CA1144561A - Method for the film sulphonation in a multitubular reactor and such a reactor suitable to embody said improved method - Google Patents
Method for the film sulphonation in a multitubular reactor and such a reactor suitable to embody said improved methodInfo
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- CA1144561A CA1144561A CA000345813A CA345813A CA1144561A CA 1144561 A CA1144561 A CA 1144561A CA 000345813 A CA000345813 A CA 000345813A CA 345813 A CA345813 A CA 345813A CA 1144561 A CA1144561 A CA 1144561A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J10/00—Chemical processes in general for reacting liquid with gaseous media other than in the presence of solid particles, or apparatus specially adapted therefor
- B01J10/02—Chemical processes in general for reacting liquid with gaseous media other than in the presence of solid particles, or apparatus specially adapted therefor of the thin-film type
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/24—Stationary reactors without moving elements inside
- B01J19/2415—Tubular reactors
- B01J19/2425—Tubular reactors in parallel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/24—Stationary reactors without moving elements inside
- B01J19/247—Suited for forming thin films
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00051—Controlling the temperature
- B01J2219/00074—Controlling the temperature by indirect heating or cooling employing heat exchange fluids
- B01J2219/00076—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements inside the reactor
- B01J2219/00085—Plates; Jackets; Cylinders
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00164—Controlling or regulating processes controlling the flow
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00168—Controlling or regulating processes controlling the viscosity
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
The invention relates to a method for sulphonating or sulphating organic liquid compounds with gaseous sulphur trioxide contained in a carrier gas, comprising: feeding the liquid reagent from a common feeding liquid chamber, maintained completely full, into a plurality of equal vertical parallel tubes through annular slots which clearance is less of one millimeter in form of a film, wherein said tubes have a length of 5 to 7 meters and an internal diameter of 20 to 30 milli-meters; feeding the gaseous reagent from a common feeding gaseous chamber on top of said plurality of vertical and parallel tubes, above said annular liquid distribution slots; wherein the feeding pressure of said gaseous reagent is about 0.1 to 0.5 bars, said feeding pressure being substantially the same as the head loss caused by the gaseous reagent flow within the indi-vidual tubes passed through by the fluids under reaction and where the feeding pressure of said liquid reagent is higher than that of said gaseous reagent, the feeding overpressure of said liquid reagent, with respect to the feeding pressure of said gaseous reagent, being about 5 to 15 cm of liquid columns and wherein said plurality of equal, vertical and parallel tubes are externally cooled by a liquid cooling medium circulating in a common shell surrounding all the tubes. The invention also relates to a device for embodying sulphonation or sulphation reactions which occurs correspondingly to the free surface of a layer of liquid reagent subject to the action of controlled amounts of gaseous reagent. The reaction product is used, after being neutralized, for preparing surface-active agents.
The invention relates to a method for sulphonating or sulphating organic liquid compounds with gaseous sulphur trioxide contained in a carrier gas, comprising: feeding the liquid reagent from a common feeding liquid chamber, maintained completely full, into a plurality of equal vertical parallel tubes through annular slots which clearance is less of one millimeter in form of a film, wherein said tubes have a length of 5 to 7 meters and an internal diameter of 20 to 30 milli-meters; feeding the gaseous reagent from a common feeding gaseous chamber on top of said plurality of vertical and parallel tubes, above said annular liquid distribution slots; wherein the feeding pressure of said gaseous reagent is about 0.1 to 0.5 bars, said feeding pressure being substantially the same as the head loss caused by the gaseous reagent flow within the indi-vidual tubes passed through by the fluids under reaction and where the feeding pressure of said liquid reagent is higher than that of said gaseous reagent, the feeding overpressure of said liquid reagent, with respect to the feeding pressure of said gaseous reagent, being about 5 to 15 cm of liquid columns and wherein said plurality of equal, vertical and parallel tubes are externally cooled by a liquid cooling medium circulating in a common shell surrounding all the tubes. The invention also relates to a device for embodying sulphonation or sulphation reactions which occurs correspondingly to the free surface of a layer of liquid reagent subject to the action of controlled amounts of gaseous reagent. The reaction product is used, after being neutralized, for preparing surface-active agents.
Description
11~4S61 The present invention relates to an improved method for the film sulphonation in multitubular reactor and to such a reactor suitable to embody said method.
The sulphonation or sulphation of the materials at present used in the surfaoe-active materials industry (dodecilbenzene branched and linear fatty alcohols, ethoxylated fatty alcohols, olefines, esters of the fatty acids) is at present obtained through various known methods.
The most used of said known methods are those comprising the reaction with gaseous mixtures containing SO3 (e.g. with converter gas) in cascade reactors where the gas is made to react in agitated vessels with the mass of liquid at a progres-sively higher concentration o the sulphbnated product, or in tubular reactors where the gas reacts continuously with the liquid arranged on a thin layer, adjusting the flows and velocities so as to have a progressive decrease in the concentra-tion of the gas, corresponding to a progressive enrichment in the concentration of the sulphonated product.
The first system offers the advantage of being in position to control in the various steps either the desired degree of advancement of the reaction or the temperature of reaction, avoiding so any formation of oversulphonated products due to an excess of temperature. Even the residence time within the reactor, i.e. the contact time, o~ the reagents may be advanta-geously controlled as for the reaction completion is concerned, by sizing suitably the last one or ones of the cascade reactors.
The second s~stem, the so-called film reactor, allows to perform the reaction in a single reactor with extremely short time of contact and with the possibility of having the gas react at dilutions progressively lower correspondingly to progressively higher reaction degrees.
~,. ~
- 1 - q~
The reaction of sulphonation in film devices is at present obtained through various systems.
1, Film sulphonation through a monotubular reactor. This type of reactor, the first to be used for the film sulphonation, comprises a single cylindric vertical tube at the upper end of which is ed a layer or film of liquid reagent which is made to go down adhering to inner of the tube. Inside said tube a flow of gaseous reagent generally consisting of gaseous sulphur tri-oxide diluted in an inert carrier gas is fed.
A cooling liquid is made to circulate on the outer surface of said tube with the purpose of controlling that the temperature of the misture during reaction remains under prefixed limits.
The limitations oL a monotubular reac,tor of this type consist of that the maximum diameter of the reactor (and thus its maximum produciton rate) is bound to the optimum feeding velocity of the gaseous reagent.
As the greatest part of the reaction, at the optimum velocity of the gas (20 - ~0 m/sec.), occurs in~ a first very short portion of the reactor, diameters (and relevant production rates) higher than 1" cause an unacceptable decrease of the cooling surface consisting of the outer surface of the tube.
This situation provokes an increasing of the peak temperature in the reaction mass to unacceptable value thus obtaining poor quality of the product (bad colour due to the formation of over-sulphonated by-products).
~ . Reactor with annular gas space, This type of reactor has two concentric vertical and co-exical cylinders, an inner and an outer one, defining an annular gas space.
The liquid reagent is ed on both the inner face of the outer cylinder and on the outer face of the inner cylinder.
By suitable selecting the ratio between the diameters of 11~4561 said two cylinders, it is possible to proportion in a suitable manner the cross section of the reactor; said cross section being formed by the area of the annulus defined by said two cylinders.
~ owever, this type of reactor too has some inconveniences.
If it is desired to increase the diameters of said two cylinders, in order to increase the production capacity, serious difficul-ties arise in the distribution of said liquid reagent in form of a film of constant thickness. That requires an extremely precise construction of the reactor and consequently a remarkable increase in its cost.
In order to obtain a ~niform distribution of said liquid reagent on the reactor walls without needing an ext-reme preci-sion in construction and assembling, according to a modifica-tion of this type of reactors, an annular rotor arranged in the upper portion of said annular gas space is provided.
Said reactor removes only partially the above inconveniences;
in fact, at least for the upper portion o said reactor, even higher precisions are requested in view of the presence of a turning element, whose distance from the two films of liquid reagent is to be carefull~ calibrated.
3. Multitubular reactors. This type of reactor consists of a bundle of single tubes, each of them of optimum sizes as for the distribution of liquid is concerned, as well as the available cooling surface and facility of mechanical construction.
In these reactors the most serious difficulty consists in assuring for each tube the exact amount of gas and liquid (equal for everyone) so as to obtain in each t~be the same molar ratio of the reagents corresponding to the one pre-fixed for the reactor.
Several authors have recently considered the problem, solving it partly through the following arrangements:
a) the use of calibrated orifices for feeding t~e liquid and gas to any single tube;
--~ b) the use of reaction calibrated tubes, all of them with the same size: diameter, wall thickness, length;
c) the use of a pressure equalizing gas introduced downstream of the distributing nozzles for ensuring the correct distribution of the reactants to the reactor tubes.
The above arrangements, though improving the operating conditions, cannot assure a perfect molar ratio between the liquid and the gaseous reagents in the individual tubes, but provide acceptable results thanks to the already described advantages depending on the use of a multitubular reactor, where any individual rube, wh~n fed with the correct amounts of fluids, assures the best operating conditions.
In such a-way, the best results obtainable are the statis-tical average value of more or less optimum values obtained by any individual tube, although in said tubes considered indivi-dually the molar ratio gas/liquid is not the optimum one if not by chance.
The precision in the gas/liquid ratio is obtained at the expense of a remarkable head loss, this characteristic occurring also in concentric tubes reactors and, particularly for the feeding of the gasious reagent, causing a considerable expenditure of energy and construction problems in the up-stream SO3-pro-duction unit.
In the view of the foregoing the invention aims at removing the above drawbacks b~ means of a combination of elements studied and tested for that purpose, i.e.:
A) Selection of the multitubular solution to assure the best conditions of thermal exchange and homogeneity in the film ~ 4S61 thickness.
B) Selection of the optimum size of the individual tubes for the t best compromise: maximum diameter (lower number of tubes) minimum height (lower head loss), but anyhow of simple mechani-cal embodiment.
C) Distributlon of the gaseous reagent with neglectable head loss, conditioned in any individual tube by the film thickness and thus by the flow-rate of the liquid reagent, by the conver-sion profiles and by the reaction temperature along the tube.
Said combination of elements allowed to obtain excellent results, needing of no calibration when changing flow and/or type of liquid reagent used.
The present invention relates to a method for sulpho-nating or sulphating organic liquid compounds with gaseous sulphur trioxide contained in a carrier gas, comprising:
- feeding the liquid reagent from a common feeding liquid chamber, maintained completely full, into a plurality of equal vertical parallel tubes through annular slots which clearance is less of one millimeter in form of a film, wherein said tubes have a length of 5 to 7 meters and an internal dlameter of 20 to 30 mlllimeters;
- feeding the gaseous reagent from a common feeding gaseous chamber on top of said plurality of vertical and parallel tubes, above said annular liquid distribution slots; wherein the feeding pressure of said gaseous reagent is about 0.1 to 0.5 bars, said feeding pressure being substantially the same as the head loss caused by the gaseous reagent flow within the indi-vidual tubes passed through by the fluids under reaction and where the feeding pressure of said liquid reagent is higher than that of said gaseous reagent, the feeding overpressure of said liquid reagent, with respect to the feeding pressure of said gaseous reagent, being about 5 to 15 cm of liquid column;
- :1144S61 - and wherein said plurality of equal, vertical and parallel tubes are externally cooled by a liquid cooling medium cir-culating in a common shell surrounding all the tubes.
Said carrier gas consists, at least partially, in the exhausted gas coming from the collecting chamber of the same reactor.
The device suitable to embody said method, of the type comprlsing a set of vertical tubes arranged in parallel and fed with the gaseous reagent at their top end through a common distribution chamber, is characterized in that the section of each tube is substantially constant from the section of feeding of said gaseous reagent to the bottom end.
Said liquid reagent is fed into each tube near its top end through a circular slot provided on a cross section of said tube. The outer surface of each tube is cooled through a sui-tably cooling fluid circulating within one or more chambers arranged outside said tubes.
Finally, said device comprises suitable means for adjusting the opening size of said slot.
In order that the invention may be clearly understood, it wlll now be described by way of example, with reference to the accompanying drawings, wherein:
Fig. 1 is a diagrammatical cross vertical section of a reactor suitable to embody the invention;
Fig. 2 shows the particular denoted by II in Fig. 1 in a larger scale;
Fig. 3 is a cross section, along line III-III of Fig.l Fig. 4 is a diagrammatical section of three tubes of said reactor, showing a first operation condition of said pipes;
L~
Figs. 5 and 6 are views similar to the one of Fig. 4, showing two different operating conditions.
As shown in the drawings, reactors 1 is formed by a set of tubes 10 vertical and parallel, arranged side by side and connected on top to a feeding chamber 70 for said gaseous reagent coming, through a conduit 12, from a plant producing gaseous SO3 preferably b~ catal~tic conversion.
Said tubes 10 are connected on the bottom to a chamber 40 for collecting the reaction products which are removed by means of a conduit 13 shown only diagrammatically.
A cooling fluid, preferably water, circulates inside the reactor cylindrical vessel, but outside said tubes 10.
As the exothermic reaction between the liquid products to be sulphonated or sulphated on one side and the gaseous reagent consisting of sulphur trioxide on the other side, occurs mainly in the first or upper portion of said tubes 10, the cooling liquid flow is preferabl~ of the same direction as the reaction mixture, that is downwards.
~ herefore, at least an upper conduit 20 for feeding the cooling liquid and a lower conduit 21 for discharging same are provided.
Suitable horizontal or subhorizontal diaphragms 22 increase the turbulence of the cooling liquid and the path thereof in a manner known per se. ~herefore, the cooling liquid circulates within a space defined b~ the outer faces of tubes 10, the inner face of the cover of reactor 1 and two tube plates 23 and 24 passed through tightl~ b~ said tubes 10.
A third tube plate 25 is arranged above said tube plate 23, so as to define, below the chamber 70 for distribution of the gaseous reagent, a second chamber 15 for distribution of the liquid reagent. One or more conduits 16 feeds said liquid 1144~1 reagent to said chamber 15. E~or the passage of the liquid reagent from said distribution chamber 15 into the individual tubes a feeding device shown in details in Fig. 2 is provided for each tube.
Still with reference to Fig. 2, each tube 10 comprises an upper portion 30 c~lindric and with a slightly larger diameter;
the upper end o~ said tube 10 is connected to the lower end of said upper portion 30 through a short frustoconical section 31.
Said upper cylindric portion 30 is provided with a suitable number of passages 38 for the liquid reagent and its outer surface is in contact, with a suitable clearance, to the inner surface of a cylindric sleeve 33 through which the tightness with said plates 23 and 25 is obtained.
Said sleeve 33 is provided with passages 36 or the liquid reagent of such size and circumpherential distribution as not to generate head losses when the liquid passes.
Inside the upper end element 30 of tube 10 is provided a second sleeve 50 whose outside surface is in contact to the inner surface of said element 30, except for a central section owing to the presence o~ a wide annular groove 51.
'rhe inner wall o~ said element 30 and said groove 51 originates an annular space which may receive the liquid reagent coming from said passages 38 and 36 which end into said groove 51.
Suitable axial passages 52, shown only diagrammatically in Fig. 2, allow said liquid reagent discharge downwards from the annular space defined by said groove 51. Said sleeve 50 comprises a lower frustoconical end with the same opening angle as the connection zone 31 between said elements 10 and 30.
Therefore, between the lower end of said sleeve 50 and said connection element 31 there is an annular slot oriented according to the generatrices of a truncated cone whose width is defined ` 11~4~61 by the vertical position of sleeve 50. Said sleeve 50 is provided upwards with a threaded crown 54 which ~ay be screwed onto the upper edge of said upper end element 30. It is possible in such a way, by screwing up or down said sleeve 50 onto said element 30, to define the section of annular passage between the lower edge of said sleeve 50 and the frustoconical connection element 31. Said annular passage, being oriented according to the generatrices of a cone, favors the distribution of said liquid reagent in form of a film, denoted by 60 in Fig.2, all around the inner wall of said tube 10.
The inner diameter of said sleeve 50 is suitably the same as the inner diameter of said tube 10, so that the gas coming from the distribution chamber 70 may be brought to brush the free surface of said film 60 without undergoing remarkable head losses.
Anyhow, it is clear that owing to the constructive simpli-city of the liquid reagen. distributor, it is very difficult to obtain a very exact adjustment of the flow-rate thereof. As a matter of fact, during the tests without feeding of gaseous reagent, a variation even up to 20% was remarked between the nominal flow-rate and the one of the individual tube 10 of said reactor.
Notwithstanding that, as it will be explained further on, in the process according to the invention it is possible to keep the deviations of the ratio between the flow-rate of the gaseous reagent and the one of the liquid reagent within strict limits.
Such a result is quite surprising, considering that the main difficulty of all the film reactors is just the correct propor-tioning of the two reagents.
According to the invention, the pressure of the gaseous reagent feeding is considerably lower than the pressures of gaseous reagent ~eeding of the known methods. Said feeding pressure is according to the invention of about 0.1 - 0.4 bars.
Depending on the liquid feedstocks used, the pressure of the liquid reagent feeding is higher than the one of the gaseous reagent for an amount equal to the height of the liquid level exi5ting in the distribution chamber for same.
Notwithstanding the low feeding pressure of the two reagents and that the ~low-rate of the liquid reagent may vary up to over 20% from a tube to another, it was surprisingly found that the molar ratio between the liquid reagent and the gaseous reagent remained very near the imposed average value with very low differences among the tubes if considered on the basis of the results obtained. A possible explanation of said surprising result is described with reference to Fig. 4, 5 and 6.
Supposing that in the interval o~ time (to -tl) in each of the three tubes 110, 210, 310 having the same diameters and length the same ideal situation occurs, i.e. the three flow-rates of the liquid reagents Ll, L2, L3 are equal, the three flow-rates of the gaseous reagent Gl, G2, G3 are equal and thus the three molar ratioS Rl, R2, R3 corresponding to the imposed optimum molar ratio are equal; then, if the diameters of said three tubes are strictly equal, equal degree of advancement of the reaction will occur along the tubes at equal levels as shown in Fig. 4, where numerals P60, P90, P98 represent the levels correspondingly to which the reaction advancement degree is 60%, 90~, and 9~%
respectively.
The length of the tubes is selected so as the time o~
contact between the two reagents may be largely sufficient, in the optimum feeding conditions as to assure practically the complete conversion of the liquid reagents (reaction advancement degree near 100%). In such a way, it is always assured the -- ~0 --11~4~61 completion of the reaction in each tube, even in conditions different from the optimum ones when such a situation occurs owing to disturbancies or the like.
Supposing now that for an~ reason in an interval of time tl - t2, the three flow-rates of the gaseous reagent Gl, G2, G3 remaining unchanged, a variation occurs in the flow-rates of the liquid reagent Ll, L2, L3, so that e.g. Ll = Lt/3, L2 = 0,9 Lt/3, L3 = 1.1 Lt/3, where l.t means the aggregate flow-rate of the liquid reagent in the three tubes which is kept constant. In tube 110 the situation remains clearly unchanged with respect to the one shown in Fig. 4 and thus the position of levels P60, P9o and P98 remains unchanged. Owing to the lower flow-rate of liquid, in tube 210 will occur a rising of levels P60, P90, P98, while the contrar~ result will be obtained in tube 310 owing to the larger flow-rate of liquid.
It is to be noted now that the differences in pressure between chambers 70 and 40 is equal to the head loss of each of said three tubes n which therefore said head loss is equal.
It is further to be noted that together with the variation of the degree of advancement of the reaction, the viscosity and thus the thickness of said film consisting of the mixture of the liquid reagent and the liquid product of the reaction changes considerably.
Particularl~, for increasing degrees of advancement of the reaction, there is an increase in the viscosity and in the thickness of the film consisting of the mixture of the liquid reagent and the liquid reaction product.
Fig. S shows that height H3 of the portion of tube 310 where the reaction advancement degree is higher than 9~ is shorter than the corresponding height Hl of tube 110, said height Hl being on its turn shorter than height H2.
Owing to their diferent lengths Hl, H2, H3, said three tubes have thus different average sections of passage for the flow of the gaseous reagent, as the average thickness of the liquid film along the tubes are different.
As the three flow-rates of the gaseous reagent in the tubes 110, 210 and 310 depend clearl~ only on the respective average sections of passage, being the pressure difference at the extremity o the three tubes the same as told above, the result is that:
in tube 210, with a passage average section smaller than the original one shown in Fig. 4, a decrease in the flow-rate of said gaseous reagent will occur, tending to bring the molar ratio between the two reagents down to the original optimum starting value;
in tube 310, with a passage average section larger than the original one shown in Fig. 4, an increase in the flow-rate of said gaseous reagent will occur, tending in this case too to shift the molar ratio up to the original optimum starting value.
It would however be possible, starting from moment tl, the case that, though remaining constant and equal the three flow-rate L1, L2, L3 of the liquid reagent, the flow-rates of the gaseous reagent vary so as to have, see Fig. 6, e.g. Gl-Gt/3, G2=0.9.Gt/3, G3=l.l.~t/3, being Gt the aggregate flow-rate of said gaseous reagent in the three tubes which is kept constant.
Clearly, in tube 110 the situation remains unchanged with respect to the one of Fig. 4, and thus the positions of levels P60, P90, P98 remain unchanged. Owing to the lower flow-rate of gas, tube 210 will face a lowering of levels P60, P90, P98, while owing to the larger delivery of gas tube 310 will face an increase in said levels. For the same considerations as in the previoùsly discussed case, there will be a decrease in the gas flow-rate in tube 310 and an increase of the flow-rate of the same gaseous reagent in tube 210, as the respective average sections of passage will be decreased in tube 310 and increased in tube 210. In this case too, the molar ratios R2 and R3 will shift towards optimum original values. Besides the above described balancing effect due to the modification of the conver-sion profiles in the tubes, there is also another important balancing effect that takes advantage from the marked variation of viscosity with the temperature. In effect, if the average temperature in the liquid film presents inside the tubes varies, correspondentl~ also the average viscosity of the liquid varies.
As a consequence, for the same flow-rate when the film average temperature increases the average thickness of the film decreases and thereore the average section of passage for the gas will increase. The contrar~ happens in case of decrease of the film average temperature. Therefore with reference to the three tubes illustrated in figure 4 and to the possible different situations corresponding to ~igure 5, for tube 210 characterized by a decrease in the flow-rate of the liquid reagent, the overall ef~ect is a less amount of material reacting in the unit time and therefore a less amount of heat of reaction released. As the temperature and flow conditions of the cooling medium remain the same, in this situation the average film temperature will be lower than the original one due to the lower reaction heat to be exchanged with the cooling medium. This resul~s in a higher average viscosity, higher average film thickness and consequently lower section of passage for the gas.
As the pressure at the extremity of the tube 210 is unchanged, the gas flow-rate G2 will decrease and therefore the ratio R2 will tend to decrease towards the original optimum value. On the contrary, in the case of the tube 310 in the conditions of figure ` ~1'14561 5, the effect of the increase in liquid flow-rate will result in an increase of the amount of material reacting in the unit time and consequently in a greater amount of heat of reaction released.
This situation is exactly the contrary of the previous one and the final consequence will be an increase in the average film temperat~re, a decrease in the average film viscosity and therefore a higher section of passage for the gas. In this ca&e the gas flow-rate will increase so increasing the ratio R3 to-wards the original optimum value. In the situation of figure 6,being the liquid flow-rates constant the average value of film temperature, is practically uneffected and therefore this balancing effect is due only to the variation in conversion profiles.
These two balancing effect are so strong as to compensate the unbalancing effect due to the variation in flow-rate of the reagents and, as it is clear from the above, do not restore the original optimum value or the flow-rates, in each tube, but only the original value of the molar ratio between the two reagents.
In effect, starting from the ideal situation of Fig. 4, when the transient period is elapsed and the balancing effects have produced their results, the unique situation compatible with the overall material balance of the whole reactor is:
GT
Rl = R2 = R3 = Rt = -LT
Therefore, despite the fact that the flow-rates in each tube are different from the ideal ones GTj3 and LT/3 the molar ratio in each tube is the correct one imposed by the external control means of the reactor.
Some examples o-f embodiment of the method described are shown herebelow:
Example No. 1: this example shows the operative features used for the sulphonation, according to the invention, of linear dodecylbenzene with a wide composition spectrum and a length of aliphatic chain between C9 and C15.
- 8ulphonable content of the feedstock98,5 %
- average molecular weight of the feedstock 267 - flow-rate of the feedstock 180 Kgs/h - concentration (by volume) of SO3 in the carrier gas 5 ~
- temperature of SO3 fed to the reactor36-40C
- pressure at the entrance of the gaseous reagent to the reactor 140 mmHg The reactor according to the invention has the following features:
- number of tubes 7 - inner diameter of tubes 25 mm - length of tubes 6000 mm Water at a temperature of 25 C is used as cooling liquid.
The temperature of the sulphonic acid at the exit from the reactor is 45C.
Analysis of the composition and characteristics of the product obtained after ageing and stabilization:
- amount of unsulphonated matter in the reaction product 1,35%
- amount of free H2S04 below 1~
- color of product 25Klett Example No. 2: this example shows the operative features used for the sulphation of synethetic laurilic alcohol (C12 - C15).
- average molecular weight of the feedstock 207 - flow-rate of the feedstock 150 Kgs/h - concentration (b~ volume) of SO3 in the carrler gas 5%
- temperature of SO3 fed to the reactor 38C
- feeding pressure of the gaseous reagent 136 mmHg The reactor used has the same features as the one used in Example No. 1.
Water at the temperature of 20C is used as cooling liquid.
The sulphated product when coming out oE the reactor has a temperature of 39C.
Analysis of the neutralized product:
- amount o~ unsulphonated matter 1,9%
- content of Na2SO4 0,g8%
- color 7Klett The neutralization was performed in an aqueous solution.
The above mentioned values of unsulphonated materials and Sodium sulphate are referred to 100% of active substance.
ExamPle No. 3: this example shows the operative features used for the sulphation of s~nthetic laurilic alcohol (C12-C15) ethoxylated with three molecules of ethylene oxide.
- average molecular weight 339 - flow-rate of the feedstock 130 Kgs/h - concentration (by volume) of SO3 in the c?rrier gas 2,5%
- temperature of SO3 ed to the reactor36C
- feeding pressure o the gaseous reagent230 mmHg The reactor used has the same features as the one used in Example No. 1. The product when coming out of the reactor has a temperature of 40C. The cooling water has a temperature of Analysis of the neutralized product:
- amount of unsulphonated matter 1,3%
- .- 1144561 - content of Na2SO4 1,4%
- color 15 Klett The neutralization was performed immediately after the sulphation in an agueous solution. The above values of unsul-phonated product and Sodium sulphate are referred to 100~ of active substance.
It is to be noted that for the three above examples, the molar ratio between the two reagents ~SO3 and liquid feedstock) was held at the value of (1.03 - 1.06): 1.
Further, the color of the final product was defined through a colorimeter Klett-Summerson with a 42 blue filter, with a 5~
solution. A cell of 40mm was used. The color was determined on the product as it comes out from the reactor without submitting it to any bleaching process.
It is to be understood that the invention is not limited to the examples shown. It is intended to cover all modifications and equivalents within the scope of the appended claims.
The sulphonation or sulphation of the materials at present used in the surfaoe-active materials industry (dodecilbenzene branched and linear fatty alcohols, ethoxylated fatty alcohols, olefines, esters of the fatty acids) is at present obtained through various known methods.
The most used of said known methods are those comprising the reaction with gaseous mixtures containing SO3 (e.g. with converter gas) in cascade reactors where the gas is made to react in agitated vessels with the mass of liquid at a progres-sively higher concentration o the sulphbnated product, or in tubular reactors where the gas reacts continuously with the liquid arranged on a thin layer, adjusting the flows and velocities so as to have a progressive decrease in the concentra-tion of the gas, corresponding to a progressive enrichment in the concentration of the sulphonated product.
The first system offers the advantage of being in position to control in the various steps either the desired degree of advancement of the reaction or the temperature of reaction, avoiding so any formation of oversulphonated products due to an excess of temperature. Even the residence time within the reactor, i.e. the contact time, o~ the reagents may be advanta-geously controlled as for the reaction completion is concerned, by sizing suitably the last one or ones of the cascade reactors.
The second s~stem, the so-called film reactor, allows to perform the reaction in a single reactor with extremely short time of contact and with the possibility of having the gas react at dilutions progressively lower correspondingly to progressively higher reaction degrees.
~,. ~
- 1 - q~
The reaction of sulphonation in film devices is at present obtained through various systems.
1, Film sulphonation through a monotubular reactor. This type of reactor, the first to be used for the film sulphonation, comprises a single cylindric vertical tube at the upper end of which is ed a layer or film of liquid reagent which is made to go down adhering to inner of the tube. Inside said tube a flow of gaseous reagent generally consisting of gaseous sulphur tri-oxide diluted in an inert carrier gas is fed.
A cooling liquid is made to circulate on the outer surface of said tube with the purpose of controlling that the temperature of the misture during reaction remains under prefixed limits.
The limitations oL a monotubular reac,tor of this type consist of that the maximum diameter of the reactor (and thus its maximum produciton rate) is bound to the optimum feeding velocity of the gaseous reagent.
As the greatest part of the reaction, at the optimum velocity of the gas (20 - ~0 m/sec.), occurs in~ a first very short portion of the reactor, diameters (and relevant production rates) higher than 1" cause an unacceptable decrease of the cooling surface consisting of the outer surface of the tube.
This situation provokes an increasing of the peak temperature in the reaction mass to unacceptable value thus obtaining poor quality of the product (bad colour due to the formation of over-sulphonated by-products).
~ . Reactor with annular gas space, This type of reactor has two concentric vertical and co-exical cylinders, an inner and an outer one, defining an annular gas space.
The liquid reagent is ed on both the inner face of the outer cylinder and on the outer face of the inner cylinder.
By suitable selecting the ratio between the diameters of 11~4561 said two cylinders, it is possible to proportion in a suitable manner the cross section of the reactor; said cross section being formed by the area of the annulus defined by said two cylinders.
~ owever, this type of reactor too has some inconveniences.
If it is desired to increase the diameters of said two cylinders, in order to increase the production capacity, serious difficul-ties arise in the distribution of said liquid reagent in form of a film of constant thickness. That requires an extremely precise construction of the reactor and consequently a remarkable increase in its cost.
In order to obtain a ~niform distribution of said liquid reagent on the reactor walls without needing an ext-reme preci-sion in construction and assembling, according to a modifica-tion of this type of reactors, an annular rotor arranged in the upper portion of said annular gas space is provided.
Said reactor removes only partially the above inconveniences;
in fact, at least for the upper portion o said reactor, even higher precisions are requested in view of the presence of a turning element, whose distance from the two films of liquid reagent is to be carefull~ calibrated.
3. Multitubular reactors. This type of reactor consists of a bundle of single tubes, each of them of optimum sizes as for the distribution of liquid is concerned, as well as the available cooling surface and facility of mechanical construction.
In these reactors the most serious difficulty consists in assuring for each tube the exact amount of gas and liquid (equal for everyone) so as to obtain in each t~be the same molar ratio of the reagents corresponding to the one pre-fixed for the reactor.
Several authors have recently considered the problem, solving it partly through the following arrangements:
a) the use of calibrated orifices for feeding t~e liquid and gas to any single tube;
--~ b) the use of reaction calibrated tubes, all of them with the same size: diameter, wall thickness, length;
c) the use of a pressure equalizing gas introduced downstream of the distributing nozzles for ensuring the correct distribution of the reactants to the reactor tubes.
The above arrangements, though improving the operating conditions, cannot assure a perfect molar ratio between the liquid and the gaseous reagents in the individual tubes, but provide acceptable results thanks to the already described advantages depending on the use of a multitubular reactor, where any individual rube, wh~n fed with the correct amounts of fluids, assures the best operating conditions.
In such a-way, the best results obtainable are the statis-tical average value of more or less optimum values obtained by any individual tube, although in said tubes considered indivi-dually the molar ratio gas/liquid is not the optimum one if not by chance.
The precision in the gas/liquid ratio is obtained at the expense of a remarkable head loss, this characteristic occurring also in concentric tubes reactors and, particularly for the feeding of the gasious reagent, causing a considerable expenditure of energy and construction problems in the up-stream SO3-pro-duction unit.
In the view of the foregoing the invention aims at removing the above drawbacks b~ means of a combination of elements studied and tested for that purpose, i.e.:
A) Selection of the multitubular solution to assure the best conditions of thermal exchange and homogeneity in the film ~ 4S61 thickness.
B) Selection of the optimum size of the individual tubes for the t best compromise: maximum diameter (lower number of tubes) minimum height (lower head loss), but anyhow of simple mechani-cal embodiment.
C) Distributlon of the gaseous reagent with neglectable head loss, conditioned in any individual tube by the film thickness and thus by the flow-rate of the liquid reagent, by the conver-sion profiles and by the reaction temperature along the tube.
Said combination of elements allowed to obtain excellent results, needing of no calibration when changing flow and/or type of liquid reagent used.
The present invention relates to a method for sulpho-nating or sulphating organic liquid compounds with gaseous sulphur trioxide contained in a carrier gas, comprising:
- feeding the liquid reagent from a common feeding liquid chamber, maintained completely full, into a plurality of equal vertical parallel tubes through annular slots which clearance is less of one millimeter in form of a film, wherein said tubes have a length of 5 to 7 meters and an internal dlameter of 20 to 30 mlllimeters;
- feeding the gaseous reagent from a common feeding gaseous chamber on top of said plurality of vertical and parallel tubes, above said annular liquid distribution slots; wherein the feeding pressure of said gaseous reagent is about 0.1 to 0.5 bars, said feeding pressure being substantially the same as the head loss caused by the gaseous reagent flow within the indi-vidual tubes passed through by the fluids under reaction and where the feeding pressure of said liquid reagent is higher than that of said gaseous reagent, the feeding overpressure of said liquid reagent, with respect to the feeding pressure of said gaseous reagent, being about 5 to 15 cm of liquid column;
- :1144S61 - and wherein said plurality of equal, vertical and parallel tubes are externally cooled by a liquid cooling medium cir-culating in a common shell surrounding all the tubes.
Said carrier gas consists, at least partially, in the exhausted gas coming from the collecting chamber of the same reactor.
The device suitable to embody said method, of the type comprlsing a set of vertical tubes arranged in parallel and fed with the gaseous reagent at their top end through a common distribution chamber, is characterized in that the section of each tube is substantially constant from the section of feeding of said gaseous reagent to the bottom end.
Said liquid reagent is fed into each tube near its top end through a circular slot provided on a cross section of said tube. The outer surface of each tube is cooled through a sui-tably cooling fluid circulating within one or more chambers arranged outside said tubes.
Finally, said device comprises suitable means for adjusting the opening size of said slot.
In order that the invention may be clearly understood, it wlll now be described by way of example, with reference to the accompanying drawings, wherein:
Fig. 1 is a diagrammatical cross vertical section of a reactor suitable to embody the invention;
Fig. 2 shows the particular denoted by II in Fig. 1 in a larger scale;
Fig. 3 is a cross section, along line III-III of Fig.l Fig. 4 is a diagrammatical section of three tubes of said reactor, showing a first operation condition of said pipes;
L~
Figs. 5 and 6 are views similar to the one of Fig. 4, showing two different operating conditions.
As shown in the drawings, reactors 1 is formed by a set of tubes 10 vertical and parallel, arranged side by side and connected on top to a feeding chamber 70 for said gaseous reagent coming, through a conduit 12, from a plant producing gaseous SO3 preferably b~ catal~tic conversion.
Said tubes 10 are connected on the bottom to a chamber 40 for collecting the reaction products which are removed by means of a conduit 13 shown only diagrammatically.
A cooling fluid, preferably water, circulates inside the reactor cylindrical vessel, but outside said tubes 10.
As the exothermic reaction between the liquid products to be sulphonated or sulphated on one side and the gaseous reagent consisting of sulphur trioxide on the other side, occurs mainly in the first or upper portion of said tubes 10, the cooling liquid flow is preferabl~ of the same direction as the reaction mixture, that is downwards.
~ herefore, at least an upper conduit 20 for feeding the cooling liquid and a lower conduit 21 for discharging same are provided.
Suitable horizontal or subhorizontal diaphragms 22 increase the turbulence of the cooling liquid and the path thereof in a manner known per se. ~herefore, the cooling liquid circulates within a space defined b~ the outer faces of tubes 10, the inner face of the cover of reactor 1 and two tube plates 23 and 24 passed through tightl~ b~ said tubes 10.
A third tube plate 25 is arranged above said tube plate 23, so as to define, below the chamber 70 for distribution of the gaseous reagent, a second chamber 15 for distribution of the liquid reagent. One or more conduits 16 feeds said liquid 1144~1 reagent to said chamber 15. E~or the passage of the liquid reagent from said distribution chamber 15 into the individual tubes a feeding device shown in details in Fig. 2 is provided for each tube.
Still with reference to Fig. 2, each tube 10 comprises an upper portion 30 c~lindric and with a slightly larger diameter;
the upper end o~ said tube 10 is connected to the lower end of said upper portion 30 through a short frustoconical section 31.
Said upper cylindric portion 30 is provided with a suitable number of passages 38 for the liquid reagent and its outer surface is in contact, with a suitable clearance, to the inner surface of a cylindric sleeve 33 through which the tightness with said plates 23 and 25 is obtained.
Said sleeve 33 is provided with passages 36 or the liquid reagent of such size and circumpherential distribution as not to generate head losses when the liquid passes.
Inside the upper end element 30 of tube 10 is provided a second sleeve 50 whose outside surface is in contact to the inner surface of said element 30, except for a central section owing to the presence o~ a wide annular groove 51.
'rhe inner wall o~ said element 30 and said groove 51 originates an annular space which may receive the liquid reagent coming from said passages 38 and 36 which end into said groove 51.
Suitable axial passages 52, shown only diagrammatically in Fig. 2, allow said liquid reagent discharge downwards from the annular space defined by said groove 51. Said sleeve 50 comprises a lower frustoconical end with the same opening angle as the connection zone 31 between said elements 10 and 30.
Therefore, between the lower end of said sleeve 50 and said connection element 31 there is an annular slot oriented according to the generatrices of a truncated cone whose width is defined ` 11~4~61 by the vertical position of sleeve 50. Said sleeve 50 is provided upwards with a threaded crown 54 which ~ay be screwed onto the upper edge of said upper end element 30. It is possible in such a way, by screwing up or down said sleeve 50 onto said element 30, to define the section of annular passage between the lower edge of said sleeve 50 and the frustoconical connection element 31. Said annular passage, being oriented according to the generatrices of a cone, favors the distribution of said liquid reagent in form of a film, denoted by 60 in Fig.2, all around the inner wall of said tube 10.
The inner diameter of said sleeve 50 is suitably the same as the inner diameter of said tube 10, so that the gas coming from the distribution chamber 70 may be brought to brush the free surface of said film 60 without undergoing remarkable head losses.
Anyhow, it is clear that owing to the constructive simpli-city of the liquid reagen. distributor, it is very difficult to obtain a very exact adjustment of the flow-rate thereof. As a matter of fact, during the tests without feeding of gaseous reagent, a variation even up to 20% was remarked between the nominal flow-rate and the one of the individual tube 10 of said reactor.
Notwithstanding that, as it will be explained further on, in the process according to the invention it is possible to keep the deviations of the ratio between the flow-rate of the gaseous reagent and the one of the liquid reagent within strict limits.
Such a result is quite surprising, considering that the main difficulty of all the film reactors is just the correct propor-tioning of the two reagents.
According to the invention, the pressure of the gaseous reagent feeding is considerably lower than the pressures of gaseous reagent ~eeding of the known methods. Said feeding pressure is according to the invention of about 0.1 - 0.4 bars.
Depending on the liquid feedstocks used, the pressure of the liquid reagent feeding is higher than the one of the gaseous reagent for an amount equal to the height of the liquid level exi5ting in the distribution chamber for same.
Notwithstanding the low feeding pressure of the two reagents and that the ~low-rate of the liquid reagent may vary up to over 20% from a tube to another, it was surprisingly found that the molar ratio between the liquid reagent and the gaseous reagent remained very near the imposed average value with very low differences among the tubes if considered on the basis of the results obtained. A possible explanation of said surprising result is described with reference to Fig. 4, 5 and 6.
Supposing that in the interval o~ time (to -tl) in each of the three tubes 110, 210, 310 having the same diameters and length the same ideal situation occurs, i.e. the three flow-rates of the liquid reagents Ll, L2, L3 are equal, the three flow-rates of the gaseous reagent Gl, G2, G3 are equal and thus the three molar ratioS Rl, R2, R3 corresponding to the imposed optimum molar ratio are equal; then, if the diameters of said three tubes are strictly equal, equal degree of advancement of the reaction will occur along the tubes at equal levels as shown in Fig. 4, where numerals P60, P90, P98 represent the levels correspondingly to which the reaction advancement degree is 60%, 90~, and 9~%
respectively.
The length of the tubes is selected so as the time o~
contact between the two reagents may be largely sufficient, in the optimum feeding conditions as to assure practically the complete conversion of the liquid reagents (reaction advancement degree near 100%). In such a way, it is always assured the -- ~0 --11~4~61 completion of the reaction in each tube, even in conditions different from the optimum ones when such a situation occurs owing to disturbancies or the like.
Supposing now that for an~ reason in an interval of time tl - t2, the three flow-rates of the gaseous reagent Gl, G2, G3 remaining unchanged, a variation occurs in the flow-rates of the liquid reagent Ll, L2, L3, so that e.g. Ll = Lt/3, L2 = 0,9 Lt/3, L3 = 1.1 Lt/3, where l.t means the aggregate flow-rate of the liquid reagent in the three tubes which is kept constant. In tube 110 the situation remains clearly unchanged with respect to the one shown in Fig. 4 and thus the position of levels P60, P9o and P98 remains unchanged. Owing to the lower flow-rate of liquid, in tube 210 will occur a rising of levels P60, P90, P98, while the contrar~ result will be obtained in tube 310 owing to the larger flow-rate of liquid.
It is to be noted now that the differences in pressure between chambers 70 and 40 is equal to the head loss of each of said three tubes n which therefore said head loss is equal.
It is further to be noted that together with the variation of the degree of advancement of the reaction, the viscosity and thus the thickness of said film consisting of the mixture of the liquid reagent and the liquid product of the reaction changes considerably.
Particularl~, for increasing degrees of advancement of the reaction, there is an increase in the viscosity and in the thickness of the film consisting of the mixture of the liquid reagent and the liquid reaction product.
Fig. S shows that height H3 of the portion of tube 310 where the reaction advancement degree is higher than 9~ is shorter than the corresponding height Hl of tube 110, said height Hl being on its turn shorter than height H2.
Owing to their diferent lengths Hl, H2, H3, said three tubes have thus different average sections of passage for the flow of the gaseous reagent, as the average thickness of the liquid film along the tubes are different.
As the three flow-rates of the gaseous reagent in the tubes 110, 210 and 310 depend clearl~ only on the respective average sections of passage, being the pressure difference at the extremity o the three tubes the same as told above, the result is that:
in tube 210, with a passage average section smaller than the original one shown in Fig. 4, a decrease in the flow-rate of said gaseous reagent will occur, tending to bring the molar ratio between the two reagents down to the original optimum starting value;
in tube 310, with a passage average section larger than the original one shown in Fig. 4, an increase in the flow-rate of said gaseous reagent will occur, tending in this case too to shift the molar ratio up to the original optimum starting value.
It would however be possible, starting from moment tl, the case that, though remaining constant and equal the three flow-rate L1, L2, L3 of the liquid reagent, the flow-rates of the gaseous reagent vary so as to have, see Fig. 6, e.g. Gl-Gt/3, G2=0.9.Gt/3, G3=l.l.~t/3, being Gt the aggregate flow-rate of said gaseous reagent in the three tubes which is kept constant.
Clearly, in tube 110 the situation remains unchanged with respect to the one of Fig. 4, and thus the positions of levels P60, P90, P98 remain unchanged. Owing to the lower flow-rate of gas, tube 210 will face a lowering of levels P60, P90, P98, while owing to the larger delivery of gas tube 310 will face an increase in said levels. For the same considerations as in the previoùsly discussed case, there will be a decrease in the gas flow-rate in tube 310 and an increase of the flow-rate of the same gaseous reagent in tube 210, as the respective average sections of passage will be decreased in tube 310 and increased in tube 210. In this case too, the molar ratios R2 and R3 will shift towards optimum original values. Besides the above described balancing effect due to the modification of the conver-sion profiles in the tubes, there is also another important balancing effect that takes advantage from the marked variation of viscosity with the temperature. In effect, if the average temperature in the liquid film presents inside the tubes varies, correspondentl~ also the average viscosity of the liquid varies.
As a consequence, for the same flow-rate when the film average temperature increases the average thickness of the film decreases and thereore the average section of passage for the gas will increase. The contrar~ happens in case of decrease of the film average temperature. Therefore with reference to the three tubes illustrated in figure 4 and to the possible different situations corresponding to ~igure 5, for tube 210 characterized by a decrease in the flow-rate of the liquid reagent, the overall ef~ect is a less amount of material reacting in the unit time and therefore a less amount of heat of reaction released. As the temperature and flow conditions of the cooling medium remain the same, in this situation the average film temperature will be lower than the original one due to the lower reaction heat to be exchanged with the cooling medium. This resul~s in a higher average viscosity, higher average film thickness and consequently lower section of passage for the gas.
As the pressure at the extremity of the tube 210 is unchanged, the gas flow-rate G2 will decrease and therefore the ratio R2 will tend to decrease towards the original optimum value. On the contrary, in the case of the tube 310 in the conditions of figure ` ~1'14561 5, the effect of the increase in liquid flow-rate will result in an increase of the amount of material reacting in the unit time and consequently in a greater amount of heat of reaction released.
This situation is exactly the contrary of the previous one and the final consequence will be an increase in the average film temperat~re, a decrease in the average film viscosity and therefore a higher section of passage for the gas. In this ca&e the gas flow-rate will increase so increasing the ratio R3 to-wards the original optimum value. In the situation of figure 6,being the liquid flow-rates constant the average value of film temperature, is practically uneffected and therefore this balancing effect is due only to the variation in conversion profiles.
These two balancing effect are so strong as to compensate the unbalancing effect due to the variation in flow-rate of the reagents and, as it is clear from the above, do not restore the original optimum value or the flow-rates, in each tube, but only the original value of the molar ratio between the two reagents.
In effect, starting from the ideal situation of Fig. 4, when the transient period is elapsed and the balancing effects have produced their results, the unique situation compatible with the overall material balance of the whole reactor is:
GT
Rl = R2 = R3 = Rt = -LT
Therefore, despite the fact that the flow-rates in each tube are different from the ideal ones GTj3 and LT/3 the molar ratio in each tube is the correct one imposed by the external control means of the reactor.
Some examples o-f embodiment of the method described are shown herebelow:
Example No. 1: this example shows the operative features used for the sulphonation, according to the invention, of linear dodecylbenzene with a wide composition spectrum and a length of aliphatic chain between C9 and C15.
- 8ulphonable content of the feedstock98,5 %
- average molecular weight of the feedstock 267 - flow-rate of the feedstock 180 Kgs/h - concentration (by volume) of SO3 in the carrier gas 5 ~
- temperature of SO3 fed to the reactor36-40C
- pressure at the entrance of the gaseous reagent to the reactor 140 mmHg The reactor according to the invention has the following features:
- number of tubes 7 - inner diameter of tubes 25 mm - length of tubes 6000 mm Water at a temperature of 25 C is used as cooling liquid.
The temperature of the sulphonic acid at the exit from the reactor is 45C.
Analysis of the composition and characteristics of the product obtained after ageing and stabilization:
- amount of unsulphonated matter in the reaction product 1,35%
- amount of free H2S04 below 1~
- color of product 25Klett Example No. 2: this example shows the operative features used for the sulphation of synethetic laurilic alcohol (C12 - C15).
- average molecular weight of the feedstock 207 - flow-rate of the feedstock 150 Kgs/h - concentration (b~ volume) of SO3 in the carrler gas 5%
- temperature of SO3 fed to the reactor 38C
- feeding pressure of the gaseous reagent 136 mmHg The reactor used has the same features as the one used in Example No. 1.
Water at the temperature of 20C is used as cooling liquid.
The sulphated product when coming out oE the reactor has a temperature of 39C.
Analysis of the neutralized product:
- amount o~ unsulphonated matter 1,9%
- content of Na2SO4 0,g8%
- color 7Klett The neutralization was performed in an aqueous solution.
The above mentioned values of unsulphonated materials and Sodium sulphate are referred to 100% of active substance.
ExamPle No. 3: this example shows the operative features used for the sulphation of s~nthetic laurilic alcohol (C12-C15) ethoxylated with three molecules of ethylene oxide.
- average molecular weight 339 - flow-rate of the feedstock 130 Kgs/h - concentration (by volume) of SO3 in the c?rrier gas 2,5%
- temperature of SO3 ed to the reactor36C
- feeding pressure o the gaseous reagent230 mmHg The reactor used has the same features as the one used in Example No. 1. The product when coming out of the reactor has a temperature of 40C. The cooling water has a temperature of Analysis of the neutralized product:
- amount of unsulphonated matter 1,3%
- .- 1144561 - content of Na2SO4 1,4%
- color 15 Klett The neutralization was performed immediately after the sulphation in an agueous solution. The above values of unsul-phonated product and Sodium sulphate are referred to 100~ of active substance.
It is to be noted that for the three above examples, the molar ratio between the two reagents ~SO3 and liquid feedstock) was held at the value of (1.03 - 1.06): 1.
Further, the color of the final product was defined through a colorimeter Klett-Summerson with a 42 blue filter, with a 5~
solution. A cell of 40mm was used. The color was determined on the product as it comes out from the reactor without submitting it to any bleaching process.
It is to be understood that the invention is not limited to the examples shown. It is intended to cover all modifications and equivalents within the scope of the appended claims.
Claims (2)
1. A method for sulphonating or sulphating organic liquid compounds with gaseous sulphur trioxide contained in a carrier gas, comprising:
- feeding the liquid reagent from a common feeding liquid chamber, maintained completely full, into a plurality of equal vertical parallel tubes through annular slots which clearance is less of one millimeter in form of a film, wherein said tubes have a length of 5 to 7 meters and an internal diameter of 20 to 30 millimeters;
- feeding the gaseous reagent from a common feeding gaseous chamber on top of said plurality of vertical and parallel tubes, above said annular liquid distribution slots; wherein the feeding pressure of said gaseous reagent is about 0.1 to 0.5 bars, said feeding pressure being substantially the same as the head loss caused by the gaseous reagent flow within the individual tubes passed through by the fluids under reaction and where the feeding pressure of said liquid reagent is higher than that of said gaseous reagent, the feeding overpressure of said liquid reagent, with respect to the feeding pressure of said gaseous reagent, being about 5 to 15 cm of liquid column;
- and wherein said plurality of equal, vertical and parallel tubes are externally cooled by a liquid cooling medium circu-lating in a common shell surrounding all the tubes.
- feeding the liquid reagent from a common feeding liquid chamber, maintained completely full, into a plurality of equal vertical parallel tubes through annular slots which clearance is less of one millimeter in form of a film, wherein said tubes have a length of 5 to 7 meters and an internal diameter of 20 to 30 millimeters;
- feeding the gaseous reagent from a common feeding gaseous chamber on top of said plurality of vertical and parallel tubes, above said annular liquid distribution slots; wherein the feeding pressure of said gaseous reagent is about 0.1 to 0.5 bars, said feeding pressure being substantially the same as the head loss caused by the gaseous reagent flow within the individual tubes passed through by the fluids under reaction and where the feeding pressure of said liquid reagent is higher than that of said gaseous reagent, the feeding overpressure of said liquid reagent, with respect to the feeding pressure of said gaseous reagent, being about 5 to 15 cm of liquid column;
- and wherein said plurality of equal, vertical and parallel tubes are externally cooled by a liquid cooling medium circu-lating in a common shell surrounding all the tubes.
2. A device suitable to embody the method claimed in claim 1, of the type comprising a set of vertical tubes arranged in parallel and fed with said gaseous and liquid reagents at their top ends, wherein it comprises:
- a common feeding liquid chamber, connected to the top end of each vertical tube through annular slots, - a common feeding gaseous chamber, connected to the top end of each vertical tube through elongated nozzles, concentrical to said vertical tubes, which outer surface defines, together with the inner surface of the vertical tube, the annular slot for feeding the liquid reagent; and wherein said tubes have a length of 5 to 7 meters and an inner diameter of 20 to 30 millimeters; said plurality of equal, vertical tubes being ex-ternally surrounded by a common shell defining a cooling chamber.
- a common feeding liquid chamber, connected to the top end of each vertical tube through annular slots, - a common feeding gaseous chamber, connected to the top end of each vertical tube through elongated nozzles, concentrical to said vertical tubes, which outer surface defines, together with the inner surface of the vertical tube, the annular slot for feeding the liquid reagent; and wherein said tubes have a length of 5 to 7 meters and an inner diameter of 20 to 30 millimeters; said plurality of equal, vertical tubes being ex-ternally surrounded by a common shell defining a cooling chamber.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT12480A/79 | 1979-02-23 | ||
| IT7912480A IT1166068B (en) | 1979-02-23 | 1979-02-23 | PROCESS PERFECTED FOR FILM SULPHONATION IN A MULTITUBULAR REACTOR WITH A MULTITUBULAR REACTOR SUITABLE FOR CARRYING OUT THAT PROCEDURE |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1144561A true CA1144561A (en) | 1983-04-12 |
Family
ID=11140662
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000345813A Expired CA1144561A (en) | 1979-02-23 | 1980-02-15 | Method for the film sulphonation in a multitubular reactor and such a reactor suitable to embody said improved method |
Country Status (11)
| Country | Link |
|---|---|
| AR (1) | AR223511A1 (en) |
| BR (1) | BR8000745A (en) |
| CA (1) | CA1144561A (en) |
| CS (1) | CS215003B2 (en) |
| DE (1) | DE3006791A1 (en) |
| FR (1) | FR2449665A1 (en) |
| GB (1) | GB2043067B (en) |
| IN (1) | IN152501B (en) |
| IT (1) | IT1166068B (en) |
| SE (1) | SE447378B (en) |
| SU (1) | SU1246892A3 (en) |
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| US10280131B2 (en) | 2014-01-13 | 2019-05-07 | P2 Science, Inc. | Terpene-derived acids and esters and methods for preparing and using same |
| US10668446B2 (en) | 2016-06-21 | 2020-06-02 | P2 Science, Inc. | Flow-through reactors for the continuous quenching of peroxide mixtures and methods comprising the same |
| US10696605B2 (en) | 2016-09-16 | 2020-06-30 | P2 Science, Inc. | Uses of vanadium to oxidize aldehydes and ozonides |
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| JPH0725712B2 (en) * | 1990-08-30 | 1995-03-22 | 昭和電工株式会社 | Method for producing 2,3-dichloro-1-propanol |
| IT1255737B (en) * | 1992-05-19 | 1995-11-15 | MULTITUBULAR FALLING FILM REACTOR | |
| NO951178L (en) * | 1995-03-28 | 1996-09-30 | Isc Intersulphoconsultant | Reactor nozzles in a falling film reactor |
| DE102005060816B3 (en) | 2005-12-21 | 2007-03-29 | Rudolf Aigner | Sulfonation and/or sulfation of liquid organic raw materials with sulfite/air-mixture comprises splitting the mixture feed into two feed points with in reaction tubes and/or annular gap region of annular gas-falling film reactor |
| DE102008000785A1 (en) | 2008-03-20 | 2009-09-24 | Evonik Röhm Gmbh | Process for the preparation of methacrylic acid |
| ITUA20162647A1 (en) * | 2016-04-15 | 2017-10-15 | Iit S R L | PROCESS AND DISTRIBUTION SYSTEM OF ORGANIC SUBSTANCE IN FALLEN FILM REACTOR, AND REACTOR SO CONSTITUTED |
| EP3866968A4 (en) | 2018-10-19 | 2022-07-27 | P2 Science, Inc. | NEW METHODS FOR DEACTIVATING OZONIDE DISMUTATION |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BR7101132D0 (en) * | 1970-02-23 | 1973-05-03 | Mazzoni G Mecc Costr | A PROCESS AND EQUIPMENT FOR SULPHONATION AND SULPHATIZATION OF ORGANIC COMPOUNDS |
| JPS5218682B2 (en) * | 1972-04-15 | 1977-05-24 | ||
| JPS5214725A (en) * | 1975-07-21 | 1977-02-03 | Kao Corp | Method of sulfonation and its apparatus |
-
1979
- 1979-02-23 IT IT7912480A patent/IT1166068B/en active
-
1980
- 1980-02-06 BR BR8000745A patent/BR8000745A/en not_active IP Right Cessation
- 1980-02-07 CS CS80834A patent/CS215003B2/en unknown
- 1980-02-13 GB GB8004820A patent/GB2043067B/en not_active Expired
- 1980-02-14 SE SE8001164A patent/SE447378B/en not_active IP Right Cessation
- 1980-02-15 CA CA000345813A patent/CA1144561A/en not_active Expired
- 1980-02-20 AR AR280020A patent/AR223511A1/en active
- 1980-02-20 SU SU802886103A patent/SU1246892A3/en active
- 1980-02-21 FR FR8003843A patent/FR2449665A1/en active Granted
- 1980-02-22 IN IN203/CAL/80A patent/IN152501B/en unknown
- 1980-02-22 DE DE19803006791 patent/DE3006791A1/en active Granted
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10280131B2 (en) | 2014-01-13 | 2019-05-07 | P2 Science, Inc. | Terpene-derived acids and esters and methods for preparing and using same |
| US10071944B2 (en) | 2014-06-20 | 2018-09-11 | P2 Science, Inc. | Film ozonolysis in a tubular or multitubular reactor |
| US10428001B2 (en) | 2014-06-20 | 2019-10-01 | P2 Science, Inc. | Film ozonolysis in a tubular or multitubular reactor |
| US10934239B2 (en) | 2014-06-20 | 2021-03-02 | P2 Science, Inc. | Film ozonolysis in a tubular or multitubular reactor |
| US10668446B2 (en) | 2016-06-21 | 2020-06-02 | P2 Science, Inc. | Flow-through reactors for the continuous quenching of peroxide mixtures and methods comprising the same |
| US10696605B2 (en) | 2016-09-16 | 2020-06-30 | P2 Science, Inc. | Uses of vanadium to oxidize aldehydes and ozonides |
Also Published As
| Publication number | Publication date |
|---|---|
| DE3006791A1 (en) | 1980-09-04 |
| SE447378B (en) | 1986-11-10 |
| GB2043067A (en) | 1980-10-01 |
| BR8000745A (en) | 1980-10-21 |
| IN152501B (en) | 1984-01-28 |
| SE8001164L (en) | 1980-08-24 |
| IT7912480A0 (en) | 1979-02-23 |
| GB2043067B (en) | 1983-05-11 |
| DE3006791C2 (en) | 1989-02-23 |
| SU1246892A3 (en) | 1986-07-23 |
| IT1166068B (en) | 1987-04-29 |
| AR223511A1 (en) | 1981-08-31 |
| FR2449665A1 (en) | 1980-09-19 |
| FR2449665B1 (en) | 1983-05-20 |
| CS215003B2 (en) | 1982-06-25 |
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