 Al which was based on a translr.-Li r; ¦ : .'H: Japanese. In • -jntrast to deflagration ohat i.: set ct: o \i pomt and pro-'okes a blast wave travelling a' sub/or,i'. .:.-e'. 4 a detorifjt irr. if a consicierabl',- more sudden a; :! co: SciUr-- ¦ ly ¦/lolent trccess that in most cases presuppos-s, b- -i le. even more special gas miixture, a deflagrcatioi" p^re; ^Ti" no rnat can develop over a specific design-related si ^r' ir,': .r entry region. Fere below, se^'eral embodiment examples of tn-r inv-n^ I'l r v; i_ 1 now be described on the basis of their accomp inyiir j ^irav, i-iqs . Fig 1 shows a " ube sheet on the gas intake si le toviet-ie; .-» 11 r a gas intake h. od of a sheli-and-tube type re^nctor aj -o ¦' J i fig to the invention in a longitudinal half-secti n. Fig 2 shows a c-ross-section through the edge • f the tiib^- slieet shown in Fig 1 at the level of Line II-: I in .^i; ': , Fcg 3 and Fig 1 show details similar to those m Fl ] \ di : Fig 2 but with an embodiment with a fitting ir;serte i int^ conventional gas intake hood for feeding in pi jcess q.-jS, Fig 5 shows a semi-longitudinal section simila-' to ¦ hr- (.-i ¦ :n Fig 1 through t-le tube sheet on the gas intake side ar: i conventional sh--Ll-shaped gas intake hood and .t fit' iri.f serted into ^t similar tC' the one in Fig 3, Fig 6a) through Fig 6f) show in each case an emO'Odiner, . -partially permieable seal as illustrated m Fig 5, i; a 1.. i r^ r scale, Ficj 7 shows a sirriilar illustration as Fig !) bui witn ar ot ' - embodiment, Fig 8 shows a S'lnematic drawing of a suppoii arrange i i ns a shel 1-and-t uoe type reactor according to the .nven' i- ri. Fig 9 shows a 5c;hemat ic drawing of a gas intal-:e hc.^d -irr ir to r he one in E ig 5 with cooling and/or heating de- ic-s ¦. ¦ ¦ ¦ vided on i t. Fig 10 shows a similar illustration as Fig 7 with r ne d^- ' e preoedinq the process gas stream fed into the reactor, i '. Fig 11 shov7s a schematic drawing of an alternative pi ;c^- gas feeding in connection with a gas intake h/'Od a.cc-rdi i ] i Fig 1. Fig 1 shov;s soruewhat schematically the gas in^-ake --no ci shel 1-and-tube type reactor according to the ^nvenr ic^n L ¦ carrying out Crttalytic gaseous phase reaction.- in ' he c- ¦ i ¦ cal range for .lef lagrations or even detonatioiis . Mere pre- cisely stated, in E"ig 1 a spsscially dessigned gas intaKe ¦-1 2, a tube sheer 4 underneath it, the reactor shell o dd : i --n to it, a ring-.-haped contact tube bundle & (h.nted at h': ' n a broken line) and gas intake pipe socket or :iOzzl^ "._ j i ¦ --i ding intc^ the '-fas intake hood 2 can all be recogni;-ea. In the usual manner, the tube bundle 8 contaitiing -: :-^ai' r i- catalyst filling is irrigated within the reactor shell - a heat transfe": medium which is - in any case in oi ei it i ¦ liquid and via which throughout the contact t.ibes : siit i: ;- temperature prtfile is maintained and excess react oii h./ .¦ i led off. As can be further seen from Fig 1, the gas intake rot^J apart from a m-iissive peripheral collar servin-; its at •;^a" ^ —rv to and sealinq--:'ff of the tube sheet 4, is re.ativ- Lr t: . £nd somewhat trumpet funnel-shaped so that berween i" .^^ ; ' t- t ube sheet 4 triere is a fiat gas distribution spac^ _4 'neected ever^ily, chat is without steps, kitiks o: so t'jr^\i, ' the gas intfiko l ice socket or nozzle 10. Attaorimerr: c! • ' ¦¦ gas intake h.,-;:-:1 2 to the tube sheet 4 is aocomplisheci '/; studs posit lone:; around it which are o^nly hin::ed at hr-rf The gas distritition space 14 is dimensioned : ri su-" n i w . that the prcoess gas feci into the contact tubes thicugh flows as evenlc as possible into the cont.act rubes, i^e. r; order to minimise turbulence as well as residence rimi-. doing so, the aesign of the gas distribution space 'na ¦ aoprC'Ximate 1 y t: e such that the radial flow component -r ^rri tne static p^ressure in the process gas remains conttaut : the radial dir the Cither hand the trumpet funnel shape of the gas in';ak ¦ hood 2 can oe approximated as well by more or less co,;i i ring elements not shown) . To produce evennes- in t fit' g/i- flow at the en* ry to the gas distribution spa-e 14, a s\| -¦-- shaped flow di'erter 16 is arranged tnere underneai h th'- jds intake pipe so-'kef or nozzle 10 and resting or. the tuoe .^-e' 4, which simultaneously constitutes a displac-r in oile.-' prevent the ga.- from impacting frontaily in tne mijdi^ ¦ ' n^ tube sheet 4. The minimum height of tlie gas d:strii ut^O'i space 14 is dei ermined in the example shown by a s^aiino" inj 18 of defined iimensions with which the gas distribut ic,- space 14 is se.-iied off from the outside. It i.- detr-rnitn- ; ir the planning s . age and must in any case be bii enc.i.gh s_ -t.^' at no point m the reactor circumference does it t'^-cwme i. , for example be -ause of unevenness in ths^ hood 2 ana/..:r- • tube sheet 4. l-Jnere required, the hood and/or the ' ub-> '-—.---' must be smooth-J or faced at the same point. Since however -i dead space 22 can hardly be at'oide i by ;-_ - iqr C'Utside of tht radially outermiost contact tub-^s, a tor example 21., but inside the gas distributi .-n sp'.;Cc: 1- v/ithout obstru;ting the entry of gas intc the radiil_i/ outermost cent-;ot tubes and since such a cieao spac- w vi, ^ i entail undesirtble residence of the process q^s, ni-d^ji-: " have been take:, at these points to displace tne pi' cess i-js out of the dea "1 space 22 or at least to "dilu" e" i' "^ :- -. composition nc": critical for deflagration. Thrs is d^.^ le - - , injecting gas i-.'nich is deactivating in regarc to tt.e let . i- gration reacti.-n feared. This could be an inert ga.-- sic:" -is M; a by-producr produced in the course of the operit]Vfc ie- action such as '1'02, occasionally simply air oi ever a m_i ¦.•ur^ of such gases. According to Fig 1 the gas in guestion, referred t her- i-e- low as flushiri'iT gas, is injected via a circular pije 24 ¦ the periphery .if the tube sheet 4, from thenc^^ inw.->rds ' junction canals 26 branching off at regular iriterv.-.is a I " - q the periphery - ¦! the tube sheet 4 and then vi i nozile b' :.-'S 28 branching c^ff upwards from the junction car^.als 6. -As can be recc-^nised fromi Fig 2, the nozzle h'^.res , 8 s 1 _ i> iri the peripheral direction of the tube sheet 4 .n or lei i' .ive the gas exiting from it a radial flow compontnt ani, Ln lat way, to flush _t through the dead space 22. Fig 3 and Fig 4 shov; another embodiment of th- gas iiicar.' eno of a shell-and-tube type reactor according tc the _ n\'en'" . ii. Here inside a lonventional shell-shaped gas i-.take hooa, r which only che edge 40 is shown here, a fitti ig re.-tii'/' '-q the gas disr ri jution space 14 can be recognis-d. Whtrre .e parts shown here and below are identical to t:,C'Se n Fi : . and Fig 2 they have the same reference numibeisi . In a further departure from the embodiments a"Scr:^iea earlier, here i circular pipe 44 for flushing gas ¦ ¦:> oe .. - i into the dead space 22 surrounds the edge 40 .f th- ^jis , - take hood and -iccordingly junction canals sini._lai o ch- junction canals Z'o extend radially throucgh the edge 4 C . '¦ iunction canals 46 run into nozzle caps 48 arr.uigeo or '; i insi.df^- of the eciqe 40 with tanqentially alignel noccles - for gas output, likewise to flush out the dead spac-- ./I ^ much as p>oss ib 1 •- . Fig 5 shows an arrangement similar to that of r'ig • r_ tj extent that here too a fitting 42 is provided for iis]de ' r,- shell-shaped gas intake hood. As can be seen, the fitfir.-. -i . is freely suspended on the gas intake hood 60, more p.t e^; -J', on its shell 62, anchored by means of stud bolts 64 as w.- as by the gas intake pipe socket or noz2:le 10 in such a ^ ., that deflagration or detonation forces possibi_y oc:ui;in; ; r; the gas distribution space 14 are led into the she^ 1 o2 . ii order to absort these forces as well as possible, ^he sh- . l 62 is shaped Like a spherical cap. In this exempl.riry embodiment the fitting 42 is cojX[\ osect ' -i slightly conic-il ring disk 66 and a profile ring 6-. r:jui i- i off inwards an 1 downwards and is supporte;d at its -.-due 'i -. a partially permeable seal 72 on the tube sheet wh^l- th- la^ -intake hood €y' is filled up outside of the fitting 41 w.' t the flushing gas for the dead space 22. From thence 'he flushing gas enters evenly, to the same extent as it i;^ '-g on an ongoing oasis to the gas intake hood via a rip^ 4, into the dead space 22 via the partially perm.eable s^a! around it . The gas mtak-^- hood 60, more precisely its massiv^, ehgf ¦ ¦, is sealeo against the tube sheet 4 in this example v ..a ¦. ' vT-- of welded lip seal 76 similar to that aescrired ii pE_^44 07 7'28 ¦'!. Actually here too a sealing ring suit i i :- - sealing ririg .t from the previously described emb' di ae:c could be used. Preferably the flushing gas stands ii: a - -^ tion i:o t h- external atmosphere as well, naturali ^-ri-.^.., k , ill relation to ine gas distribution space 14 L;nder ni^jh pressure in or,1er to function as a blockiriq medium. Fig 6a) through Fig 6f) show variously different c;jc'r-nr , considered embodiments for the partially permieable se;;] from Fig 5. Ac:-^rding to Fig 6a) the partially permieat If- —rdi 71 consists ol i ring 80, of itself of a circular or - vk-: il- rerady elliptica^ cross-section made frorri a pc^r^us aid sj ;rir - ly compressiole material such as, for instance, graijhite ' s- sue compressed from a ring-shaped projection ^^ i of .h.- t' - ting 42 into a corresponding ring groove 8 4 of the ¦ uf e : r^^-et 4. According tc- Fig 6b) the seal 72 consists cr a C-sfap't : profiled and preferably metallic hoop 36 having on .ts O'.: side towards the tube sheet 4 a number of regularly spric^^ i radial or even .-omewhat tangential furrows 88; and nc: dl .: l ¦ .q to Fig 6c) the -^eal consists of a massive elastic s^a^ i,n : ring 90 similar to sealing ring 18 in connect! ;n wi" h ra i i -: or even somewhai tangential bore holes 92 m a proic-ctio; -4 similar to the projection 82 in Fig 6a; . Accor ling to ^'i. --g j the se?al 72 is .:ormed from a ring 98 provided -.-.'ith !aOi_a. r somewhat tangent lal furrows 9 6 and having a ba.-ically ro :i i cross-section ar,a being formed of metal or of another -la i elastic materia"., the ring lying in a ring grc-'ve li 0 ^n.- At- a projectic^n 10_ similar to the projection 82. Acccidi :g Fig 6e) and of' sheet profile rings 10- or 106 or ar.gl-td cross-sections are used as seals 72 which in turn and xs emerges frc.m Fiq 6e) can have furrows 108 to t^e tute --hi-' ¦: -1 similar to the lurrows 88. Such profile rings ¦ an bt- f , e> i. ^- in regard tc high pressure imipacting on one si;ie in iraet ' open up for the llushing gas a smaller or grearer flow- through cross-section. Fig 7 shows an i^rrangement sirriilar to the one .mown lU F: where however tre flushing gas enters radially chro-u^h tl- tube sheet 4 mti a ring-shaped space 120 between a .ve. de. : 10 Lip seal 122 ;imilar to the welded lip seal 6 an tvo • ose ly ':onnectea sheet rings 12 4 and 12 5 outside jf tre •'i' ¦ . nq \Z. The essentially cylindrical sheet ring 1^2 atr -ic.ne 1 rightly to the edge of the fitting 42 6?xtend>- wher I .os- mc a ring groove 128 of the tube sheet 4 in ord-^r to, ii t,- .-; l nanner, form a partially permeable seal m re^ati:-i "o ' i.-- qas distributi ;'n space 14, similar to the paitial_L/ pei rr:-.Tbl- ring 72 known from Fig 5. The stud bolts 64 known 2r:m i-; j 2 are replaced in this example by pierced crylinirica. sne^t.-- 130. E'ig 8 shows ho.-/ the tube? sheet 4 on the gas i-itake side ni be supported t-iwards the gas output end of the rea;t';r ;. - rh- event that m '; ne gas intake region a def lagr dtiori or ev--; a detonation should occur. In the example shown ther-^- a c^; : ; es ponding support 140 is formed as a multi-winged met ai c-:uii'.'- nent or is made of at least two radially extertding metal -orn ponents essentially formed by two sheets 141 standtng ii\ "he shape of an x which, prcjferably loosely, engaae into tor • >-.-- ponding grooves 142 on the underneath of the * ube t hO'-t ¦ tii" fit into corresponding radial lanes of the tare bur.dl.- « in addition the ce-ntre of the tube sheet 4 can, ;)S shtwn, Li- supported inside the tubeless medium region 144 near ' hr- bing by means if diagonal struts or by a sheet metal -or:- i ^ on the sheets 14 1. This makes it possible under certain r cumstances to o :• with a single sheet 141 thus saving pei i -.(.¦- up to two tubeless lanes. In place of the sheet metil ct' - 146 one could also have a cylindrical, prismatic or p', rai' i sliaped metal component . The support 140 may but need not, as shown, run thr -uon ' the tube sheet 148 on th€^ gas output side or t " a s-'parat plate. In any C:ise, however, it must be m a p^ sift 'ti tc gride the supporting forces into the reactor snell. Tc compensate the different heat expansions the sneets ItKC sheet 141 cari h^rre, especially in the vicinity of t; c _}ci intake-side tubT sheet 4, longitudinally extending :':2^'.s rtliet slots 15i as well as correspondLng recesses ^: :-y their attachment to the reactor shell 6. Other'.-.ise Mie .• f. , . , wherever this c-: uld be functional for flow-technica_ r-a.- t ¦- or to save weight, be pierced or replaced with a sk-le\a: )^¦ sign. Resting the support 140 on the gas output side t.;bi- sheet 148 has, n:t least of all, the advantage that th-n --¦/-n the latter is supported against deflagration pressur- ]c^ .-- propagating throigh the tubing towards the gas 3utpu'- .-^ po - or v/hich could be generated there from a subsequent igr it According to DE 198 06 810 Al the gas intake side tui:;e sh^-r 4 can be heat-insulated (not shown) in order tc keep tte .-i ; distribution spa 'e 14 "cool" and also to reduce tend^fn'.ie- towards deflagra' ion or even detonation. Fig 9 provides r.. r the same purpose - with an a rrangr^menl similar to that -> n Fig 5 or Fig 7 - at various {:oint.^ ; i -. ^ on the gas intake- hood 2 for coolant canals 160 whicl- '-tri, however and espe'-'ially when the reactor is started uf. , iJ - function as heat n\edium canals and can additionally or -1 bute to reducing heat stresses. Fig 10 shows the :ias intake end 170 of a shell-cind-tuoe t ;: - reastor according to Fig 7 with upstream facilities t r.^r p; paration of process gas. In the example shown, at an\ q v. P'Oint 174 a secor ;1 process gas component, such as a t yd; c carbon gas, is f e g into a main pipe 172 in which a suit i\ ¦ tempered process gas basic component flC'WS under appr Dp] i -¦ ¦ - pressure, for exaniple air, the so-called main fisw. Tne s- cond process gas component is fed in in a quantity n-:.': ; ei dering the process gas capable of deflagration wtiiie -id:-i tiorial partial quantities of the second or even addit^o-a process gas comp-^rients are added at 176 or 178 q^v/nstree.m d check val\'e •^irrangement 180. At the latest -iftei tf;- ; -i 1 n point 17P tr.e process gas is in the explos:ve i--nq-r. Ail of the process gas components fed in are .-" ubseourr it mixed in several coordinates by means of seveial sr;-c-s;- mi:^xers 182, 184 and 186 and mixed gently, that is r i^r it stance with the greatest possible avoidanc:e ot turtjl-:nc. - ;r addition care is taken in pipe routing to avoi :1 any u'".ev. - ness. Furthermicre, the pipe 188 between the chi-ck -.'il-.e .¦ rangement 180 arid the gas intake hood 2 is kep' as ih'. r: i- possible to pre\'ent the accumulation of high def lagi at lo; pressures. The check valve arrangement ISO prcients an/ ; ..-.t wave generated ]n the pipe 188 or downstream tr_erefi orr t' -'¦ propagating further into the main pipe 172 and causing d.i^-. . ges to the orgars feeding into the latter. The check vd'— arrangement 180 is located in a chamber 190 simaltaneoL.s.; forming a desiraole pressure relief volurrie for such i ;_ l wa\'e. The chambe •_ 190 can have any shape and can con'airi practically unlimited volume just as additional chamoeis likewise be adde.i at the same point. If require'!, th'^- lir feed-in point f^-i can incidentally likev\?ise be rolloi-.eci t', i mixer (not shown , preferably m front of (i.e. upstieaii: ¦ -^ check valve arrar_gement 180. Nevertheless, the reed-iri ,c : 174 can be locateii far ahead of the check valve arrargene,. in 'Drder to attaiti in this way a favourable mixing, in Mi- other hand, possioly downstreami the check valve arrangerier ¦ 180, a single additional feed-in point such as 1 '6 ani ¦ single mixer coulj also be sufficient. The check valve arrangement 180, the chamber 191', the pio.- 188 and the mixer-: 182 through 186 included in triemi a:.d 'r. feed-in facilitiec as well as the reactor itself are c:±:. designed as to st;engh and stability to withstan: the gi-.c est deflagration r detonation pressures occarrirg ir, th^m. This applies, as stated, despite the previously lescrioed measures to avoiii as much as possible netonati' ns ar i -il.- de LLagrac icns. Fig 11 shows an arrangement in principle simil-r tc th-it Fig 10 but m C'/nnection with a gas intake hoc.; 2 a._ cc.-:d, ¦. j to Fig 1, the mi.xers as v/ell as a curvature in the r ip- . - ¦ being omitted, the pipe in this case being part icul.:-.r 1 / short, lyiixers entail in any case disturbances .n ga; iLow-, something that makes the relevant process gas f-ven r.ore .-: i - ¦ ceptible co deliagration. For producing particalarl- aefi i gration-crit ica.: process gas miixtures one should the-refot'- try to avoid mii;-:ers as much as possible. Morec"'er tne oo-f - ble starting or Duild-up length for the generation ¦£ a j-' nation should be shortened. According tC' Fig 11 the check valve arrangement 18Ci i::- d,- posed cent reel over the gas intake hooa 2 on the axi s - f • : - gas intake pipe socket or nozzle 10, and instead of tre • .'v feed-in points L76 and 178 in Fig 10 a single fine sparg t i point or device 192 is provided while there are no ni;-er- , The fine spargi;ig device 192 has a number of spargi'ig an t ¦ 194 distributed across the pipe cross-sect:ion, i.e. at i—v-t five but preferably 50 such sparging units 194 per -n-^' or -'.'i-: more, and whicn can be designed to have nozzles an^ i;.di vidual tiirottling devices simiilar to the sparging i^nii s t tne contact tube entry according to DE 100 21 986 AI rin>l l wnich are able to give the p-rocess gas components spaj ge - ¦ m a twist. In this way, feed-in of the second piocess g.ts :ti" ponent, such as a hydrocarbon, is so finely districuted ¦¦¦ i regularly admiiiistered that there is no need ror mi:xe-"s i producing a hoii ogeneous process gas flow. In principle, f he process gas components sparaed ii -_ in ; • present in liquid or gaseous form, cold or hcoted-'4:. W;' liquids it is feasible to iriject themi by miean- of i.n i.n-- 14 gais. Either .vay, sparging can oe done at high oress^ir- ;• order to p.roiuc-:- partial vaporisation ccmk)ine:i with biea'-- jp of" the flow sirtiLlar to the way this is pi:acti?-:-d in t-eci ; ; automotive tuel zo the cylinder chamber of cornoustijn engines. The sparging zc-rie can be furnished with a shell hea^^ei at : accordingly the feed pipes for the second prc'cess gas rai r^e heated or heat-insulated. The design of t ne reactor components as to staoilit ; .:.nc strength depends on the type and concentration of trie mcr-- rials to be prC'iessed. It is usually undertaken for st at nary operations. When starting up a shel1-and-tube iy[e actor of the t\oe described above care must ccnsequenrlv t-- taken that at ri : time the deflagration or detonation ;-ti> !.)rh estimated for ;perations is exceeded. Normall\ one 3tc-.r"_ ip with only one -f the various process gas components ( t hf- ;; uti flow). When a ertain mass flow of this has been atia nf then the secorr;; process gas component is addeo. If m th plant's operat : :ns itself an inert gas like Ct is ;jr(_dU' -¦ i then startup cau be accc'mplished by including it, r^sse-nt li li, in accordance '.-. ith EP 1 180 508 Al. Whether in starting i ^i: inert gas is t. be fed in additionally or whetner t ne dct i-i of deflagratior and detc^nation severity can be redu ie>l ;- Oi ¦ i'. by varying pre.-sure and temperature to operational Ie-'e_ is governed by thr details of the process. As already mern ioned in the beginning, startuf. can ani in . entail the ignitable range. Just as in normal iperati; n, • 1-. in startup bes.ides the process gas compositicr other [.ar -r -- ters such as, rri-st especially, pressure and temperatuie, oiv'^- to be taken iir" .i^ acc:ount . Both of them affect ihe cef a^i tion and det c n.-i t. ion behaviour. It is possible to vary pressure and t-:-mperature during startup. In tr at Wav, wri- 15 starting up pressure can be reduced while the ^empeiat jr*- ;. th'S gas distribution space 14 is raised. At tti- latest towards the end if the startup phase both are ' nen ;-d: ^s'- : tC' the operatioridl levels intended. If a shel L-and-i: ube type reactor is run in the lov-;e] i:;f.: i- gration range, ^" nat is with only a minimal risi of uer La.;-; i ¦- tion and minor deflagration pressure to be taken in-o ac- count, and if I'l doing so a recycle gas out of the e^it : ts inert gas is fed into the mam flow, then star-:up i ui oe i ¦¦- ccmplished in the following manner: First via the main pipe 172 air or oxygen is r-rd iri ai tr- main flow. Then one starts feeding in a hydrocarbon fiow . , .t the sparging device 194 (Fig lli . As long as tne hy Ir ; la.-: oi concentration is low there is no risk of deflagratim. Tr - recycle gas recovered likewise basically consists lul. c' materials from the miain flow. As the startup process -idv.^ri^-s and hydrocarbons are added the reaction product is iliea:', being produced as the result of which the recyiie gas a\ : ^-.-^dy contains a portion of inert gas like carbon dioxide, .n ¦ i ¦- further course of the startup process the hydiocarl^n tJ .-. is increased. But since the main flow by then already icntd • _ .^ significant portion of the inert gas at no tine a ^ri- !¦¦ level is reached. In principle, in this way tre attempt made to avoid tdie explosive range in the starrup pi aS'- order to enter into the explosive range only -Ahen -"ut';^'- nt process stability has been achieved. In principle, the same applies as well to opeiatioi s ,_n ' -i- upper explosive:- range. Here, however, the hydrocart ii" f; -,-; is normally administered via the feed pipe 172 ai maii r .o\while, for instance, oxygen is fed in via the spaijir',! i-- lc- 194 . Accordinq to rhe current level of knowhow, a shel.-a id^ ¦ te type reactO't -jrcording to the invention can re ad'-.^rra'i- is used fc'r oxidation, hydratic-n, dehydration, ritratioi , k /" ation and similar processes and then especially f:; r ^ h^- ; l^' duction of ketones, methyl-isobutyl-ketones, mercaot-n, .-¦¦¦ prene, anthra^iriinone, o-cresol, ethylene riexarie, 1 jri'ji acetylene, \'in.-: acetate, isopropyl chloride, naphth-ri len- acid anhydride, vinyl chloride, oxo-alcohol, oyrot 1, si , ¦ 'l rrethanformic a-'id nitrite, polyphenylene oxide, di;rie;;nyj - phenol, pyridinaldehyde, Therban, alpha olefins, v tn,-^i- ---, prussic acid, aniline, formic acid nitrate, di f luc-iomet-" i -, 4-methyl-2-penT-anon and tetrahydrof uran as wo-^i as in p.-i ¦ i - cular the oxidation of dj methylbenzols (m,o,p) into the corrc sf-^n^: i.j monoaldehydes and dialdehydes, oxidation of dimethylbenzols (m,o,p) into the correspond i? mi3nocarbonic ar :i dicarbonic acids or the^ir anhydrioes, oxidation of t r iiriethylbenzols into the correspondir, .j monoaldehydes, Jialdehydes and trialdehydes, oxidation of t r imethylbenzols into the correspondiri :j -^ cii^ ir bonic acids, :ii larbonic acids and tricarbonic acids 01 v •¦ ¦ r anhydrides, oxidation of du-ol into pyromellitic acid anhydride. oxidation of gaimia picoline or beta picoline into q-inura picoline-carbo- -1 Ldehyd, oxidation of garrima picoline or beta picoline irito iic- nicotinic ac_d ¦ r nicotinic acid, oxidation of priji-ene intC' acrolein, oxidation cl aci'V.lein into acrylic acid, oxidatio^n of prop^ane into acrolein, oxidation C'f p-rcpane into acrylic acid, oxidation of butane into maleic acid anhydride, oxidation ci refined product into maleic acid anhydrio-, oxidation C'f i-t:..;tenes into methacrolem, oxidation of met riacrolein into methacrvlic acia, oxidation jf no-thacrolein into methyl-met;Maoi /late, x; O'f i-butano in":.' methacrolein, O'xidation of a -butane into methacrylic ac;id, ammoxidat iC'n o - dimethylbenzols (m,o,p) into : he corresponding iijnonitriles and dinitriles, arrimoxidat Lori ,: : trimethylbenzols into the cor-/espc^ndifiq rriononit riles , iinitriles and trinitriles, ammoxidation c' propane to acrylonitrile, ammoxidatiori c; propene into acrylonitrile, ammoxidation ci beta picoline into 3-cyanopyr;dine, anamoxidation ci gamma picoline into 4-cyanopy/idinf , oxidation of miethanol into formaldehyde, oxidation of naf-hthalene; and/or o-xylol possitly mixed . phthalic acid inhydride, oxidation of etnane into acetic acid, oxidation of ertanol into acetic acid, oxidation of geianiol into citral, oxidation of et'iene into ethyloxide, oxidation of pr^^pene into propylene oxide, o>;idation of nyirogen chloride into chlorine, oxidation of gl/jol into glyoxal and hydration of mia -oic acid anhydride into butane dio: A shell-and-tube type reactor according to the present inven- tion presents among others the following features and advant- ages: The volume of space available to the process gas prior to its entry into the contact tubes can be kept to a minimum according to design and technical flow vantage points. The space volume available to the process gas prior to its entry into the contact tubes, dead spaces, in which the process gas could fully or partially come to rest, may be avoided as far as possible from design and technical-flow vantage points. In administering at least the process gas already ready to react diversions and most especially uneveness may be avoided as much as possible. The gas intake hood (2; 60) may be fastened to the edge of the tube sheet (4) on the gas intake side by means of studs. The gas intake hood (2; 60) and/or its fitting (42) can be cooled and/or heated. The gas intake hood (2; 60) and/or its fitting (42) may have canals (160) through which coolant or heat transfer medium can flow. The support may have a number of longitudinally aligned pressure relief slots (150) and/or recesses (152). The support may extend up to the tube sheet (148) on the gas output side. The support is loosely joined to the tube sheet (4; 148) in question. The support may fit into a recess (142) in the tube sheet (4; 148) in question. We Claim: 1. Shell-and-tube type reactor for carrying out catalytic gaseous phase reactions, comprising a contact tube bundle (8) through which the relevant reaction gas mixture flows and which contains a catalytic filling, extends between a gas intake-side tube sheet (4) and a gas output-side tube sheet (148) and is flushed by a heat transfer medium iinside a surrounding reactor shell (6), further comprising a gas intake and a gas output hood (2; 60) spanning the two tube sheets for administering the relevant process gas to the contact tubes or evacuating the reacted process gas to the contact tubes or evacuating the reacted process gas from the contact tubes and comprising a process gas main pipe (172) for feeding the process gas into the gas intake hood (2) characterized in that the process gas main pipe (172) comprises a first section, in which the process gas is in a non-explosive range, and in process gas flow direction behind it a second section, in which the process gas is in an explosive range; the process gas main pipe (172) comprises in its first section a check valve arrangement (180), the check valve arrangement (180) comprising at least two paralleled check valves; a pressure reduction space is disposed in the first section downstream of the check valve arrangement (180), the pressure reduction space being formed at least partially by a chamber (190) housing the check valve arrangement (180), and the check valve arrangement (180) and the gas intake-side tube sheet (4) and all parts therebetween, which bear the process gas pressure under normal operation conditions, are also designed for stability for the maximum pressure caused by a deflagration or detonation. 2. Shell-and-tube type reactor as claimed in claim 1, wherein the process gas main pipe (172) comprises at least one feed-in point (178) for feeding in a partial quantity and/or a component of the process gas, due to which the process gas passes from the non- explosive range into the explosive range. 3. Shell-and-tube type reactor as claimed in claims 1 or 2, wherein a device for injecting a flushing gas into dead spaces, in which the process gas prior to its entry into the contact tubes could otherwise fully or partially come to rest, the flushing gas being inert in relation to the relevant reaction. 4. Shell-and-tube type reactor as claimed in claim 3, wherein a device for injecting flushing gas radially outside of the contact tube bundle (8) at the edge of the tube sheet (4) on the gas intake side. 5. Shell-and-i:ube type reactor as claimed in claim 4, wherein a device for injecting the flushing gas in question with a tangential flov/ component. 6. Shell-and-tube type reactor as claimed in one of the previous claims, wherein the gas intake hood (2) is designed flat and funnel- shaped and with a distance to the gas intake-side tube sheet (4), which decreases in the radially outward direction, and with a central gas intake. 7. Shell-and-tube type reactor as claimed in claim 6, wherein the gas intake hood (2) is rounded off at least approximately like a trumpet funnel and is designed to flatten out towards the edge. 8. Shell-and-tube type reactor as claimed in one of the claims 1 through 5, wherein in a basically conventional shell-shaped gas intake hood (60) coaxially a flat funnel-shaped fitting (42) is arranged from which a central pass-through is connected sealed up with the gas intake and the edge of which is sealed towards the edge of the tube sheet (4) on the gas intake side. 9. Shell-and-tube type reactor as claimed in claim 8, wherein the fitting (42) is rounded off at least approximately like a trumpet funnel and is designed to flatten out towards the end. 10. Shell-and-tube type reactor as claimed in claim 8 or 9, wherein the fitting (42) is supported at several points, preferably regularly spaced out, on the gas intake hood (60). 11. Shell-and-tube type reactor as claimed in one of the claims 8 through 10 in connection with claim 3, wherein the sealing (72) on the edge of the fitting (42) is to a limited extent gas-permeable and the flushing gas in question is injected over it. 12. Shell-and-tube type reactor as claimed in claim 11, wherein the sealing (72) in question consists of a partially permeable material such as, for instance, graphite tissue. 13. Shell-and-tube type reactor as claimed in claim 11, wherein the sealing (72) in question has discrete gas penetration canals such as, for instance, drill holes (92) or furrows (88, 96; 108). 14. Shell-and-tube reactor as claimed in claim 11 or 12, wherein the sealing (72) in question consists of a profile (86; 104; 106) potentially flexible under high pressure. 15. Shell-and-tube type reactor as claimed in one of the claims 11 through 14, wherein the sealing (72) in question is connected on the outside with a space through which the flushing gas is fed. 16. Shell-and-tube type reactor as claimed in claim 15, wherein the space in question is limited by a radially inside seal (72) and a radially outside seal (76). 17. Shell-and-tube type reactor as claimed in claim 16, wherein the flushing gas is under high pressure in relation to the external atmosphere. 18. Shell-and-tube type reactor as claimed in one of the claims 15 through 17, wherein the space in question basically consists if the residual space of the gas intake hood (60). 19. Shell-and-tube type reactor as claimed in one of the previous claims, wherein the gas intake hood (2; 60), the tube sheet (4) on the gas intake side and/or, where there is one, the relevant fitting (42) are connected to each other via a welded lip seal (76; 122). 20. Shell-and-tube type reactor as claimed in one of the previous claims, wherein on the tube sheet (4) on the gas intake side. pointed towards the gas intake, a spike-shaped flow diverter (16) is arranged narrowing down in that direction. 21. Shell-and-tube type reactor as claimed in one of the previous claims, vv^herein a support for the gas intake side tube sheet (4) is disposed between the gas intake-side tube sheet (4) and the gas output-side tube sheet (148) and is mounted to the reactor shell (6). 22. Shell-and-tube type reactor as claimed in claim 21, wherein the support at least in part consists of two metal components (141) which extend radially outwardly from the reactor's longitudinally axis. 23. Shell-and-tube type reactor as claimed in claim 22 and with a ring- shaped contact tube bundle (8), wherein the support consists partially of an additionally basically cylindrical, prismatic, conic or pyramid-shaped metal component (146) in the tubeless interior of the contact tube bundle, said metal component (146) in turn being supported by the radial metal components (141). 24. Shell-and-tube type reactor as claimed in one of the previous claims, wherein the tube sheet (4) on the gas intake side is heated- insulated. 25. Shell-and-l;ube type reactor as claimed in one of the previous claims, wherein a first process gas component flows in the process gas main pipe (172) and the process gas main pipe (172) comprises in the process gas flow direction prior to the gas intake hood (2; 60) a first feed-in point (174) for a second process gas component to be added to the first process gas component and thereafter at least one further feed-in point (176; 178; 192) for the rest of the second or an additional process gas component. 26. Shell-and-tube type reactor as claimed in claim 25, wherein at least one mixer (182, 184, 186) follows the last feed-in point (178). 27. Shell-and-tube reactor as claimed in one of the claims 25 and 26, wherein at least one second feed-in point is formed by a fine sparging device (192) with a number of sparging units (194) distributed across the cross-section of the canal. 28. Shell-and-tube type reactor as claimed in claim 27, wherein the sparging units (194) are furnished with individual throttling devices and/or devices producing a twist. 29. Shell-and-tube type reactor as claimed in one of the claims 25 through 28, wherein at least one of the feed-in-points (174, 176., 178; 192) is arranged to receive the relevant process gas component in a liquid condition, possibly heated-up or to heat up said process gas component. 30. Shell-and-tube type reactor as claimed in claim 29, wherein the relevant feed-in point (174, 176, 178; 192) has a means of the injecting the liquid process gas component. 31. Shell-and-tube type reactor as claimed in claim 29 or 30, wherein the relevant feed-in point (174, 176, 178; 192) is in a position to atomise and/or to vaporize the process gas component in question. 32. Shell-and-tube type reactor as claimed in one of the claims 25 through 31, wherein the feed-in point (174, 176, 178; 192) and/or its administration has heating devices and/or is heat-insulated. 33. Shell-and-tube type reactor as claimed in one of the claims 25 through 32, wherein the check valve arrangement (180) is present between the first and the second feed-in point (174, 176; 194) there. 34. Shell-anci-tube type reactor as claimed in one of the previous claims, wherein it can be used for oxidation, hydration, dehydration, nitration, alkylation processes and so forth. 35. Shell-and-tube type reactor as claimed in claim 34, wherein it can be used for the production of ketones, methyl-isobutyl-ketones, mercaptan, isoprene, anthrachinone, o-cresol, ethylene hexane, furfurol, acetylene, vinyl acetate, isopropyl chloride, naphthalene acid anhydride, vinyl chloride, oxo-alcohol, pyrotol, styrol, methanformic acid nitrile, polyphenylene oxide, dimethylphenol, pyridinaldehyde, Therban, alpha olefins, vitamin B6, prussic acid, aniline, formic acid nitrate, difluoromethane, 4-methyl-2-pentanon and tetrahydrofuran as well as in particular the oxidation of dimethylbenzols (m, o, p) into the corresponding monoaldehydes and dialdehydes, oxidation of dimethylbenzols (m, o, p) into the corresponding monocarbonic and dicarbonic acids or their anhydrides, oxidation of trimethylbenzols into the corresponding monoaldehydes, dialdehydes and trialdehydes, oxidation of trimethylbenzols into the corresponding monocarbonic acids, dicarbonic acids and tricarbonic acids or their anhydrides. oxidation of durol into pyromellitic acid anhydride, oxidation of gamma picoline or beta picoline into gamma picoline- carbo-aldehyd, oxidation of gamma picoline or beta picoline into isonicotinic acid or nicotinic acid, oxidation of propene into acrolein, oxidation of acrolein into acrylic acid, oxidation of propane into acrolein, oxidation of propane into acrylic acid, oxidation of butane into maleic acid anhydride, oxidation of refined product into maleic acid anhydride, oxidation of i-butenes into methacrolein, oxidation of methacrolein into methacrylic acid, oxidation of methacrolein into methyl-methacrylate, oxidation of i-butane into methacrolein, oxidation of i-butane into methacrylic acid, ammoxidation of dimethylbenzols (m, o, p) into the corresponding monoitriles and dinitriles, ammoxidation of trimethylbenzols into the corresponding mononitriles, dinitriles and trinitriles, ammoxidation of propane to acrylonitrile, ammoxidation of propene into acrylonitrile, ammoxidation of betapicoline into 3-cyanopyridine, ammoxidation of gamma picoline into 4-cyanopyridine, oxidation of methanol into formaldehyde, oxidation of naphthalene and/or o-xylol possibly mixed into phthalic acid anhydride, oxidation of ethane into acetic acid, oxidation of ethanol into acetic acid, oxidation of geraniol into citral, oxidation of ethene into ethyloxide, oxidation of propene into propylene oxide, oxidation of hydrogen chloride into chlorine, oxidation of glycol into glyoxal and hydration of maleic acid anhydride into butane diol. 36. A process for operating a shell-and-tube type reactor as claimed in one of the previous claims, wherein the shell-and-tube type reactor is run in production operations with such a charge of a first process gas component with at least one further process gas component with which occasional deflagration or even detonations must be reckoned with. 37. A process for operating a shell-and-tube type reactor as claimed in one of the claims 1 through 35, wherein for starting up the reactor the concentrations of the process gas components and possibly additional parameters as well are measured on an ongoing basis in such a way that the violence of deflagrations or even detonations occurring does not exceed that reckoned with for operating conditions. Shell-and-tube type reactor for carrying out catalytic gaseous phase reactions, comprising a contact tube bundle (8) through which the relevant reaction gas mixture flows and which contains a catalytic filling, extends between a gas intake-side tube sheet (4) and a gas output-side tube sheet (148) and is flushed by a heat transfer medium inside a surrounding reactor shell (6), further comprising a gas intake and a gas output hood (2; 60) spanning the two tube sheets for administering the relevant process gas to the contact tubes or evacuating the reacted process gas to the contact tubes or evacuating the reacted process gas from the contact tubes and comprising a process gas main pipe (172) for feeding the process gas into the gas intake hood (2) characterized in that the process gas main pipe (172) comprises a first section, in which the process gas is in a non-explosive range, and in process gas flow direction behind it a second section, in which the process gas is in an explosive range; the process gas main pipe (172) comprises in its first section a check valve arrangement (180), the check valve arrangement (180) comprising at least two paralleled check valves; a pressure reduction space is disposed in the first section downstream of the check valve arrangement (180), the pressure reduction space being formed at least partially by a chamber (190)housing the check valve arrangement (180), and the check valve arrangement (180) and the gas intake-side tube sheet (4) and all parts therebetween, which bear the process gas pressure under normal operation conditions, are also designed for stability for the maximum pressure caused by a deflagration or detonation.

Full Text

Shell-ar.'Ci-t ube type reactxr for carrying . ut cata y
gaseous pnas-r reactions and a procedure for operitinq r n
same
I The invention relates to a shell-and-tube typ~ rea-'t'-r
j according to t le generic terms -of patonfe-Ji;4r^-3L-m—i a.:' '.vel . is
, \ pirocedure for ,'perating such a reactor.
S'^uch a she! I-and-tube type reactor is app'roximatei / Know,
from DE 100 21 986.1. In that specific case hr-v/eve: tne
endeavour tc- rr^duce the risk of deflagration -^las l-rd thf
inventor, zo s )me extent, to feed a criticall/ exp lo::^ iv>:.
component of tne process gas brought to reaction j-'i : he
reactor only immediately before or even in tne rea-t;or,
tubes. Moreover, the volume available to that component
is until then fitting inserted into an otherwise cc'nventional more jr
less spheri::al cap-shaped gas intake hood. These mea.rui^. - -.t
based on the t-llowing insights:
1) In order tr. attain the greatest possible |;roduc-:i.n
capacity m r-^Lation to the size of the react 3r s-,'-5t';m ¦ is
desirable t i he able to maximise the process gas r'large .¦- t h
the criticall\ explosive components sucn as ixyger: acd
liydrogen.
2) The risk c-t a deflagration increases, besides i \ ie.i.;t i in
to the charge, with the amount of time m whiih tf-- ^ wc
components are ooth resident in the same space.
i'nere have pre- lously been attempts to guard ngairi.--t exf r. -
sive damages t • >jm any eventually occurring de : lagr it „ oii-- ; y
installing lup' jre disks in reactor systems. ;-ut i' * ne i .m
is to further increase the charge and thus th- output ai .vel.
then the use c-: rupture disks is inadequate lu viev/ .-,: r t ,-
heightened risr;s of deflagration. Replacement of tne rup' ire
cisks, expensi .'e enough in themselves, m the case ot a :¦-
flagration req_iires relatively protracteci rep^air v,'_;rK an:
concomitantly ..rotracted down times. The rupt are or" rupt .. i ^
disks is conne ~ted with a blast wave which ca:'i be leard i liie.
away as a bang and simply for that reason is maccep:: at . ; - !¦
siddition noxious gases can escape into the encironiaer t.
Moreover, after a deflagration and the concomitantly ne^ ^ssi -
tated replacenvsnt of the rupture disks the re-starlirig - i idi-
reactor required in each case is difficult ani time-'.; or.-..-
ming, especially since during the build-up tc^ a great ei
charge in operating mode care must be taken tnat p^ssir;-:
through the deflagration range of the gas mixture :ui; re: ' iv
being fed mte the reactor is avoided.
Such a deflagration range can be illustrated ^n a tw. three-componen*: diagram like the one shown ir. Hanciburh .•- -
Explosionsschut zes by Henrikus Steen {Verlag Wiley-V/H,
ed, 2000, page 332) where the third component, is an ne.' uo-
added for dilution such as nitrogen. It has keen snown ¦ ' it
the danger of a deflagration only obtains v;itnin a w:nci> .-.
like range thfit is moreover dependent upon pressure,
temperature aii:: geomietry.
According t,o C'E 198 06 810 Al the temperature of t .te ti;i r
sheet on the gas intake side can be reduced cy a tea^ ; ¦ .- >
lat ion layer ^applied to it in order to prever.t; hazardou.
lateral reactions including ignition and def1^gration.
"tP I 180 50c Al i^riows how to avoid the defiagr^cior cauq^^
thcouqh oonstarit measurement and modificatLcn ;t th- p-o- . :-
gas composition luring startup of a reactor, i: v;hi-ri ;a;-
initially an in-rt gas is added that is then s.ccessivrl:
replaced by ali-ady reacted process gas after me irdc:!
sets in.
Or this basis, me present invention is based _n th-- :ir^"
instance on the problem of being able to increase ir-ie :h.-i r j-r
of process gas lo be moved forward to reactiC'O in -i risk ,---.'
and additional!/ economic manner.
This problem is solved by the invention with t ne feat:.rt'. f
Claim 1 to which those of the subclaims then make a furt.'>-M.
contribution.
I Secondly the ircv-ention is based on the problen of :pe-a*; -i'J
' shell-and-tube type reactor according to the -nventioi t ,
taking corrunerc lal advantage of its spsscial pr'.^.-pert : es . [¦ .-
¦i
pproblem is sol\-ed by each of the two process :laim.. - :) .^ ^
i 40.
The reactor or the invention miay for one thin;] eve.-: te ¦ (. - r
ated with a critically explosive charge of the pr^o -e^s .i-: '
be moved forward to reaction, for another thi ig h\- g-ir,;
through an igriitable range during startup, scmethiig the
significantly tacilitates and accelerates the pro.-^s- - ¦
startup.
For the follo-/:ing considerations a distincti'n mius^ be :'i-o^
oetween a deflagration and a detonation (or ^xplo;icn>,
distinction that nonetheless was not made in rhe ^le 'a ¦ .. i/
cited EP 1 18' 508 Al which was based on a translr.-Li r; ¦ : .'H:
Japanese. In • -jntrast to deflagration ohat i.: set ct: o \i pomt and pro-'okes a blast wave travelling a' sub/or,i'. .:.-e'.
4
a detorifjt irr. if a consicierabl',- more sudden a; :! co: SciUr-- ¦ ly
¦/lolent trccess that in most cases presuppos-s, b- -i le.
even more special gas miixture, a deflagrcatioi" p^re; ^Ti" no
rnat can develop over a specific design-related si ^r' ir,': .r
entry region.
Fere below, se^'eral embodiment examples of tn-r inv-n^ I'l r v; i_ 1
now be described on the basis of their accomp inyiir j ^irav, i-iqs .
Fig 1 shows a " ube sheet on the gas intake si le toviet-ie; .-» 11 r
a gas intake h. od of a sheli-and-tube type re^nctor aj -o ¦' J i fig
to the invention in a longitudinal half-secti n.
Fig 2 shows a c-ross-section through the edge • f the tiib^-
slieet shown in Fig 1 at the level of Line II-: I in .^i; ': ,
Fcg 3 and Fig 1 show details similar to those m Fl ] \ di :
Fig 2 but with an embodiment with a fitting ir;serte i int^
conventional gas intake hood for feeding in pi jcess q.-jS,
Fig 5 shows a semi-longitudinal section simila-' to ¦ hr- (.-i ¦ :n
Fig 1 through t-le tube sheet on the gas intake side ar: i
conventional sh--Ll-shaped gas intake hood and .t fit' iri.f
serted into ^t similar tC' the one in Fig 3,
Fig 6a) through Fig 6f) show in each case an emO'Odiner, . -partially permieable seal as illustrated m Fig 5, i; a 1.. i r^ r
scale,
Ficj 7 shows a sirriilar illustration as Fig !) bui witn ar ot ' -
embodiment,
Fig 8 shows a S'lnematic drawing of a suppoii arrange i i ns
a shel 1-and-t uoe type reactor according to the .nven' i- ri.
Fig 9 shows a 5c;hemat ic drawing of a gas intal-:e hc.^d -irr ir
to r he one in E ig 5 with cooling and/or heating de- ic-s ¦. ¦ ¦ ¦
vided on i t.
Fig 10 shows a similar illustration as Fig 7 with r ne d^- ' e
preoedinq the process gas stream fed into the reactor, i '.
Fig 11 shov7s a schematic drawing of an alternative pi ;c^-
gas feeding in connection with a gas intake h/'Od a.cc-rdi i ] i
Fig 1.
Fig 1 shov;s soruewhat schematically the gas in^-ake --no ci
shel 1-and-tube type reactor according to the ^nvenr ic^n L ¦
carrying out Crttalytic gaseous phase reaction.- in ' he c- ¦ i ¦
cal range for .lef lagrations or even detonatioiis . Mere pre-
cisely stated, in E"ig 1 a spsscially dessigned gas intaKe ¦-1
2, a tube sheer 4 underneath it, the reactor shell o dd : i --n
to it, a ring-.-haped contact tube bundle & (h.nted at h': ' n
a broken line) and gas intake pipe socket or :iOzzl^ "._ j i ¦ --i
ding intc^ the '-fas intake hood 2 can all be recogni;-ea.
In the usual manner, the tube bundle 8 contaitiing -: :-^ai' r i-
catalyst filling is irrigated within the reactor shell -
a heat transfe": medium which is - in any case in oi ei it i ¦
liquid and via which throughout the contact t.ibes : siit i: ;-
temperature prtfile is maintained and excess react oii h./ .¦ i
led off.
As can be further seen from Fig 1, the gas intake rot^J
apart from a m-iissive peripheral collar servin-; its at •;^a" ^ —rv
to and sealinq--:'ff of the tube sheet 4, is re.ativ- Lr t: .
£nd somewhat trumpet funnel-shaped so that berween i" .^^ ; ' t-
t ube sheet 4 triere is a fiat gas distribution spac^ _4
'neected ever^ily, chat is without steps, kitiks o: so t'jr^\i, '
the gas intfiko l ice socket or nozzle 10. Attaorimerr: c! • ' ¦¦
gas intake h.,-;:-:1 2 to the tube sheet 4 is aocomplisheci '/;
studs posit lone:; around it which are o^nly hin::ed at hr-rf
The gas distritition space 14 is dimensioned : ri su-" n i w .
that the prcoess gas feci into the contact tubes thicugh
flows as evenlc as possible into the cont.act rubes, i^e. r;
order to minimise turbulence as well as residence rimi-.
doing so, the aesign of the gas distribution space 'na ¦
aoprC'Ximate 1 y t: e such that the radial flow component -r ^rri
tne static p^ressure in the process gas remains conttaut :
the radial dir the Cither hand the trumpet funnel shape of the gas in';ak ¦
hood 2 can oe approximated as well by more or less co,;i i
ring elements not shown) . To produce evennes- in t fit' g/i-
flow at the en* ry to the gas distribution spa-e 14, a s| -¦--
shaped flow di'erter 16 is arranged tnere underneai h th'- jds
intake pipe so-'kef or nozzle 10 and resting or. the tuoe .^-e'
4, which simultaneously constitutes a displac-r in oile.-'
prevent the ga.- from impacting frontaily in tne mijdi^ ¦ ' n^
tube sheet 4. The minimum height of tlie gas d:strii ut^O'i
space 14 is dei ermined in the example shown by a s^aiino" inj
18 of defined iimensions with which the gas distribut ic,-
space 14 is se.-iied off from the outside. It i.- detr-rnitn- ; ir
the planning s . age and must in any case be bii enc.i.gh s_ -t.^'
at no point m the reactor circumference does it t'^-cwme i. ,
for example be -ause of unevenness in ths^ hood 2 ana/..:r- •
tube sheet 4. l-Jnere required, the hood and/or the ' ub-> '-—.---'
must be smooth-J or faced at the same point.
Since however -i dead space 22 can hardly be at'oide i by ;-_ - iqr
C'Utside of tht radially outermiost contact tub-^s, a
tor example 21., but inside the gas distributi .-n sp'.;Cc: 1-
v/ithout obstru;ting the entry of gas intc the radiil_i/
outermost cent-;ot tubes and since such a cieao spac- w vi, ^ i
entail undesirtble residence of the process q^s, ni-d^ji-: "
have been take:, at these points to displace tne pi' cess i-js
out of the dea "1 space 22 or at least to "dilu" e" i' "^ :- -.
composition nc": critical for deflagration. Thrs is d^.^ le - - ,
injecting gas i-.'nich is deactivating in regarc to tt.e let . i-
gration reacti.-n feared. This could be an inert ga.-- sic:" -is
M; a by-producr produced in the course of the operit]Vfc ie-
action such as '1'02, occasionally simply air oi ever a m_i ¦.•ur^
of such gases.
According to Fig 1 the gas in guestion, referred t her- i-e-
low as flushiri'iT gas, is injected via a circular pije 24 ¦
the periphery .if the tube sheet 4, from thenc^^ inw.->rds '
junction canals 26 branching off at regular iriterv.-.is a I " - q
the periphery - ¦! the tube sheet 4 and then vi i nozile b' :.-'S
28 branching c^ff upwards from the junction car^.als 6.
-As can be recc-^nised fromi Fig 2, the nozzle h'^.res , 8 s 1 _ i> iri
the peripheral direction of the tube sheet 4 .n or lei i' .ive
the gas exiting from it a radial flow compontnt ani, Ln lat
way, to flush _t through the dead space 22.
Fig 3 and Fig 4 shov; another embodiment of th- gas iiicar.' eno
of a shell-and-tube type reactor according tc the _ n\'en'" . ii.
Here inside a lonventional shell-shaped gas i-.take hooa, r
which only che edge 40 is shown here, a fitti ig re.-tii'/' '-q
the gas disr ri jution space 14 can be recognis-d. Whtrre .e
parts shown here and below are identical to t:,C'Se n Fi : .
and Fig 2 they have the same reference numibeisi .
In a further departure from the embodiments a"Scr:^iea
earlier, here i circular pipe 44 for flushing gas ¦ ¦:> oe .. - i
into the dead space 22 surrounds the edge 40 .f th- ^jis , -
take hood and -iccordingly junction canals sini._lai o ch-
junction canals Z'o extend radially throucgh the edge 4 C . '¦
iunction canals 46 run into nozzle caps 48 arr.uigeo or '; i
insi.df^- of the eciqe 40 with tanqentially alignel noccles -
for gas output, likewise to flush out the dead spac-- ./I ^
much as p>oss ib 1 •- .
Fig 5 shows an arrangement similar to that of r'ig • r_ tj
extent that here too a fitting 42 is provided for iis]de ' r,-
shell-shaped gas intake hood. As can be seen, the fitfir.-. -i .
is freely suspended on the gas intake hood 60, more p.t e^; -J',
on its shell 62, anchored by means of stud bolts 64 as w.-
as by the gas intake pipe socket or noz2:le 10 in such a ^ .,
that deflagration or detonation forces possibi_y oc:ui;in; ; r;
the gas distribution space 14 are led into the she^ 1 o2 . ii
order to absort these forces as well as possible, ^he sh- . l
62 is shaped Like a spherical cap.
In this exempl.riry embodiment the fitting 42 is cojX[\ osect ' -i
slightly conic-il ring disk 66 and a profile ring 6-. r:jui i- i
off inwards an 1 downwards and is supporte;d at its -.-due 'i -.
a partially permeable seal 72 on the tube sheet wh^l- th- la^
-intake hood €y' is filled up outside of the fitting 41 w.' t
the flushing gas for the dead space 22. From thence 'he
flushing gas enters evenly, to the same extent as it i;^ '-g
on an ongoing oasis to the gas intake hood via a rip^ 4,
into the dead space 22 via the partially perm.eable s^a!
around it .
The gas mtak-^- hood 60, more precisely its massiv^, ehgf ¦ ¦,
is sealeo against the tube sheet 4 in this example v ..a ¦. ' vT--
of welded lip seal 76 similar to that aescrired ii
pE_^44 07 7'28 ¦'!. Actually here too a sealing ring suit i i :- -
sealing ririg .t from the previously described emb' di ae:c
could be used. Preferably the flushing gas stands ii: a - -^
tion i:o t h- external atmosphere as well, naturali ^-ri-.^.., k ,
ill relation to ine gas distribution space 14 L;nder ni^jh
pressure in or,1er to function as a blockiriq medium.
Fig 6a) through Fig 6f) show variously different c;jc'r-nr ,
considered embodiments for the partially permieable se;;]
from Fig 5. Ac:-^rding to Fig 6a) the partially permieat If- —rdi
71 consists ol i ring 80, of itself of a circular or - vk-: il-
rerady elliptica^ cross-section made frorri a pc^r^us aid sj ;rir -
ly compressiole material such as, for instance, graijhite ' s-
sue compressed from a ring-shaped projection ^^ i of .h.- t' -
ting 42 into a corresponding ring groove 8 4 of the ¦ uf e : r^^-et
4. According tc- Fig 6b) the seal 72 consists cr a C-sfap't :
profiled and preferably metallic hoop 36 having on .ts O'.:
side towards the tube sheet 4 a number of regularly spric^^ i
radial or even .-omewhat tangential furrows 88; and nc: dl .: l ¦ .q
to Fig 6c) the -^eal consists of a massive elastic s^a^ i,n :
ring 90 similar to sealing ring 18 in connect! ;n wi" h ra i i -:
or even somewhai tangential bore holes 92 m a proic-ctio; -4
similar to the projection 82 in Fig 6a; . Accor ling to ^'i. --g j
the se?al 72 is .:ormed from a ring 98 provided -.-.'ith !aOi_a. r
somewhat tangent lal furrows 9 6 and having a ba.-ically ro :i i
cross-section ar,a being formed of metal or of another -la i
elastic materia"., the ring lying in a ring grc-'ve li 0 ^n.- At-
a projectic^n 10_ similar to the projection 82. Acccidi :g
Fig 6e) and of' sheet profile rings 10- or 106 or ar.gl-td
cross-sections are used as seals 72 which in turn and xs
emerges frc.m Fiq 6e) can have furrows 108 to t^e tute --hi-' ¦: -1
similar to the lurrows 88. Such profile rings ¦ an bt- f , e> i. ^-
in regard tc high pressure imipacting on one si;ie in iraet '
open up for the llushing gas a smaller or grearer flow-
through cross-section.
Fig 7 shows an i^rrangement sirriilar to the one .mown lU F:
where however tre flushing gas enters radially chro-u^h tl-
tube sheet 4 mti a ring-shaped space 120 between a .ve. de. :
10
Lip seal 122 ;imilar to the welded lip seal 6 an tvo • ose
ly ':onnectea sheet rings 12 4 and 12 5 outside jf tre •'i' ¦ . nq
\Z. The essentially cylindrical sheet ring 1^2 atr -ic.ne 1
rightly to the edge of the fitting 42 6?xtend>- wher I .os- mc
a ring groove 128 of the tube sheet 4 in ord-^r to, ii t,- .-; l
nanner, form a partially permeable seal m re^ati:-i "o ' i.--
qas distributi ;'n space 14, similar to the paitial_L/ pei rr:-.Tbl-
ring 72 known from Fig 5. The stud bolts 64 known 2r:m i-; j 2
are replaced in this example by pierced crylinirica. sne^t.--
130.
E'ig 8 shows ho.-/ the tube? sheet 4 on the gas i-itake side ni
be supported t-iwards the gas output end of the rea;t';r ;. - rh-
event that m '; ne gas intake region a def lagr dtiori or ev--; a
detonation should occur. In the example shown ther-^- a c^; : ; es
ponding support 140 is formed as a multi-winged met ai c-:uii'.'-
nent or is made of at least two radially extertding metal -orn
ponents essentially formed by two sheets 141 standtng ii\ "he
shape of an x which, prcjferably loosely, engaae into tor • >-.--
ponding grooves 142 on the underneath of the * ube t hO'-t ¦ tii"
fit into corresponding radial lanes of the tare bur.dl.- « in
addition the ce-ntre of the tube sheet 4 can, ;)S shtwn, Li-
supported inside the tubeless medium region 144 near ' hr-
bing by means if diagonal struts or by a sheet metal -or:- i ^ on the sheets 14 1. This makes it possible under certain r
cumstances to o :• with a single sheet 141 thus saving pei i -.(.¦-
up to two tubeless lanes. In place of the sheet metil ct' -
146 one could also have a cylindrical, prismatic or p', rai' i
sliaped metal component .
The support 140 may but need not, as shown, run thr -uon '
the tube sheet 148 on th€^ gas output side or t " a s-'parat
plate. In any C:ise, however, it must be m a p^ sift 'ti tc
gride the supporting forces into the reactor snell. Tc
compensate the different heat expansions the sneets ItKC
sheet 141 cari h^rre, especially in the vicinity of t; c _}ci
intake-side tubT sheet 4, longitudinally extending :':2^'.s
rtliet slots 15i as well as correspondLng recesses ^: :-y
their attachment to the reactor shell 6. Other'.-.ise Mie .• f. , . ,
wherever this c-: uld be functional for flow-technica_ r-a.- t ¦-
or to save weight, be pierced or replaced with a sk-le\a: )^¦
sign. Resting the support 140 on the gas output side t.;bi-
sheet 148 has, n:t least of all, the advantage that th-n --¦/-n
the latter is supported against deflagration pressur- ]c^ .--
propagating throigh the tubing towards the gas 3utpu'- .-^ po -
or v/hich could be generated there from a subsequent igr it
According to DE 198 06 810 Al the gas intake side tui:;e sh^-r
4 can be heat-insulated (not shown) in order tc keep tte .-i ;
distribution spa 'e 14 "cool" and also to reduce tend^fn'.ie-
towards deflagra' ion or even detonation.
Fig 9 provides r.. r the same purpose - with an a rrangr^menl
similar to that -> n Fig 5 or Fig 7 - at various {:oint.^ ; i -. ^ on the gas intake- hood 2 for coolant canals 160 whicl- '-tri,
however and espe'-'ially when the reactor is started uf. , iJ -
function as heat n\edium canals and can additionally or -1
bute to reducing heat stresses.
Fig 10 shows the :ias intake end 170 of a shell-cind-tuoe t ;: -
reastor according to Fig 7 with upstream facilities t r.^r p;
paration of process gas. In the example shown, at an\ q v.
P'Oint 174 a secor ;1 process gas component, such as a t yd; c
carbon gas, is f e g into a main pipe 172 in which a suit i\ ¦
tempered process gas basic component flC'WS under appr Dp] i -¦ ¦ -
pressure, for exaniple air, the so-called main fisw. Tne s-
cond process gas component is fed in in a quantity n-:.': ; ei
dering the process gas capable of deflagration wtiiie -id:-i
tiorial partial quantities of the second or even addit^o-a
process gas comp-^rients are added at 176 or 178 q^v/nstree.m
d check val\'e •^irrangement 180. At the latest -iftei tf;- ; -i
1 n point 17P tr.e process gas is in the explos:ve i--nq-r.
Ail of the process gas components fed in are .-" ubseourr it
mixed in several coordinates by means of seveial sr;-c-s;-
mi:^xers 182, 184 and 186 and mixed gently, that is r i^r it
stance with the greatest possible avoidanc:e ot turtjl-:nc. - ;r
addition care is taken in pipe routing to avoi :1 any u'".ev. -
ness. Furthermicre, the pipe 188 between the chi-ck -.'il-.e .¦
rangement 180 arid the gas intake hood 2 is kep' as ih'. r*: i-
possible to pre\'ent the accumulation of high def lagi at lo;
pressures. The check valve arrangement ISO prcients an/ ; ..-.t
wave generated ]n the pipe 188 or downstream tr_erefi orr t' -'¦
propagating further into the main pipe 172 and causing d.i^-. .
ges to the orgars feeding into the latter. The check vd'—
arrangement 180 is located in a chamber 190 simaltaneoL.s.;
forming a desiraole pressure relief volurrie for such i ;_ l wa\'e. The chambe •_ 190 can have any shape and can con'airi
practically unlimited volume just as additional chamoeis
likewise be adde.i at the same point. If require'!, th'^- lir
feed-in point f^-i can incidentally likev\?ise be rolloi-.eci t', i
mixer (not shown , preferably m front of (i.e. upstieaii: ¦ -^
check valve arrar_gement 180. Nevertheless, the reed-iri ,c :
174 can be locateii far ahead of the check valve arrargene,.
in 'Drder to attaiti in this way a favourable mixing, in Mi-
other hand, possioly downstreami the check valve arrangerier ¦
180, a single additional feed-in point such as 1 '6 ani ¦
single mixer coulj also be sufficient.
The check valve arrangement 180, the chamber 191', the pio.-
188 and the mixer-: 182 through 186 included in triemi a:.d 'r.
feed-in facilitiec as well as the reactor itself are c:±:.
designed as to st;engh and stability to withstan: the gi-.c
est deflagration r detonation pressures occarrirg ir, th^m.
This applies, as stated, despite the previously lescrioed
measures to avoiii as much as possible netonati' ns ar i -il.-
de LLagrac icns.
Fig 11 shows an arrangement in principle simil-r tc th-it
Fig 10 but m C'/nnection with a gas intake hoc.; 2 a._ cc.-:d, ¦. j
to Fig 1, the mi.xers as v/ell as a curvature in the r ip- . - ¦
being omitted, the pipe in this case being part icul.:-.r 1 /
short, lyiixers entail in any case disturbances .n ga; iLow-,
something that makes the relevant process gas f-ven r.ore .-: i - ¦
ceptible co deliagration. For producing particalarl- aefi i
gration-crit ica.: process gas miixtures one should the-refot'-
try to avoid mii;-:ers as much as possible. Morec"'er tne oo-f -
ble starting or Duild-up length for the generation ¦£ a j-'
nation should be shortened.
According tC' Fig 11 the check valve arrangement 18Ci i::- d,-
posed cent reel over the gas intake hooa 2 on the axi s - f • : -
gas intake pipe socket or nozzle 10, and instead of tre • .'v
feed-in points L76 and 178 in Fig 10 a single fine sparg t i
point or device 192 is provided while there are no ni;-er- ,
The fine spargi;ig device 192 has a number of spargi'ig an t ¦
194 distributed across the pipe cross-sect:ion, i.e. at i—v-t
five but preferably 50 such sparging units 194 per -n-^' or -'.'i-:
more, and whicn can be designed to have nozzles an^ i;.di
vidual tiirottling devices simiilar to the sparging i^nii s t
tne contact tube entry according to DE 100 21 986 AI rin>l l
wnich are able to give the p-rocess gas components spaj ge - ¦ m
a twist. In this way, feed-in of the second piocess g.ts :ti"
ponent, such as a hydrocarbon, is so finely districuted ¦¦¦ i
regularly admiiiistered that there is no need ror mi:xe-"s i
producing a hoii ogeneous process gas flow.
In principle, f he process gas components sparaed ii -_ in ; •
present in liquid or gaseous form, cold or hcoted-'4:. W;'
liquids it is feasible to iriject themi by miean- of i.n i.n--
14
gais. Either .vay, sparging can oe done at high oress^ir- ;•
order to p.roiuc-:- partial vaporisation ccmk)ine:i with biea'-- jp
of" the flow sirtiLlar to the way this is pi:acti?-:-d in t-eci ; ;
automotive tuel zo the cylinder chamber of cornoustijn
engines.
The sparging zc-rie can be furnished with a shell hea^^ei at :
accordingly the feed pipes for the second prc'cess gas rai r^e
heated or heat-insulated.
The design of t ne reactor components as to staoilit ; .:.nc
strength depends on the type and concentration of trie mcr--
rials to be prC'iessed. It is usually undertaken for st at
nary operations. When starting up a shel1-and-tube iy[e
actor of the t\oe described above care must ccnsequenrlv t--
taken that at ri : time the deflagration or detonation ;-ti> !.)rh
estimated for ;perations is exceeded. Normall\ one 3tc-.r*"_ ip
with only one -f the various process gas components ( t hf- ;; uti
flow). When a ertain mass flow of this has been atia nf
then the secorr;; process gas component is addeo. If m th
plant's operat : :ns itself an inert gas like Ct is ;jr(_dU' -¦ i
then startup cau be accc'mplished by including it, r^sse-nt li li,
in accordance '.-. ith EP 1 180 508 Al. Whether in starting i ^i:
inert gas is t. be fed in additionally or whetner t ne dct i-i
of deflagratior and detc^nation severity can be redu ie>l ;- Oi ¦ i'.
by varying pre.-sure and temperature to operational Ie-'e_ is
governed by thr details of the process.
As already mern ioned in the beginning, startuf. can ani in .
entail the ignitable range. Just as in normal iperati; n, • 1-.
in startup bes.ides the process gas compositicr other [.ar -r --
ters such as, rri-st especially, pressure and temperatuie, oiv'^-
to be taken iir" .i^ acc:ount . Both of them affect ihe cef a^i
tion and det c n.-i t. ion behaviour. It is possible to vary
pressure and t-:-mperature during startup. In tr at Wav, wri-
15
starting up pressure can be reduced while the ^empeiat jr*- ;.
th'S gas distribution space 14 is raised. At tti- latest
towards the end if the startup phase both are ' nen ;-d: ^s'- :
tC' the operatioridl levels intended.
If a shel L-and-i: ube type reactor is run in the lov-;e] i:;f.: i-
gration range, ^" nat is with only a minimal risi of uer La.;-; i ¦-
tion and minor deflagration pressure to be taken in-o ac-
count, and if I'l doing so a recycle gas out of the e^it : ts
inert gas is fed into the mam flow, then star-:up i ui oe i ¦¦-
ccmplished in the following manner:
First via the main pipe 172 air or oxygen is r-rd iri ai tr-
main flow. Then one starts feeding in a hydrocarbon fiow . , .t
the sparging device 194 (Fig lli . As long as tne hy Ir ; la.-: oi
concentration is low there is no risk of deflagratim. Tr -
recycle gas recovered likewise basically consists lul. c'
materials from the miain flow. As the startup process -idv.^ri^-s
and hydrocarbons are added the reaction product is iliea:',
being produced as the result of which the recyiie gas a\ : ^-.-^dy
contains a portion of inert gas like carbon dioxide, .n ¦ i ¦-
further course of the startup process the hydiocarl^n tJ .-. is
increased. But since the main flow by then already icntd • _ .^
significant portion of the inert gas at no tine a ^ri- !¦¦
level is reached. In principle, in this way tre attempt
made to avoid tdie explosive range in the starrup pi aS'-
order to enter into the explosive range only -Ahen -"ut';^'- nt
process stability has been achieved.
In principle, the same applies as well to opeiatioi s ,_n ' -i-
upper explosive:- range. Here, however, the hydrocart ii" f; -,-; is
normally administered via the feed pipe 172 ai maii r .o\while, for instance, oxygen is fed in via the spaijir',! i-- lc-
194 .
Accordinq to rhe current level of knowhow, a shel.-a id^ ¦ te
type reactO't -jrcording to the invention can re ad'-.^rra'i- is
used fc'r oxidation, hydratic-n, dehydration, ritratioi , k /"
ation and similar processes and then especially f:; r ^ h^- ; l^'
duction of ketones, methyl-isobutyl-ketones, mercaot-n, .-¦¦¦
prene, anthra^iriinone, o-cresol, ethylene riexarie, 1 jri'ji
acetylene, \'in.-: acetate, isopropyl chloride, naphth-ri len-
acid anhydride, vinyl chloride, oxo-alcohol, oyrot 1, si , ¦ 'l
rrethanformic a-'id nitrite, polyphenylene oxide, di;rie;;nyj -
phenol, pyridinaldehyde, Therban, alpha olefins, v tn,-^i- ---,
prussic acid, aniline, formic acid nitrate, di f luc-iomet-" i -,
4-methyl-2-penT-anon and tetrahydrof uran as wo-^i as in p.-i ¦ i -
cular the
oxidation of dj methylbenzols (m,o,p) into the corrc sf-^n^: i.j
monoaldehydes and dialdehydes,
oxidation of dimethylbenzols (m,o,p) into the correspond i?
mi3nocarbonic ar :i dicarbonic acids or the^ir anhydrioes,
oxidation of t r iiriethylbenzols into the correspondir, .j
monoaldehydes, Jialdehydes and trialdehydes,
oxidation of t r imethylbenzols into the correspondiri :j -^ cii^ ir
bonic acids, :ii larbonic acids and tricarbonic acids 01 v •¦ ¦ r
anhydrides,
oxidation of du-ol into pyromellitic acid anhydride.
oxidation of gaimia picoline or beta picoline into q-inura
picoline-carbo- -1 Ldehyd,
oxidation of garrima picoline or beta picoline irito iic-
nicotinic ac_d ¦ r nicotinic acid,
oxidation of priji-ene intC' acrolein,
oxidation cl aci'V.lein into acrylic acid,
oxidatio^n of prop^ane into acrolein,
oxidation C'f p-rcpane into acrylic acid,
oxidation of butane into maleic acid anhydride,
oxidation ci refined product into maleic acid anhydrio-,
oxidation C'f i-t:..;tenes into methacrolem,
oxidation of met riacrolein into methacrvlic acia,
oxidation jf no-thacrolein into methyl-met;Maoi /late, x;
O'f i-butano in":.' methacrolein,
O'xidation of a -butane into methacrylic ac;id,
ammoxidat iC'n o - dimethylbenzols (m,o,p) into : he
corresponding iijnonitriles and dinitriles,
arrimoxidat Lori ,: : trimethylbenzols into the cor-/espc^ndifiq
rriononit riles , iinitriles and trinitriles,
ammoxidation c' propane to acrylonitrile,
ammoxidatiori c; propene into acrylonitrile,
ammoxidation ci beta picoline into 3-cyanopyr;dine,
anamoxidation ci gamma picoline into 4-cyanopy/idinf ,
oxidation of miethanol into formaldehyde,
oxidation of naf-hthalene; and/or o-xylol possitly mixed .
phthalic acid inhydride,
oxidation of etnane into acetic acid,
oxidation of ertanol into acetic acid,
oxidation of geianiol into citral,
oxidation of et'iene into ethyloxide,
oxidation of pr^^pene into propylene oxide,
o>;idation of nyirogen chloride into chlorine,
oxidation of gl/jol into glyoxal and
hydration of mia -oic acid anhydride into butane dio:
A shell-and-tube type reactor according to the present inven-
tion presents among others the following features and advant-
ages:
The volume of space available to the process gas prior to its
entry into the contact tubes can be kept to a minimum
according to design and technical flow vantage points.
The space volume available to the process gas prior to its
entry into the contact tubes, dead spaces, in which the
process gas could fully or partially come to rest, may be
avoided as far as possible from design and technical-flow
vantage points.
In administering at least the process gas already ready to
react diversions and most especially uneveness may be avoided
as much as possible.
The gas intake hood (2; 60) may be fastened to the edge of
the tube sheet (4) on the gas intake side by means of studs.
The gas intake hood (2; 60) and/or its fitting (42) can be
cooled and/or heated.
The gas intake hood (2; 60) and/or its fitting (42) may have
canals (160) through which coolant or heat transfer medium
can flow.
The support may have a number of longitudinally aligned
pressure relief slots (150) and/or recesses (152).
The support may extend up to the tube sheet (148) on the gas
output side.
The support is loosely joined to the tube sheet (4; 148) in
question.
The support may fit into a recess (142) in the tube sheet (4;
148) in question.
We Claim:
1. Shell-and-tube type reactor for carrying out catalytic gaseous phase
reactions, comprising a contact tube bundle (8) through which the
relevant reaction gas mixture flows and which contains a catalytic
filling, extends between a gas intake-side tube sheet (4) and a gas
output-side tube sheet (148) and is flushed by a heat transfer
medium iinside a surrounding reactor shell (6), further comprising a
gas intake and a gas output hood (2; 60) spanning the two tube
sheets for administering the relevant process gas to the contact
tubes or evacuating the reacted process gas to the contact tubes or
evacuating the reacted process gas from the contact tubes and
comprising a process gas main pipe (172) for feeding the process
gas into the gas intake hood (2) characterized in that the process
gas main pipe (172) comprises a first section, in which the process
gas is in a non-explosive range, and in process gas flow direction
behind it a second section, in which the process gas is in an
explosive range;
the process gas main pipe (172) comprises in its first section a
check valve arrangement (180), the check valve arrangement (180)
comprising at least two paralleled check valves;
a pressure reduction space is disposed in the first section
downstream of the check valve arrangement (180), the pressure
reduction space being formed at least partially by a chamber (190)
housing the check valve arrangement (180), and the check valve
arrangement (180) and the gas intake-side tube sheet (4) and all
parts therebetween, which bear the process gas pressure under
normal operation conditions, are also designed for stability for the
maximum pressure caused by a deflagration or detonation.
2. Shell-and-tube type reactor as claimed in claim 1, wherein the
process gas main pipe (172) comprises at least one feed-in point
(178) for feeding in a partial quantity and/or a component of the
process gas, due to which the process gas passes from the non-
explosive range into the explosive range.
3. Shell-and-tube type reactor as claimed in claims 1 or 2, wherein a
device for injecting a flushing gas into dead spaces, in which the
process gas prior to its entry into the contact tubes could otherwise
fully or partially come to rest, the flushing gas being inert in
relation to the relevant reaction.
4. Shell-and-tube type reactor as claimed in claim 3, wherein a device
for injecting flushing gas radially outside of the contact tube
bundle (8) at the edge of the tube sheet (4) on the gas intake side.
5. Shell-and-i:ube type reactor as claimed in claim 4, wherein a device
for injecting the flushing gas in question with a tangential flov/
component.
6. Shell-and-tube type reactor as claimed in one of the previous
claims, wherein the gas intake hood (2) is designed flat and funnel-
shaped and with a distance to the gas intake-side tube sheet (4),
which decreases in the radially outward direction, and with a
central gas intake.
7. Shell-and-tube type reactor as claimed in claim 6, wherein the gas
intake hood (2) is rounded off at least approximately like a trumpet
funnel and is designed to flatten out towards the edge.
8. Shell-and-tube type reactor as claimed in one of the claims 1
through 5, wherein in a basically conventional shell-shaped gas
intake hood (60) coaxially a flat funnel-shaped fitting (42) is
arranged from which a central pass-through is connected sealed up
with the gas intake and the edge of which is sealed towards the
edge of the tube sheet (4) on the gas intake side.
9. Shell-and-tube type reactor as claimed in claim 8, wherein the
fitting (42) is rounded off at least approximately like a trumpet
funnel and is designed to flatten out towards the end.
10. Shell-and-tube type reactor as claimed in claim 8 or 9, wherein the
fitting (42) is supported at several points, preferably regularly
spaced out, on the gas intake hood (60).
11. Shell-and-tube type reactor as claimed in one of the claims 8
through 10 in connection with claim 3, wherein the sealing (72) on
the edge of the fitting (42) is to a limited extent gas-permeable and
the flushing gas in question is injected over it.
12. Shell-and-tube type reactor as claimed in claim 11, wherein the
sealing (72) in question consists of a partially permeable material
such as, for instance, graphite tissue.
13. Shell-and-tube type reactor as claimed in claim 11, wherein the
sealing (72) in question has discrete gas penetration canals such as,
for instance, drill holes (92) or furrows (88, 96; 108).
14. Shell-and-tube reactor as claimed in claim 11 or 12, wherein the
sealing (72) in question consists of a profile (86; 104; 106)
potentially flexible under high pressure.
15. Shell-and-tube type reactor as claimed in one of the claims 11
through 14, wherein the sealing (72) in question is connected on
the outside with a space through which the flushing gas is fed.
16. Shell-and-tube type reactor as claimed in claim 15, wherein the
space in question is limited by a radially inside seal (72) and a
radially outside seal (76).
17. Shell-and-tube type reactor as claimed in claim 16, wherein the
flushing gas is under high pressure in relation to the external
atmosphere.
18. Shell-and-tube type reactor as claimed in one of the claims 15
through 17, wherein the space in question basically consists if the
residual space of the gas intake hood (60).
19. Shell-and-tube type reactor as claimed in one of the previous
claims, wherein the gas intake hood (2; 60), the tube sheet (4) on
the gas intake side and/or, where there is one, the relevant fitting
(42) are connected to each other via a welded lip seal (76; 122).
20. Shell-and-tube type reactor as claimed in one of the previous
claims, wherein on the tube sheet (4) on the gas intake side.
pointed towards the gas intake, a spike-shaped flow diverter (16) is
arranged narrowing down in that direction.
21. Shell-and-tube type reactor as claimed in one of the previous
claims, vv^herein a support for the gas intake side tube sheet (4) is
disposed between the gas intake-side tube sheet (4) and the gas
output-side tube sheet (148) and is mounted to the reactor shell (6).
22. Shell-and-tube type reactor as claimed in claim 21, wherein the
support at least in part consists of two metal components (141)
which extend radially outwardly from the reactor's longitudinally
axis.
23. Shell-and-tube type reactor as claimed in claim 22 and with a ring-
shaped contact tube bundle (8), wherein the support consists
partially of an additionally basically cylindrical, prismatic, conic or
pyramid-shaped metal component (146) in the tubeless interior of
the contact tube bundle, said metal component (146) in turn being
supported by the radial metal components (141).
24. Shell-and-tube type reactor as claimed in one of the previous
claims, wherein the tube sheet (4) on the gas intake side is heated-
insulated.
25. Shell-and-l;ube type reactor as claimed in one of the previous
claims, wherein a first process gas component flows in the process
gas main pipe (172) and the process gas main pipe (172) comprises
in the process gas flow direction prior to the gas intake hood (2;
60) a first feed-in point (174) for a second process gas component
to be added to the first process gas component and thereafter at
least one further feed-in point (176; 178; 192) for the rest of the
second or an additional process gas component.
26. Shell-and-tube type reactor as claimed in claim 25, wherein at least
one mixer (182, 184, 186) follows the last feed-in point (178).
27. Shell-and-tube reactor as claimed in one of the claims 25 and 26,
wherein at least one second feed-in point is formed by a fine
sparging device (192) with a number of sparging units (194)
distributed across the cross-section of the canal.
28. Shell-and-tube type reactor as claimed in claim 27, wherein the
sparging units (194) are furnished with individual throttling
devices and/or devices producing a twist.
29. Shell-and-tube type reactor as claimed in one of the claims 25
through 28, wherein at least one of the feed-in-points (174, 176.,
178; 192) is arranged to receive the relevant process gas
component in a liquid condition, possibly heated-up or to heat up
said process gas component.
30. Shell-and-tube type reactor as claimed in claim 29, wherein the
relevant feed-in point (174, 176, 178; 192) has a means of the
injecting the liquid process gas component.
31. Shell-and-tube type reactor as claimed in claim 29 or 30, wherein
the relevant feed-in point (174, 176, 178; 192) is in a position to
atomise and/or to vaporize the process gas component in question.
32. Shell-and-tube type reactor as claimed in one of the claims 25
through 31, wherein the feed-in point (174, 176, 178; 192) and/or
its administration has heating devices and/or is heat-insulated.
33. Shell-and-tube type reactor as claimed in one of the claims 25
through 32, wherein the check valve arrangement (180) is present
between the first and the second feed-in point (174, 176; 194)
there.
34. Shell-anci-tube type reactor as claimed in one of the previous
claims, wherein it can be used for oxidation, hydration,
dehydration, nitration, alkylation processes and so forth.
35. Shell-and-tube type reactor as claimed in claim 34, wherein it can
be used for the production of ketones, methyl-isobutyl-ketones,
mercaptan, isoprene, anthrachinone, o-cresol, ethylene hexane,
furfurol, acetylene, vinyl acetate, isopropyl chloride, naphthalene
acid anhydride, vinyl chloride, oxo-alcohol, pyrotol, styrol,
methanformic acid nitrile, polyphenylene oxide, dimethylphenol,
pyridinaldehyde, Therban, alpha olefins, vitamin B6, prussic acid,
aniline, formic acid nitrate, difluoromethane, 4-methyl-2-pentanon
and tetrahydrofuran as well as in particular the oxidation of
dimethylbenzols (m, o, p) into the corresponding monoaldehydes
and dialdehydes,
oxidation of dimethylbenzols (m, o, p) into the corresponding
monocarbonic and dicarbonic acids or their anhydrides,
oxidation of trimethylbenzols into the corresponding
monoaldehydes, dialdehydes and trialdehydes,
oxidation of trimethylbenzols into the corresponding
monocarbonic acids, dicarbonic acids and tricarbonic acids or their
anhydrides.
oxidation of durol into pyromellitic acid anhydride,
oxidation of gamma picoline or beta picoline into gamma picoline-
carbo-aldehyd,
oxidation of gamma picoline or beta picoline into isonicotinic acid
or nicotinic acid,
oxidation of propene into acrolein,
oxidation of acrolein into acrylic acid,
oxidation of propane into acrolein,
oxidation of propane into acrylic acid,
oxidation of butane into maleic acid anhydride,
oxidation of refined product into maleic acid anhydride,
oxidation of i-butenes into methacrolein,
oxidation of methacrolein into methacrylic acid,
oxidation of methacrolein into methyl-methacrylate,
oxidation of i-butane into methacrolein,
oxidation of i-butane into methacrylic acid,
ammoxidation of dimethylbenzols (m, o, p) into the corresponding
monoitriles and dinitriles,
ammoxidation of trimethylbenzols into the corresponding
mononitriles, dinitriles and trinitriles,
ammoxidation of propane to acrylonitrile,
ammoxidation of propene into acrylonitrile,
ammoxidation of betapicoline into 3-cyanopyridine,
ammoxidation of gamma picoline into 4-cyanopyridine,
oxidation of methanol into formaldehyde,
oxidation of naphthalene and/or o-xylol possibly mixed into
phthalic acid anhydride,
oxidation of ethane into acetic acid,
oxidation of ethanol into acetic acid,
oxidation of geraniol into citral,
oxidation of ethene into ethyloxide,
oxidation of propene into propylene oxide,
oxidation of hydrogen chloride into chlorine,
oxidation of glycol into glyoxal and
hydration of maleic acid anhydride into butane diol.
36. A process for operating a shell-and-tube type reactor as claimed in
one of the previous claims, wherein the shell-and-tube type reactor
is run in production operations with such a charge of a first
process gas component with at least one further process gas
component with which occasional deflagration or even detonations
must be reckoned with.
37. A process for operating a shell-and-tube type reactor as claimed in
one of the claims 1 through 35, wherein for starting up the reactor
the concentrations of the process gas components and possibly
additional parameters as well are measured on an ongoing basis in
such a way that the violence of deflagrations or even detonations
occurring does not exceed that reckoned with for operating
conditions.

Shell-and-tube type reactor for carrying out catalytic gaseous phase
reactions, comprising a contact tube bundle (8) through which the relevant
reaction gas mixture flows and which contains a catalytic filling, extends
between a gas intake-side tube sheet (4) and a gas output-side tube sheet
(148) and is flushed by a heat transfer medium inside a surrounding reactor
shell (6), further comprising a gas intake and a gas output hood (2; 60)
spanning the two tube sheets for administering the relevant process gas to
the contact tubes or evacuating the reacted process gas to the contact tubes
or evacuating the reacted process gas from the contact tubes and comprising
a process gas main pipe (172) for feeding the process gas into the gas intake
hood (2) characterized in that the process gas main pipe (172) comprises a
first section, in which the process gas is in a non-explosive range, and in
process gas flow direction behind it a second section, in which the process
gas is in an explosive range; the process gas main pipe (172) comprises in its
first section a check valve arrangement (180), the check valve arrangement
(180) comprising at least two paralleled check valves; a pressure reduction
space is disposed in the first section downstream of the check valve
arrangement (180), the pressure reduction space being formed at least
partially by a chamber (190)housing the check valve arrangement (180), and
the check valve arrangement (180) and the gas intake-side tube sheet (4) and
all parts therebetween, which bear the process gas pressure under normal
operation conditions, are also designed for stability for the maximum
pressure caused by a deflagration or detonation.

Documents:

01461-kolnp-2005-abstract.pdf

01461-kolnp-2005-claims.pdf

01461-kolnp-2005-description complete.pdf

01461-kolnp-2005-drawings.pdf

01461-kolnp-2005-form 1.pdf

01461-kolnp-2005-form 2.pdf

01461-kolnp-2005-form 3.pdf

01461-kolnp-2005-form 5.pdf

01461-kolnp-2005-international publication.pdf

1461-KOLNP-2005-FORM-27-1.pdf

1461-KOLNP-2005-FORM-27.pdf

1461-kolnp-2005-granted-abstract.pdf

1461-kolnp-2005-granted-claims.pdf

1461-kolnp-2005-granted-correspondence.pdf

1461-kolnp-2005-granted-description (complete).pdf

1461-kolnp-2005-granted-drawings.pdf

1461-kolnp-2005-granted-examination report.pdf

1461-kolnp-2005-granted-form 1.pdf

1461-kolnp-2005-granted-form 18.pdf

1461-kolnp-2005-granted-form 2.pdf

1461-kolnp-2005-granted-form 26.pdf

1461-kolnp-2005-granted-form 3.pdf

1461-kolnp-2005-granted-form 5.pdf

1461-kolnp-2005-granted-reply to examination report.pdf

1461-kolnp-2005-granted-specification.pdf

abstract-01461-kolnp-2005.jpg

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Patent Number

239165

Indian Patent Application Number

1461/KOLNP/2005

PG Journal Number

11/2010

Publication Date

12-Mar-2010

Grant Date

09-Mar-2010

Date of Filing

27-Jul-2005

Name of Patentee

MAN DWE GMBH

Applicant Address

WERFSTRASSE 17, 94469 DEGGENDORG

Inventors:

#	Inventor's Name	Inventor's Address
1	GUTLHUBER, FRIEDRICH	GARTENSTRASSE 4,94626 METTEN
2	LEHR, MANFRED	LEEBSTRASSE 11, 94469 DEGGENDORF

PCT International Classification Number

B01J 8/00

PCT International Application Number

PCT/EP2003/000977

PCT International Filing date

2003-01-31

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	NA	2005-07-27	Not Applicable