BR102017003031A2 - process of combining the use of alcohols under supercritical conditions activated by high frequency electromagnetic fields to obtain continuous flow biodiesel - Google Patents

Abstract

The process of combining the use of alcohols in supercritical conditions activated by high frequency electromagnetic fields to obtain biodiesel in continuous flux. biodiesel production process from any glyceride-based grease, without the use of catalysts, using supercritical conditions and microwaves; monitored, controlled and automated by an operation center (32) and expert software (31) that makes it continuous production, for optimal delivery of the desired reaction products. uses alcohol (l) as solvent and a fatty material / alcohol mixture (4) which after being pumped and subjected to high pressures, temperatures and microwave radiation (5) makes the alcohol supercritical (3) and the fatty material mixture / alcohol (4), which after mixing at a given molar ratio with microwave irradiation under supercritical pressure and temperature conditions renders the supercritical grease / alcohol mixture (6), and after having its pressure and temperature reduced in the reliever (7) introduces it into the separator (8), where the vapor-shaped alcohol (9) will be present in the upper phase, biodiesel (10) in the intermediate phase and glycerol (11) in the lower phase.

Description

(54) Title: PROCESS OF COMBINING THE USE OF ALCOHOLS IN SUPERCRITICAL CONDITIONS ACTIVATED BY HIGH FREQUENCY ELECTROMAGNETIC FIELDS FOR THE OBTAINING OF BIODIESEL IN CONTINUOUS FLOW (51) Int. Cl .: C07C 67/02; C10L 1/02; H05B 6/02; G05B 13/00 (73) Holder (s): TERMO NORTE ENERGIA S. A., TECHNOLOGY AND INNOVATION MANAGEMENT CENTER - CGTI (72) Inventor (s): JOSÉ ΜΑΚ; JÚLIO SANCHO LINHARES TEIXEIRA MILITÃO; ANTONIO CARLOS DUARTE RICCIOTTI; PAULO ANDRADE LIMA FILHO (85) Start date of the National Phase:

02/15/2017 (57) Abstract: PROCESS OF COMBINING THE USE OF ALCOHOLS IN SUPERCRITICAL CONDITIONS ACTIVATED BY HIGH FREQUENCY ELECTROMAGNETIC FIELDS TO OBTAIN BIODIESEL IN CONTINUOUS FLOW. Biodiesel production process from any glyceride-based grease, without the use of catalysts, using supercritical conditions and microwaves; monitored, controlled and automated by an operation center (32) and specialized software (31) that makes it of continuous production, for the optimal obtaining of the desired reaction products. It uses alcohol® as a solvent and a mixture of fatty material / alcohol (4) which after being pumped and subjected to high pressures, temperatures and microwave-type radiation (5) makes the alcohol supercritical (3) and the fatty material / alcohol mixture (4), which after mixing at a given molar ratio, with microwave-type irradiations, under supercritical pressure and temperature conditions makes the grease / alcohol mixture supercritical (6), and after having its pressure and temperature reduced in the relief ( 7) introduces it in the separator (8), where the alcohol in the form of steam (9) will be present in the f (...)

1/27 “PROCESS OF COMBINING THE USE OF ALCOHOLS IN SUPERCRITICAL CONDITIONS ACTIVATED BY HIGH FREQUENCY ELECTROMAGNETIC FIELDS TO OBTAIN BIODIESEL IN CONTINUOUS FLOW”.

Technical field of the invention.

[001] The present invention belonging to the chemical sector refers to a process for producing biodiesel from any glyceride-based grease, in a continuous process, without the use of catalysts, using supercritical conditions and high electromagnetic fields. frequency.

[002] The process for batch or continuous biodiesel production can use as raw material any fatty materials, including low quality, solid, with a high level of acidity and humidity.

Background of the invention.

[003] Despite the various technologies for obtaining biodiesel launched in recent years, most of the industrial sector continues to use the same method as a century ago, transesterification. This method converts glycerides into methyl and ethyl esters in one step, usually using an alcohol in an alkaline medium, generating a mixture where both the reagents and the products are partially soluble during the process. The balance of phases of the reagents and products becomes crucial for improving the reaction conditions and final separation of the products (France, B. B .; 2008); and the yield for the production of biodiesel is

2/27 affected by the temperature, concentration and nature of the catalyst, in addition to the molar relationship between alcohol and vegetable oil (Encinar, J. M., et al .; 2002).

[004] In industry, production with conventional heating is hampered by the process of heat transfer to the reaction, which occurs from the hot surface of the reactor, by conduction and convection, which tends to condition the reaction speed to the transfer of heat (Alvarez, Μ. H .; 2008). Alternatively, the use of microwave-type radiation has made it possible to minimize this problem. Polar molecules when irradiated by an electromagnetic field tend to orient themselves, and as the waves in the electromagnetic field are faster than the reorientation of these molecules, there is a friction between them that results in heating of the medium (Santos, A. L. F .; 2007). In addition to this thermal effect, microwaves have a specific, non-thermal effect on the unpairing of the spins of molecules' atoms, which lead to new mechanisms, as a rule, faster than conventional ones and, in fact, the aid of this radiation decreases the reaction time and the percentage of conversion increases, however, in the same way as the conventional process, purification operations of the final product to remove the catalyst and impurities are carried out with an increase in the total time for completion and in the generation of waste. Continuous transesterification processes using continuous flow microwaves have been proposed (Barnard T. M .; 2007); however, few industrial units use it. Therefore, the main disadvantages that

3/27 can be highlighted in the aforementioned processes involve the impossibility of reusing the catalyst, the need for treatment, both of the reagents and of the final products in order to minimize the amounts of free fatty acids and water.

[005] Another proven efficient technology involves the use of supercritical conditions and dispenses with the use of catalysts, simplifying the process of purifying the final product, which is restricted to the removal of surplus alcohol and separation by decantation or centrifugation. The process consists of increasing the pressure and temperature to values that exceed the critical conditions of the alcohol, in a reduced time. [006] Thus, the various published works on biodiesel production indicate that the parameters that influence the alkaline transesterification reaction using conventional heating or microwave, are related to the alcohol / oil molar ratio, type and quantity of the catalyst, amount of acids free fatty substances in the raw material, reaction time, reaction temperature, agitation rate and presence of water in the reaction medium. As for the transesterification reaction in supercritical conditions, the literature indicates that the only variables in the process are system pressure and temperature, in addition to the alcohol / oil molar ratio. Although this technology is not yet fully consolidated, the various works in the literature prove its importance by highlighting the need for further studies in this area, especially with regard to continuous processes. As an example, Biodiesel was

4/27 produced from forage turnip oil using the method of transesterification in non-catalytic supercritical methanol, where it was observed that the process reached yields of up to 86.3%, in 75 minutes, under pressure and temperature of 15 MPa (148 atm) and 430 ° C (Dambiski, L .; 2007). In fact, the international scientific literature shows several specific works on the conditions of the use of methanol in supercritical conditions, highlighting: “Preparation of biodiesel from soybean oil using supercritical methanol and cosolvent”, (Cao, W., Han, H., Zhang, J .; 2005); “Biodiesel from sunflower oil in supercritical methanol with calcium oxide. Process Biochemistry ”, (Demirbas, A .; 2006); “Kinetics of transesterification in rapeseed oil to biodiesel fuel as treated in supercritical methanol”, (Kusdiana, D .; Saka, S .; 2001);

“Synthesis of biodiesel in supercritical fluids”, (Madras, G .; Kolluru, C .; Kumar, R .; 2004); “Reactivity of triglycerides and fatty acids of rapeseed oil in supercritical alcohols. Bioresource Technology ”, (Warabi, Y .; Kusdiana, D .; Saka, S .; 2004).

[007] A great advantage of this process is being able to use the oil directly, without the need for pre-treatment to eliminate water and free fatty acids. The chemical mechanism seems to involve the direct nucleophilic attack of alcohol on the carbonyl group of the glyceride (Kusdiana, D .; Saka, S .; 2004). In the same work, it was observed that the methanol / oil molar ratio of 42: 1 at 350 ° C converts 95% of the glyceride in 30 minutes. In another study, the literature shows that the molar alcohol / oil ratio is one of the variables that most influence the

5 / Π conversion of the transesterification reaction of vegetable oils under supercritical conditions (Rathore, V .; Madras, G .; 2007). In a continuous flow system, a transesterification reaction of soybean oil was tested, using supercritical methanol, with a 40: 1 methanol / oil molar ratio, pressure of 35 MPa, reaction temperature of 310 ° C and residence time of 25 minutes , with an estimated conversion rate of 77%. The authors concluded that the gradual heating of the system could reduce losses caused by secondary reactions of unsaturated methyl esters at high temperatures (He, H .; Wang, T .; Zhu, S .; 2007).

[008] The analysis of the literature related to the production of methyl or ethyl esters of vegetable oils showed that the vast majority of works refer to the new sources of raw materials and to the variation of the methods previously presented. In the use of methanol, or even ethanol, at supercritical temperatures, the energy balance of the process, compared to the conventional one, showed that the energy for the production of biodiesel in the conventional one is 17.9 MJ / 1 of biodiesel. Only the conventional transesterification process consumes 4.3 MJ / 1, while in the supercritical method the consumption is 3.3 MJ / 1, a reduction of 1 MJ for each liter of biodiesel produced. In relation to costs using canola oil with methanol, the supercritical process has a lower cost than the conventional one (Medeiros, M. F .; et al .; 2006). Ethyl esters of algae Nannochloropsis salina in a supercritical medium, mediated by microwave, were obtained in a reactor

6/27 of silicon carbide (SiC), with the advantage of direct use of the raw material, without prior extraction of the fatty material. The method proved the feasibility of combining the techniques in various conditions (Patil, P. D .; et al .; 2013). To analyze the influence of variables in the mentioned process, the response surface analysis was used (Patil, P. D .; et al .; 2011).

[009] In research at the Institute's patent bank

National Industrial Property - INPI the following patents stand out in the field of this invention: the patent PI0503214-8 which refers to a process for obtaining fuels from thermal-catalytic cracking of triglycerides using microwaves as a source of heat and which comprises the transformation of triglycerides from animal, vegetable or sewage sources into hydrocarbons that can be used as substitute fuels for diesel, kerosene and gasoline; the patent PI0619990-9, which refers to a simple and efficient process for cracking with properly sustained hydrocarbon radiation, provides for deep destruction processing of hydrocarbon chains using decomposition of the hydrocarbon chain under a wide variety of irradiation conditions and ranges temperature (from room temperature to 450 ° C), with several embodiments including: (i) a special case of cracking with thermal radiation referred to as cracking with high temperature radiation (HTRC), (ii) cracking with radiation at temperature (LTRC) and (iii) cracking with cooling radiation

7/27 (CRC); the patent PI0905232-1 which refers to a process for reducing naphthenic acidity and simultaneously increasing the API Grade of petroleum, heavy, extra-heavy oil and mixture of oils and their fractions under microwave irradiation and in the presence of materials absorbing microwaves, preferably those that absorb radiation at localized sites forming nanoreactors, pure or in mixtures, such as spent hydrotreating catalysts; the patent PI0406113-6 which refers to an equipment for use in chemical processes in continuous flow, in a tubular cylindrical shape with a conveyor thread inside and with a heating system using electromagnetic waves like microwaves arranged linearly along the upper generatrix the tube; the patent PI0403530-5 which refers to a process for the production of biodiesel using vegetable oils or animal fat and microwave induction that produces monoalkyl esters of fatty acids via transesterification or esterification of vegetable oils or animal fats and fatty acids in general, by acidic, basic or acidic / basic catalysis, with microwave radiation coupled to the reaction cavity; and the patent PI0502891-4 on biodiesel production process in continuous medium without catalyst, consisting of pumping a mixture of vegetable alcohol through a pump to a tubular reactor where the mixture will be subjected to high pressure and temperature, obtaining at the outlet unreacted alcohol (ethanol or methanol), glycerol and a mixture of esters (biodiesel) that is taken to the reactor outlet reservoir where there is an upper alcohol phase, which is

8/27 rerouted by an alcohol return pipe to the pump inlet, the intermediate phase (biodiesel) and the lower phase (mostly glycerol) which are conducted to the separation tank or decantation tank, where the separation is made final, the alcohol being removed through the alcohol return pipe and using biodiesel and glycerol as the final product.

[010] US Patent Nos. US4,582,629 and US4,947,129 stand out in the US patent bank, which describe processes for separating water contained in oil using radiation with a wavelength between 1 and 300 millimeters commonly called micro -waves; US8,039,652 which describes the process for transesterification, esterification and esterification-transesterification for the production of biofuels improved by one or more of the following characteristics: 1) the application of microwaves or radio frequency energy, 2) passage of reagents on heterogeneous catalysts at high speed in order to achieve high shear conditions, 3) emulsifying reagents such as a homogeneous catalyst or 4) maintaining the reaction at a pressure equal to or greater than the autogenous pressure; and US8,188,305 patent, which describes a process and equipment for obtaining biodiesel and alcohol from a raw material for mixing free fatty acids and / or glycerides mixed with a simple alcohol, such as methanol, the method uses high pressure and temperature to produce alkyl esters in supercritical conditions and an electrostatic probe to generate

9/27 an electric field of about 300 volts per inch inside the reactor, which causes glycerol molecules to precipitate out of the raw material mixture, which when precipitated reaches a level to make contact with the electrostatic probe, whose electrical circuit is closed, which causes its output, when the level drops, the drain closes, the glycerol absorbs water and the drainage of the glycerol naturally dehydrates the fuel. [011] In spite of the timid use of high frequency electromagnetic fields and the innovations presented in the patents aimed at the elimination of water in petroleum, the improvement of the simultaneous increase of API Degree and reduction of naphthenic acidity in oils and mixtures of oils, and the increase in efficiency to obtain light fractions of complex organic molecules, some of the processes presented have as a disadvantage the use of catalysts that increase the acidity of the products obtained and collaborate in the corrosion of the engines and equipment used with the products obtained. Others use mixtures of glycerides with alcohol at high pressure and temperature, supercritical conditions, to obtain unreacted alcohol (ethanol or methanol), glycerol and a mixture of esters (biodiesel).

[012] One of the patents describes a microwave reactor with an innovative geometric layout. Others contemplate the use of microwave radiation in transesterification, esterification and esterification-transesterification processes for use in the production of biofuels. The main problems observed in these processes is the low

10/27 selectivity of the products obtained, in relation to those obtained in supercritical conditions, as well as little or no monitoring, control and automation of the same.

[013] On the other hand, the patent PI0502891-4 that does not use catalyst, but alcohol in supercritical conditions and the patent US8,188,305 that also does not use catalyst, but alcohol in supercritical conditions combined with the use of an electrostatic electric field for the production biodiesel, glycerol and unreacted alcohol are more efficient, but do not use high frequency electromagnetic fields or monitoring and control systems.

Basics of the invention.

[014] In view of the characteristics and problems presented in the processes and in the purpose of overcoming them, a new and unprecedented process of transesterification was developed in supercritical conditions, using alcohols combined with the use of high frequency electromagnetic fields like micro -waves, which allows a more selective and consequently more efficient cracking. The new process is based on a configuration with new constituent elements, among which stands out: the use of alcohol in supercritical and irradiated conditions, the use of grease / alcohol in supercritical and irradiated conditions, the mixture of products previously obtained in a given molar ratio also radiated and under supercritical pressure and temperature conditions, a low pressure and temperature separator that separates alcohol vapor from glycerol and

11/27 of biodiesel.

[015] The entire process uses an autonomous system with non-classical logic capable of monitoring, controlling and automating it, through sensors that permanently measure the temperatures and pressures of inlet and outlet in the constituent elements, the viscosity of the products being processed in the reactor and the electrical quantities: microwave generation frequencies and powers, whose records are processed by software in electronic microprocessors and stored in memories.

[016] With the data obtained by sensing, the autonomous system intervenes in the process in order to make it more efficient through adjustments in the physical quantities involved. Added to this system is the control center, normally installed in the operation center, which provides real-time supervision of the operations in the process at the plant, and which allows the operator to remotely intervene in the controls if necessary. In this center, histories of measurements, operations and system controls are also created, as well as pre-programmed alarms, capable of signaling abnormal occurrences to the operator at the operation center. The automatic and non-classic control and the new functionalities combined with the aspects of the new constituent elements make it possible to obtain an unprecedented system capable of monitoring, controlling and automating the entire process with precision, in order to make it continuous batch production, for optimum obtaining of the desired chemical constituents with

12/27 maximum efficiency.

Description of the process of the invention.

[017] The invention of the “PROCESS OF

COMBINATION OF THE USE OF ALCOHOLS IN FIELD-ACTIVATED SUPERCRITICAL CONDITIONS

HIGH FREQUENCY ELECTROMAGNETICS FOR OBTAINING BIODIESEL IN CONTINUOUS FLOW ”, is based on the transesterification reaction in supercritical conditions, in which an irradiated alcohol, by microwave high frequency electromagnetic waves, in supercritical conditions and an alcohol / matter mixture grease, also irradiated by microwaves under supercritical conditions are mixed at a given molar ratio, with microwave-type irradiations, under supercritical temperature and pressure conditions, and enter a separator that after relieving the pressure and temperature of the mixture separates the vapor of alcohol, glycerol and biodiesel.

[018] The process has high pressure hydraulic pumps, between 20 and 60 MPa, for alcohol injection and the grease / alcohol mixture; receiver of reaction products in cylindrical shape with conical top cover for coupling the condenser of the reaction vapors, for recovery of excess alcohol, exits at the bottom and median for exit of the reaction products (glycerol and biodiesel); stainless steel jacketed condenser for cold water circulation, with water circulation and cooling system for liquefying the recovered alcohol; and

13/27 microwave generators with frequencies and powers ranging from 2 GHz to 4 GHz and powers according to the dimensions and volumes involved in the process.

[019] The process commands are carried out based on a command map previously programmed according to definitions derived from process analysis with certain characteristics of the raw material (fatty material / alcohol mixture) in the laboratory and subsidized by information received from the pressure sensors, temperature and infrared installed next to the reactors. This information is received by a programmable logic controller and subsequently treated by multivariate statistical techniques, to be used as part of the input variables of an empirical model that uses an expert computer system to search for answers and learn from the experiences of the process, for prediction of products in the process.

[020] The heating of the reactors and the separator with high frequency radiation allows for a more selective cracking than conventional heating due to the dielectric properties of the raw material to be processed. This is due to the dipole rotation mechanism, which is dependent on the frequency of the applied electric field and the relaxation time of the raw material, and the ionic conduction mechanism, which is dependent on the dissipation factor, given by the relationship between the dielectric loss and the dielectric constant of the raw material to be processed and the radiation power

14/27 applied.

[021] The physical-chemical variations of the injected raw material and the products formed in the output reactor are identified by the analysis of the light absorbance in the infrared field in three sets of infrared sensors (emitters and receivers) installed in the initial, middle and final part the separator; and through its indications it is possible to monitor the injected organic classes and the organic classes of the products obtained, in addition to assisting in the determination of the viscosity and estimation of the cetane index (alkane of formula CH ₃ (CH ₂ ) i4CH3 (C 16H34)) that it is used as a standard in evaluating the properties of biodiesel.

[022] The reaction products obtained in the low pressure and temperature separator are pumped to a separating funnel or to a conventional fractionated distillation tower where the products obtained are separated according to their different boiling points.

Detailed description of the invention process.

[023] The process according to the present invention is further explained by means of the attached drawings, in which:

[024] Figure 1 shows a flow chart of the basic process for the production of biodiesel in supercritical conditions with high frequency electromagnetic fields.

[025] Figure 2 shows the simplified schematic representation of the continuous production of biodiesel in supercritical condition combined with high electromagnetic fields.

15/27 frequency.

[026] Figure 3 shows the main monitoring sensors and process controls together with the various processing modules.

[027] Figure 4 shows the data flow from the monitoring, control and automation system of the biodiesel production process in supercritical conditions with high frequency electromagnetic fields.

[028] Figure 5 shows the block diagram of the process monitoring, control and automation system for the production of biodiesel in supercritical conditions with high frequency electromagnetic fields.

[029] Figure 6 shows in a simplified way the sequence of operations performed by the software of the specialist system.

[030] In accordance with what the above figures illustrate, figure 1 shows the flow chart of the basic process for the production of biodiesel in supercritical conditions with high frequency electromagnetic fields. The process basically uses alcohol (l) as a solvent and as a raw material any grease (2) based on glycerides, including low quality, solid, with a high acidity and moisture index, which after mixing forms the fatty material / alcohol ( 4), which after being pumped and subjected to high pressures, temperatures and high-frequency microwave radiation (5) makes the alcohol supercritical (3) and the fatty material / alcohol mixture supercritical (ó).

16/27 [031] The supercritical condition is one that places the substance or mixture above its Critical Point, in which there is no longer a distinction between the liquid and gaseous phases, being able to undergo effusion through solids like a gas and dissolving materials like a liquid.

[032] In the supercritical conditions and irradiated by the microwave (5), the supercritical alcohol (3) and the fatty material / alcohol mixture (4) are mixed in a given molar ratio, with microwave irradiations (5), in supercritical pressure and temperature conditions forming the supercritical grease / alcohol mixture (ó) which, after having its pressure and temperature reduced in the relief (7), introduces it into the separator (8), where the alcohol in the form of steam (9) will be present in the upper phase and is separated from the intermediate phase where the biodiesel (10) is found and from the lower phase where the glycerol is found (11). [033] Figure 2 shows the schematic and simplified representation of the continuous production of biodiesel in supercritical condition combined with high frequency electromagnetic fields, with the various processing modules for carrying out the exposed process; where the alcohol tank (12) stores the ethanol or methanol that will be used as a solvent in the process, the grease tank (13) that will be processed, and that through the solenoid valve (15) feeds the mixing and preheating tank (sponge) which mixes with the solvent from the alcohol tank (12) through the solenoid valve (14) and where the temperature is maintained at around 90 ° C.

17/27 [034] The high pressure hydraulic pump (17) injects alcohol (l) into the reactor (19), keeping it under pressure, while it is irradiated until it reaches supercritical conditions. Together the high pressure hydraulic pump (l8) injects the fatty material / alcohol (4) also under pressure, which is mixed with the supercritical alcohol (3) from the reactor (19) via the register (21) in the reactor (20), so that the new mixture on thermal heating and high pressure is irradiated by the microwave (5) until reaching supercritical conditions and forming the supercritical grease / alcohol (ó) in a given desired molar ratio, which when delivered to the pump (22 ) that relieves its pressure and temperature injects it into the separating vessel (23). The molar ratio of the mixture of alcohol (l) with the fatty material / alcohol (4) in the reactor (20) varies between 1:38 and 1: 43.5 depending on the fatty material used as raw material.

[035] High pressure hydraulic pumps (17 and 18) must provide pressures between 20 and 60 MPa, for the injection of alcohol (l) and fatty material / alcohol (4) respectively in the reactors (19 and 20) that must be with temperatures between 135 ° C and 450 ° C. The separating vessel (23) is cylindrical with a conical top cover for coupling the condenser (24) which has cold water circulation and cooling to condense the reaction vapors and recovery of excess alcohol. Outputs in the separator vessel (23) are at the bottom and median for the output of the reaction products (glycerol and biodiesel respectively), and the microwave generators (28) must generate frequencies between 2 GHz and 4 GHz and variable powers

18/27 between 600 and 4000 W to be irradiated inside the reactors (19 and 20) and inside the separator vessel (23). The residence time of the mixture inside the reactor (20) is given by the ratio of the volume of the reactor (20) by the flow of the mixture that must be between 30 seconds and 90 minutes and is controlled by the high pressure hydraulic pumps (17 and 18 ) and the pump (22) that relieves the pressure and temperature of the reaction products obtained and makes the suction for injection in the separator (23).

[036] Alcohol, methanol or ethanol, in the form of steam alcohol (9) removed from the condenser (24) is retained in the recovered alcohol tank (25) which, after passing through the register (26), is delivered to the treatment tank alcohol (27) that can be delivered to the alcohol tank (12) through the solenoid valve (29).

[037] In figure 3, the main monitoring sensors and process controls can be seen along with the various processing modules. The monitoring matrix is composed of temperature, pressure and commercial infrared sensors, and controls that can change the heating of the different modules in order to initially study the process according to the peculiarities of the plant, and later adjust it for the operating point for the production of biodiesel (10) to be carried out with maximum efficiency. The mass transport system actuators, registers, valves and controls are installed to control the material flow in order to guarantee a continuous process.

[038] In the mixing and preheating tank (16)

19/27 there is a temperature sensor (34) type NTC (negative coefficient resistance with temperature) whose function is to monitor the temperature around 90 ° C of the fatty material / alcohol (4) to be processed, and the control of temperature of the armored heating elements (35). In addition to the high pressure hydraulic pumps (17 and 18) rotating with variable frequency there are injection pressure controls (36 and 37) respectively capable of varying the pressure in a range between 20 and 60 MPa.

[039] In the reactors (19 and 20) there are temperature sensors (38 and 40) type thermocouples that monitor the temperatures that must be in the range of 135 ° C to 450 ° C, as well as the controls of the heating elements (39 and 41) respectively that heat them up.

[040] Along with the pump (22) that relieves the pressure and temperature of the reaction products formed in the reactor (20) there is a variable control (42) capable of adjusting the pressure and the suction level of the reaction products formed for insertion in the separating vessel (23).

[041] Inside the cylindrical separating vessel (23) with conical top cover there is a thermocouple temperature sensor (43), the temperature control (44) of the heating elements and three sets of installed infrared sensors (emitters / receivers) at the bottom - IF sensor (45), median - IF sensor (46) and upper - IF sensor (47) responsible for monitoring the organic classes obtained, in addition to supporting the determination of viscosity and the estimation of

20/27 cetane found in the biodiesel (10) produced.

[042] In the microwave generators (28) there are the power controls (48) responsible for the waves radiated inside the reactors (19 and 20) and inside the separator vessel (23), which control the powers between 600 and 4000 W. [043] Figure 4 shows the data flow from the monitoring, control and automation system of the biodiesel production process in supercritical conditions with high frequency electromagnetic fields. The physical-chemical characteristics of the raw material to be processed are inserted in the initial file (49) of the operation center (32) which issues the physical-chemical adjustment report (50) to the operator (51) to adjust the process before it is inserted in the grease tank (13). After loading the raw material, starting the system (52) and selecting the programmed command map (53) for processing, the operation center (32) is activated and will send the parameter setting information (pressure and temperature) to the programmable logic controller (30) that will control the various adjustment interfaces (54), so that the supercritical cracking system with microwave (55) transforms the fat / alcohol material (4) and obtains the desired reaction products. Conversely, the data from the temperature and infrared sensors (56) that monitor the operating variables of the microwave supercritical cracking system (55), feed measured information to the sensor interfaces (57) that send them to the programmable logic controller (30) that transfers them to the control panel

21/27 of operation (32) and make them available on the screen (58) to the operator (5 1).

[044] Figure 5 shows the block diagram of the process monitoring, control and automation system for the production of biodiesel in supercritical conditions with high frequency electromagnetic fields. In it you can see the control panel (32) and the programmable logic controller (30) responsible for processing the signals coming from the input interface (59) internal to the programmable logic controller (30) where the process input variables are received , are external signals from measurements of the temperature sensor (34) installed next to the mixing and preheating tank (16), of the temperature sensors (38 and 40) installed in the reactors (19 and 20), respectively, of the temperature sensor temperature (43) installed in the separator vessel (23) and the infrared sensors IF (45), IF (46) and IF (47) installed inside the separator vessel (23). In the output interface (60) internal to the programmable logic controller (30) the control devices for the process variables are connected: the valves (14, 15 and 29) solenoid types; the temperature control of the armored heating elements (35) of the mixing and preheating tank (16); the injection pressure controls (36 and 37) of the high pressure hydraulic pumps (17 and 18) respectively; the controls of the heating elements (39 and 41) that heat the reactors (19 and 20) respectively; the variable control (42) of the pump (22) that adjusts the pressure and the suction level of the products

22/27 reactions formed in the reactor (20) for insertion in the separating vessel (23); the temperature control (44) of the heating elements of the separating vessel (23); and the power controls (48) of the microwave generators (28) responsible for generating the irradiated waves in the reactors (19 and 20) and in the separator vessel (23).

[045] Microwave generator system power sources (28) transform the 50 Hz or 60 Hz AC power signal (74) into signals in the 2 GHz to 4 GHz high range powers, through a set of microwave generating valves, type “magnetrons”, and their own power sources. For better efficiency of the power controls (48), multilevel inverter circuits are used to improve the use of energy from the microwave valve power supplies, in addition to the benefit of providing linear control and no longer on / off type that , in continuous production, can generate incomplete processes.

[046] The programmable logic controller (30) has a structure similar to the architectures of digital computers, basically formed by the central processing unit (62) where the microprocessor (63), the memory bank (64) are located, both for data as for the programs, the interconnection bus (65) through which the input signals and the control signals circulate, addressing memories and data flow, and the communication connector (66). It is through this connector that the data flows bi-directionally between the

23 / η programmable logic controller (30) and the control unit (32) composed of a PC type microcomputer where the software of the specialist system (3 1) is installed. The programmable logic controller (30) also has the display (61) where you can view the information that helps its operation and programming manually.

[047] The basic principle of operation of the programmable logic controller (30) is the execution by the microprocessor (63) of a program, called “executable” under the responsibility of the manufacturer of the programmable logic controller (30) that performs the reading actions of the input interface (59), executes the user control program (67) and updates the output interface (60). The “executable” performs a specific sequence of instructions selected from a set of operations offered by the manufacturer of the programmable logic controller (30), which performs the controls of the desired parameters, activating or not the memory bank (64), the output interface (60) based on the monitoring of the state of the memory bank (64) and / or the collected information existing in the input interface (59) and / or the information provided by the specialist system software (33) that continuously supervises the operation of the programmable logic controller (30).

[048] The microprocessor-CPU (68) of the operation center (32) receives via the communication connector (66) and the input port (69) the input data (59) integrated in 10-second periods and stored in the Bank of

24/27 memories (64) of the programmable logic controller (30), stores them in the database (70) and sends them to the specialist system (31) which, depending on the characteristics of the raw material and products obtained, transcribed by the sensor information (56) of temperatures and infrared that monitor the operating variables of the microwave supercritical cracking system (55).

[049] All processing intelligence of the programmable logic controller (30) is carried out under the supervision of the expert system (33), which, through cyclic requests every 10 seconds, the input signals and the characteristics related to the products obtained determine the actions in the settings interfaces (54).

[050] The command signals for the control valves of the microwave supercritical cracking system (55) and the pre-programmed threshold values are stored on the programmed command map (53) along with the specialist system (31). of the input signals that signal alarms on the screen (58) if they are reached.

[051] The operation center (32) instantly makes available on the screen (58) the information collected and integrated in 10 seconds from the supercritical cracking system with microwave (55), as well as alarms. The on-screen displays (58) of the specialist system software (33) also allow the operator (51) to intervene in the system manually if necessary.

[052] The operation center (32) has the

25/27 microprocessor-CPU (68) that continuously processes in its temporary memory (71) the specialist system software (33), with information from the input data (59), from the programmable logic controller (30), and via the interconnection bus (72) that communicates externally with the screen (58), with the initial file (49) and issues the physical-chemical adjustment report (50).

[053] There is also powering the control unit (32), the programmable logic controller (30), the temperature and infrared sensors (56), the sensor interfaces (57) and the adjustment interfaces (54) of the control system. supercritical cracking with microwave (55), the power supply (73), energized normally by the electric power network (74) and in the moments of lack of energy in it, by a bank of rechargeable batteries (75).

[054] Figure 6 shows in a simplified way the sequence of operations performed by the software of the specialist system (33). In it, the signals from the temperature and infrared sensors (56) that monitor the operation of the microwave supercritical cracking system (55) are formed at the sensor interfaces (57) and delivered at the input interface (59) of the logic controller programmable (30) that sends them to the operation center (32) where the specialist system software (33) is installed.

[055] The expert system (33) is a computational system that operates based on Case Based Reasoning (CBR) and Fuzzi logic, and that controls the system of

26/27 microwave supercritical cracking (55) through the settings interfaces (54) with information from the inference module (76). The inference module (76) makes decisions based on knowledge acquired in the laboratory and stored on the programmed command map (53) and on symptoms related to the responses of the variables resulting from the parameters imposed on the process; these relationships are stored in the database (70) of the operation center (32) and lead the specialist system (33) to continuous learning from experiences.

[056] The data conformed to the input interface (59) of the programmable logic controller (30) are converted into a numeric input (77) and converted into fuzzy sets in fuzzification (78) that are used in the inference module (76) to variation of control parameters. The inference (76) is decided according to the knowledge base contained in the rules base (79) and in the programmed command map database (53) selected according to the physical-chemical characteristics of the raw material to be processed and constant in the initial file (49). One of the most important functions of the database contained in the programmed command map (53) is to store and provide information necessary for the proper functioning of the fuzzification (78), rule base (79) and defuzzification (80) modules.

[057] The defuzzification module (80) converts a Fuzzi set generated by the inference (76) into a numerical value that after being conformed to electrical signals in the

27/27 several settings interfaces (54) that will impose the new operating parameters on the microwave supercritical cracking system (55); which in turn are monitored by the temperature and infrared sensors (56) next to the supercritical cracking system with microwave (55) and which through the sensor interfaces (57) are converted into information for the numerical entry (77) . [058] The process described here, object of the present invention patent, may have the construction of its basic constituent elements in different materials and sizes, as well as in different accessory configurations according to the needs of each user and the fatty / alcoholic material (4 ) to be processed. Of course, other changes can be made to the “PROCESS OF COMBINING THE USE OF ALCOHOLS IN SUPERCRITICAL CONDITIONS ACTIVATED BY HIGH FREQUENCY ELECTROMAGNETIC FIELDS TO OBTAIN BIODIESEL IN CONTINUOUS FLOW” without losing the innovation presented here.

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Claims (5)

1. “PROCESS OF COMBINING THE USE OF ALCOHOLS IN SUPERCRITICAL CONDITIONS ACTIVATED BY HIGH FREQUENCY ELECTROMAGNETIC FIELDS FOR THE OBTAINING OF CONTINUOUS FLOW BIODIESEL”, characterized by being a continuous process, without the use of catalysts, in which alcohol (l) (ethanol or methanol) used as a solvent in the process and stored in the alcohol tank (12) is injected by the high pressure hydraulic pump (17) in the reactor (19), keeping it under pressure between 20 and 60 MPa and temperature between 135 ° C and 450 ° C and irradiated by microwave (5) until reaching supercritical conditions and becoming supercritical alcohol (3); in which the grease (2), including of low quality, solid, with a high acidity and humidity index stored in the grease tank (13) feeds together with the alcohol (l) a mixing and preheating tank (16 ) with a temperature around 90 ° C which is injected by the high pressure hydraulic pump (18) in the reactor (20) together with the supercritical alcohol (3) in order to obtain a mixture of fatty material / supercritical alcohol (ó) in a molar ratio between 1:38 and 1: 43.5 depending on the grease matter (2) used, and maintained at a pressure between 20 and 60 MPa, temperature between 135 ° C and 450 ° C and irradiated by microwave ( 5) until it reaches supercritical conditions and becomes a supercritical grease / alcohol mixture (ó); that after being sucked by the pump (22) that relieves the pressure and the temperature of the mixture injects it into the separating vessel (23), where the alcohol in the form of 2/5 steam (9) will be present in the upper phase, biodiesel (10) in the intermediate phase and glycerol (ll) in the lower phase; and that next to the outlet of the separating vessel (23), the condenser (24) is cooled with ice water, which condenses the vapors and recovers the excess alcohol (l) in the separating vessel (23) and deposits it in the alcohol tank. recovered (25) which after going through the register (26) is delivered to the alcohol treatment tank (27) which can send it to the alcohol tank (12) through the solenoid valve (29); that the whole process is monitored, controlled and automated by the operation center (32) which, after receiving the physicochemical characteristics of the raw material to be processed in the initial file (49), issues the physical-chemical adjustment report (50) to the operator (51 ) to adjust the process, and that after starting the system (52) and selecting the programmed command map (53) sends the parameter setting information (pressure and temperature) to the programmable logic controller (30) that will control the various adjustment interfaces (54), so that the supercritical cracking system with microwave (55) transforms the fatty material / alcohol mixture (4) and obtains the desired reaction products, and inversely, the data coming from the sensors (56 ) of temperatures and infrared that monitor the operating variables of the microwave supercritical cracking system (55) feed information measured by the sensor interfaces (57) that send them to the programmable logic controller (30) which and transfer them to the operation center (32) where they are processed by the 3/5 specialist system software (31) and made available on the screen (58) to the operator (51) who, if necessary, can also manually intervene in the supercritical cracking system with microwave (55). 2. “PROCEDURE FOR COMBINING THE USE OF ALCOHOLS IN SUPERCRITICAL CONDITIONS ACTIVATED BY HIGH FREQUENCY ELECTROMAGNETIC FIELDS FOR OBTAINING BIODIESEL IN CONTINUOUS FLOW” according to claim 1, characterized by the residence time of the mixture inside the reactor (20 ) where the supercritical fatty material / alcohol mixture is produced (ó) is given by the volume ratio of the reactor (20) by the flow of the mixture that must be between 30 seconds and 90 minutes, depending on the dimensions and volumes involved, and is controlled the high pressure hydraulic pumps (17 and 18) and the pump (22) that relieves the pressure and temperature of the reaction products obtained and makes the suction for injection in the separator (23) where the alcohol in the form of vapor (9) is obtained in the upper phase, biodiesel (10) in the intermediate phase and glycerol (l 1) in the lower phase. 3. “PROCESS OF COMBINING THE USE OF ALCOHOLS IN SUPERCRITICAL CONDITIONS ACTIVATED BY HIGH FREQUENCY ELECTROMAGNETIC FIELDS FOR THE OBTAINING OF BIODIESEL IN CONTINUOUS FLOW” according to claim 1, characterized by the power sources of the micro generators system waves (28) transform the current signal 4/5 alternating 50 Hz or 60 Hz electrical network (74) in signals in the range of 2 GHz to 4 GHz of high powers, through a set of microwave generating valves, type "magnetrons", and by their own power sources, which for better efficiency of power controls (48), multilevel inverter circuits are used to improve the use of energy from the microwave valve power supplies, in addition to the benefit of providing linear and not of the on / off type, so that irradiations are better suited to continuous and batch production of biodiesel (10). 4. “PROCEDURE FOR COMBINING THE USE OF ALCOHOLS IN SUPERCRITICAL CONDITIONS ACTIVATED BY HIGH FREQUENCY ELECTROMAGNETIC FIELDS FOR THE OBTAINING OF CONTINUOUS FLOW BIODIESEL” according to claim 1, characterized by the specialist system software (31) installed on the microcomputer of operation center (32), responsible for monitoring, controlling and automating the biodiesel production process by combining the use of alcohols in supercritical conditions activated by high frequency electromagnetic fields like microwaves (5) in continuous flow, using Fuzzi logic and controls the supercritical cracking system with microwave (55) through the adjustment interfaces (54) with information from the inference module (76) that makes decisions based on knowledge acquired in the laboratory and stored in the 5/5 programmed command map (53), and the responses of the variables resulting from the parameters imposed on the process, which compared with the relationships stored in the database (70) leads the specialist system (33) to continuous learning from experiences , and with the use of data conformed to the input interface (59) of the programmable logic controller (30) which are converted into a numeric input (77), and later converted into fuzzy sets in fuzzification (78) and which after being used by inference module (76) for varying the control parameters according to the knowledge base contained in the rules base (79) and the programmed command map database (53), selected according to the physical-chemical characteristics of the matter press to be processed and contained in the initial file (49), supplies them to the fuzzification module (78) that feeds the rules base (79) and, the defuzzification (80), which converts a Fuzzi set generated by inference (76) in a numerical value which, after being formed into electrical signals at the various adjustment interfaces (54), will impose the new operating parameters on the microwave supercritical cracking system (55), which are then monitored by temperature sensors and (56) infrared that through the sensor interfaces (57) are converted into information for the numerical input (77) that again feeds the specialist system (3 1). 1/6