| EP0570844A1 | 1993-11-24 | |||
| US4183897A | 1980-01-15 |
| 1. | I . Introduαion The classical and most important challenge to any construαor/inventor of a multitube falling film reaαor, has so far been limited to find a reliable and simple solution to the main problem: Completely homogeneous distribution of organic feed from a plurality of individual nozzles all fed from a common chamber filled with organic compound/reactant and achieved without the necessity of complicated and less reliable mechanical arrangements for final adjustments of all individual flows. A plurality of individual channels or annular slots, will have identical (mini mum deviation) flows provided that the pressure drops in the same slots are identical. For a nozzleset according to this invention, the pressure drop is determined by following four, free variables: the opening, width of the said slot the length of the said slot roughness of sur aces in contaα with said organic liquid concentric position of male part relatively to female part It should be added that the concentric position has a lower impaα on the pressure drop than the others, but a major and vital impaα on the film thickness distribution. A reaαor with no need for calibration, is only possible when the construαion keeps the four variables constant. In document EP A 570 844, representing the established and known technology for a similar multitube falling film reaαor, for instance the length of the annular slot is not defined to a degree making the same length constant. (Position numbers from now til end of para 5.1., refers to document EP A 570 844 fig I and fig 3). The length of the channel is given by the distance between the lip of chamber 16 female part and the lowest point 18 of male part. This meaning that the position of the female lip relative to the male part is determined by: distance between lip and lower surface of ring/flange 21 compressibility of sealing at 29 torque applied on bolts 2. |
| 2. | and that the point 18 on male part, relative to the female part, is determined by: distance lower surface of ring/flange I I to point 18 compressibility of sealing 19 torque applied on bolts 1 During operational conditions being always different form those during calibration, the said cylindrical plates will move relatively to each other. This movement even small in size, will SUBSTITUTE SHEET increase towards the centre of the said plates, and have a significant impaα on the very small tolerances needed for the definition of the length of the said slot. Additionally, it is well known that machining on the internal surface of a given component hardly than reach the very finest tolerances achieved on the external surface, compare the said lip of the female part. It is obvious that the established and known technology not can meet the neccesity of constant four free variables, proven and demonstrated by the technology itself, and by the faα that the application of strips/shims of different thicknesses is a must to compensate for all uncontrolled variables. The invention described in this document and with relation to known technology as described in EP A 570 844, can be charaαerized by the once for all well defined length of the annular slot. Without this definition, it should be impossible to design a NCN multitube falling film reaαor. In following claims, all details concerning this definitions and other aspects/properties of the new technology, are described. |
| 3. | 2 The main claim in this invention comprises a multitube falling film reaαor for continuous manufaαuring of sulphonated and/or sulphated products, products formed by a chemical reaction taking place in the said reaαor and between liquid organic compounds and diluted, gaseous sulfur trioxide. The said reaαor being equipped with a plurality of identical nozzlesets, is charaαerized by the faα that no complicated and less reliable adjustment is needed to reach a completely homogeneous distribution of organic flow from all the individual and parallel nozzlesets in operation. Adjustment means to influence by shims or similar the position of the male part of the nozzleset relatively to the female part of the nozzleset. The need for no calibration is achieved by a well defined annular slot 21 having a constant opening and a constant length, the latter being completely independent of all variations in operational conditions. The length 47 of this annular slot is only determined by its own length and within described limits independent of the position of the male part of the nozzleset relatively to the female part of the nozzleset. Detailed description of the invention and construαion follows in para. |
| 4. | 10. |
| 5. | 3 Said reaαor described under para 2 to be applied for heterogenenous, continuous chemical reaαions, charaαerized by one of the two reactants being present as gaseous reaαant and the other participating reaαant present as a liquid at ambient temperatur or temperatures corresponding to the reaαion conditions, the said reaαor assembled as a conventional multitube shell and tube heat exchanger with separated chambers for gaseous reaαant 4, liquid organic reaαant 1 1 , cooling liquid 25 and colleαion of finished produαs 53. |
| 6. | Reactor as said under para 3 and particularly well suited for the produαion of anionic rawmaterials, surfaαants, for the cosmetic and detergent industry, and where the organic reactant could be one of the frequently used rawmaterial like alkylates, fatty alcohols, etoxilated fatty alcohols, alfaolefins, methylesters and other typical to the said industry, the other reaαant as said diluted gaseous sulfur trioxide. |
| 7. | Reactor as said under para 4, comprising a plurality of nozzlesets, from two to more than hundred, and where the said liquid organic reaαant is fed to the common organic chamber I I through a plurality of separated feeding tubes 12, the organic chamber SUBSTITUTE SHEET 1 1 being defined by cylindrical plate 9 and 18, counterflange 16 and finally cylindrical spacer fixed and welded to plate 9 and flange 16. Reaαor as said under para 4 charaαerized by a diluted gaseous reactant fed to the common chamber 4 limited by flange 8, cylindrical plate 9 and conical top cap 3, and that finished produα are colleαed in chamber 53 defined by a conical cap 32, cylindrical plate 29 and counterflange 31 , the cylindrical plate 29 equipped with stuffing boxes 28/30 for reaαortube 24 and arranged at the reaαor bottom/outlet. |
| 8. | 6 Reaαor as said under para 5, where each nozzleset comprises a male part 10 fixed to the said plate 9 by bolts 5 and a tightening ring 6 and sealing 7, and where the height of the said integral flange 38 exaαly equals the machined depth of the tightening ring 6 at 35 and forms an even surface against sealing 7, and by the clearance 39 between the male part 10 and the well defined hole in the said plate 9, clearance 36 between bolts 5 and said ring 6 and sealing 7, and by clearance between said integral flange 38 and said ring 6 at 37, all to give a perfeα sealing between chamber 4 and chamber 1 1 without any radial forces aαing on the male part 10 and/or without any forces transferred between the two cylindrical plates 9 and 18. The female part of the nozzleset in said reaαor is fixed to the cylindrical plate 18 according to the same principles as for the male part 10 to said plate 9, but without having the same clearance between female part 19 and corresponding hole in the cylindrical plate 18. |
| 9. | Reaαor as said under para 6, with the said male part of the nozzleset perfeαly concentric relatively to male part 19 and achieved by guiding surface at 51 on the male part 10 exaαly fits into the same guiding surface of the female part 19 at 52 and that said concentric location is only determined by the guiding surfaces and the length 52 of the same surfaces, and by feeding channels 40 externally machined on the male part 10 having a number between two and twelve leed the organic feed from chamber I I at 13 to the expansionchamber 20, and by the seleαion of six 6 feeding channels a maximum of guiding surface is achieved in combination with said deareating properties, and by the ratio between effeαice guiding length 52 and the external diameter of male part 10 is designed to be within the range I . I 3.0 and for this particular case is 1 .5 to secure maximum concentric guiding. The said reaαor having a said female part 19 equipped internally with a machined half 44 of the expansionchamber 20, the other halv 45 being machined externally on the male part 10 and by the well defined length 47 of the annular slot 21 achieved by a distance 46 between the lower lip 48 on the female part 19 and the lower lip 49 on the said male part 10. The said lip 49 in the said reaαor always at the lowest location for the two lips 48 and 49 and the distance 46 permanently larger than zero and permanently smaller than one/each of the length of the two halves 44 and 45 of the expansionchamber 20. |
| 10. | Reaαor as said under 7, but having different lengths for the two said halves 44 and 45 together forming the expansionchamber 20 and described by following relation: 0< Distance 46 < length of any of the two halves 44 and 45 . |
| 11. | Reaαor as said under 8 in which liquid organic reaαant is being fed from a common chamber 1 1 through externally machined channels 40 on male part 10 to SUBSTITUTE SHEET expansionchamber 20 and further through a permanently well defined annular slot 20 forming a homogeneously falling film on the internal periphery of the female part 19 meeting the second reactant, gaseous diluted sulfur trioxide fed from the common chamber 4 through cylindrical opening in the total length of the male part 10 and the reaαion starts spontaneously, and by the said reaαor the annular slot is so well defined under all operational conditions that any arrangements for calibration nor recalibration are ever needed before startup and/or after uncontrolled stops or routine maintenance due to the faα that the well defined and constant opening of the annular slot in combination with a constant length 47 of the annular slot automatically compensate for any relative movement between the male part 10 and the female part 19 or opposite in a way that all nozzlesets deliver the average ± 0.2%. |
| 12. | Reaαor as said under 9, having the same and well defined annular slot 21 but where the expansionchamber 20 is machined on the male part 10 only. For this alternative construαion, there is obviously no need for a definition of the distance 46 as described under para 8. SUBSTITUTE SHEET. |
Background of the invention.
Multitube falling film reactors represent today a well established technology, and is frequently the preferred reactorprinciple for sulphonation and sulphation reactions, both giving advanced products; surfactants for the cosmetic and detergent industry. The reactors are assembled according to conventional principles for a multitube shell and tube heat-exchanger with different baffle-arrangements and cooling liquids, 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 outlet
When producing surfactants for the said industry, the gaseous and diluted reactant is sulfur trioxide, typical organic compounds are liquids at 15 °C or higher, the main variety of raw-material being alkylates, fatty alcohols, etoxilated fatty 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 hydrogen is linked to an oxygen atom, sulphonated for the linkage hydrogen-carbon.)
The overall chemical reactions taking place, are characterized by the fact that diluted, gaseous S0 3 is a very aggressive/reactive reactant, and that the reactions are all extremely rapid and exothermic. Altogether, these properties challenge the control of the molar ratio between the reactants, and only with the very best control of both total and local molar ratio, the best products are achieved. Any deviation in the molar ratio will unavoidably result in increased quantity of undesired by-products, and the main product will suffer from bad colour, lower active matter content, higher content of sulphates, higher content of nonsulphated/-sulphonated organic compounds and consequently lower yield with a higher raw-material consumption. In a MTR, where the numbers of individual and parallel reactor-element could be from two to more than hundred, the most important parameter is the local molar ratio between the reactants, and therefore the best possible and most homogeneous distribution of organic compound to 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 S0 3 fed 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 sulfur trioxide and finally organic compounds, the total molar ratio can be kept almost constant and without any significant impact on the final product properties.
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The local molar ratio, defined the same way but between local flows of said reactants for each individual nozzle-element, is predominantly depending on an even and homogeneous feed, kg/hour of organic reactant to each individual nozzle-set from one common, organic chamber, since a gas carrying a far lower viscosity has a higher tendency of even distribution according to the principle of "the way of lowest resistance". The nozzle-set construαion will therefore appear as the decisive and critical element for individual organic flow and local molar ratio. In a MTR, all the nozzle-sets are fed from one common, organic chamber. The nozzle-construction also allows a reactor to consist of only one reactor element, where the total molar ratio becomes equal and identical to the local molar ratio, accuracy only depending on the external dosing system.
Of great and vital importance is also an even and homogeneous distribution of the organic film formed circumferentially 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 the same accuracy as the dosing/metering of organic compounds of the nozzle-set for all reactor elements. It means altogether that the film-formation should be determined by the same accuracy as the dosing/metering of organic compounds, i.e. a well defined annular slot in respect of length an width for all known, operational conditions.
There are several, different concepts of constructions available on the market and already patented, relevant in this connection are following patents:
US 3.918,917 Νitto Chemical Industry Co., Ltd.
US 4, 183,897 Construzioni Meccaniche G. Mazzoni S.p.A
FR 2,449,665 Ballestra Chimica S.p.A
EP 0,570,844 Al Meccaniche Moderne S.r.l
These patents and constructional concepts can be described and grouped by following:
- precalibrated and selected/grouped orifices(materials totally different from this patent), characterized by a relatively long distance between the zone for metering/dosing and the zone for film formation.
(Pre-selected/grouped orifices should not be mixed up with the terminology nozzle-set and nozzle-set construction described in this document.)
- conical or cylindrical slots where even a lower accuracy( compared to this invention) of organic feed only can be achieved through a mechanical adjustment of the slots length or opening by shims. If the slot opening and slot length were well defined in these constructions, and besides appeared with the accuracy described in mentioned patents, no adjustment by shims would be necessary. It is obvious that the location of the male part relatively to the female part by shims, will be influenced by different pressure working on the main flanges/cylindrical plates(pressures different from the conditions during calibration), by the torque on single bolts for tightening, by sealing material and finally by the distance between the cylindrical plates. The fact that all individual nozzle-sets have to be calibrated before start-up, also clearly demonstrates the unsufficient definition of the opening and length of the slots, resulting in a less homogeneous distribution of the
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film (different thickness around the wetted periphery) on the internal surface of the female part of the nozzle-set.
The main differences/disadvantages for already known and operative constructions compared to the nozzle-set construction described in this document, can be summarized by following:
- higher tendency of air-pockets and thereby partly blocking of organic feed during start-up.(Air-pockets in the space between male and female part of the nozzle-set.)
- partly more complex components, less easy to machine.
- need for time-consuming calibration both before start-up and after an uncontrolled stop during operation, or after a routine washing/cleaning procedure. The accuracy of this calibration will also be influenced by the fact that normal plant conditions are always different from calibration conditions.
- generally lower accuracy for individual organic feed compared to the total average of organic feed for all nozzle-sets in operation.
- generally will lower accuracy of metering mean increased variation in film thickness.
- tightening arrangement for the male and female part of the nozzle-set will influence the accuracy of individual nozzle-set supply and also said accuracy for neighbouring nozzle-sets.
- the neccessity of shims adjustment creates very frequently tendency of increased leakages.
- accuracy of metering will strongly depend on the torque applied for tightening the bolts.
- the individual supply from each nozzle-set will further also be depending on pressure variations during normal operation, pressures working on the different cylindrical plates and giving different impact depending on the location of the nozzle-set on the said plates.
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Description of the invention.
Summary of the invention.
The nozzle-set represents the most vital component/part of any multitube falling film reactor, and this invention relates mainly to the design, construction and assembling of all the individual components comprising a nozzle-set.
The nozzle-set reported in this document, is characterized by a well defined annular slot having a fixed length and a fixed width under all known operational conditions.
The necessity of complicated and less reliable arrangement for calibration like shims etc is eliminated, and the invented nozzle-set will also give a substantial increase in the homogeneity of the film thickness. There is no need for calibration before start-up, or time-consuming re-calibration after a stop in the plant.
A model of the reactor with more than 30 parallel I nozzle-sets in full size have been tested, and by introducing the average flow x^, g min, for all nozzle-sets, all individual flows are covered by the range: x w ± 0.2%
An accuracy level like this, has uptil now not been reported, and the reactor with the new nozzle-set will be named the NCN reactor, which means: No Calibration Needed.
The NCN nozzle-set may be installed in all MTR reactors designed for heterogene reactions, even for reactions where for instance reactive particles are present and suspended in an inert liguid, (inert to the gaseous reactant).
Attached figures and definitions/terminology
Fig I is a longitudinal section of a complete and assembled multitube falling film reactor Type NCN, with three individual nozzle-sets fixed to reactor-tubes partly in seαion.
Fig 2 is a detailed assembly drawing for one complete nozzle-set comprising a female part, a male part, respeαive tightening arrangement, tightening bolts and sealing system all arrangend on two individual and separated cylindrical plates. Fig 3 is a cross seαion of Fig 2 A-A enlarged, and shows in detail the six channels for liquid.organic feed to the expansion chamber.
Nozzle-set: A complete unit comprising a female part, a male part, respeαive tightening arrangement, tightening bolts and sealing system.
eaαortube: A conventional tube, total length 5 - 7 m, and fixed to the female part of the nozzle-set.The reaαortube represents in this way the zone for the chemical reaαion taking place, and transfers heat of reaαion to the surrounding and circulating cooling liquid.
Reaαor-element:: A complete unit having as integral parts one nozzle-set, one reactortube and finally sealing arrangements.
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Multitube falling film reaαor, Fig I : A complete reaαor unit including from two to more than hundred reaαor-elements together with separate chambers for distribution of gaseous reactant, liquid organic reactant, cooling liquid, colleαing chamber for finished produα and conneαions for all material flows.
Reaαorhead: Includes the nozzle-sets and the organic chamber defined and limited by a cylindrical plate fixed to a cylindrical spacer fixed to a counter-flange bolted and sealed to the lowest cylindrical plate.
Calibration of nozzle-set: Manual and time-consuming work for all individual nozzle-sets, at least the reaαorhead must be fully assembled to accomplish this procedure. A quantity of organic reaαant normally corresponding to the nominal capacity of the reaαor, is fed to the common organic chamber, and all the individual flows leaving nozzle-sets or reaαortubes, are carefully determined by weighing. Based on the measuring results from this procedure, an aritmetic average for the individual flows is calculated, for instance X ιv . Any deviation outside a predetermined and acceptable range, will have to be adjusted for by replacement of the shims having thicknesses different from the ones originally installed. Normally this procedure will have to be repeated uptil several times to reach a range described by:
X. v ± ι .o%
For reaαortechnology of yesterday, average ± 2.5% is quite usual and rather seldomly average ± 1.0% is reached. Unfortunately, the same reaαortechnology can neither confirm nor guarantee this range/limit of deviation during normal, operational conditions.
Detailed description of the invention.
With reference to the attached figures, Fig I , Fig 2 and Fig 3, together with the definitions and terminology listed in para 3, a complete, multitube falling film reaαor vil include more than two reaαor-elements in parallell, cnamber 4 for distribution of the gaseous reactant, chamber 1 1 for distribution of organic reactant, chamber 25 for cooling liquid and chamber 53 for colleαing of finished produα, chamber 53 being defined by plate/flange 29/31 and the conical bottom cap 32, all mentioned parts from reaαor top to reaαor bottom/outlet. All the chambers are separated from neighbouring chamber with plates/flanges 8, 9 16, 18, 27, 29 and 31 , sealing systems, outer cylindrical mantle and conical caps 3/32 at top and bottom respeαively. At the outlet of each reaαor-element, stuffing-boxes 28/30 installed in plate 29 efficiently prevent leakage between cooling-chamber 25 and colleαing chamber 53. These stuffing boxes allows thermal, longitudinal expansion of reaαor-tubes during normal plant conditions/operation.
The upper chamber 4 being fed through I and limited by a conical top cap 3 and the upper plate 9 together with the flange 8, evenly distributes the gaseous reaαants to all individual reaαor-elements.
Liquid, organic reaαant being fed from a central pipe-line and distributed to the organic chamber 1 1 through several feeding-tubes 12. This chamber 1 1 is also equipped with a
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on/off ball-valve for de-areation during start-up and operation. The chamber 1 1 is vented to the surrounding atmosphere. The operating pressure in chamber 1 1 is given by the pressure drop through the annular slot 21 and the gas pressure in the reaαortube 24.
Liquid, organic reaαant is fed from the common chamber 1 1 to each separate nozzle-set at 13 along the total periphery of female part 10 and further to the expansion-chamber 20 through the longitudinal feeding channels Fig 2 Fig 3 40. The organic reactant is perfeαly metered and distributed through the annular slot 21 forming a continuous and uniform falling film 50 on the internal surface of the female part 19. At the outlet of the slot 21 , the liquid organic reactant from chamber 1 1 meets the gaseous reactant from chamber 4, immediately starting the exothermic and heterogeneous chemical reaαion. The heat of the reaαion is transferred to the outer surface of the reaαor-tube, and continuously removed by the circulating cooling liquid in chamber 25. The cooling liquid fed to the same chamber through 26, leaving at 22.The finished produα from all reaαor-elements is colleαed at the bottom of the reaαor in chamber 53, leave at 34 and further downstream treated in a special separator/cyclone for the separation of gas/liquid.
The complete nozzle-set will according to this document include a male part 10, a female part 19, tightening arrangements 5/6 and 14/15 respeαively, and sealings 7/17 respeαively.
Female part 19 equipped with integral tightening flange 41 , is fixed to the plate 18 by the tightening ring 15 and two - four bolts 14. The cylindrical plate 18 separates the organic chamber 1 1 from the cooling chamber 25. The integral flange on female part 19 has an heigth equal to the depth of the tightening-ring 15 at 43, thus forming a completely even surface and together with sealing 17 comprise a sealing system between the female part 19 and the plate 18. Built-in distance/clearance 42 between the said female flange 41 and the said tightening ring 15, efficiently prevents radial forces to occur and aαing on the female 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, the position is determined by the applied torque on the bolts 14, sealing thickness/compressibility and additionally by different pressure- and temperature-conditions during operation. A cylindrical seαion/spacer between flange 16 and upper plate 9 forms together with the lower plate 18 the said organic chamber 1 1. To avoid eccentnsity between plate 9 and 18, plate 18 is equipped with at least two conical guiding pins entering corresponding holes in flange 16 with a high degree of precision.
The female part 19 is internally machined forming one half 44 of the expansion chamber 20. This machined part 44 of the expansion chamber 20 is identical to the other machined half 45 located at the outer surface of the male part 10. Together the two halves comprise the said expansion chamber 20. The female part 19 is fixed to the reactortube 24, length 5 - 7 m, at 23.
The male part 10 is equipped with a similar, integral flange 38 with the height corresponding to the depth of the tightening ring 6 at 35. Together, flange 38 and ring 6 form a completely even surface and together with sealing at 7 comprises a sealing system
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between the male part 10 and the plate 9. Built-in distance/clearance 37 between the said male flange 38 and the said tightening ring 6, efficiently prevents radial forces to occur and atting on the male part 10 through 38.
The said tightening ring 6 is equipped with oversized holes for bolts. In combination with the said clearance 37, the clearance between the holes in the plate 9 and male part 10, the said oversized holes 36 efficiently prevent any radial forces to occur and aα on the said flange 38 nor the total male part 10 of the nozzle-set. The important centering of the male part 10 into the female part 19, is according to above only determined by the guiding zone 52.
Longitudinal channels 40 machined on the outer surface of the male part 10, leeds the organic feed from the chamber 1 1 to the expansion chamber 20. The size and number of these channels are carefully seleαed to give maximum guiding surface in combination with low, linear velocity of the liquid making this nozzle-set self-deareating during start-up and operation. Self-deareating as terminology is concequently applied for any gaseous component being present before start-up and/or dispersed gasparticles in the bulk flow of organic that might occur during normal operation. The male part 10 of the said nozzle-set is externally machined to form one half 45 of the expansion chamber 20. Charaαeristic for this invention and construαion is that both the length 47 and the opening of the annular slot 21 is defined once for all and under all known operational conditions, provided that the lower lips 48 and 49 of the halves 44 and 45 respeαively under the said conditions always will be separated a distance 46 and with the lip 49 at the lower position. The feed of organic liquid to or from the nozzle-set, will according to this invention only depend on the channel length 47 which is well defined for all nozzle-sets and constant opening of the annular slot 21 formed between the male and female part.The said distance 46 between the said lips 48 and 49, will be determined according to following relation:
The length of half-chambers 44 and/or 45 in expansionchamber 20 >distance 46>0 The lip 49 always located at the lower position of the two lips 48 and 49.
The distance 46 between lip 48 and 49 being normally 2.0 - 3.0 mm, will permanently and automatically compensate for all sorts of external forces tending to move in longitudinal direαion the male part 10 relatively to the female part 19 or opposite.
The pressure drop in the annular slot 21 determines the flow from each nozzle-set, and with the annular slot being constant even when male parts moves relatively to the female part or opposite(lιmιts stated in above relation), the same pressure drop will remain constant and finally thereby the flow.
In 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 within the limits of said relation and thus giving a constant slot length 47 indepent of variations in operational conditions. The nozzle-set will permanently need no mechanical arrangements for adjusting the relative position of male and female part to influence or adjust the individual flows, and there will be no need neither for calibration nor re-calibration.
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The invention therefore comprises a multitube falling film reaαor with a nozzle-set as described in details above, showing an uptil now unknown accuracy and without the necessity of complicated and less reliable mechanical arrangements for final adjustments of all individual flows. Additionally, any need for calibration before start-up, or re-calibration in conneαion with uncontrolled stops and routine maintenance, is eliminated compared to other, similar construαions.
The invention has been described according to one embodiment of the invention, and alternatives may be made by one skilled in the art. The invention embraces all such alternatives which are clearly in family to and within the spirit and proteαive scope of the following claims.
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