BRPI0605000B1 - Device and system for processing high temperature and pressure loads in the presence of microwaves - Google Patents

Description

DEVICE AND SYSTEM FOR HIGH-TEMPERATURE LOAD PROCESSING AND PRESSURE IN THE PRESENCE OF

MICROWAVE

FIELD OF THE INVENTION The present invention relates to a device for processing hydrocarbon fillers and / or mixtures, which operates under high temperature and pressure, including hydrogen, and in batch mode. More specifically said device for processing or hydroprocessing hydrocarbon charges and / or mixtures is provided with a source of emission of electromagnetic radiation in the microwave range. Additionally, the present invention relates to a charge processing and / or hydrocarbon mixing system using said device. Said system has the possibility to operate in the presence of a catalyst or not, which, along with the load, is subjected to the irradiation of said microwaves. Said system operates at high temperature and pressure, including hydrogen, along with microwave irradiation.

RELATED TECHNIQUES Heating by electromagnetic radiation in the microwave range is not only a well-established procedure for domestic use, but is also widely used industrially for the processing of various materials.

The devices that allow this type of heating have been designed to be used in: crosslinking and rubber crosslinking; treatment of discarded materials after consumption; drying of food, polymeric materials, wood and processed products (ceramic molds - automotive industry); production of ceramic and refractory artifacts; acceleration of the concrete curing process; chemical syntheses; polymerization of plastics; sterilization of materials; welding of plastics; recycling and recovery of materials; destruction of polymeric waste, fracturing or grinding of rocks, etc. The technique of heating through the incidence of microwave radiation in an absorbing material offers the advantage of optimizing the thermal effects on these types of materials by virtue of their rapid, direct and localized heating in the absorbing species.

Likewise, the effect of said radiation on the absorbing material ceases upon removal of the microwave radiation source. Other advantages related to the use of electromagnetic radiation in the microwave range for heating can be highlighted as: energy savings over conventional heating in certain processes where punctual and selective heating is desired in materials having different microwave absorption coefficients; shorter processing time; specific interactions between microwaves, microwave absorbing reagents and active sites; Fast, selective and more even heating with minimized wall effects.

Currently, industrial microwaves can be generated by a variety of devices such as magnetrons, power grid tubes, klystrons, klystrodes, crossed-field amplifier, travelllng wave tubes (TWT). ) and "gyrotrons".

Electromagnetic radiation in the microwave range may be conducted between the emitting source and the charge or mixture to be radiated through electromagnetic waveguides. These guides can extend for several meters making meandering traces with low microwave attenuation. In addition, the microwave generator device may be remote from its power source. The core of a device provided with a source of electromagnetic energy emission in the microwave range such as a microwave reactor is a specific valve capable of generating this type of electromagnetic radiation. Said emitter of electromagnetic radiation consists, for example, of a device under vacuum, which converts the low frequency electrical energy into an electromagnetic field that oscillates in a high frequency (microwave).

In the case of a magnetron device, a constant potential difference is applied between the poles: anode, which is a hollow circular cylinder with characteristic cavities in its periphery, and cathode. Electrons are accelerated from cathode to anode, but the presence of a strong magnetic field between the two poles (produced by an electromagnet) causes the electrons to describe a curved path and follow a spiral path, producing a radiofrequency (RF). . An antenna conducts electromagnetic radiation present in the cavities around the anode to the outside of the magnetron. The produced waves are guided by a waveguide to the cavity in which the material to be processed is contained. The metal walls inside the device absorb little energy, most of the energy being reflected until absorbed by the irradiated material.

One of the most important aspects related to the device object of the present invention is the selective heating of materials, since interaction with microwaves varies with the properties of the material. This aspect is of particular relevance in the use of materials with catalytic activity, since it is desired to combine this feature with the preferential microwave heating. The action of microwaves on the reaction medium may occur by their interaction with polar molecule dipoles of reactant liquids and gases as well as by their interaction with solid materials, or even specifically with their active sites, added to the reaction medium.

The conductive materials of electricity (metals, for example) almost completely reflect the microwaves, heating mainly by ohmic losses, being superficial and less intense the higher their conductivity. On the other hand, isotant materials, also called dielectrics, may be transparent or opaque to microwaves according to their dielectric loss factor, also referred to as the imaginary part of electrical permittivity, hereinafter referred to only as loss factor. It is a function of the frequency of electromagnetic radiation and the temperature of the material.

Low loss factor dielectrics are microwave-transparent and unlikely to heat up, while those with high loss factor convert electromagnetic energy i to thermal energy, heating with microwave absorption and concomitant attenuation as they occur. propagate within. This process is called dielectric heating, and unlike conduction or convection heating (used in conventional combustion or electrical resistances as heat sources), it can act differently on charges, reagents and catalysts even though they are in direct contact with each other. themselves and mixed homogeneously. The description of the microwave heating process involves several physicochemical concepts such as temperature, heat capacity, chemical bonding, molecular structure, dipole moment, induced polarization, dielectric constant or relative permittivity, complex permittivity (real and imaginary), conductivity, joule effect, ohmic losses, etc. Microwave dielectric heating is a convenient and effective way to perform chemical reactions in more appropriate (usually polar) media. The growing need to process increasingly heavy oils, containing high contaminant levels, high viscosity, naphthenic acidity, and capable of forming difficult-to-separate oil-water emulsions, is a major challenge for the national refinery park. Several approaches aimed at facilitating the processing of this type of oil and obtaining products with higher added value have been suggested. Radiation of materials by electromagnetic energy in the microwave range is used in various industrial applications as an alternative way of heating specific systems. Articles and patents claim the successful use of microwave technologies to accelerate heat-demanding chemical processes and some other applications in oil processing. However, there are no suitable systems for microwave assisted processing of high temperature loads and high hydrogen pressures.

In this report, cargo is defined as: crude oil, hydrocarbon mixtures, petroleum processing fractions, vegetable oils, organic products such as alcohols and esters, inorganic products as catalysts, and mixtures of these products, among others. The microwave-assisted radiation-assisted processing technique in the microwave range (hereinafter simply referred to as microwave) has been studied based on the ability to cause interaction or rapid heating of materials according to their dielectric characteristics, allowing initiating chemical reactions due to the acceleration of their kinetics, and consequently modifying the properties of these irradiated materials in short times. > Most technological advances in the field of petroleum refining engineering began in 1913 with the introduction of the thermal cracking technique and then with the advent of the catalytic cracking technique in 1936. The introduction of catalytic systems has allowed for reactions to be obtained. faster and more selective, while the hydrogenation processes allowed the removal of contaminants and the adaptation of petroleum fractions to the specifications required by industrial processes.

At the same time, advancements in the field of oil exploration (crude oil) and natural gas engineering, drilling and transportation technologies 5 have allowed growth in demand for oil and petroleum based products. This allowed an increase in world crude oil production from 150 million barrels per year in 1900 to approximately 22 billion barrels per year in 2000. The impacts on the world economy and the international political significance related to Cl oil had huge impacts on the world. social panorama of the twentieth century.

At the same time, there has been increasing pressure on the chemical industries by both civil society and government officials to improve the development of processes that are less and less environmentally harmful. Within this industrial scenario, one of the main problems that should be highlighted is the large volume of contaminants such as toxic effluents produced by various chemical processes.

Efforts have been made to minimize the emission of contaminants by various measures, such as the use of appropriate alternative reagents, processes that exhibit greater conversions and selectivity to desired products, the use of specific catalysts, and the recycling of reagents and reagents. catalysts employed in these processes.

For this purpose, solid catalysts have been developed for the purpose of removing said contaminant dispersing agents in effluents, as well as in the acceleration and selectivity of chemical reactions, in order to reduce the formation of undesirable byproducts and improve the efficiency of the reaction process.

Heavy oil reactions have been conducted under mild conditions using acidic and basic solid catalysts in conjunction with microwave irradiation or the use of supercritical fluids to develop processes in the absence of organic solvents. The principle of these reactions is microwave irradiation of the reagents together with solid catalysts as presented by BANDGAR, B.P .; UPPALLA, L.S .; KURULE, D.S. "Solvent-free one-pot rapid synthesys of 3 carboxycoumarins using focused microwaves". Green Chem. 1, p.243,1999e PIPUS, G .; PLAZL, I .; KOLOINI, T. "Esterification of Benzolc Acld wth 2-Ethylhexanol In a Microwave Stirred-Tank Reactor", Ind. Eng. Chem. Res. 41 (5), p.1129-1134,2002. The use of water in extreme conditions, such as at temperatures above 200 ° C, forms a supercritical fluid which allows the solubilization of support molecules and organic compounds. This solubilization allows the organic reactions to be carried out in the total absence of environmentally undesirable organic solvents. Microwave energy is preferably absorbed by the catalyst active sites, but not by the hydrocarbon charge such as heavy oil, or the reservoir container. The application of this technology allows indirect heating of the hydrocarbons of the cargo, such as petroleum, fractions and derivatives, by occasional heating by the presence of catalysts, which transmit the energy (heat) by conduction (CUNDY, C. “Microwave Technlques In the Synthesis and Modifficlon of Zeolite Catalysts. A Review Collect ", Czech. Chem. Commun. 63: p.1699-1723,1998).

Organic reactions with heterogeneous catalysis have been widely applied in the industrial context. These reactions are successful because the catalysts supported on porous compounds have an optimal dispersion of reactive sites, increasing the selectivity and efficiency of traditional reactions.

Initial experiments with microwave reaction acceleration technique were performed with solvents of high dielectric coefficients such as dimethyl sulfoxide and dimethylformamide, causing overheating during the reactions. However, the application of this technique has recently stood out with reaction studies on solid supports under solvent free conditions. (VARMA, R.S. "Solvent-free accelerated organic syntheses using microwaves", Pure Appl. Chem., Vol. 73 (1), p. 193-198,2001).

In reactions on solid support under solvent free conditions, organic compounds adsorbed on the surfaces of inorganic oxides such as alumina, silica gel, clays or modified supports absorb this radiation, while solid supports do not absorb it. The temperature in the inorganic structure during the reaction is relatively low, but during the process, the temperatures near the reagents on the support surface are extremely high. Microwave irradiation-assisted reactions, in the absence of any solvents, also provide the opportunity to work with open flasks as a function of the processed load, avoiding risks of high pressures (VARMA, RS “Solvent-free accelerated organic syntheses using microwaves”). , Pure Appl. Chem., Vol. 73 (1), pp. 193-198, 2001). The application of the methodology and the association of electromagnetic energy emission devices for the processing of hydrocarbon mixtures are usually presented in the specialized literature, as shown below: EBERHARD et al. (“Microwave-enhanced Hydrogenations at Medium Pressure Using a Newly”) Construct Reactor ”- Tetrahedron Letters, 46, pp. 1247-1249, 2005) teach about the construction of a microwave assisted hydrogenation reactor which allows the operation to be performed at a pressure value of up to 2500 kPa (25 bar ), by modifying a commercial model microwave oven. COUTINHO et al. (“Evaluation of the Application of Microwave Technology in Heating Different Water-Oil Emulsions” - presented at the 3rd Brazilian Oil and Gas R&D Congress, Salvador / Ba, Brazil, October 2005) show the processing of petroleum emulsions raw water in a commercial model microwave reactor adapted to operate at pressures up to 3500 kPa (35 bar) ”. PIPUS and collaborators (“Esterification of Benzoic Acid with 2-Ethylhexanol in a Microwave Stirred-Tank Reactor”, Ind. Eng. Chem. Res., 41 (5), p.1129 -1134, 2002) studied catalytic esterification reactions of benzoic acid. To this end they developed a microwave application system, which were generated by a 2.45 GHz Magnetron valve that provided about 460 W of power coupled to a waveguide and finally to a stirred reaction tank in which the microwaves penetrated through a side window made of a specific polymer. The reaction vessel volume was 500mL and the maximum temperature and pressure conditions tested were 256 ° C and 1200 kPa (12 bar), respectively.

Studies on dehydrogenation have been done by KIM and colleagues (“Dielectric catalysts for Microwave- Induced Dehydrogenation or Ethane into ethylene” Paper 467, 9 * Asian Pacific Confederation of Chemical Engineering Congress). In these studies the authors treat an ethane dehydrogenation process in a quartz reactor using a microwave system comprising a generator, a waveguide and adjustable power metering devices to maintain power in the range. ranging from 0.25 to 2.5 kW.

It is described in US Patent Document 2005133498, a method and associated instrument for performing microwave-assisted continuous chemical reactions with pressure monitoring and simultaneous cooling. However, the equipment described cannot be employed in hydrogenation reactions under severe temperature and pressure conditions.

US 2004069776 describes a device for heating a sample, such as a chemical mixture. More specifically it is a microwave heating device comprising a microwave generator, a waveguide to guide the generated microwaves and a deflector. In said device the resonance conditions and the coupling factor of radiation from the waveguide to the resonant cavity are easily adjustable by rotating the deflector. Resonance conditions and coupling factor can be adjusted in response to the dielectric properties of the sample to optimize the amount of power absorbed and thereby control the heating process of the sample. The proposed device, however, does not operate under severe temperature and pressure conditions.

In patent document JP 2002113350, a chemical reaction vessel operating at high temperature and pressure values is proposed. Said vessel is provided with a device that serves as a microwave source to promote the onset of the chemical reaction. The reaction vessel has cavities in the waveguide or a coaxial line installed in a first window which serves as a partition between the reaction vessel and the waveguide. Materials that can be heated in this reaction vessel are microwave absorbers and / or catalytic wave absorbers. The chemical reaction vessel proposed in JP 2002113350 is also provided with additional high temperature and high pressure fluid systems in a supercritical state and / or electronic reaction system, photochemical reaction system, reaction system using ultrasonic waves, and a reaction system using an external heating method. Said document JP 2002113350 shows a complex system for processing loads under critical conditions, so as to utilize various additional systems to maintain system stability. EP 0501285 describes a device for initiating and / or promoting chemical and / or physical reactions under pressure in microwaveable samples, having vessel inserts receiving at least partially microwave permeable samples having a special arrangement so as to be connected by means of at least one hole coupling to a microwave generator impermeable thereto. In order to enable high reaction pressure and an economical mode, it is proposed according to the invention that the arrangement of the device comprises one or more pressure vessels of material resistant to high pressure whose coupling holes are sealed such that microwave permeable and also resistant to high pressure.

A device for carrying out large-scale chemical reactions is described in US 6120741. Said device comprises a microwave generator and a microwave application vessel which contains a high capacity reactor and a cover. Said vessel is shaped like a cylinder and has a microwave inlet in the lower wall of the vessel, positioned towards its longitudinal axis X, and an open upper end, whereby the generator supplies the single-module microwaves along “V” axis of the vessel. The vessel size is ideal to match the resonant microwave wavelength along the X axis. The cover must seal the top opening of the vessel. This cover has a conduit which connects the interior of the vessel to the external environment so that vessel is under atmospheric pressure.

Although the literature is largely provided with technologies for microwave hydrocarbon charge processing, no commercial reactor model employing microwave radiation intended for laboratory and industrial use is suitable for simultaneous operation at high levels. temperature and pressure values and in the presence of hydrogen.

In order to solve the aforementioned problems, the present invention features a device designed to process hydrocarbons, in particular petroleum heavy hydrocarbon streams, which is provided with a source of electromagnetic energy emission in the microwave range. Said device comprises a reaction vessel specially designed for microwave use and capable of operating under severe temperature and pressure conditions, and also in the presence of hydrogen. Depending on applications, including the need to save energy, said device may combine the use of conventional sources of energy with the use of microwaves separately or simultaneously.

SUMMARY OF THE INVENTION The present invention relates to a device for processing fillers, preferably hydrocarbon fillers, which basically comprises three modules. A first module comprising an electrical power supply and an electromagnetic energy emission source in the microwave range; a second module which comprises a reaction vessel; and further, a third module comprising an instrumented waveguide and its accessories.

For the purpose of facilitating the understanding of the present invention, in this report "instrumented waveguide" means a coupling system which allows the radiation of electromagnetic energy in the microwave range to be conducted in a orientated manner. reaction vessel, i.e. interconnects the microwave source with the reaction vessel. The instrumented waveguide consists of a longitudinal portion which basically comprises an isolating module, rectangular and circular section waveguides, an interface set which is provided with wave sensors and at least one microwave transparent window. The instrumented waveguide is connected to the reaction vessel through a specific microwave-transparent window, but capable of withstanding the high temperatures and even hydrogen pressure present within the reaction vessel. The device of the present invention is designed to operate at high temperature and pressure values in batch mode, with or without gas recirculation, especially hydrogen, with or without the addition of microwave absorbing materials, in addition to the fact that it is not limited to operating only through the use of the incidence of electromagnetic radiation, ie, this device is capable of operating using other sources of energy.

Heterophasic exothermic and endothermic reactions are also promoted through the use of said device. Said device further promotes the treatment of fillers and / or mixtures of heavy hydrocarbons in order to hydrogenate, hydrocrack and hydrotreate hydrocarbons such as heavy petroleum fractions. The device of the present invention has unique features which allow it to operate at a temperature of up to approximately 500 ° C and a pressure value of up to approximately 20MPa (200 bar / 2900 psi). More specifically, the material to be treated is preferably subjected to the incidence of electromagnetic radiation in the microwave range at a preferred frequency of 2.45 GMz and under a maximum power of 3 kW. The microwave source can be chosen depending on the process and the volume of the load to be treated. The choice of different microwave radiation frequencies, depending on the process and load, allows to maximize their interaction with the active sites and their penetration depth in the reaction medium. The choice of continuous or peak microwave source power is also a function of the process and reactor vessel volume. Total microwave power can be obtained using a single high power microwave source or a set of lower power microwave sources, all of which are coupled to the reactor vessel through instrumented waveguides.

Additionally, the present invention further relates to a load processing system comprising the device of the present invention for processing loads in general associated with an electronic unit for automatic system control and with interface for operator supervision. .

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 shows a schematic representation of a front view of the system for processing hydrocarbon fillers and / or mixtures object of the present invention. Figure 2 shows a schematic representation of a front view of the device for processing hydrocarbon fillers and / or mixtures. Figure 3 shows a schematic representation of the microwave transparent window used in the system of the invention.

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a device for a system used to process, react, synthesize and treat fillers, preferably hydrocarbon mixtures, in the presence or absence of a catalyst, by exposing said charges to radiation incidence. microwaves under severe temperature and pressure conditions, in batch mode, with or without gas recirculation, including hydrogen. This device is associated with an electronic control and supervision unit that allows the user a clearer and easier process visualization and control and that monitors critical variables to the system integrity and can trigger safety measures if necessary.

In the device object of this invention, the use of electromagnetic energy in the microwave range offers reaction systems an alternative form of excitation and selective heating of charge and / or mixture, enabling an increase in reaction kinetics and reaction effectiveness. The device of the present invention further ensures good energy transfer to the processed materials in order to allow the processes to be performed sequentially to have higher efficiency, higher yield, better activity and selectivity, reducing the viscosity of the treated oil as well. as generating products with less aggressiveness to the environment and with higher added value. Furthermore, it provides information that allows us to understand the physicochemical mechanisms involved in the microwave heating process and to compare the results obtained with those obtained through conventional heating. Microwave dielectric heating is a convenient and effective way to perform chemical reactions in more appropriate (usually polar) media. The load processing device, object of the present invention, consists basically of three modules. A first module comprising a charge power supply and an electromagnetic energy emission source; a second module which comprises a reaction vessel; and further, a third module comprising an instrumented waveguide and its accessories.

Said instrumented waveguide is a coupling system which allows radiation of electromagnetic energy in the microwave range to be conducted in a oriented manner to the reaction vessel. The source of energy emission is coupled to the instrumented waveguide, which orientates microwave radiation to the reaction vessel. Said instrumented waveguide, in the present example, consists of a longitudinal portion, which basically comprises an isolating module, rectangular and circular section waveguides, an interface set, which is provided with wave sensors and at least one Microwave transparent window. The charge processing device of the present invention is not limited to operating solely with the use of electromagnetic energy, said device allows processes such as the hydrocarbon charge handling process to take place also with the use of energy sources. conventional, as described in the literature, or with the simultaneous use of both energy sources.

Microwave irradiation is applied to the reaction vessel on the material to be processed in the presence or absence of a catalyst to provide selective heating which varies according to the dielectric properties of the material to be processed. In the preferred embodiment of the invention the processed charge is a heavy hydrocarbon stream.

The volumes applied to the device object of the present invention during the requested processes, as well as the energy power values applied to the load processing device may be scaled to suit the operating conditions to the type of demand to be processed. The device of the present invention has a unique feature which enables it to operate under elevated temperature and pressure conditions. The pressure applied to said device may range from values around atmospheric pressure to 20 MPa (200 bar / 2900 psi). However, in the example below, a pressure value in the range of approximately 13.8 to about 17.2 MPa (138 to 172 bar / 2000-2500 psi) should be applied to the device, with an approximate value even more preferred. of 17.2 MPa.

With respect to temperature, the device of the invention preferably operates at 400 ° C, although this temperature value may vary from room temperature to 500 ° C.

At the outer upper end of the reaction vessel of the device object of the invention, ie at the top of the reaction vessel, are operating and safety instrumentation, namely quick-acting valves, such as pressure regulating valves, pressure relief valves. pressure relief, supply and cargo collection valves and products, safety discs, and pressure and temperature sensors. The hydrocarbon processing device has an external coating for thermal insulation and containment in case of leakage. For purposes of the invention, the term "leakage" refers to both charge leakage and microwave radiation leakage.

Due to the operating conditions, the sealing system as well as the outer casing of said device needs to be secure, so it can be used grafoit, welding and pressing metal-ceramic, and special metals like 304 stainless steel, 316 stainless steel , and "kovar" '. The microwave radiation emission on the charge is performed continuously or in small emission intervals (pulses). In the example below, microwave radiation should preferably be carried out continuously with a preferred power of 2 kW, however said power may vary in the range of 2 to 3 kW. In the case of pulse energy emission, the maximum power in this example is preferably close to 8 kW. The instrumented waveguide of the device of the present invention consists of a longitudinal portion which comprises at least one microwave transparent window coupled to the reaction vessel; This window allows the incidence of microwave electromagnetic energy directly on the load, with the least possible losses. In the preferred form of the present invention the reaction vessel of the charge processing device is provided with only one window.

To process larger volumes of charge the reaction vessel may rely on multiple microwave source systems, each coupled to its reaction vessel window via an instrumented waveguide.

In order to minimize the losses on radiation incidence, the degree of radiation incidence on the load can be simulated and calculated using a specific commercial computer program. The transparent window can be designed in various types of materials such as sapphire, quartz, glass, ceramics, etc. These materials have very small dielectric losses in the microwave frequency and withstand high temperature and pressure values. The thickness measurements of said window are suitable to withstand the variations in temperature and pressure that are being employed during the process.

Another feature of this invention is the choice made of the components in the assembly, so that there is minimal disturbance of the electromagnetic field, while avoiding power losses within the system. For this purpose, holes (properly sealed against hydrogen and microwave leaks) are drilled for temperature measurements, for injection and load collection (material), specially designed so that there is no interference in the reaction medium.

In the device object of the invention the microwave cavity and the device itself were designed to ensure a good energy transfer to the materials (loads and catalysts), allowing to improve the yield and the quality of the processed charge, to understand the physicochemical mechanisms involved in this. process and compare the results obtained with those of conventional heating. The load processing system of the present invention basically comprises the device object of the invention and an electronic control and supervision unit which has means for feedback of information via wave sensors and transducers which are located in the longitudinal portion of the device. device, and directly connected to the electronic control unit. The electronic control and supervision unit allows the information to be encoded by programmable logic controllers (PLCs) and a supervisory system, which manages the operation of the load processing system, and allows its interaction with the operator.

In order to better understand the load handling device and system object of the present invention, it will be detailed below, as well as each of its component elements, based on the accompanying Figures.

As shown in Figure 1, the load processing system comprises a load processing device (A), and an electronic unit (B) for automatic system control and interface for operator supervision. Figure 2 shows specifically the device (A) for processing charges, preferably hydrocarbons, having been specially developed for this system, which is formed by three distinct parts: a first module comprising a charge power supply (1) and a (2) electromagnetic energy emission source; a second module which comprises a reaction vessel (3); and further, a third module comprising an instrumented waveguide (5) and its accessories.

In the first module, the load power supply (1) is directly connected to the microwave radiation power source (2) by means of cables (4) that support high voltages. The energy source (2) is coupled to the instrumented waveguide (5), which orientates the microwave radiation to the reaction vessel (3). The microwave radiation energy emission source (2) used in the present invention is a thermionic valve, such as a magnetron valve, which is responsible for generating electromagnetic radiation at the microwave frequency. The electromagnetic frequency used in the present invention, but not limiting, is 2.45 GHz. This electromagnetic frequency value has shown a great influence on the reaction kinetics of various syntheses and organic reactions. However, other frequency values can be used by exploring the absorption and penetration depth of a given microwave frequency applied to a specific load and catalyst, maximizing the interaction between microwaves and catalyst active sites. One way to measure the absorption capacity of electromagnetic radiation in the microwave range by a material is to check its dielectric properties. Thus, to determine the electromagnetic frequency to be applied during the treatment process, the dielectric loss factor (loss factor or loss tangent) of the material to be processed should be verified, as this factor gives a good indication of the distance that Electromagnetic radiation is capable of penetrating a particular material and how much that material can dissipate from this energy to the medium in the form of heat or other interactions. The instrumented waveguide (5) consists of a longitudinal portion which allocates the other fittings of the third module of the device (A) object of the invention and operates under atmospheric pressure. The longitudinal portion is provided with an isolating module (6) which protects the source of energy emission (2) from possible reflected waves so as to avoid the harmful effects that may be caused by the reflected energy. Said isolating module (6) comprises a three-door circulator and a dummy load, which are not shown in the Figures. The longitudinal portion is further provided with a rectangular section wave glutton (7), a rectangular to circular transition segment (8) and a coupling circular section segment (9) to the reaction vessel window (11) ( 3). Said configuration, however, is not limiting of the invention. In the longitudinal portion of the waveguide can be attached curved segments that change their inclination allowing other physical arrangements of the components.

In order to control the actual power of electromagnetic energy incident under the hydrocarbon charge or mixture, the longitudinal portion is provided with transmitted and reflected wave sensors (10) coupled to a specific segment of the waveguide instrumented with appropriate sensors. The actual power of electromagnetic energy is monitored by wattmeters, which are directly connected to the wave sensors (10).

In the rectangular section waveguide (7) there is an adjustment system (not shown in the Figures) which enables the impedance of the coupling circular section segment (9) coupled to the reactor to be matched to the impedance of the segment coupled to the reactor. microwave source in order to achieve maximum absorption of electromagnetic energy in the microwave range transmitted to the charge.

At the lower end of the reaction vessel (3) of the device is a microwave transparent window (11). The present invention further enables the reaction vessel (3) to be provided with multiple windows, adequately distributed over their outer surfaces, and coupled to a microwave source, which may operate at different frequencies, in pre-regulated operating ranges or no, by instrumented waveguides, so that the necessary total power appropriate to the material to be processed can be achieved.

Because the coupling circular section segment (9) is coupled to the base of the reaction vessel (3), this segment must be capable of operating under elevated temperature and pressure values.

At the outer upper end of the reaction vessel (3) is located the safety and operational instrumentation (12) relative to the temperature and pressure portion which ensures the safety of the load handling system. Said operational and safety instrumentation (12) comprises an additional material loading and collection system, thermocouple connections for temperature monitoring and pressure sensors, safety and relief valves, and a gas inlet.

Another feature of device (A) is that within the reaction vessel (3) there is a small pumping or stirring apparatus, for example of the oil charge (not shown in the Figures). This pumping apparatus allows to keep the load in constant agitation in order to guarantee its complete homogeneity. The pumping apparatus is made of a transparent microwave material.

When operating in severe temperature and pressure conditions, the operating system must be protected from failure. In order to ensure tightness and sealing of the operating system in the event of a failure, the window (11) as well as the reaction vessel (3), instrumented waveguide (5) and other accessories are sealed by means of gaskets. made of special material such as “grafoil”.

If the transparent window (11) is made of ceramic, in addition to the use of sealing gaskets, the transparent window (11) can be manufactured with a special configuration in which its conical segment is permanently fixed, for example by means of welds, to a special metal flange. The metal with which the flange is made must have the same dilation value as ceramic. Figure 3 schematically shows a possible configuration of the window (11) of the present invention. Returning to Figure 1, we have seen that the load handling system is provided with the device (A) object of the present invention and an electronic control unit (B). , in which the feedback is controlled by means of the wave sensors (10) located on the longitudinal portion of the instrumented waveguide (5), which are directly connected to the electronic control and supervision unit (B).

Said electronic control and supervision unit (B) comprises programmable logic controller - PLC (13), which contains the analog and digital input and output modules of all field element signals required for control of the processing system. Said PLC (13) digitizes and processes, through a computer program (software), the signal of the microwave radiation power (transmitted and reflected) identified by the wave sensors (10). The electronic control and supervision unit (B) further comprises a central processing unit (14), provided with an operator interface monitor (15), which has additional integrated signal handling and storage modules. The electronic control and supervision unit (B) provides a graphical interface to the processed data and the process monitoring by the operator in a clearer and easier view. An electronic control unit (B) data acquisition module (16) interfaces the field elements with process control. The charge processing device (A), developed to operate the present charge processing system, enables hydrogenation processes to be carried out to reduce or eliminate sulfur (HDS), nitrogen (HDN), oxygen (HDO) content. , aromatics (HDA), and metals (HDM), as well as hydrocracking processes (HCC), as well as the carrying out of exothermic and endothermic reactions of heavy hydrocarbons and their fractions. The present invention further enables the reduction or elimination of sulfur and nitrogen contents as well as the disaromatization and cracking of heavy molecules present in the hydrocarbon filler.

Reactions accelerated by microwave irradiation involve selective absorption by polar molecules, since the supporting molecules are inert to the dielectric loss in this frequency region (300 MHz to 300 GHz). The process used in the present invention is based on the action of microwave radiation on the active sites of the adsorbent material or catalyst incident on the charge. Different types of microwave radiation absorbing materials, such as liquid or solid, powdered or extruded materials may be used in the present invention. The device permits microwave radiation processing of hydrocarbon charges with supported catalysts, zeolitic or other catalyst beds.

Microwave absorbent materials comprise coke fines tailings; catalysts or mixture of catalysts disposed of fluid catalytic cracking units, such as zeolitic catalysts; catalysts or mixture of discarded hydrotreating unit catalysts consisting of transition metals (Co-Mo, NI-Mo, etc.) supported on refractory oxides chosen from: alumina, silica, titanium, zirconium and / or mixtures, among others, where the material supporting the active phase of the absorbent material may preferably be transparent to microwaves. The mass ratio of microwave absorbing material / hydrocarbon mixture is in the range 0.05 to 1, preferably in the range 0.1 to 0.5. However, said values are not limiting to the present invention. Another embodiment of the present invention is the use of microwave radiation applied to oils or their fractions, multiphase oil mixtures and microwave radiation absorbers as catalysts in the form of emulsions or oil sludges. Heavy and water. Microwave radiation penetrates deep into heavy oil / water emulsions and sludge, can perform separate actions that work to break down oil / water, water / oil and water / solid structures, and reduce naphthenic acidity of the hydrocarbon filler. . Microwave radiation interacts with water much more strongly than with oil.

Heavy oil water emulsions absorb microwaves. The energy is preferably deposited in water. This heating differential causes a temperature gradient and a subsequent reduction in surface tension stability that stabilizes the emulsion. The larger the heating differential, the greater the breakdown of the emulsion.

Another embodiment of the present invention is to perform an energy emission modeling by using a commercial electromagnetic field simulation computer program. Said modeling allows to simulate the energy distribution and the appropriate angle of incidence through the waveguide in an effective way to achieve greater transfer and / or optimization of the incident energy under load.

In order that the invention may be better understood, the invention will now be detailed in the form of examples. However, the examples described herein are purely illustrative and not limiting forms of the invention. EXEMPL01: Fabrication of the bed processing device The selection of materials for fabrication of the device was made in such a way that there was minimal disturbance of the electromagnetic field, avoiding the power losses within the system as much as possible. The first module of the device comprises a power supply and a power emission source. The power supply of the power supply has low noise and has been selected for providing great stability and reliability for the processing of heavy hydrocarbon batch loads. This source is compatible with the requirements required for the power supply of the microwave emission source. For these experiments a magnetron valve was used. The second module of the device comprises the reaction vessel. Said reaction vessel was made of metallic material, preferably stainless steel 304, or 316. The reaction vessel used in laboratory experiments has approximate dimensions of 100 mm in external diameter and height of 150 mm, which values are not limiting of the present invention, since These values can easily be scaled and suitable for use on an industrial scale. The third module of the device comprises an instrumented waveguide and its accessories as discussed above. Said instrumented waveguide was also made of metallic material, such as stainless steel. The instrumented waveguide acts properly coupled to the power source. The reaction vessel as well as the instrumented waveguide has been properly sealed against leakage using suitable commercially available materials such as grafoil and metal ceramic welding. The instrumented waveguide window was made of ceramic. EXAMPLE 2: Operating conditions of the device. 5 The device operated in batch mode at 450 ° C and 150 bar hydrogen pressure.

In the reaction vessel microwave radiation was focused on the material to be processed.

In the present embodiment the processed material was a heavy hydrocarbon charge in the presence of a supported catalyst as a catalyst and microwave absorber.

Supported catalysts and zeolites are the most important heterogeneous catalysts used in the petroleum industry. It should be noted that most of the world's gasoline is produced by petroleum fluid catalytic cracking (PCC) process, using zeolitic catalysts treated before or after this process in hydrotreating units with supported catalysts.

Before the hydrocarbon filler was introduced into the reaction vessel, said vessel was already partially filled with the catalyst and the preheated filler. The charge processed in the device was initially subjected to a pulsed radiation of 8 kW power and in a second moment to continuous microwave radiation with the application of a power of 2 kW. > EXAMPLE 3: Results observed.

In the comparison performed to evaluate the heating forms, it was noted that there were differences between conventional heating and the heating promoted with microwave radiation during the processing of heavy oil in the presence of catalysts.

The results showed that transformations of organic compounds on catalysts can be induced by microwave irradiations. Catalytic data confirmed that catalysts can be effective catalysts, which provide high selectivity, particularly under conditions of high temperature and pressure. The results also showed slightly higher yield and selectivity than those for conventional heating.

By comparing catalyst activities in microwave and conventional heating modes, it was shown that microwave heating could greatly reduce the reaction temperature or pressure and could clearly expand or reduce the operating temperature or pressure range with these catalysts. This opens the possibility of working in less severe reaction conditions, which can represent, overall, a great energy saving involved in the process.

It has also been found to be possible to use different liquid or solid microwave absorber materials, powdered or extruded, catalysts generally suitable for specific processes. The device object of the invention allows microwave processing of hydrocarbon fillers with supported catalysts, zeolitic or other catalyst beds.

It has also been found possible to apply microwaves to process crude oil, hydrocarbon mixtures, fractions from petroleum processing, vegetable oils, organic products such as alcohols and esters, inorganic products as catalysts, and mixtures thereof, among others. , either in the form of emulsions or in the form of heavy oil sludge and water.

An advantage of using the device of the invention is the ability to adjust fillers whose compositions are inadequate so that they can be used as fillers for further processing.

That is, adjusting the load to the specifications required by the following process. The advantage of using the device object of the invention is the guarantee of a good energy transfer to the processed materials in order to allow the processes to be performed sequentially to have higher efficiency, higher yield, better activity and selectivity. As a result, it becomes possible to reduce the viscosity of the treated oil, as well as to generate products with lower aggressiveness to equipment and the environment and with higher added value. The invention described herein as well as the alternative aspects discussed should be considered as a possible embodiment. It should, however, be clear that the invention is not limited to these embodiments and those skilled in the art will appreciate that any particular feature introduced therein must be understood solely as something that has been described for ease of understanding and cannot be made without departing from the inventive concept described. The limiting features of the object of the present invention are related to the claims that are part of this report.

Claims (27)

1. DEVICE FOR HIGH-TEMPERATURE LOAD PROCESSING AND MICROWAVE PRESSURE, characterized in that it comprises: - a first module comprising a load power supply (1) connected to a power source (2) by means of cables (4) that withstand high voltages; - a second module comprising a reaction vessel (3) with at least one specific microwave-transparent window but capable of withstanding high temperatures and even hydrogen pressure, and - a third module comprising the instrumented waveguide (5). ) and its accessories. LOAD PROCESSING DEVICE according to claim 1, characterized in that it is coupled to a system which allows processing, reacting, synthesizing, treating hydrocarbons at high temperatures and batch pressure by exposing the hydrocarbons rather than the incidence. electromagnetic radiation in the microwave range through at least one transparent microwave window and under severe temperature and pressure conditions in batch mode with or without hydrogen gas recirculation. LOAD PROCESSING DEVICE according to claim 1, characterized in that the instrumented waveguide (5) is a coupling system which allows microwave radiation to be conducted in a oriented manner to the reaction vessel (3). LOAD PROCESSING DEVICE according to Claims 1 and 3, characterized in that the instrumented waveguide (5) is made of metallic material, preferably of stainless steel and consists of a longitudinal portion which basically comprises: - a module isolator (6) comprising a three-port circulator and a dummy load and is intended to protect the source of energy emission (2) from possible reflected waves; - a rectangular section waveguide (7), a rectangular to circular transition segment (8) and a coupling circular section segment (9) to the reaction vessel window (11), to which coupling longitudinal or curved segments that alter their inclination allowing other physical arrangements of the components describing curves with varying angles; a set of interfaces which is provided with transmitted and reflected wave sensors (10) to control the actual power of electromagnetic energy absorbed by the hydrocarbon charge or mixture; - at least one microwave transparent window (11), which allows the incidence of electromagnetic energy in the microwave range to be directly on the charge or the hydrocarbon mixture with the least possible losses. LOAD PROCESSING DEVICE according to claim 1, characterized in that said device operates additionally with the use of conventional energy sources. LOAD PROCESSING DEVICE according to claim 1, characterized in that said device operates additionally with the simultaneous use of a conventional power source and a microwave power source. LOAD PROCESSING DEVICE according to claims 5 and 6, characterized in that the emission of electromagnetic energy on the total charge can be carried out either in continuous or pulsed form. LOAD PROCESSING DEVICE according to claim 1, characterized in that the reaction vessel (3) is provided with a small oil pumping apparatus which serves to keep the load in constant agitation to ensure its complete homogeneity. LOAD PROCESSING DEVICE according to claims 4,6 and 7, characterized in that the continuously applied power ranges from 0 to 3 kW. LOAD PROCESSING DEVICE according to claims 4 and 7, characterized in that in the case of pulse energy emission, the maximum power is preferably close to 8 kW. LOAD PROCESSING DEVICE according to claim 1, characterized in that the pressure value applied to said device ranges from values around atmospheric pressure to 20 MPa, but more preferably ranges from 13.8 to approximately 17 ° C; 2 MPa. LOAD PROCESSING DEVICE according to claim 1, characterized in that the temperature value applied to said device ranges from 20 to 500 ° C. LOAD PROCESSING DEVICE according to Claims 1 and 4, characterized in that the transition segment (8) allows the transition between the rectangular section waveguide (7) and the coupling circular section segment (9). and adjust the wave incidence accordingly. LOAD PROCESSING DEVICE according to claims 1 and 4, characterized in that the actual power of electromagnetic energy is monitored by controllers directly connected to the wave sensors (10). LOAD PROCESSING DEVICE according to claims 1 and 4, characterized in that the rectangular section waveguide (7) has an additional adjustment system to enable the impedance of the total process load to be matched to the impedance of the Rectangular section waveguide. LOAD PROCESSING DEVICE according to claims 1 and 4, characterized in that the thickness measurements of the microwave-transparent window (11) are suitable to withstand temperature and pressure variations and are designed in various types of materials such as sapphire, quartz, glass, ceramics, among others. LOAD PROCESSING DEVICE according to claim 4, characterized in that the microwave-transparent window (11) may additionally have a special configuration in which its conical segment is permanently attached to a special metal flange if made of ceramic. . LOAD PROCESSING DEVICE according to Claim 4, characterized in that the microwave-transparent window (11) serves as the full load transition window from the rectangular section waveguide (7) to the circular section segment of The coupling (9) is located at the lower end of the reaction vessel (3). LOAD PROCESSING DEVICE according to claim 4, characterized in that a coupling circular section segment (9) is located at the lower end of the transition window (11) and operates under atmospheric pressure. LOAD PROCESSING DEVICE according to claim 4, characterized in that a circular section waveguide is preferably coupled to the base of the reaction vessel (3) by means of the microwave radiation transparent window (11) and operating under elevated conditions. temperature and pressure values. LOAD PROCESSING DEVICE according to claim 4, characterized in that the external upper end of the reaction vessel (3) is provided with operational instrumentation and ensures the safety of the load processing system. LOAD PROCESSING DEVICE according to claim 1, characterized in that it enables processes for reducing or eliminating the sulfur (HDS), nitrogen (HDN), oxygen (HDO), aromatic (HDA) content, and metal (HDM), as well as hydrocracking process (HCC) and the carrying out of exothermic and heterothermal heavy hydrocarbon endothermic reactions and their fractions. LOAD PROCESSING DEVICE according to claim 1, characterized in that it enables the reduction of acidity and the reduction or elimination of sulfur and nitrogen contents, as well as the de-aromatization and cracking of heavy molecules present in hydrocarbon fillers. Cargo processing device according to claim 1, characterized in that it enables the application of microwaves to process crude oil, hydrocarbon mixtures, fractions from petroleum processing, vegetable oils, organic products such as alcohols and esters, inorganic catalysts, and mixtures of these products, inter alia, in the form of emulsions and in the form of heavy oil sludge and water. HIGH TEMPERATURE AND MICROWAVE PRESSURE LOAD PROCESSING SYSTEM characterized by comprising the load handling device as claimed in claims 1 to 24 and an electronic unit (B) for automatic system control and with interface for supervising operator. HYDROCARBON PROCESSING SYSTEM according to claim 25, characterized in that said system is provided with an electronic control and supervision unit (B), in which the information feedback is controlled by means of the wave sensors (10) and transducers and provides the graphical interface for the presentation of the processed data and the process monitoring by the operator. Hydrocarbon processing system according to Claims 25 and 26, characterized in that the electronic control and supervision unit (B) comprises: - a programmable logic controller - PLC (13), which contains the input and output modules analogue and digital signals of all field element signals required for processing system control; said PLC (13) digitizes and processes, by means of a computer program, the microwave radiation power signal (transmitted and reflected) identified by the wave sensors (10); - a central processing unit (14), provided with a monitor (15) for interface with the operator, which has additional integrated signal processing and storage modules; - a data acquisition module (16) which interfaces the field elements with process control.