WO2009130339A1 - Apparatus for the continuous sulphonation or sulphatisation of organic compounds in a film having a controllable thickness - Google Patents

Abstract

An apparatus for the continuous sulphonation or sulphatisation of organic compounds in a film having a controllable thickness comprises: a system for feeding SO₃ diluted to the desired concentration in a carrier gas at the reaction temperature to the reaction system (106) through the module (201) belonging to the head (202). The modular reactant distribution head (202) has four modules (301, 307, 313, 316): a first module (301) for feeding SO₃ diluted in the inert diluting gas to the head (202); a second module (307) for feeding the inert compensation gas to the head (202); a third module (313) for feeding the organic liquid to the head (202); a fourth module (316) for coupling the tubular reactor to the modular reactant distribution head (202).

Description

 CONTINUOUS EQUIPMENT FOR SULFONATION / SULFATATION OF ORGANIC COMPOUNDS IN REGULABLE THICKNESS FILM

FIELD AND OBJECT OF THE INVENTION

The present patent refers to a device for carrying out the continuous sulfonation / sulphation of sulphonatable / sulfatable organic compounds, in a monotubular reactor of descending liquid film and parallel flow. This equipment allows the use of liquid SO ₃ as a source of the sulfonation / sulfation agent to minimize the formation of oleum, which negatively affects the quality of the final product. Thanks to the novel reagent distribution head, the monotubular reactor allows for the first time to regulate the thickness of the liquid reagent film and thus control and optimize the contact time between reagents. In addition, this equipment allows to manipulate with great precision all the control variables of an industrial scale process (flow, concentration and stoichiometric ratio of the reagents fed and their temperatures, as well as the reaction temperature), being useful both for the optimization of the operating conditions of industrial reactors, such as to produce small quantities of product (300 to 400 grams per hour) suitable for quality control of the final product in facilities that produce substances whose sulfonation / sulfation are of interest, or for the quality control of the raw material, of an industrial sulfonation / sulfation process, as well as to be able to evaluate new production lines.

STATE OF THE TECHNIQUE

The sulfonation or sulphation of organic compounds with hydrogen atoms capable of reacting with SO ₃ (which we will now call generically as organic) is a process widely used at industrial level to obtain surfactant raw materials, especially for the formulation of detergents , especially in sulfonation / sulfation processes of organic in liquid phase such as alkylbenzenes, alcohols, ethoxylated, definite alcohols, etc. We have to differentiate between sulfonation and sulfation because, although SO ₃ is a common reagent in both processes, the chemical reaction is different depending on the nature of the organic compound. Thus, in the case of organic compounds that have suitable double bonds or ester groups (in the case of alkylbenzenes, alpha olefins and methyl esters), the sulfonation reaction will occur, while If the organic has functional groups of alcohol or ethoxide type, sulfation occurs.

The gaseous SO ₃ is generated at industrial level by combustion of elemental sulfur in liquid phase with oxygen to give SO ₂ , followed by the conversion of SO ₂ into SO ₃ catalyzed by catalysts such as vanadium pentoxide (V ₂ O ₅ ) in the presence of oxygen The oxygen used for both stages is usually the content itself in the ambient air. Due to the high reactivity of SO ₃ in the sulfonation / sulfation reaction, which can lead to problems in controlling the reaction, this reagent is usually diluted before being introduced into the reactor to a range of 4% - 8% concentration (in volume) by a stream of inert gas (generally air), which also serves to cool the reagent to the optimum reaction temperature (in combination with other cooling systems, if necessary). The problem associated with this stage is that an initial air drying process must be carried out (air cooling and water adsorption in a hygroscopic solid) to prevent the SO ₃ that is generated from reacting with the water vapor present in the air, forming sulfuric acid mists that, apart from corrosion problems of the installation, end up generating oleum (SO ₃ dissolved in sulfuric acid). This oleum significantly worsens the quality of the final product (especially the color) due to hypersulfonation / hypersulphation ("burned") phenomena of the organic. In addition, there are certain problems related to the control of the composition of the gaseous stream associated with the own stability of the combustion and conversion process (especially due to the decrease over time of the activity of the conversion catalyst, as well as the occasional presence of water in the fed air by varying the ambient humidity). In most of the current sulfonation / sulfation processes at the industrial level, multitubular down-film reactors are used, in which the organic reagent descends in the form of a liquid film through the inner surface of each tube, while the gaseous reagent (SO ₃ diluted in a dilution gas) circulates parallel to it through the free circular space of the axial zone of the tube. A cooling fluid (usually water) circulates on the outside of the tubes, which allows the heat generated in the reaction to be evacuated due to its exothermic nature; thus avoiding an increase in temperatures along the reactor that would result in a lower conversion and an increase in the burning processes. There is a fundamental parameter that determines the effectiveness of these equipment, which is the adequate formation of the liquid film film in the upper part of the reactor.

Regarding the formation of the liquid film on the inner surface of each Tubular reactor, it is essential to ensure that it is uniform, that is to say, that it has an equivalent thickness at all points for each differential element of reactor length, such that its cross section according to the perpendicular to the axial axis of the reactor is shaped circular crown. In this way an equivalent local reagent concentration is achieved in each cross section of the film and the liquid gas contact is maximized. If this film is not uniform in terms of its thickness, the sulfonation / sulfation reaction is not either. In addition, if the film does not have a well-defined circular section, in the area with greater film thickness the reaction does not develop completely (due to the shorter contact time between reagents with respect to the ideal film situation for circulating the liquid at a higher speed that in the ideal situation), while in the area of lower film thickness, since the speed of circulation of the liquid is lower (longer contact time between reagents), the "burning" processes (hypersulfonation / hypersulphation) are intensified. The hypersulfonated / hypersulphated material can adhere to the internal wall of the reactor, generating "islets" that divert the flow of the film intensifying the asymmetry thereof. In any case, and due to the high reactivity of SO ₃ , all reactors tend to experience a certain degree of burning over time (adhesion of hypersulfonated / hyperpersulphated products, especially in the initial area of the reactor, which is where the reaction is more energetic), which forces the inside of the tubes to be cleaned periodically to facilitate the formation of a uniform film. Therefore, it is of special interest to have equipment in which the process of disassembly and assembly of the reactor and the head for cleaning is simple. ,

To ensure adequate film formation, the fundamental element is the system that distributes the reagents in each tubular reactor, with two alternatives. There are distributors without compensation gas, consisting of a cylinder on whose axis the SO ₃ circulates, with an injector concentric to it on its external part, in such a way that the organic is dosed by the annular space between the cylinder and the injector, in such a way that when it is introduced into the tubular reactor I does it in the form of a film through the internal wall, while the gas circulates through the axial zone. As an example of these we can cite USP patents No. 5,445,801 and USP No. 5,911,958. On the other hand there are distributors with compensation gas. This type of distributors is similar to the previous one, but in this case, there is an inlet between the SO ₃ input and the organic one through which an inert compensation gas (such as air or nitrogen) is injected, which improves the distribution of the liquid through the inner wall of the reactor to "push it" towards the walls of the same once it leaves the injector, and thus favor a more uniform film. As an example of this distributor we can cite the USP patent No. 4,183,897.

The thickness of the liquid film is of great importance in terms of the contact time between reagents and the "local" concentration of reagents (molar ratio in a given section of the reactor between SO ₃ and the organic one accessible thereto). Thus, for a given flow rate of organic and a stoichiometric amount of SO ₃ , the greater the thickness of the liquid film in the wall, the lower the feed rate of the film and, therefore, the greater the contact time. between the reagents. In that same case, by increasing the film thickness, the "local" concentration of SO ₃ with respect to the "accessible" organic one is increased by a greater limitation to the transfer of matter derived from the smaller film surface and its greater thickness. Therefore, the regulation of the film thickness allows optimizing the contact between reagents (in terms of contact time and local concentration) in order to adapt it to the specific casuistry of each organic system-SO ₃ .

At the exit of the sulfonation / sulfation reactor it is necessary to incorporate a system to separate the sulphonates / sulfates generated from the exhaust gases. Other fundamental elements in a sulfonation / sulfation process are the ripener and the hydrolysis reactor. Since conversions of the order of 90% are achieved in the sulfonation reactor itself, a second reactor is necessary to complete the reaction, by means of the SO ₃ that is dissolved in the liquid phase once this is separated from the exhaust gases at the outlet of the first reactor. They can be full-mix or pseudo-flow piston reactors (association of full-mix reactors in series). Both types of ripeners have a cooling jacket to extract residual reaction heat, as well as an internal coil if the reactor size is very large. The second equipment to consider is the hydrolysis reactor. This equipment is necessary when the sulfonation of alkylbenzenes is carried out, since during the initial stage of sulfonation anhydrides are generated (derived from the condensation of two sulfonic acid molecules). When hydrolyzed, these anhydrides generate sulfonic acid. It is therefore necessary to incorporate water into the process (approximately 0.5% by weight of the total production) to fully hydrolyze said anhydrides, and thus increase the amount of final sulfonic acid. Hydrolysers consist of a complete mixing reactor with a suitable cooling system, which may be based on a cooling jacket, an internal coil or a combination of both (if the size of the reactor is very large).

For all the aforementioned, the need to develop a device that allows regulating the thickness of the liquid film to optimize contact time and local reagent concentrations has been detected, which can be used at the pilot plant scale and which, at the same time, allow to control and modify in such a precise way all the variables of the process at industrial scale. Due to its characteristics, this equipment is specially designed to work on a small scale (by the use of high-precision HPLC pumps but with a small flow, by the use of a single reactor, by the use of glass as the reactor construction material, for the use of liquid SO ₃ as a source of the sulfonation / sulphation agent, by the vaporization system of SO ₃ , etc.), the optimum production of sulphonates / sulfates being of the order of 300 to 400 grams per hour.

This objective is achieved by means of the invention as defined in claim 1. Preferred embodiments of the invention are defined in the dependent claims.

DESCRIPTION OF THE INVENTION

The present invention relates to a continuous equipment for sulfonation / sulphation in a film of adjustable thickness of sulfonable / sulfatable hydrocarbons comprising:

- a monotubular vertical reactor that has a modular head for the distribution of reagents,

- a suitably diluted and thermostatized SO ₃ delivery system, preferably based on a vaporization of liquid SO ₃ that allows its vaporization in the same containers in which it is marketed

- a reactor cooling system, based on a plurality of cooling jackets located sequentially along the monotubular vertical reactor,

- a gas-liquid separator located at the outlet of the monotubular vertical reactor,

- a laminar filter, - a maturation reactor, ^s

- a hydrolysis reactor, and

- an absorption tower,

The modular head for the distribution of the reagents consists of four modules sequentially coupled to each other, according to the following arrangement:

- a first module corresponding to the SO ₃ feed diluted in the inert gas dilution,

- a second module corresponding to the supply of the inert compensation gas,

- a third module that corresponds to the feed of the organic liquid to the head, and - a fourth module that corresponds to the coupling of the tubular reactor to the modular head for the distribution of the reagents so that the diluted SO ₃ is fed to the first module by means of a nozzle and is distributed through a first tubular element that crosses the rest of the modules of the head and is partially introduced into the tubular reactor; and so that the inert compensation gas that is fed by a plurality of nozzles equivalent to the second module is distributed in the annular space comprised between the first tubular element and a second tubular element concentric to the first and of greater diameter, through which it circulates the inert dilution gas to the lower end of said second tubular element at that point accessing the tubular reactor, and so that the organic liquid that is fed by a plurality of connections equivalent to the third module is distributed in the annular space comprised between the second tubular element and the tubular reactor concentric to said second tubular element and of greater diameter, the organic liquid circulating to the lower end of the second tubular element at that point accessing the tubular reactor, such that as the first tubular element is extended further beyond the lower or free end of the second tubular element, at the point in which said second tubular element ends the contact between the compensation gas and the organic liquid, "pushing" the gas into the liquid towards the inner wall of the glass reactor, and thus favoring the formation of a uniform liquid film. It should be clear that the effect of the compensation gas on the organic liquid does not vary the thickness of the liquid film but does make its section uniform. By modifying the wall thickness of the tube corresponding to the tubular reactor for constant external diameters of the second tubular element, the width of the annular space defined between the two and, therefore, the organic film thickness is modified.

The first module may be cylindrical and made of stainless steel and may comprise an upper portion and a lower portion of smaller diameter than the previous one and greater height than the same, presenting a central axial axis hole that begins with the nozzle and that crosses both portions, a plurality of through holes being arranged in the upper portion for the insertion of connecting elements of the first module with the second module, such as bolts or elements equivalent.

In what refers to the second module, it can be similarly cylindrical and stainless steel, it can have a flat area in its outer contour with blind holes for fixing to a panel, being crossed by a central hole of axial axis and by at least three through holes connecting with said central hole in which the nozzles whose axis is perpendicular to the axis of revolution of the second module are inserted and are located in an intermediate zone with respect to the total height of the second module, being distributed equidistant from each other. The second module may have a cylindrical upper recess for the engagement of the lower portion of the first module and a cylindrical lower recess for the connection of the second module with the third module, a plurality of holes being arranged at the upper edge defined by the upper recess. coinciding in position and in number with the holes arranged in the first module and on the base of the upper recess, a plurality of through holes may be arranged which, together with a lower recess made in the second module, will connect said second module with the third module.

The third module may be cylindrical and stainless steel and may comprise an upper portion that fits into the lower recess of the second module and a lower portion of greater diameter than the previous one having a cylindrical recess, the third module being traversed through a central hole axial axis and at least three through holes that connect with said central hole, in which the nozzles whose axis is perpendicular to the axis of revolution of the third module are inserted, being located in an intermediate zone with respect to the total height thereof and being distributed equidistant from each other. On the lower edge of said third module, determined by the recess, a plurality of blind holes will be made and on the upper base a plurality of blind holes coinciding in position and number with the through holes of the second module will be arranged to be able to couple them by bolts or equivalent elements.

Finally, the fourth module may also be cylindrical and stainless steel and may comprise an upper portion that fits into the lower recess of the third module and a lower portion of larger diameter than the previous one, the fourth module being traversed through a central shaft hole axial. In the lower portion of said fourth module a plurality of through holes coinciding in position and number with the blind holes of the third module will be practiced to be able to couple said modules by means of bolts or equivalent elements.

On the other hand, both the first and second tubular elements will be metallic because in this way the machining is simplified obtaining the appropriate dimensions.

The defined configuration of the different modules that make up the head, makes its interconnection very simple, so that before the need to clean it or in case of any breakdown, the head can be disassembled and mounted quickly. On the other hand, the feeding of both the organic and the inert compensation gas through multiple equidistant entry holes, makes their distribution to the annular spaces through which they circulate more uniform, which results in greater uniformity of the flows at the point of entry to the reactor, and therefore, in a more uniform liquid film.

The joints between the four modules of the head may have sealing means to avoid unwanted mixtures of the different components involved in the sulfonation reaction.

More specifically, there will be a first toroidal seal of the coupling between the first and second modules, which is located on a groove made in a radial direction on the periphery of the lower portion of the first module, a second toroidal seal of the coupling between the second and third modules, which is located on a groove made in a radial direction on the periphery of the upper portion of the third module and a third toroidal seal of the coupling between the third and fourth modules, which It is located on a groove made according to a radial direction on the periphery of the upper portion of the fourth module.

In addition, auxiliary seals will be arranged at the head joints with the tubular elements and with the tubular reactor. Specifically, a first toroidal auxiliary sealing gasket will be arranged in the coupling between the first tubular element and the second module, arranged on a countersunk made at the lower end of the central hole of the first module, a second toroidal auxiliary sealing gasket in the coupling between the second tubular element and the third module, arranged on a countersunk made at the upper end of the central hole of the third module and a third toroidal auxiliary seal in the coupling between the upper end of the tubular reactor and the fourth module, arranged on a countersunk made in the upper end of the central hole of the fourth module. >

The axial axis of the head and the axial axis of the tubular reactor are made to coincide along a vertical axis by fixing the distribution head to a vertical panel through the flat area located in the outer part of the second module, the support of the lower end of the tubular reactor in a support element fixed to the vertical panel and the action on stabilizer elements located at intermediate points located between the point of insertion of the reactor in the head and the lower support of said reactor, which allow regulating the inclination of the reactor. The support element consists of a horizontal washer whose internal diameter coincides with the external diameter of the tubular reactor and whose axis of revolution coincides with the axial axis of the tubular head, both axes being aligned in the vertical direction, and because the stabilizing elements consist of horizontal washers with a diameter greater than that of the tubular reactor, with its axis of revolution aligned with the axial axis of the reactor head, each washer having at least three through holes through said washer in a horizontal direction, being equidistant from each other, being coupled in each hole a screw, so that the axial axis inclination of the tubular reactor can be modified by acting on each of the screws. The object of the stabilization is to achieve that the inner wall of the tubular reactor is completely parallel to the first and second tubular elements by which the gas phase is dosed, and that are partially introduced into it. In this way, the annular space between tubes will be uniform throughout its horizontal section, and therefore the film of liquid generated will also be. This control is very important since, as discussed below, the control of the film thickness is achieved by means of tubular reactors of different wall thickness, so that the change and perfect alignment of the reactor to modify said thickness is simplified. In addition, as mentioned, the inside of the tube becomes dirty over time, so it is necessary to clean it periodically, so that it must be disassembled, cleaned and reassembled. Thanks to the modular design of the reaction system, the decoupling of the tubular reactor from the head and the subsequent assembly and perfect vertical alignment is very simple and fast.

Another of the outstanding features of the equipment object of the invention is that the contribution of SO ₃ diluted to the concentration of interest in a carrier gas at the reaction temperature, which feeds the reaction system through the head module is obtained by a liquid SO ₃ vaporization system comprising a thermally insulated closed chamber for the vaporization, dilution and thermal conditioning of SO ₃ , comprising the deposits of liquid SO ₃ , an oleum separator, a mass flow control system of the SO ₃ vaporized, an electric heater of the inert dilution gas and a first blower that has an electrical resistance for the vaporization of SO ₃ and to avoid the existence of cold spots in the conduits of the fluids that produce the condensation thereof, because the electronic components of the control loop of the flow control system of the vaporized SO ₃ , of the control loop of the electric heater of the inert dilution gas and the loop of control of the resistance of the first blower is located in the outer part of the closed chamber and because the electronic part of the control loop of the flow control system of the vaporized SO ₃ is cooled by a second blower thereof located in the outside of the closed chamber

The electronic part of the control loops is located on the outside of the chamber to avoid that the elevated temperature inside the chamber can affect the controller (it can be descalibrated or lose functionality), resulting in errors or drifts in the end value of the controlled variable, or causing said controller to stop working completely.

Finally, another outstanding feature of the invention is the fact that the tubular reactor is made of glass, since thanks to the physical characteristics of said material such as its transparency and its surface finish, the residues resulting from the hypersulfonation reactions produced in said Reactors are visible and can be detected for cleaning when necessary. In addition, the low intrinsic surface roughness of the glass makes the organic liquid film very uniform.

DESCRIPTION OF THE DRAWINGS

Next, a series of drawings that help to better understand the invention and that expressly relate to embodiments of said invention that are presented as illustrative and non-limiting examples thereof are described very briefly.

Figure 1 represents a scheme in which all components of the equipment are continuously included for sulfonation / sulphation in a film of adjustable thickness of sulphonatable / sulfatable hydrocarbons object of the present invention.

Figure 1A represents a side view of the modular head-tubular reactor assembly constituting the reactor, in which a partial section of the assembly support panel has been practiced as well as two partial sections in the transition zones between the cooling jackets that They are part of the cooling system of the tubular reactor.

Figure 2 represents a longitudinal section of the modular head assembly- tubular reactor

Figure 2A shows a first detail on a larger scale of a portion of the modular head-tubular reactor assembly, in which the distribution of the inert compensation gas to the annular space by which it is dosed to the reactor is produced. Figure 2B shows a second detail on a larger scale of a portion of the modular head-tube reactor assembly in which the distribution of the organic to the annular space by which it is dosed to the reactor occurs.

Figure 2C shows a third detail on a larger scale of a portion of the modular head-tubular reactor assembly, in which the variation of the annular distribution space of the organic to the tubular reactor is shown by varying the thickness of the wall of said tubular reactor.

Figure 3A shows a plan view of the first module comprising the modular head of the reaction system.

Figure 3B shows a sectional view according to the cutting plane A-A of Figure 3A.

Figure 4A shows a perspective view of the second module comprising the modular head of the reaction system.

Figure 4B shows a plan view of the second module represented in Figure 4A. Figure 4C shows a sectional view according to the cutting plane A-A of Figure 4B.

Figure 4D shows a sectional view according to the cutting plane B-B of Figure 4B.

Figure 4E shows an elevation of the second module, represented in Figure 4A.

Figure 4F shows a sectional view according to the D-D cutting plane of Figure 4E.

Figure 5A shows a perspective view of the third module comprising the modular head of the reaction system. Figure 5B shows a top plan view of the second module shown in Figure 5A.

/ Figure 5C shows a sectional view according to the cutting plane A-A of Figure 5B.

Figure 5D shows a sectional view according to the cutting plane B-B of Figure 5B.

Figure 5E shows an elevation of the third module represented in Figure 5A. Figure 5F shows a sectional view according to the plane of cut DD of Figure 5E. '

Figure 5G shows a bottom plan view of the second module shown in Figure 5A. Figure 6A shows a plan view of the fourth module comprising the modular head of the reaction system.

Figure 6B shows a sectional view according to the cutting plane A-A of Figure 6A.

Figure 7A shows a side view of the first tubular element that is part of the reaction system.

Figure 7B shows a view in longitudinal section according to the plane A-A of section of Figure 7A.

Figure 7C shows a side view of the second tubular element that is part of the reaction system. Figure 7D shows a view in longitudinal section according to the plane B-B section of Figure 7C.

Figure 8 shows a sectional view along the longitudinal plane of one of the sleeves that make up the cooling system of the reaction system.

Figure 9 shows a diagram of a maturator that is part of the continuous equipment for sulfonation / sulphation in film of adjustable thickness of sulphonatable / sulfatable hydrocarbons object of the present invention.

Figure 10 shows a diagram of a hydrolysis reactor that is part of the continuous equipment for sulfonation / sulphation in film of adjustable thickness of sulphonatable / sulfatable hydrocarbons object of the present invention. Figure 11 shows a diagram of a gas-liquid cone separator that is part of the continuous equipment for sulfonation / sulfation in a film of adjustable thickness of sulphonatable / sulfatable hydrocarbons object of the present invention.

Figure 12 shows a diagram of a laminar filter that is part of the continuous equipment for sulfonation / sulphation in a film of adjustable thickness of sulphonatable / sulfatable hydrocarbons object of the present invention.

Figure 13 shows a diagram of an absorption tower that is part of the continuous equipment for sulfonation / sulphation in film of adjustable thickness of sulphonatable / sulfatable hydrocarbons object of the present invention. Figure 14 shows a scheme of the liquid SO ₃ vaporization system that is part of the continuous equipment for sulfonation / sulfation in film of Adjustable thickness of sulfonable / sulfatable hydrocarbons object of the present invention.

DESCRIPTION OF AN EMBODIMENT OF THE INVENTION The equipment object of the present invention constitutes an integral unit for carrying out the sulfonation / sulfation of sulfonable / sulfatable organic liquid compounds. Figure 1 shows a particular embodiment of the integral concept of this installation, which uses nitrogen as a dilution and compensation gas. Stream 1 corresponds to the total feed of the inert dilution gas, usually nitrogen, to the process. The inert dilution gas can come either from a bottle, or directly from the utilities (set of basic services, such as supplies of nitrogen, compressed air, water, etc.) from an industrial plant. Once its pressure is adjusted by means of the manual pressure reducing element 2, which has a pressure gauge with field indication 3, and is passed through a filter to retain the solid impurities, it is divided into three streams by means of a four-way automatic valve. The current 4 corresponds to the inert compensation gas, whose mass flow rate is measured and controlled by the control loop 5, which has a bypass line regulated by a manual valve. This line then has a non-return valve, before joining the reaction system 106 by three points through its head 202.

Stream 7 corresponds to the inert dilution gas. Its mass flow rate is measured and controlled by means of the control loop 8, which has a bypass line regulated by a manual valve. A safety valve 9 is placed behind this control loop, followed by a non-return valve. Next, this current is introduced into an electric heater 10, located inside a thermally insulated closed chamber 22, to be heated to its proper temperature, a phenomenon that is controlled by means of the control loop 11, which measures the temperature of the inert dilution gas at the outlet of the electric heater 10 and acts on the power of the electrical resistance thereof. At the outlet of this heater 10, the generated current 12 is divided into two new currents by means of a three-way manual valve. The first resulting current, 120, is used to adjust the final concentration of SO ₃ to be fed to the sulfonation / sulfation reaction system, joining with SO ₃ (132, from 13 through 130 and 131) that it has been vaporized inside the storage vessels 140 and 141, and whose mass flow has been controlled by a control system of flow 15, thus generating the diluted SO ₃ current 27. The other generated current 121 is used in cleaning operations (by hot gas dragging) of potential residues of the mass flow controller system 15 through stream 130, 131 and 132, so that the resulting gaseous stream is subsequently sent to the reaction system and the gas treatment systems through the stream 27 itself, although it can also be used to sweep the line 130 with hot gas, being subsequently sent to Ia absorption tower 19 through lines 16 and 21.

The third stream 18 in which the initial inert gas supply, usually nitrogen, is divided, has a flow control valve 17, and is divided into the thermally insulated closed chamber 22 into two streams 180 and 181 by an automatic valve three way. This inert gas is used, as operated with the valve set, both for the inertization with cold gas of the line 13, by sweeping towards the reaction system and the subsequent gas treatment systems through the streams 13, 130 , 131, 132 and 27, or directly through currents 13, 130 and 16 towards the absorption tower 19, as for the sweep of the deposits of liquid SO ₃ towards the absorption tower of SO ₃ 19, through of lines 200 and 201, which converge on the thermostatted line 21.

The liquid SO ₃ is stored in the metal container itself in which it is sold, and placed in its corresponding support inside the thermally insulated closed chamber 22. In normal operation, only one of the tanks will be used as a source of liquid SO ₃ , although if the sulfonation / sulfation is very long in time or the flow rates of organic are large, the two tanks 140, 141 may be used sequentially. / To vaporize the SO ₃ contained in the storage tanks 140, 141 and maintain an ambient temperature that prevents the condensation of the SO ₃ at some cold point of the installation (valves, elbows, etc.), the SO ₃ tanks, all the lines containing vaporized SO ₃ and the heater 10 of the entrainment gas are located inside the thermally insulated chamber 22. In said chamber 22 a first centrifugal blower 23 is placed that has an electrical resistance to generate a stream of hot air, whose power is regulated by the control loop 24, which measures the temperature in the wall of the storage container and acts on The power of the resistance. This temperature will be set at a value always higher than 44.7 ⁰ C, which is the vaporization temperature of the liquid SO ₃ at atmospheric pressure.

Once a stationary temperature situation is reached, depending on The temperature of the tank will have a certain equilibrium vapor pressure of SO ₃ , which will be measured by the pressure sensor 25. Since the system is designed to consume approximately one mole / hour of SO ₃ , the heat absorbed in its vaporization It will be small and will not change the temperature inside the tank because it will be easily taken from the hot environment inside the chamber 22 (always at a higher temperature than the vaporization), so that the outlet pressure can be kept constant, although it can be incorporated a pressure controller in line 13 to regulate said pressure.

Once the SO _{3 has been} vaporized, and opening the appropriate valves of the line 13, this is conducted through the line 13 to an oleum separator 26. At the entrance to this oleum separator 26 a pressure gauge 25 is available Subsequently (through 130 and 131) its flow is regulated by the mass flow control system 15, and is connected by line 132 with the stream 12 of inert dilution gas giving rise to line 27, which is located thermostatized by means of an electric blanket 28, represented in Figure 1 with a broken line arranged on line 27, whose temperature is regulated by thermostat 29 (to precisely control the supply temperature to the reaction system and avoid the condensation of SO ₃ ).

Stream 27 passes through an auxiliary drop separating device 30, whose objective is to retain the drops of sulfuric acid or oleum that could have formed if the inert dilution gas from stream 1 carried some moisture, which may be periodically purged by means of the manual valve located in its lower part.

In the case of the electronic part of the mass flow control system (15) we must take into account that the optimal mass flow control system 15 for this process at the scale of the MFC ("Mass Flow Controller" type pilot plant, controller) mass flow) has a peculiarity, and is that the SO ₃ must pass through the controller itself. Therefore, the area of the mass flow control system 15 through which the SO ₃ circulates must be at a temperature high enough to prevent the condensation / solidification of the SO ₃ . But, on the other hand, the electronic part of said system (which is integrated in the same equipment) must not be at an elevated temperature because it would eventually break down or cause drift problems. The solution adopted in the most appropriate configuration of this equipment consists in placing the mass flow control system 15 in a hole located in the wall of the chamber 22 itself, such that the area through which the SO ₃ circulates is the one that is oriented inwards, while the area where the Ia is located electronics are oriented towards the outside of chamber 22.

In any case, since the frame of the mass flow control system 15 conducts heat, the electronic part would eventually heat up and fail. To avoid this phenomenon, it has been decided to incorporate a second blower 31 by the outer part of the chamber 22, whose air flow (at room temperature) is focused on the electronic part of the mass flow control system 15, of such so that it serves as refrigeration and prevents it from overheating.

Next, the stream 27 containing SO ₃ diluted in the inert dilution gas and at the appropriate temperature is introduced to the reaction system 106 by the top of the head 202. It is important to note that the equipment and currents indicated above for obtaining SO ₃ suitably diluted in a carrier gas at the reaction temperature from liquid SO ₃ , are not necessary for the practice of this invention if an external source of properly conditioned SO _{3 is} available. In those industrial facilities or laboratories that have a system for generating SO ₃ as described in the state of the art (from elemental sulfur, by oxidation by stages or other methods), said SO ₃ diluted to Ia can be used directly concentration and temperature of interest to feed the reaction system 106 through the head 202. In the case of using SO ₃ external to the liquid SO ₃ vaporization system mentioned above, the injection of said gas will be carried out directly to the head 202, Once its concentration, flow, temperature and pressure have been adjusted to the specific needs of the sulfonation / sulfation reaction.

On the other hand, the organic compound to be sulphonated / sulphated is stored in the tank 32, from which it accesses the process through stream 33. After passing through a filter, said stream is fed to the metering pump 34. Said pump is a pump for HPLC (high performance liquid chromatography), characterized by high precision in the dosing of liquids for long periods, since it has an integrated flow control loop 35, which ensures the correct dosing of the organic at reactor. Then there is a set of valves consisting of a three-way valve and two manual valves, which allow the line to be purged. Subsequently, the current 33 is taken to the electric heater 36, whose mission is to heat the organic to the reaction temperature. Said heater has a control loop, 37, which measures the temperature of the wall of the heating zone and, in case of variation with respect to the set point, acts adequately on the power of the electrical resistance. At the outlet of the heater 36 there is a pressure sensor 38. The organic is subsequently fed to the reactor 315 through the three entries of head 202 corresponding to the organic one.

The reaction system 106 comprises a vertical glass tubular reactor 315, which has in its upper part a reagent-modulating head 202-modulate to adequately form the organic laminar film to be lowered by the inner surface of the reactor .

The correct distribution of the liquid is favored thanks to the inert compensation gas, usually nitrogen, which pushes the organic film towards the wall and unifies the thickness thereof. This nitrogen is fed at room temperature to moderate (in collaboration with the cooling water) the temperature in the initial section of the reactor, where the reaction is more energetic. As it constitutes less than 10% of the inert gas stream in which the SO ₃ is diluted, its temperature is not substantially modified (mainly because the reaction itself is exothermic and tends to heat the system).

To optimize the formation of the film, two stabilizers 333 are available that allow the verticality of the tubular reactor 315 to be regulated. Since the head 202, like the lower end of the tubular reactor 315, is perfectly fixed (once its vertical axis is aligned by means of a level) to a vertical panel 330 made of sheet metal located at the rear and serving as a support, and the lower part of the reactor is supported by a clamping washer 332, by means of the stabilizing elements 333 we can regulate the inclination of the tubular reactor 315 to ensure that the glass reactor and the gas distribution tubes are perfectly vertical and parallel.

The diluted SO ₃ circulates in parallel to the organic film through the axial zone of the reactor.

The reactor has a cooling system based on three individual cooling jackets 39, 40 and 41 placed sequentially along the reactor, through which the cooling water circulates either countercurrently or parallel to the direction of flow in the reactor . These cooling jackets have a hollow central area of the same internal diameter as the external diameter of the glass reactor, which is where it is inserted, so that they fit perfectly and no restrictions on energy transfer are incorporated. To achieve optimum cooling, a cryogenic system is available

42, which cools the water that will then be sent to each of the sleeves 39, 40 and 41 by means of the pump that is incorporated. To control the amount of water flowing through each jacket, each of them has a control loop associated with an electro valve. Thus, the jacket 39 has the control loop 43, which measures the temperature at the exit of the first section of the reactor and acts on the flow of fresh water that enters the jacket by means of the corresponding electro valve. Likewise The control loops 44 (on the shirt 40) and 45 (on the shirt operate)

41).

At the outlet of the reaction system 106 a gas-liquid separator is provided

46, which separates the gas phase (nitrogen plus unreacted SO ₃ ) to send it through stream 47 to the exhaust gas treatment system, while

The liquid phase (sulfonated / sulphated organic and unreacted organic) is sent through line 48 to the auxiliary reactors where the reaction is to be completed.

Considering the line 48, at the outlet of the separator 46, a temperature meter 49 with indication on the panel, and then a manual valve is provided. Subsequently, the stream 48 is introduced by the bottom to the maturation reactor 50, in which the sulfonation / sulfation is completed. Said reactor has a cooling jacket, which in turn has a cryogenic equipment 51 with a built-in recirculation pump. There are two temperature sensors 52 and 53 with indication on the panel to know the temperature in the lower and upper zone of the reactor. The reactor 50 has an agitation system with an electric motor, which has a measurement and speed control system 54, which can be controlled from the panel. This reactor also has seven effluent outlets placed at different heights to modify in a controlled manner the residence time in the reactor, each of which has a manual opening / closing valve 129. The reactor outlets converge in the current 55, which has a manual valve and a sample extraction system by means of a three-way valve and a manual valve.

Subsequently, the stream 55 is fed to the hydrolysis reactor 56, by the lower part thereof, to achieve the hydrolysis of the anhydrides that may have formed. Said reactor has a cooling jacket, which in turn has a cryogenic equipment 57 with a built-in recirculation pump. There are two temperature sensors 58 and 59 with indication on the panel to know the temperature in the lower and upper zone of the reactor. The reactor 56 has an agitation system with an electric motor, which has a measurement and speed control system 60, which can be controlled from the panel. This reactor also has three effluent outlets placed at different heights to modify the residence time in the reactor, each of which has a manual opening / closing valve 145.

To carry out the addition of the hydrolysis water, there is a water storage tank 61, which communicates with the reactor through the stream 62, in which a manual valve is provided followed by a pump dosing 63. The flow control in this pump is achieved by using a frequency inverter 64. The outputs of the reactor 56 are joined in the current 65, which has a manual valve and leads to the tank 66, in which stores the final sulphonated / sulfated product.

5 Stream 47, composed of nitrogen plus unreacted SO ₃ , is sent to the exhaust gas treatment system. Once it emerges from the gas-liquid separator of cone 46, it is sent to a laminar filter 67. In said filter, those drops of liquid (hypersulfonated / hyperpersulphated product, sulfonated / sulphated and organic unreacted product) that could not have been removed

10 separated in the previous stage, which accumulate in the bottom of this equipment, being able to be drained periodically by means of a manual valve.

Dry gases leave the filter at the top, and through line 68 they are introduced by the bottom of the absorption tower 19, below the inlet of the thermostated line 21. The absorption tower has as its object

15 absorb residual SO ₃ in a liquid phase that stabilizes it. In principle, water can be used, which will react with SO ₃ to form sulfuric acid, which in turn can solubilize more SO ₃ producing the oleum. The organic liquid itself can also be used. The absorption tower 19 is a cylindrical glass vessel, inside which hollow glass cylinders are located whose objective is 0 to increase the contact area between the gas with SO ₃ (which tends to ascend naturally through the tower) and the liquid (circulating in countercurrent thanks to a drive system 70).

The liquid phase is extracted from the lower part of the tower, generating the current 69. Said current is driven by the pump 70, whose flow control is achieved

25 by means of a frequency inverter 71. At the output of the pump is a

_? cooling coil 72, so that the absorbent liquid passes through the tube side and the cooling water through the housing. Thus, the acid that has been heated in the tower is cooled as a consequence of the fact that the reaction between SO ₃ and water is exothermic.

30 The cooling water is cooled to the appropriate temperature by the cryogenic equipment 73, which has an integrated pump. At the outlet of the coil, the temperature of the acid is measured by thermocouple 74, which has an indication on the panel. Once cooled, the acid is reintroduced to the tower 19 at its top. Above the injection point of the refrigerated acid there is the gas outlet

35 purified, which has a valve and a glass globe to avoid projections of acid to the outside caused by gas bubbling. The dosing pump 32, the cryogenic equipment 42, 51, 57 and 73 and the stirrers 54 and 60, have a control system that can be operated (mass flow rate, coolant temperature and stirring speed, respectively) both in the field and in panel. In the most suitable configuration for this equipment, shown in Figure 1A

(vertical section of the assembly on the left side and horizontal sections of the fixing and alignment elements on the right), the reaction system 106 is fixed to a vertical panel 330 of sheet metal (whose verticality is verified by a level), by Two points: through the head 202 and the lower part of the tubular reactor 315. With respect to the head 202, it has (as will be detailed below) a flat area 101 with three holes 431 perpendicular to the axial axis of the head 202 for Ja insertion of three Alien screws, whose entrances are perfectly aligned with each other along the axial axis of the head. In turn, the vertical panel 330 has three through holes 432 vertically aligned and located at the same distance from each other as the distance at which the holes in the head 202 are located. The fixing of the head 202 to the vertical panel 330 is achieved by an intermediate piece 85 of flat sides that has three through holes aligned with each other and located at equal distances from each other than the holes in the panel and head 202. By inserting three screws 433 Alien that cross the panel 330, the intermediate piece 85 and partially inserted in the head 202, said head is fixed to the panel so as to ensure the verticality of its axial axis.

The lower part of the tubular reactor 315 is inserted in a horizontal washer 332 of the same internal diameter as the external diameter of the tubular reactor, which is fixed to the vertical clamping panel 330. The axis of revolution of the washer 332 is perfectly aligned vertically with the axial axis of the head 202 of the reaction system. Fundamental elements are the vertical stabilizers 333 The stabilizers 333 are based on two circular metal washers fixed to the vertical panel 330 and arranged in a horizontal position, and with their axis of revolution aligned vertically with the axial axis of the head 202 of the reaction system . Said washers have four through holes 334 located at 90 ° to each other, and have an internal diameter greater than the external diameter of the tubular reactor. A through screw 335 of sufficient length is inserted into each hole. By acting on the stabilizers (by inserting or removing the screws 335, whose tip touches the outer wall of the tubular reactor 315, which are located in the sections of the reactor where the cooling jackets 39, 40 and 41 are attached, the inclination is controlled of the tubular reactor with respect to its fixed lower end, thus allowing a perfect alignment of the axial axis of the reactor and of the head 202 with the vertical.

Figure 2 shows the configuration of the reaction system 106, formed by the modular head 202 and the tubular reactor 315, and in figures 2A, 2B and 2C, extensions of different areas of said assembly have been represented to clarify the connection of the head 202 with the first tubular element 303, with the second tubular element 309 and with the tubular reactor 315 itself.

More specifically, the SO ₃ diluted in the inert dilution gas, which in the present embodiment will be nitrogen is introduced by point 321 at a predetermined concentration and temperature. On the other hand, the compensation gas, which in the present embodiment will be nitrogen, is introduced by points 322 (three inputs). In addition, the suitably thermostated organic liquid is introduced into the distribution head 202 through points 323 (three inlets). Head 202 consists of four coupled basic modules.

The first module 301 corresponds to the input of SO ₃ diluted in the carrier gas and previously thermostated. It consists of a cylindrical structural block of stainless steel, an inlet nozzle 302 for SO ₃ , a first tubular steel element 303 following the nozzle through which SO ₃ circulates, four anchor bolts 304 to fix it to the next block , a first toroidal joint 305 to ensure the tightness of the coupling between modules and a first auxiliary toroidal joint 306 to ensure the coupling between the first tubular element 303 of SO ₃ circulation and the second module 307.

The second module 307 corresponds to the compensation nitrogen input and its distribution in the annular circulation space 341, consists of a cylindrical stainless steel structural block and is attachable to the first module 301 and the third 313, and in it they locate three through holes 404 defining three nozzles 308 for the compensation gas inlet, being distributed so that they are located equidistant from each other, and through which the compensation gas accesses the annular space 341 between the first tubular element 303 of circulation of the SO ₃ and the second tubular element 309 of concentric steel to the first tubular element 303 and of greater diameter than the same, by which it is led to the tubular reactor 315. This second module 307 joins the next 313 by means of three bolts 310, such that the sealing of the coupling between both modules is achieved by a second toroidal joint 311, and Ia Sealing of the second tubular element 309 at the junction point between modules is achieved with a second auxiliary gasket 312 toroidal.

The third module 313 corresponds to the entrance of the organic liquid to the head 202 and its distribution, consists of a cylindrical stainless steel structural block and has three through holes 416 that connect to a central hole 415, whose axis is perpendicular to the axis of revolution of the third module 313, and are located in an intermediate zone with respect to the total height thereof being distributed in such a way that there are located equidistant from each other, said orifices 416 defining three nozzles 314, of organic inlet arranged at 120 ° to each other. After the entry, the organic is distributed in the annular space 320 delimited between the outer surface of the second tubular element 309 and the inner surface of the glass cylinder that acts as a tubular reactor 315. The fourth module 316 corresponds to the lower closure of the head 202 of the Reaction system and its coupling with the tubular reactor 315, consists of a stainless steel cylindrical structural block with a through hole 423 and in it the tubular reactor 315 formed by a hollow glass cylinder is inserted, so that a annular space 320 for the distribution of organic, defined between the inner surface of the tubular reactor 315 itself and the outer surface of the second tubular element 309. The tightness at the junction between the tubular reactor 315 and the fourth module 316 is achieved by a third joint auxiliary 317 toroidal. The third organic input module 313 and the fourth lower closure module 316 are fixed to each other by means of four bolts 319, and the sealing of this joint is achieved by a third toroidal joint 318.

The four modules described, which are part of the head 202 have their matching axes of revolution.

Finally, we have the glass tubular reactor 315, which is inserted in the head 202 through the fourth lower closing module 316, and inside which the first 303 and second 309 tubular element are partially inserted.

At the exit of the tubular element 303, the SO ₃ dissolved in nitrogen is contacted with the organic liquid film, thus allowing adequate contact between both phases along the rest of the glass reactor, in which the reaction is verified . In Figures 3A and 3B the first module 301 is shown, which is cylindrical and stainless steel and comprises an upper portion 400 and a lower portion 401 of smaller diameter than the previous one and greater height than the same, both portions being 400 and 401 crossed by a central hole 402 along its axis of revolution, in which the nozzle 302 is inserted, the plural portion of through holes 403 being arranged in the upper portion 400 for the passage of joining elements 304 of the first module 301 with the second module 307. In Figures 4A to 4F the second module 307, which is cylindrical and stainless steel, is shown, having a flat area 101 in its outer contour with three blind holes 431 for anchoring to panel 330, and is crossed by a central hole 411 along its axis of revolution and by at least three through holes 404, into which the nozzles 308 are inserted, whose axis is perpendicular to said axis of revolution, which connect with said central hole 411, and they are located in an intermediate zone with respect to the total height thereof being distributed so that they are located equidistant from each other. The second module 307 has a cylindrical upper pocket 405 for the engagement of the lower portion 401 of the first module 301 and a lower cylindrical pocket 406 for the connection of the second module 307 with the third module 313, being arranged at the upper edge 407 defined by the upper recess 405 a plurality of blind holes 408 coinciding in position and in number with the holes 403 arranged in the first module 301 that allow the joining of modules 301 and 307 by means of bolts 304, and because on the base 409 of the upper recess 405 a plurality of through holes 410 are arranged for the insertion of the bolts 310 that allow their coupling with the third module 313, thanks to a lower recess 406 made in module 307 by means of which it is connected to the third module 313.

In Figures 5A to 5G the third module 313 is shown, which is cylindrical and stainless steel and comprises an upper portion 412 that fits into the lower recess 406 of the second module 307 and a lower portion 413 of larger diameter than the previous one which has a cylindrical pocket 414 to be coupled to the next module 316, the third module 313 being traversed through a central hole 415 along its axis of revolution and by at least three through holes 416 in which the nozzles 314 are inserted, whose axis is perpendicular to said axis of 'revolution, which connect with said central hole 415, and are located in an intermediate zone with respect to the total height thereof being distributed so that they are located equidistant from each other, and because in the lower edge 417 determined by the recess 414 a plurality of blind holes (418) are made for coupling by bolts 319 to the module 316, and at the base upper 419 a plurality of blind holes 420 are arranged in position and number with the through holes 410 of the second module 307, for coupling of both modules by means of bolts 310.

In Figures 6A and 6B, the fourth module 316, which is cylindrical and stainless steel, and comprises an upper portion 421 that fits into the recess 414 of the third module and a lower portion 422 of greater diameter than Ia is shown. above, the fourth module 316 being traversed through a central hole 423 along its axis of revolution, and in the lower portion a plurality of through holes 424 coinciding in position and number are made with the blind holes 418 of the third module 313 for their coupling by means of bolts 319. In Figures 7A to 7D ₁ a longitudinal section of both the first 303 and second tubular elements 309 that serve to distribute the gaseous streams has been represented, and in addition cross sections of the said tubular elements have been represented.

The joints between the different modules 301, 307, 313, 316 that make up the head 202 will consist of the arrangement of several joints, each arranged in the joints thereof. A first toroidal joint seal 305 of the coupling between the first 301 and second modules 307, which is located on a groove 425 made in a radial direction on the periphery of the lower portion 401 of the first module 301. A second toroidal joint 311 of tightness of the coupling between the second 307 and the third modules 313, which is located on a groove 426 made in a radial direction on the periphery of the upper portion 412 of the third module 313. A third toroidal joint 317 sealing the coupling between the third 313 and the fourth modules 316, which is located on a groove 427 made in a radial direction on the periphery of the upper portion 421 of the fourth module 316.

On the other hand, the tightness between the head 202 and the tubular reactor 315 and the first 303 and second 309 tubular elements will be ensured, providing a series of auxiliary joints in the joints between said elements. For this purpose a first auxiliary gasket 306 toroidal sealing will be arranged in the coupling between the first tubular element 303 and the second module 307, arranged on a countersink

428 made in the lower end of the central hole 402 of the first module 301. A second auxiliary gasket 312 toroidal sealing in the coupling between the second tubular element 309 and the third module 313, arranged on a countersink

429 made at the upper end of the central hole 415 of the third module 313. A third auxiliary gasket 317 toroidal sealing in the coupling between the upper end of the tubular reactor 315 and the fourth module 316, arranged on a countersink 430 practiced at the upper end of the central hole 423 of the fourth module 316.

Figure 8 shows the design of one of the three cooling jackets 39, 40 and 41 twins that allow cooling with water cooled by an external cryogenic device 42 of the walls of the reaction system of sulfonation / sulfation 106. It consists of a hollow cylinder 124 whose walls are also hollow, in such a way that the sulfonation / sulfation tubular reactor 315 is inserted in the axial axis of the cooling jacket, and is cooled by transferring heat through its wall and from the internal wall of the refrigerator to the cold water that circulates between the walls of the refrigerator. It has four connections, two connections 125 of the GL25 type (for the ends of the jacket, through which the reactor is inserted), and two connections 114 of the GL14 type (for the entry and exit of the cooling water).

Figure 9 shows the design of the maturation reactor 50 which consists of a cylindrical glass vessel 126 surrounded by a cooling jacket 127. At the bottom of the reactor there is an inlet 128 for the reagents (through a connection GL18). It has seven outlet valves 129 that allow us to collect the product at different heights, equivalent to having seven different residence times, and that converge in two common outlet valves 133 with GL18 connections. It has a motorized agitator 134 with adjustable rotation speed, and the insertion of the agitator shaft is carried out through a mechanical seal 135 to prevent the outflow of gases to the outside. The reactor has three baffles 136 baffles that partially compartmentalize the reactor into four zones. It has an inlet 137 and an outlet 138 of cooling water, through GL18 connections. It also has three inputs 139 (through GL14 connections) for the insertion of thermocouples that allow controlling the temperature at three different heights.

Figure 10 shows the design of the hydrolysis reactor 56, which consists of a glass cylindrical vessel 142 surrounded by a cooling jacket 143. At the bottom of the reactor there is an inlet 144 for the reagents (through a GL18 connection). It has three outlet valves 145 that allow us to collect the product at different heights, equivalent to having three different residence times, and that converge on a common outlet valve 146. It has a motorized agitator 147 with adjustable rotation speed, and the insertion of the agitator shaft is carried out through a mechanical seal 148 to prevent the outflow of gases to the outside. The reactor has three baffles 149 baffles that partially compartmentalize the reactor into four zones. It has an inlet 150 and an outlet 151 of cooling water, through GÜ8 connections. It also has two inputs 152 (through GL14 connections) for the insertion of thermocouples that allow controlling the temperature at two different heights. It also has an extra outlet conduit 151 at the bottom of the reactor, with a hole 2 mm internal which leads to a GL14 output connection.

Figure 11 shows the design of the gas-liquid cone separator 46, which consists of a hollow glass cylinder 152 that has a glass cone 153 in its central area, attached to the interior of the tube by four points. It has an inlet 154 for the gas-liquid system in the upper part, by means of a female ball joint R 29/15. It also has an outlet 155 for the gas in the upper part, through a GL25 connection for 9 mm tubes. Finally, it has an outlet 156 for the liquid collected in the lower part of the equipment, by means of a GL25 connection for 8 mm tubes and a key 157 in the lower zone for purging the liquid.

Figure 12 shows the design of the laminar filter 67, which consists of a hollow cylinder 158 of glass with a series of baffles 159 arranged obliquely arranged to the axial axis of the equipment. It has an inlet 160 for the gas-liquid system in the lower part, by means of a male ball joint R 29/15, and an outlet 161 for gases in the upper part through a GL25 connection, as well as an outlet 162 through a GL32 connection , which will normally be blinded, also having an outlet with a key 163 for the possible liquid collected at the bottom of the equipment.

Figure 13 shows the design of the absorption tower 19 of residual SO ₃ . It consists of a hollow cylinder 164 of glass, which has several inputs and outputs. In the lower zone there are two inlets 165, 166 for gases to be treated introduced through GL25 connections, another inlet 167 with a manual valve 168 and a GL18 connection and a manual valve 169 at the bottom for purge operations. It has a perforated plate170 located in a normal way to the axial axis, on which the filling 171 (Raschig rings, etc.) that will increase the interfacial area of gas-liquid contact is supported. In the upper part it has an inlet 172 for the water / acid that absorbs the residual SO ₃ that is introduced through the bottom. This inlet is made through two GL18 connections and a hollow ring 173 of glass with holes that adequately distributes the liquid in the upper part of the reactor. In the upper area of the equipment there is a female mouth 174 of the type 29/32 with thread in which a male plug 175 of the type 19/32 is fixed, which has a manual closing valve 176. Water or the organic itself can be used as the SO ₃ absorption agent

Finally, in figure 14 the design of a thermally insulated closed chamber 22 is represented, which could be materialized in a thermostated cabinet, where the SO ₃ is vaporized, its flow is controlled and diluted in the entrainment gas. Said cabinet is made of sheet metal and has an insulator The elements that characterize said cabinet are the following: First, there are two storage tanks 140, 141 for the storage of liquid SO ₃ , consisting of the steel cylinders in which it is marketed this product (N ⁰ CAS 7446-1-9). These cylinders are fixed by means of clamps 177 or other equivalent fixing element (which ensures the stability of the tank and facilitates loading and unloading) to the rear wall of the cabinet. In order to provide the energy necessary both to vaporize the liquid SO ₃ and to keep all the parts of the system at a temperature that avoids the condensation and / or crystallization of the SO ₃ , a first centrifugal blower 23 is used that has an electrical resistance 178 in the drive line. By means of a suitable control loop 24, the temperature in the cylinder wall is measured and the resistance power is modified. The entire electronic part of the control loop 24 is located in the external part of the chamber 22. From the upper part of the storage tanks 140, 141 the vaporized SO ₃ is extracted, through the set of lines and valves existing in the upper part. Subsequently, its pressure is measured by the sensor 25. This pressure will depend on the temperature inside the cylinder. The SO ₃ is passed through an oleum separator 26 comprising expansion chamber, so that drops are deposited if formed.

Once this is done, its flow is regulated by a mass flow control system 15. The electronic part of said mass flow control system 15 is located outside the chamber 22 so that it is not disturbed by the temperature. In addition, a second blower 31 is placed on the outside and focusing on said electronics, to cool it and avoid thermal drifts or other undesirable alterations in the stability of the controller. Line 7 introduces dry inert gas into the cabinet. This is passed through an electric heater 10 that has a container with an electric resistance 179 that serves to thermostatize this current to the working temperature. To control the heating there is a control loop 11, which measures the temperature at the outlet and acts accordingly on the power of the resistance to keep the set point set. At the outlet, it is mixed with the vaporized SO ₃ to reach the desired dilution degree, and is sent through the thermostated line 28 to the second module of the modular head 202 of the reaction system 106. An input (current is also available) ) 18 of inert gas that serves both to send the residual SO ₃ of the tanks to the absorption tower 19 through the thermostated line 21 and to purge the gas lines that go to the reaction system 106, operating properly on the valve set represented. All connections mentioned in Figures 8 to 14 will be standard connections for GL type glass.

Claims

1. Continuous equipment for sulfonation / sulfation of organic compounds in adjustable thickness film comprising: - a reaction system (106) consisting of a monotubular vertical reactor (315) that has a modular head (202) for the distribution of the reagents, - a contribution system of SO ₃ diluted to the concentration of interest in a carrier gas at the reaction temperature, which feeds the reaction system (106) through the module (201) of the head (202), - a reactor cooling system, based on a plurality of cooling jackets located sequentially along the monotubular vertical reactor (315), - a gas-liquid separator (46) located at the outlet of the monotubular vertical reactor (315), - a laminar filter (67), - a maturation reactor (50), - a hydrolysis reactor (56), and - an SO ₃ absorption tower (19), characterized in that, the modular head (202) for the distribution of the reagents is constituted by four modules (301, 307, 313, 316) sequentially coupled to each other, according to The following arrangement: - a first module (301) corresponding to the feed of SO ₃ diluted in the inert dilution gas to the head (202), - a second module (307) corresponding to the feed of the inert compensation gas to the head (202), - a third module (313) corresponding to the feed of the organic liquid to the head (202), and - a fourth module (316) corresponding to the coupling of the tubular reactor to the modular head (202) for the distribution of the reagents so that the diluted SO ₃ is fed to the first module (301) by means of a nozzle (302) and is distributed through a first tubular element (303) that crosses the rest of the modules of the head (202) and is partially introduced into the tubular reactor (315); and so that the inert compensation gas that is fed by a plurality of nozzles (308) to the second module (307) is distributed in the annular space (341) comprised between the first tubular element (303) and a second tubular element ( 309) concentric to the first and of greater diameter, through which the inert dilution gas circulates to the lower end of said second tubular element (309) at that point accessing the tubular reactor, and so that the organic liquid that is fed by a plurality of nozzles (314) to the third module (313) is distributed in the annular space (320) comprised between the second tubular element (309) and the tubular reactor (315) concentric to said second tubular element and of greater diameter, the organic liquid circulating to the lower end of the second tubular element (309) accessing the tubular reactor at that point, producing contact between the gas inert compensation and organic liquid, and pushing the gas into the liquid towards the inner wall of the glass tubular rector (315) to favor the formation of a uniform liquid film whose thickness is determined by the width of said annular space (320) in function of the thickness of the wall of the tubular reactor (315). 2. Equipment according to claim 1, characterized in that the first module (301) is cylindrical and stainless steel and comprises an upper portion (400) and a lower portion (401) of smaller diameter than the previous one and greater height than the same, both portions (400, 401) being crossed by a central orifice (402) along its axis of revolution in which the nozzle (302) is inserted, the plurality of through holes (403) being arranged in the upper portion (400) ) for the passage of joining elements of the first module (301) with the second module (307). 3. Equipment according to claim 1, characterized in that the second module (307) is cylindrical and stainless steel, having a flat area (101) in its outer contour with three blind holes (431) for anchoring, and is crossed by a central hole (411) along its axis of revolution and at least three through holes (404), into which the nozzles (308) are inserted, whose axis is perpendicular to said axis of revolution, the holes being connected (404) with said central hole (411), being located in an intermediate zone with respect to the total height of the second module (307) and being distributed equidistant from each other; because the second module (307) has a cylindrical upper recess (405), for the engagement of the lower portion (401) of the first module (301) and a cylindrical lower recess (406) for the connection of the second module with the third module (313), a plurality of blind holes (408) coinciding in position and in humerus with the holes (403) arranged in the first module (301) being arranged at the upper edge (407) defined by the upper recess (405) insertion of the coupling elements between modules, and because on the base (409) of the upper recess (405) a plurality of through holes (410) are arranged for the passage of joining elements of the second module (307) with the third module (313). 4. Equipment according to claim 1, characterized in that the third module (313) is cylindrical and stainless steel and comprises an upper portion (412) that fits into the lower recess (406) of the second module (307) and a lower portion ( 413) of greater diameter than the previous one, which has a cylindrical recess (414), the third module (313) being traversed through a central hole (415) along its axis of revolution and at least three through holes (416) in which the nozzles (314) are inserted, whose axis is perpendicular to said axis of revolution, the holes (416) being connected with said central hole (415), being located in an intermediate zone with respect to the total height thereof and being distributed equidistant from each other, and because at the bottom edge (417) determined by the recess (414) a plurality of blind holes (418) are made for the insertion of the coupling elements with the module (316), and in the base upper (419) a plurality of blind holes (420) are arranged in position and number with the through holes (410) of the second module (307) for the insertion of the coupling elements with the module (307). 5. Equipment according to claim 1, characterized in that the fourth module (316) is cylindrical and stainless steel and comprises an upper portion (421) that fits into the recess (414) of the third module and a lower portion (422) of larger diameter than the previous one, the fourth module (316) being crossed by a central hole (423) along its axis of revolution, and because in the lower portion a plurality of through holes (424) coinciding in position are made and number with the blind holes (418) of the third module (313) for the insertion of the coupling elements with the module (313). 6. Equipment according to claims 1 to 5, characterized in that at the junctions between ^" the modules (301), (307), (313), (316) comprise: - a first toroidal seal (305) of the sealing of the coupling between the first (301) and second modules (307), which is located on a groove (425) made in a radial direction on the periphery of the lower portion (401) of the first module (301) - a second toroidal joint (311) of tightness of the coupling between the second (307) and the third modules (313), which is located on a groove (426) made in a radial direction, on the periphery of the upper portion (412) of the third module (313). - a third seal (318) toroidal sealing of the coupling between the third (313) and the fourth modules (316), which is located on a groove (427) made according to a radial direction on the periphery of the upper portion (421) ) of the fourth module (316). Equipment according to claims 1 to 6, characterized in that a first toroidal auxiliary seal (306) is arranged in the coupling between the first tubular element (303) and the second module (307), arranged on a countersink (428) practiced at the lower end of the central hole (402) of the first module (301); - a second auxiliary seal (312) toroidal sealing in the coupling between the second tubular element (309) and the third module (313), arranged on a countersink (429) made in the upper end of the central hole (415) of the third module (313); Y - a third auxiliary gasket (317) toroidal sealing in the coupling between the upper end of the tubular reactor (315) and the fourth module (316), arranged on a countersunk (430) made in the upper end of the central hole (423) of the fourth module (316). 8. Equipment according to claim 1, characterized in that the axial axis of the head (202) and the axial axis of the tubular reactor (315) are matched along the vertical axis by fixing the distribution head (202) to a vertical panel (330 ) through the flat area (101) located in the outer part of the second module (307), the support of the lower end of the tubular reactor (315) in a support element fixed to the vertical panel (330) and the actuation on elements stabilizers (333) located at intermediate points located between the point of insertion of the reactor in the head (202) and the lower support of said reactor, which allow regulating the inclination of the reactor. 9. Equipment according to claim 8, characterized in that the element _^ support consists of a horizontal washer (332) whose inside diameter matches the outside diameter of the tubular reactor (315) and whose revolution axis coincides with the axis of the head ( 202) tubular, both axes being aligned in the vertical direction, and because the stabilizing elements (333) consist of horizontal washers with a larger diameter than the tubular reactor (315), with its axis of revolution aligned with the axial axis of the head (202) , each washer having at least three holes (334) through through said washer according to a horizontal direction, being equidistant from each other, a screw (335) being coupled in each hole, so that the axial axis inclination of the tubular reactor can be modified by acting on each of the screws. 10. Equipment according to claims 1 to 9, characterized in that the contribution of SO ₃ diluted to the concentration of interest in a carrier gas at the reaction temperature, which feeds the reaction system (106) through the module (201) of the head (202) is obtained by a liquid SO ₃ vaporization system comprising: - a thermally insulated closed chamber (22) for the vaporization of SO ₃ , which comprises the tanks (140, 141) of the liquid SO ₃ , a separator of oleum (26), a mass flow control system (15) of the vaporized SO ₃ , an electric heater (10) of the inert dilution gas and a first blower (23) that has an electrical resistance (178) to provide energy for the vaporization of SO ₃ and to avoid the existence of cold spots in the conduits of the fluids that produce the condensation thereof, because the electronic components of the flow control system of the vaporized SO ₃ (15), of the control loop l (11) of the electric heater (10) of the inert dilution gas and of the control loop (24) of the resistance of the first blower (23) are located in the outer part of the closed chamber (22) and because Ia Electronic part of the mass flow control system (15) of the vaporized SO ₃ is cooled by a second blower (31) thereof located outside the closed thermally insulated chamber (22). 11. Equipment according to the preceding claims, characterized in that the tubular reactor (315) is made of glass. 12. Equipment according to the preceding claims, characterized in that the cooling system of the monotubular vertical reactor (315) comprises at least three individual cooling jackets (39, 40, 41) placed sequentially along the tubular reactor (315), by the which circulates a refrigerant fluid, which have a hollow central area of the same internal diameter as the external diameter of the tubular element (315) through which it is inserted fitting tightly and a cryogenic system (42) for fluid cooling refrigerant.