Baixe Multitube FFR patent e outras Notas de estudo em PDF para Engenharia Química, somente na Docsity! United States Patent (5 Dahl 5,911,958 Jun. 15, 1999 USO0S911958A ti] Patent Number: [45] Date of Patent: [54] MULTITUBI LLING FILM REACTOR FOR THE CONTINUOUS MANUFACTURING OF SULFONATED AND/OR SULFATED COMPOUNDS [76] Inventor: Birger Dahl, Villaveien 1, Sarpsborg, Norway [21] Appl No: 08/930,415 22) PCTFiled: Mar 22, 1996 [86] PCT No: PCT/NOS6/00065 $371 Date: Sep. 29, 1997 $ 102(€) Date: Sep. 29, 1997 187) PCT Pub. No: WO96/30117 PCT Pub. Date: Oct. 3, 1996 57 mea [52] US. ci [58] Field of Search . BOI 8/06 422/197; 422202 422/197, 196, 422:202 [56] References Cited U.S. PATENT DOCUMENTS 4.886,089 12/1989 Gabrlik et al. SA4S SUL 8/1995 Pisoni, FOREIGN PATENT DOCUMENTS 570 844 of OW Furopean Pat. OM. . Primary Examiner—Timothy MeMabon Arrorney, Agent, or Firm—Christensca O'Connor Johnson Kindness PLIC 57 ABSTRACT Multitube [alling film reactor (MUR) for continuous manu- factucing of sulfonated andior sulfated products using gascous, diluted sulfur trioxiíde, (SO scam) 10 produce surface active agents or simply surfactants, useful in the casmetic and delergent industry. Bach individual noz2le-set comprises a male part (19) and the other hall (45) on ibe male part (16). Lhe male part (0) lorms together with the female part (19), an annular slot (21) with a constant and under all operational conditions well defined length (47), which together with a fixed opening Avidth determines the individual pressure drop ol lhe said slot and Ihereby the individual organic low. Wilh this arrangement, completely homogenous distribution of organic fecd is achieved without the necessiry of calibration. 5 Claims, 3 Drawing Shects U.S. Patent Jun. 15, 1999 Sheet 1 of 3 5,911,958 5,911,958 1 MULTTIUBE FALLING FILM REACTOR OR THE CONTINUOUS MANUFACTURING OF SULFONATED AND/OR SULFATED COMPOUNDS This application is the U.S. national stage application of International application Ser. No. PCT/NO/00065, filed Mar. 22, 1996, which is a continuation ol Norwegian application Ser. No. 95.1178, filed Mar. 28, 1995, and claims the benefit of the filing dares thercof under 35 U.S.C. $119. BACKGROUND O! 1 INVENTION Multitube falling film reactors represent today à well established technology, and is Irequently the preferred reac- torprinciple for sulphonation and sulphation reactions, both giving advanced products; surfacrants for the cosmetic and detergent industry. The reactors arc assembled according to conventional principles for a multitube shell and tube héat- exchanger wilh different ballle-arrangements and cooling líquids, with water as the dominating cooling liquid. Typical for all reactors are separate chambers for diluted gas, organic compound, cooling liquid and collection of finished products, chambers mentioned from top of reactor to bottom ouflet, When producing surfactants for the said industry, the * gascous and diluted reactant is sulfur trioxide, typical organic compounds are liquids at 15º C. or higher, the main variety of raw-malerial being alkylates, atly alcohols, eloxi- lated Tay alcohols, alpha-olefins and methyl-esters. Any chemical compound equipped with a socalled flexible hydrogen atom might be sulphonated or sulphated. (Sulphated for all compounds where bydrogen is linked to an oxygen atom, sulphonaled for the linkage hydrogen- carbon.) The overall chemical reactions taking, place, are charac- tecized by the fact that diluted, gascous SO, is a very aggressiveireactive reactant, and that the reactions arc all extremely rapid and exolhermic. Altogelher, these properties challenge the control ol (he molar ralio between lhe reactants, and only with the very best control of both total and local molar ratio, the best producis arc achieved. Any deviation in lhe molar ratio will unavoidably result in increased quantity ol undesired by-producis, and (he main product will sufer Irom bad colour, lower active malter content, higher content of sulphates, higher content of nonsulphated;-sulphonated organic compounds and conse- quently lower yield with a higher raw-material consumption. In à MIR, where the numbers o! individual and parallel reactor-element could be from two to more than hundred, the most important parameter is the local molar ratio berweca the reactants, and therefore the best possible and most homogensous distribution of organic compound 19 each individual reactor-element. Even the smallest deviation in local molar ratio, can not be fully compensated for later in the process. To avoid any misunderstanding, total molar ratio is defined as the ratio between the total number of moles SO; Ted to the reactor divided by the total number of moles organic compound fed to the same reactor. By advanced dosing system for liquid sulfur/liquid sulfur dioxide/liquid sulfor trioxide and finally organic compounds, the total molar ratio cam be kept almost constant and without any significant impact on the final product properties. “The local molar ratio, defined lhe same way bul between local flows of said reactants for cach individual nozzle- element, is predominantly depending on an even and homo- E as E 55 60 2 gencous fecd, kg/hour of organic reactant to cach individual noz/le-sel Irom one common, organic chamber, since a gas rrying a far lower viscosily bas a higher tendency ol even distribution according, to the principle of “the way of lowest resistance”. The nozzle-set construction will therefore appear as lhe decisive and critical element for individual organic flow and local molar ratio. In a MTR, all the nozzle-sets are fed from onc common, organic chamber. The nozzle-construction also allows a reactor to consist of only one Teactor element, where the total molar ratio becomes equal and identical to lhe local molar ratio, accuracy only depending on the external dosing, system. Of grcat and vital importance is also an even and bomo- geneous distribution ol the organic film formed circumler- entially on the internal, surface of the female part. This can be achieved, provided that the film distribution/formation on the internal surface of the said female part is determined by lhe same accuracy as the dosingimetering of organic com- pounds of lhe noz7le-sel for all reactor elements. 1t means altogether that the film-formarion should be determined by the same accuracy as the dosingimetering of organic compounds, i.e. à well defincd anmular slot in respect of length an width [or all known, operational conditions here are several, dilerent concepts ol constructions available on the market and already patented, relevantin this connection are following, parents: U.S. Pat. No. 3,918,917 Nitto Chemical Industry Co., Ltd. U.S. Pat. No. 4,183,897 Construzioni Meccaniche G. Mazzoni S.p.A VR 2,449,665 Ballestra Chimic: . EP 0,570,844 Al Meccaniche Modeme Sl Thesc parents and constructional concepts can be described and grouped by following precalibrated and seleciedigrouped orifices (materials totally dillerent from this patent), characterized by a relatively long distance benween lhe zone for metering; dosing and the zone for film formation. (Pre-selected, Brouped orífices should nor be mixed up with the terminology nozzle-sel and nozzle-set construction described in this document) conical or cylindrical slots where even à lower accuracy (compared to this invention) of organic fed only can be achieved through a mechanical adjustment of the slots length or opening by shims. LI lhe slot opening and slot lenglh were well defined in these constructions, and besides appeared wilh the accuracy described in mentioned patents, no adjustment by shims would be necessary. Ir is obvious that the location of the male part relatively 19 lhe lemale part by shims, will be influenced by dillerent pressure working on lhe main fianges;eylindrical plates(pressuces different from the conditions during calibration), by the torque on single bolts for tightening, by scaling material and finally by lhe distance between the cylindrical plates. The fact that all individual nozzle-sets have to be calibrated before startup, also clearly demonstrates the unsufi- cient definition of the opening, and length of the slots, resulting in a less homogeneous distribution of the film (different thickness around (he welled periphery) on the intemal surface ol the female part o! the nozzle-seL. The main dificrencesidisadvantages for already known and operative constructions compared to the nozzle-ser construction described in fhis document, can be summarized by following: higher tendency o! air-pockeis and thereby parily block- ing of organic feed during star-up. (Air-pockets in the space between male and female part of the nozzle-set.) 5,911,958 3 partly more complex components, less casy to machine. need for time-consuming calibration both before start-vp and alter an uncontrolled stop during operation, or alter a routine washingicleaning procedure. The accuracy of this calibration will also be inflvenced by the fact that normal plant conditions are always different from cali- bration conditions. generally lower accuracy for individual organic Ieed compared to lhe total average of organic Ieed for all noz/le-seis in operation. generally will lower accuracy of melering mean increased variation in film thickness. tightening arrangement for the male and female part of the nozzle-set will influence the accuracy of individual noz/le-set supply and also said accuracy for neigbbour- ing noz/e-se lhe neccessity of shims adjustment creates very frequently tendeney of increased lcakages. accuracy of metering will strongly depend on the torque aplica for tightening the bolts. lhe individual supply lrom each nozÃe-sel will furiber also be depending on pressure variations during normal operation, pressures working on lhe dillerent cylindri- cal plates and giving different impact depending on the location of the nozzle-set on the said plates. DESCRIPTION OF THE INVENTION Summary o! the Invention “The noz7le-sel represents lhe most vital component;part of any multitube falling film reactor, and (his invention relates mainly to the design, construction and assembling ol all the individual components comprising a nozzle-set. The nozzle-set reported in this document, is characterized by a well defined annular slot having à fixed length and a fixed width under all known operational conditions. “The necessity of complicated and Tess reliable arrange- ment for calibration like shims cre is climinated, and the invented nozzle-set will also give a substantial increase in the homogencity of the film thickness, There is no necd for calibration belore start-up, or time-consuming re-calibration after a stop im the plant. A model ol lhe reactor wilh more than 30 parallel nozzle-sets in full size have beco tested, and by introducing, the average flow x,,, p/min, for all nozzle-sets, all individual Nows are covered by the range: Mar 26% An accuracy level like this, bas uptil now not been reported, and the rcactor with the new nozzle-ser will be named the NCN reactor, which means: No Calibration Needed, “The NCN nozzle-set may be installed in all MPR reacto designed for heterogene reactions, even for reactions where for instance reactive particles are present and suspended in am inerl liguid, (inert Lo lhe gaseous reaclant). ATTACHED FIGURES AND DEFINITIONS, “TERMINOLOGY FIG. 1 is à longitudinal section of a complete and assembled multitube falling film reactor Type NCN, with hree individual no2/e-sels fixed 10 reactor-tubes partly in section. FIG. 2 is a detailed assembly drawing for one complere nozzle-ser comprising a female part, a male parr, respective x 5 4 tighrening arrangement, tightening bolis and scaling system all arrangend en two individual and separaled cylindrical plau VIG. 3 is à cross section of FIG. 2 A—A enlarged, and shows in derail the six channels for Liquid, organic feed to the expansion chamber. Nozzle-set: A complete unit comprising a female part, a male part, respective tightening arrangement, tighlening bolts and sealing system. Reactortube: A conventional tube, total lengih 5-7 m, and fixed to the [emale part of the nozale-set. The reactortube represents in this way the zone for the chemical reaction taking place, and transfers heat of reaction to the surround- ing and circulating cooling liquid. Reactor-element: A complete unit having as inlegral paris one nozide-sel, one reacloriube and finally sealing arrange- ments. Multitube falling film reactor, FIG. 1: A complete reactor unit including from two to more than hundred reactor- elements together wilh separate chambers [or distribution of gastous reactant, liquid organic reaciant, cooling liquid, collecting chamber for finished product and connections for all material fows. Reactorhead: Includes the nozzle-sets and the organic chamber defined and limited by a cylindrical plate fixed to a eylindrical spacer fixed to à counter-ange bolted and sealed 10 lhe lowest cylindrical plate. Calibration of noz/le-set: Manual and time-consuming work for all individual nozzle-scts, at least the reactorhead must be fully assembled to accomplish this procedure. A quantily of organic reactant normally corresponding to the nominal capacily ol the reactor, is led to lhe common organic chamber, and allthe individual flows leaving nozzle- sets or reactortubes, are carefully determined by weighing. Based on thc measuring, results from this procedure, an antmetic average for the individual Dows is caleulated, Tor instance X,,. Any devialion ouiside a predetermined and acecptable range, will have to be adjusted for by replace- ment of the shims having thicknesses different from the ones originally installed. Normally this procedure will have to be repealed uptil several times to reach a range described by: Kal 0% For rcactortechnology of yesterday, average Xe is quite usual and rather seldomly average =1.0% is reached. Unfortunately, the same reactortechnology can neither con- firm nor guarantee this rangedimit ol deviation during normal, operational conditions. DETAILED DESCRIPEON OPTOE INVENTION With reference to the attached figures, FIG. 1, [1G. 2 and 5 []G. 3, together wilh the definitions and terminology listed in para 3, à complete, multitube falling film ceactor vil include more than two reactor-clements in parallel, cham- ber 4 for distribution of the gascous reactant, chamber 11 for distribution of organic reaciant, chamber 25 lor cooling liquid and chamber 53 [or collecting of finished product, chamber 53 being defincd by plate/fiange 29/31 and the conical bottom cap 32, all mentioned parts from reactor top to reactor hottom;outlet. All the chambers are separated from veighbouring chamber with plates/llanges 8, 9, 16, 18, 27, 5 29 and 31, sealing syslems, outer cylindrical manile and conical caps 3/32 at top and bottom respectively. At the outlet of cach reactor-clement, stufiing-boxes 28:30 installed 5,911,958 5 in plate 29 cfficiently prevent Icakage berwecn coolin chamber 25 and collecting chamber 53. Lhese stuffing boxes allows thermal, longitudinal expansion of reactor-lubes dur- ing normal plant conditions/operation. The upper chamber 4 being, fed through 1 and limited by a conical top cap 3 and the upper plate 9 together with the llange 8, evenly distributes the gaseous reactants to all individual reactor-elements. Viguia, organic reactant being fed from a central pipe-line and distributed to the organic chamber 11 through several fceding-tubes 12. This chamber 11 is also equipped with a onjoff ball-valve for de-arcation ducing start-up and opera- tion. The chamber TU is vented to the surrounding atmo- sphere. The operating pressure in chamber TI is given by lhe pressure drop through the annular slot 21 and the gas pressure in the reactormbe 24. Liquid, organie reactant is fed from the common chamber 11 to each separate noz7le-set al 13 along the total periphery of female part 10 and further 19 (he expansion-chamber 20 through the longitudinal feeding channels FIG. 2/FIG. 3 40. The organic reactant is perfectly metered and distributed through the anular slot 21 forming, a continuous and unilorm falling film 50 on the internal surface of the lemale part 19. AL lhe ouller of the slot 21, the liquid organic reactant from chamber 11 mects the pascous reactant from chamber 4, immediately starting the exothermic and heter geneous chemical reaclion. The heat ol the reachion transferred to lhe outer surface ol the reacior-tube, and conlinuously removed by Lhe circulating cooling liquid in chamber 25. The cooling liquid fed to the same chamber through 26, leaving at 22. The finished product from all reaclor-elements is collected at the bottom ol the reactor in chamber 53, leave aí 34 and [urlher dowostream treated in a special separatoreyclone for the separation of gasilíquid. The complete nozzle-set will according, to this document include a male part 10, a female part 19, tighiening arrange- ments 5/6 and 14/15 respectively, and sealings 7/17 respec- Female part 19 equipped with integral tightening flange 41, is fixed to the plate 18 by the tightening ring 15 and two-four bolis 14. The cylindrical plate 18 separates the organic chamber 11 from the cooling chamber 25. The integral ange on female part 19 has an eigih equal to the depth of the tightening-ring 15 aí 43, fhus forming à com- pletely even surface and together with scaling, 17 comprise a scaling system berweca the female part 19 and the plate 18. Builtin distancejclearance 42 between lhe said Temale Iange 41 and the said lighiening ring 15, elhiciently prevents radial lorces 10 occur and acting on lhe Temale part 19 through 41. The position of the female part 19 is according to above only determined by the cylindrical opening in plate 18. Longitudinally, lhe position is determined by lhe applied torque on the Dolls 14, sealing hickness/compressibility and addirionally by different pressure- and temperature- conditions during operation. A cylindrical scetionispacer between llange 16 and upper plate 9 forms together wilh the lower plate 18 lhe said organic chamber Tt. To avoid eccentrisity between plate 9 and 18, plate 18 is equipped with ar Icast two conical guiding pins entering correspond- ing holes in flange 16 with a high degree of precision. “The female part 19 is internally machined forming one hall dá of the expansion chamber 20. This machined part 44 of the expansion chamber 20 is identical 19 lhe olher machincd half 45 located at the outer surface of the male part 10. Together the two halves comprise the said expansion 4 6 chamber 20. The female part 19 is tixed to the reactorrube 24, lenglh 5-7 m, aí 23. “The male part 10 is equipped with à similar, integral Hange 38 with the height corresponding to the depth of the tightening ring 6 at 35. Together, flangc 38 and ring é form a completely even surface and togelher with sealing at 7 comprises a sealing system between lhe male part 10 and the plate 9. Built-in distancciclearance 37 betweca the said male Hangc 38 and the said tightening ring 6, cfficiently prevents radial forces 19 occur and acting on the male part TO ibrough 38. The said tightening ring 6 is equipped with oversized holes for bolts. In combination with the said clearance 37, the clearance berweca the holes in the plate 9 and male part 10, the said oversized holes 36 eflicienlly prevent any radial forces to occur and acl on the said lange 38 nor the total male part 10 of the nozzle-scr. The important centering of the male part 10 into the female part 19, is according to above only determined by lhe guiding zone 52. Longitudinal channels 40 machined on the outer surface ol the male part 10, leeds lhe organic feed Irom lhe chamber 1 to the expansion chamber 20. The size and number of thesc channels arc carefully selecled to give maximum guiding surface in combination with low, lineaer velocity of the liquid making this noz/e- set self-dearcating during startup and operation. Self- dearcating as terminology is concequently applied for any gaseous component being present belore slart-up andior dispersed gasparticles in the bulk low of organic hat might occur during normal operation. The male part 10 of the said nozzle-set is externally machined to form onc half 43 of the expansion chamber 20. Characleristic [or this invention and construction is that both the length 47 and the opening of the annular slot 21 is defived once for all and under all known operational conditions, provided that the lower lips 48 and 49 of the halves dá and 45 respectively under the said conditions always «will be separated a distance 46 and wilh the Tip 49 at lhe lower position. The Teed of organic liquid to or Irom the noz/le-set, will according to this invention only depend on the channel length 47 which is well defincd for all nozzle-sets and constant opening of the annular slot 21 formed benveen the male and lemale part. The said distance 46 between lhe said lips 48 and 49, will be determined according, to following relation: The length of balf-chambers 44 andior 45 in expansion- chamber 20 >distance 46>0 The lip 49 always located ar the lower position ol lhe two lips 48 and 49 lhe distance 46 between lip 48 and 49 being normally 2.0-3.0 mm, will permanently and automatically com- pensate for all sorts of external forces tending, to move in longitudinal direction the male part 10 relatively to the female part 19 or opposite. Lhe pressure drop in (he annular slot 21 determines the Now from cach nozzle-sct, and with the annular slot being, constant even when male parts moves relatively to the Temale part or opposite (limits staled in above relation), the same pressure drop will remain constant and finally thereby the flow. Ta other words, for any complete nozzle-set equipped with a constant slot opening 21, the flow will remain constant as long as the distance 46 is wilhin the limits of said relation and thus giving à constant slot Tengih 47 indepent of variations in operational conditions. The nozzle-ser will permanently need no mechanical arrangements for adjusting lhe relative position o! male and [emale part to influence or adjust the individual Nlows, and (here will be no need neither lor calibrafion nor re-calibration. The invention therefore comprises a multitube falling film reactor with a nozzle-ser as described in details above,