WO2019151848A2 - Continuous hydrothermolytic method for transforming triglycerides into refined products - Google Patents

Continuous hydrothermolytic method for transforming triglycerides into refined products Download PDF

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Publication number
WO2019151848A2
WO2019151848A2 PCT/MX2019/050005 MX2019050005W WO2019151848A2 WO 2019151848 A2 WO2019151848 A2 WO 2019151848A2 MX 2019050005 W MX2019050005 W MX 2019050005W WO 2019151848 A2 WO2019151848 A2 WO 2019151848A2
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stream
continuous
water
triglycerides
hydrotermolytic
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PCT/MX2019/050005
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Spanish (es)
French (fr)
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WO2019151848A3 (en
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Antonio José De Jesús De San Juan Bosco ECHEVARRIA PARRÉS
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Echevarria Parres Antonio Jose De Jesus De San Juan Bosco
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C07C1/207—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms from carbonyl compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12M—APPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
    • C12M1/00—Apparatus for enzymology or microbiology
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

Definitions

  • the present invention is related to bio-oil synthesis processes from organic matter by means of hydrotermolysis, and more particularly, with a continuous hydrotermolytic process to transform microalgae biomass with its triglycerides into bio-oil under supercritical pressure and temperature conditions.
  • US Patent No. 7, 691, 159 B2 describes a method for the conversion of triglycerides to biofuels comprising the steps of: a. precondition the unsaturated triglycerides to form a modified triglyceride mixture, the triglycerides having their structurally altered carbon structure by means of (i) catalytic conjugation isomerization resulting in conjugated triglycerides; (1) delation combining said conjugated triglycerides with an alkene by Diels-Alder reaction, resulting in conjugated triglycerides and cyclized triglycerides; and (iii) crosslinking the main fatty acid carbon chains of said conjugated and cyclized triglycerides; b ..
  • Patent No. 7,691, 159 B2 The disadvantages of the method described in Patent No. 7,691, 159 B2 are the following: it only processes refined vegetable oils; requires distilled water processing; catalytic agents are required; it requires pre-conditioning of the oil to favor the formation of cyclic chains; Does not process cellulose.
  • US Patent 8,350, 102 B2 describes a process for converting biomass to fuel, comprising the steps of: hydrolyzing a lipid biomass to form free fatty acids, catalytically deoxygenating free fatty acids to form n-alkanes and reform at least a portion of the n-alkanes into a mixture of compounds in the correct chain length, conformation and proportion to be useful as fuels
  • the prepared product comprises mixtures of hydrocarbon compounds selected from the group consisting of n-alkanes, isoalkanes, aromatics, cycloalkanes and combinations thereof.
  • US Patent 8,884,086 describes an integrated process for the catalytic hydroprocessing of a sulfur-containing petroleum-based raw material, and the catalytic hydroprocessing of biomass-derived raw material, a process that comprises the steps of: (a) passing said raw material of petroleum origin containing sulfur together with a first stream containing hydrogen to a first hydroprocessing zone and contacting said raw material of petroleum origin with hydrogen in the presence of a hydroprocessing catalyst under hydroprocessing conditions to produce a first stream of effluent from the hydroprocessing zone; (b) passing said raw material derived from biomass together with a second stream containing hydrogen to a second hydroprocessing zone and contacting said second stream containing hydrogen with said raw material of biomass origin in the presence of a hydroprocessing catalyst in hydroprocessing conditions to produce a second stream of effluent from the hydroprocessing zone; (c) passing said effluent stream from the first hydroprocessing zone to a separation zone in which said effluent stream is separated into a stream of steam containing hydrogen and hydrogen
  • biofuels that can process raw biomass, including, for example, whole algae; that does not require catalytic agents and that does not generate residues such as glycerol.
  • the applicant developed a continuous hydrothermolytic process to transform biomass of microalgae with their triglycerides into refining products, under conditions of pressure and sub and supercritical temperatures.
  • the process of the present invention is capable of processing raw biomass without requiring any pre-processing, including whole seaweed, which is mixed with water, which does not need to be distilled. Additionally, no catalytic agents are required and no residues such as glycerol are produced.
  • the process of the present invention comprises in its most general modality, mixing and emulsifying the biomass with water and feeding it continuously under supercritical pressure and temperature conditions to a continuous reactor where high thermal energy isothermal conditions are maintained throughout of an internal trajectory to achieve a hydrothermolysis reaction and achieve the conversion of biomass under stable conditions to bio-oil.
  • the process of the present invention provides subsequent stages of fractionation to obtain various types of biofuels such as biodiesel and bioturbosin.
  • biofuels such as biodiesel, bioturbosin.
  • Figure 1 is a diagram of the process of the present invention.
  • Figure 2 is a diagram of the reforming profile of the reactor.
  • Figure 3 is a perspective view of the continuous flow reactor of the method of the present invention showing its internal components.
  • Figure 4 is a front view of the internal tubular core of the reactor of the present invention. DETAILED DESCRIPTION OF THE INVENTION
  • the process of the present invention uses raw biomass and water as raw material and comprises the steps of:
  • step d) produce bioturbosin from the kerosene obtained in step d) by feeding the kerosene a secondary reactor packed with nickel using water as a source of hydrogen to allow saturation of the chain and the formation of a stream of bioturbosin and traces of bionafta;
  • step f) purify the bioturbosin produced in step e) by feeding the bioturbosin and traces of bionafta stream to a secondary fractionator where the bionaphta is separated and bioturbosin is obtained.
  • the hydrocarbon stream of step d) is hydroxy deoxygenated and hydrogenated in a multi-body packed reactor with Nickel Molybdenum and Nickel Cobalt, with interpass chillers to reduce the risk of coking, at the exit of the first pair of bodies, the stream
  • the reactor effluent is enriched with toluenes, ethylbenzenes, C8, C9, C11, C12 and heavy as cresols and C14 to C16 as well as long chain nitriles greater than C18.
  • the process of the present invention further comprises condensing the light hydrocarbons (light bionate) from the upper stream of the primary fractionator obtained in step d) and separate incondensables and water, by feeding said higher current to a condenser for later storage and disposal;
  • the continuous hydrotermolytic process transforms biomass of microalgae with its triglycerides into refining products.
  • the present invention uses microalgae water and biomass with its triglycerides as raw material.
  • Said specific modality of the continuous hydrotermolytic process to transform microalgae biomass with its triglycerides into refining products of the present invention comprises the steps of:
  • P-101 that sucks the water from a storage tank (TQ-WATER) with a maximum percentage of 1% potassium hydroxide (not a catalyst) to favor the breakdown of cellulose chains and at the same time as a measure preventive to prevent coking in the reactor and create a stream (4) of microalgae biomass with its triglycerides by means of a centrifugal pump (P-100) that sucks said microalgae biomass with its triglycerides from a storage tank (TQ-BIOMASS) , where the proportion of water to biomass of microalgae with their triglycerides is between 10 to 50%, preferably 35% with respect to the volume of water and where the conditions of both streams are as follows:
  • step b) creating a pressurized stream (11) of the homogenized and emulsified mixture of water and biomass of microalgae with their triglycerides obtained in step b) by suctioning said mixture from the emulsifying tank represented by the stream (9) by means of a high pressure pump (P-102) that raises the pressure of the mixture from 0 kg / cm 2 g to a pressure of between 150 and 350 atm, preferably 280 atm, where the conditions of the pressurized stream (11) created They are as follows:
  • TQ-CAP capacitance tank
  • d) continuously process the pressurized stream of the homogenized and emulsified mixture of water and biomass of microalgae with its triglycerides (11) by means of hydrotermolysis by continuously feeding the pressurized stream of the homogenized and emulsified mixture of water and microalgae biomass with its triglycerides (11) created in stage c) and leaving the capacitance tank to a pressurized heated continuous flow reactor (CRV-100, CRV-101, CRV-102) whose operating conditions are between 300 ° C C at 500 ° C preferably 400 ° C and a pressure between 150 to 350 atm, preferably 280 atm, where the conversion of the mixture of water and biomass of microalgae with its triglycerides into a direct current (20) of a mixture rich in light and defined hydrocarbons in addition to aromatic compounds derived from the fed biomass (bio-oil).
  • the residence time of the continuous pressurized stream inside the reactor is 13 minutes to 28 minutes, preferably 15 minutes
  • a direct current (20) of a specific mixture of nonenos, methyl and dimethyl pyrazine hydrocarbons derivatives, cyclopentanones, phenols, cresols, propane, propylene, C17, C18 unsaturated, C02, as well as more aromatic COs is produced.
  • polycyclic, tetradecene, naphthalene, indole, indenos, amines and long chain amides, coumaryl and coniferyl derivatives with the following conditions:
  • the components of the mixture of light hydrocarbon derivatives, unsaturated kerosene and biodiesel are the following:
  • step e depressurize the reactor output current (20) obtained in step d) to a subcritical pressure of the order of 1 atm with the respective temperature drop to 345 C by Joule-Thompson effect by a pressure valve regulator train (VLV-100, VLV-101, VLV-102) to produce a depressurized stream (23) comprising a mixture of Nonenos, methyl and dimethyl pyrazine, cyclopentanones, phenols, cresols, propane, propylene, C17, C18 unsaturated, C02, as well as CO plus polycyclic aromatics, tetradecenes, naphthalenes, idols, indennes, amines and long chain amides, coumaryl and coniferyl derivatives;
  • a primary fractionator T-100 comprising a column with heater (COLUMN), a reboiler (REHERVER 101) and a three-phase reboiler (THREE PHASE REHERVIDER) where two streams are separated:
  • a stream (39) comprising polycyclic aromatics, tetradecenes, naphthalenes, idols, indennes, amines and long chain amides, coumaryl and coniferyl derivatives these latter by-products of the depolymerization of the cell wall of the microalgae biomass.
  • g) feed the current (25) obtained by the dome of the primary fractionator obtained in step f) to a capacitor (V-103) where it separates:
  • an upper vent stream comprising approximately: 11% furfural, 70% CO2, 19% propane at a flow rate of approximately 0.20 Kg / hr;
  • an intermediate stream (31) comprising hydrocarbons HCO, C9 to C12, Benzenes, C8-C6 cyclic;
  • a lower stream (WATER-01) comprising light condensates and water which is sent to a recovered water tank for re-injection into the process, since said water contains some hydrocarbons;
  • h) divide the intermediate stream (31) into a first stream (27) and a second stream (33) of hydrocarbons HCO, C9 to C12, Benzenes, C8-C6 cyclic, by a shunt (TEE-100), where the current (27) is recycled to the primary fractionator T-100 in order to rectify the current with the gases and vapors that are directed to the dome;
  • a stream (54) comprising: the components of the stream of HCO hydrocarbons (51) plus hydrogen;
  • step j) passing the HCO hydrocarbon stream mixed with hydrogen (54) obtained in step j) through a preheater (E-104) that heats the mixture at temperatures of 180 to 300 ° C depending on the biochemistry of the biomass with in order to reduce the integral thermal load and condition the load prior to the entry to the next stage of hydrodeoxygenating and hydrogenating (only in the start-up phase since hydrogenation is unstable in the reactor bed of said stage) once the stationary conditions, approximately after 10 or 15 minutes by adjusting conditions up to 180-200 ° C ”.
  • the preheated current is referred to as (55);
  • step k hydrodeoxygenate and hydrogenate the hydrocarbon stream mixed with preheated hydrogen (55) obtained in step k) by feeding it to a multi-body packed reactor with molybdenum nickel and cobalt nickel (CRV-103, CRV-104, CRV-105 ), working at: 49 Kg / cm 2 and 190 ° C using water as a source of hydrogen, with intercoolers (E105, E-106) to reduce the risk of coking, where at the exit of the first pair of bodies,
  • the reactor effluent stream has been enriched with toluenes, ethylbenzenes, C8, C9, C11, C12 and heavy as cresols and C14 to C16 as well as long chain nitriles greater than C18.
  • the output stream (66) of the packed reactor specifically comprises: noneno, carbon dioxide, cyclohexane, propane, lignin, benzene, formic acid, cellulose, water, triglycerides, HDC-CELHDR- 01, furfurals, hydrogen, glycerol, ALC-C18-PARAF, methane, HYD-CEL-C5-OL, PM- cyclohexane-group, PM-arom-OL, HDC-CEL-HDR-02.
  • step n) feeding the cooled stream (67) obtained in step m) to a three-phase separator (V-100) where a stream (69) of Hydrogen, Propane and Methane comprising volatile hydrocarbons, a stream (71) is obtained of liquid hydrocarbons C8, C9, C12, C16 and C18 and some aromatics comprising the target cuts and a stream (70) of dense aromatic rings, cellulose polymerization residues comprising heavy condensates plus water;
  • o send the stream (71) of liquid hydrocarbons C8, C9, C12, C16 and C18 and some aromatics to a secondary column (T-101) that operates at a temperature of 400 C and that includes a heater and a reboiler (V -102), where a lighter stream (73) of lighter naphtha is separated by the dome of the secondary column (T-101) which can be used as fuels (such as hydrocarbons from the vent current of the stage g)); A stream (75) of Bioturbosin is created in the middle of the secondary column and a stream (78) of biodiesel and heavy is created in the bottom.
  • step f) (39) is sent to the three-phase reboiler,
  • T-100 the primary fractionation column
  • T-100 the primary fractionation column
  • an intermediate stream comprising cyclohexane, lignin, cellulose, water and triglycerides, which is condensed by an interface capacitor (E-102) and sent to a capacitance tank (V-101, TQ INTERMEDIATE CAPACITANCE) where said intermediates are received in liquid form.
  • gases comprising noneno, CO2, cyclohexane, propane, lignin, benzene, formic acid, water, methanol, and furfural, which returns to the primary fractionation column (T-100) for a new rectification process
  • an intermediate stream comprising cyclohexane, lignin, cellulose, water and triglycerides, which is condensed by an interface capacitor (E-102) and sent to a capacitance tank (V-101, TQ INTERMEDIATE CAPACITANCE) where said intermediates are received in liquid form.
  • the bottom stream (53) of the three-phase reboiler comprising: carbon dioxide, cyclohexane, propane, lignin, formic acid, water, methanol, and furfural, which leaves at a temperature of 147.1 degrees, is driven by a pump (P-105) to a cooler (E-103) which lowers the temperature of the current to a temperature of 60 ° C, creating the cooled current (41) that has the same components as the current (53).
  • a current (47) (comprising cyclohexane, lignin, cellulose, water and triglycerides) is created from the capacitance tank (v-101, TQ INTERMEDIATE CAPACITANCE), created by a pump (P-100), which is divided by a shunt (TEE-102), in the currents (48) and (49) having the same components as the current (47), where the current (49) is referred to in the step
  • the cooled current (41) that comes from the bottom of the three-phase reboiler is divided into the currents (42) and (43) by a shunt (TEE-101), where the current (43) is referred to in the stage (i)
  • the streams (42) and (48) are mixed by the mixer (MIX-105) where the stream (50) is created comprising intermediate and heavy recirculation (cyclohexane, lignin group, PM-lignin-1, cellulose, water and triglycerides), which is returned to the linear mixer (MIX-100) and the high-speed emulsifier tank (TQ-MIXER) for reprocessing, to ensure adequate formation of light and intermediate components and to reduce the formation of heavy and in order not to have material outside the specification that destroys the catalyst which is found in the multi-body reactors to carry out hydrodeoxygenation and hydrogenation (CRV-103 CRV-104 CRV-105).
  • intermediate and heavy recirculation cyclohexane, lignin group, PM-lignin-1, cellulose, water and triglycerides
  • TQ-MIXER high-speed emulsifier tank
  • step h To the stream (33) of HCO hydrocarbons obtained in step h) is added the stream (49) that comes from the capacitance tank and the stream (43) that comes from the bottom of the three-phase reboiler, using a MIX-106 mixer giving Start to step (k), in order to guide the process towards the production of the desired products (light, heavy or intermediate) when the process is already stabilized.
  • the pressurized continuous flow reactor where the hydrotermolysis of the homogenized and emulsified mixture of water and biomass of microalgae with its triglycerides is carried out has a path through which the pressurized stream flows, which is heated in its entirety equally by means heating
  • the continuous flow reactor comprises:
  • an external tubular shaped housing (100) having: an interior space (101), an internal wall (102), a first open end (103) having a coupling ring (104) surrounding the opening; a second end (105) ending in an open tubular extension (106) having a diameter smaller than the outer shell (100), wherein said tubular extension (106) has an opening (not shown) surrounded by an external coupling ring (107) and where the external housing (100) has a first (108) and second (109) separate upper openings, arranged longitudinally in the upper portion of the external housing (100);
  • cover (110) tightly fitting to the first open end (103) of the outer housing (100) and which is attached to the coupling ring (104) of the first open end (103) by means of bolts, said cover ( 110) having a first (112) and a second (113) separate colinial openings arranged along a horizontal axis in an upper portion of said cover (110);
  • a heating element (114) comprising a tubular shaped member having a first closed end (not shown) and a second closed end (115) having a coupling disk (116), wherein the heating element (114) it is housed inside the inner space (101) of the outer shell (100), arranged longitudinally along the inner length of the outer shell (100) and concentrically with said outer shell (100), having a diameter such that it allows it to extend along the open tubular extension (106) in a tight manner, such that the coupling disc (1 16) covers the open tubular extension (106) and is coupled to the external coupling ring ( 107) of said open tubular extension (106) by means of bolts.
  • the heating element (1 14) includes internal heating means which in a specific embodiment comprise an electrical resistance, although in other embodiments it may comprise a gas burner;
  • each support ring (117) tightly holds a portion of the section transverse of the heating element (114), which passes through each opening of said plurality of support rings (117);
  • the internal tubular core inlet is connected to the high pressure pump (P-102), and the inner tubular core outlet is connected to the pressure valve regulator train ( VLV-100, VLV-101, VLV-102).
  • the interior (101) of the outer shell (100) is filled with a thermal fluid, which in a preferred embodiment comprises a mixture of sodium and potassium nitrate that allows heat transfer, at a pressure of 1.5 kg / cm 2 g , so that both the heating element and the inner tubular core are submerged therein.
  • a thermal fluid which in a preferred embodiment comprises a mixture of sodium and potassium nitrate that allows heat transfer, at a pressure of 1.5 kg / cm 2 g , so that both the heating element and the inner tubular core are submerged therein.
  • the heating element (114) heats the thermal fluid to a temperature of 400 C, which in turn heats the internal tubular core (118).
  • the supercritical process by hydrotermolysis reaction is carried out continuously within the internal tubular core (118) to which the current of the homogenized and emulsified mixture of water and biomass of microalgae with its triglycerides (11) enters which enters through the Inner tubular core inlet.
  • the thermal fluid carries the pressurized current from a temperature of 32 C to an activation temperature of 400 ° C as the mixture circulates through the inner tubular core (1 18).
  • the hydrotermolysis reaction proceeds and the conversion of the mixture into a mixture rich in light and defined hydrocarbons is carried out in addition to aromatic compounds derived from the biomass fed in a time of 15 minutes permanence that depends on the temperature inside the reactor in accordance with the graph of Figure 2, which is the time it takes for a portion of the mixture to travel the entire internal tubular core circuit of such that as the mixture approaches the second end (120) of the circuit of the Internal tubular core (118), the hydrotermolysis reaction and therefore the conversion of reagents to a mixture rich in light hydrocarbons and olefins in addition to aromatic compounds is completely completed.
  • the function of the expansion tank (112) is to receive the thermal fluid that has expanded inside (101) of the outer casing (100) and keep it during operation at the same reactor temperature thanks to a second element of internal heating (124) that extends into the expansion tank.
  • process of the present invention can make use of continuous flow reactors that have other designs, as long as it allows the pressurized current to reach the activation temperature and that it maintains the pressure necessary to carry out the reaction of hydrotermolysis continuously.
  • the internal flow path may comprise a spiral that can be heated by any suitable means other than a thermal medium.
  • mixing and homogenizing, depressurizing, separation and purification steps can be carried out using any available equipment designed for this purpose and to operate continuously in conjunction with the continuous flow reactor.
  • the continuous hydrotermolytic process to transform microalgae biomass with its triglycerides into refining products of the present invention is not limited to the modality described above and that experts in the field will be trained, by the teachings set forth herein, to effect changes in the continuous hydrotermolytic process to transform microalgae biomass with its triglycerides into refining products of the present invention, the scope of which will be established exclusively by the following claims.

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Abstract

The invention relates to a continuous hydrothermolytic method for transforming microalgae biomass with the triglycerides thereof into refined products, under conditions of pressure and sub- and supercritical temperatures, which method can process raw biomass without the need for any type of preprocessing, including whole algae mixed with water and which does not need to be distilled, and without requiring catalytic agents or producing waste such as glycerol.

Description

PROCESO HIDROTERMOLITICO CONTINUO PARA TRANSFORMAR TRIGLICERIDOS EN PRODUCTOS DE REFINACION ANTECEDENTES DE LA INVENCION  CONTINUOUS HYDROTERMOLITIC PROCESS FOR TRANSFORMING TRIGLICERIDES IN REFINING PRODUCTS BACKGROUND OF THE INVENTION
A. CAMPO DE LA INVENCION  A. FIELD OF THE INVENTION
La presente invención está relacionada con procesos de síntesis de biopetróleo a partir de materia orgánica por medio de hidrotermólisis, y más particularmente, con un proceso hidrotermolítico continuo para transformar biomasa de microalgas con sus triglicéridos en biopetróleo bajo condiciones de presión y temperaturas supercríticas. The present invention is related to bio-oil synthesis processes from organic matter by means of hydrotermolysis, and more particularly, with a continuous hydrotermolytic process to transform microalgae biomass with its triglycerides into bio-oil under supercritical pressure and temperature conditions.
B. DESCRIPCION DEL ARTE RELACIONADO B. DESCRIPTION OF RELATED ART
En el arte, son conocidos una gran variedad de procesos para la producción de biopetróleo a partir de materia orgánica mediante su procesamiento por medio de hidrotermólisis, algunos de los cuales se citan a continuación.  In the art, a wide variety of processes for the production of bio-oil from organic matter are known through its processing by means of hydrothermolysis, some of which are cited below.
La patente norteamericana No.7, 691 , 159 B2 describe un método para la conversión de triglicéridos a biocombustibles que comprende las etapas de: a. preacondicionar los triglicéridos insaturados para formar una mezcla de triglicéridos modificada, teniendo los triglicéridos su estructura de carbono estructuralmente alterada por medio de (i) isomerización por conjugación catalítica dando como resultado triglicéridos conjugados; (l¡) delación combinando dichos triglicéridos conjugados con un alqueno mediante reacción de Diels-Alder, dando como resultado triglicéridos conjugados y triglicéridos ciclizados; y (iii) reticular las cadenas principales de carbono de ácidos grasos de dichos triglicéridos conjugados y ciclizados; b.. poner en contacto dicha mezcla de triglicéridos modificada con una mezcla de agua que comprende un catalizador, teniendo dicha mezcla de agua una temperatura suficiente para llevar la mezcla de triglicéridos y agua modificada a una temperatura de al menos 240°C. causando que los triglicéridos modificados se sometan a una hidrotermólisis catalítica para producir un aceite de hidrocarburo crudo; y C. de refinar dicho aceite de hidrocarburo crudo para producir diversos grados de biocombustibles.  US Patent No. 7, 691, 159 B2 describes a method for the conversion of triglycerides to biofuels comprising the steps of: a. precondition the unsaturated triglycerides to form a modified triglyceride mixture, the triglycerides having their structurally altered carbon structure by means of (i) catalytic conjugation isomerization resulting in conjugated triglycerides; (1) delation combining said conjugated triglycerides with an alkene by Diels-Alder reaction, resulting in conjugated triglycerides and cyclized triglycerides; and (iii) crosslinking the main fatty acid carbon chains of said conjugated and cyclized triglycerides; b .. contacting said modified triglyceride mixture with a mixture of water comprising a catalyst, said mixture of water having a temperature sufficient to bring the mixture of triglycerides and modified water to a temperature of at least 240 ° C. causing the modified triglycerides to undergo catalytic hydrothermolysis to produce a crude hydrocarbon oil; and C. refining said crude hydrocarbon oil to produce varying degrees of biofuels.
Las desventajas del método descrito en la patente No.7,691 ,159 B2 son los siguientes: solo procesa aceites vegetales refinados; requiere agua destilada el procesamiento; se requieren agentes catalíticos; requiere pre acondicionamiento del aceite para favorecer la formación de cadenas cíclicas; no procesa celulosa.  The disadvantages of the method described in Patent No. 7,691, 159 B2 are the following: it only processes refined vegetable oils; requires distilled water processing; catalytic agents are required; it requires pre-conditioning of the oil to favor the formation of cyclic chains; Does not process cellulose.
La patente norteamericana 8,350, 102 B2 describe un proceso para convertir biomasa a combustible, comprendiendo los pasos de: hidrolizar una biomasa lipídica para formar ácidos grasos libres, desoxigenar catalíticamente los ácidos grasos libres para formar n-alcanos y reformar al menos una porción de los n-alcanos en una mezcla de compuestos en la longitud de cadena correcta, conformación y proporción para que sean útiles como combustibles Particularmente, el producto preparado comprende mezclas de compuestos hidrocarbonados seleccionados del grupo que consiste en n-alcanos, isoalcanos, aromáticos, cicloalcanos y combinaciones de los mismos. US Patent 8,350, 102 B2 describes a process for converting biomass to fuel, comprising the steps of: hydrolyzing a lipid biomass to form free fatty acids, catalytically deoxygenating free fatty acids to form n-alkanes and reform at least a portion of the n-alkanes into a mixture of compounds in the correct chain length, conformation and proportion to be useful as fuels Particularly, the prepared product comprises mixtures of hydrocarbon compounds selected from the group consisting of n-alkanes, isoalkanes, aromatics, cycloalkanes and combinations thereof.
Las desventajas del proceso descrito en la patente norteamericana 8,350, 102 B2 son las siguientes: el proceso solo procesa biomasa de origen animal; produce un residuo de glicerol; emplea un catalizador del tipo iónico; y el producto requiere tratamiento HEFA.  The disadvantages of the process described in US Patent 8,350, 102 B2 are the following: the process only processes biomass of animal origin; produces a glycerol residue; employs an ionic type catalyst; and the product requires HEFA treatment.
Por otro lado, la patente norteamericana 8,884,086 describe un proceso integrado para el hidroprocesado catalítico de una materia prima de origen petrolero que contiene azufre, y el hidroprocesamiento catalítico de materia prima derivada de biomasa, proceso que comprende las etapas de: (a) pasar dicha materia prima de origen petrolero que contiene azufre junto con una primera corriente que contiene hidrógeno a una primera zona de hidroprocesamiento y poner en contacto dicha materia prima de origen petrolero con hidrógeno en presencia de un catalizador de hidroprocesamiento en condiciones de hidroprocesamiento para producir una primera corriente de efluente de la zona de hidroprocesamiento; (b) pasar dicha materia prima derivada de biomasa junto con una segunda corriente que contiene hidrógeno a una segunda zona de hidroprocesamiento y poner en contacto dicha segunda corriente que contiene hidrógeno con dicha materia prima de origen de biomasa en presencia de un catalizador de hidroprocesamiento en condiciones de hidroprocesamiento para producir una segunda corriente de efluente de la zona de hidroprocesamiento; (c) pasar dicha corriente efluente de la primera zona de hidroprocesamiento a una zona de separación en la que dicha corriente efluente se separa en una corriente de vapor que contiene hidrógeno y sulfuro de hidrógeno y una corriente de producto de petróleo líquido; (D) pasar al menos una porción de dicha corriente de vapor que contiene hidrógeno y sulfuro de hidrógeno separada de dicha primera corriente de efluente de la zona de hidroprocesamiento en dicha segunda zona de hidroprocesamiento como al menos una porción de dicha segunda corriente que contiene hidrógeno; y (e) pasar dicha segunda corriente de efluente de la zona de hidroprocesamiento a una zona de separación en la que dicha corriente efluente se separa en una corriente de vapor que contiene sulfuro de hidrógeno e hidrógeno y una corriente de producto derivado de biomasa líquida. On the other hand, US Patent 8,884,086 describes an integrated process for the catalytic hydroprocessing of a sulfur-containing petroleum-based raw material, and the catalytic hydroprocessing of biomass-derived raw material, a process that comprises the steps of: (a) passing said raw material of petroleum origin containing sulfur together with a first stream containing hydrogen to a first hydroprocessing zone and contacting said raw material of petroleum origin with hydrogen in the presence of a hydroprocessing catalyst under hydroprocessing conditions to produce a first stream of effluent from the hydroprocessing zone; (b) passing said raw material derived from biomass together with a second stream containing hydrogen to a second hydroprocessing zone and contacting said second stream containing hydrogen with said raw material of biomass origin in the presence of a hydroprocessing catalyst in hydroprocessing conditions to produce a second stream of effluent from the hydroprocessing zone; (c) passing said effluent stream from the first hydroprocessing zone to a separation zone in which said effluent stream is separated into a stream of steam containing hydrogen and hydrogen sulfide and a stream of liquid petroleum product; (D) passing at least a portion of said steam stream containing hydrogen and hydrogen sulfide separated from said first effluent stream from the hydroprocessing zone in said second hydroprocessing zone as at least a portion of said second stream containing hydrogen ; and (e) passing said second effluent stream from the hydroprocessing zone to a separation zone in which said effluent stream separates into a vapor stream that It contains hydrogen sulfide and hydrogen and a product stream derived from liquid biomass.
Las desventajas del proceso descrito en la patente No. 8,884,086 son las siguientes: tiene por objeto primario el diésel; no utiliza como reactivo agua; la diagramación comprende el proceso estándar de refinación atmosférica; requiere remoción de gas sulfhídrico por aminas; emplea un catalizador en fase primarias.  The disadvantages of the process described in the patent No. 8,884,086 are the following: its primary purpose is diesel; does not use water as a reagent; the layout includes the standard atmospheric refining process; requires removal of hydrogen sulfide gas by amines; employs a primary phase catalyst.
Es por lo tanto deseable contar con un proceso para la producción de biocombustibles que pueda procesar biomasa cruda, incluyendo por ejemplo algas completas; que no requiera agentes catalíticos y que no genere residuos como por ejemplo el glicerol.  It is therefore desirable to have a process for the production of biofuels that can process raw biomass, including, for example, whole algae; that does not require catalytic agents and that does not generate residues such as glycerol.
En vista de las necesidades anteriormente descritas, el solicitante desarrollo un proceso hidrotermolítico continuo para transformar biomasa de microalgas con sus triglicéridos en productos de refinación, bajo condiciones de presión y temperaturas sub y supercríticas.  In view of the needs described above, the applicant developed a continuous hydrothermolytic process to transform biomass of microalgae with their triglycerides into refining products, under conditions of pressure and sub and supercritical temperatures.
El proceso de la presente invención es capaz de procesar biomasa cruda sin necesitar de ningún tipo de pre-procesamiento, incluyendo alga entera, la cual se mezcla con agua, que no necesita ser destilada. Adicionalmente, no se requieren agentes catalíticos y no se producen residuos como el glicerol.  The process of the present invention is capable of processing raw biomass without requiring any pre-processing, including whole seaweed, which is mixed with water, which does not need to be distilled. Additionally, no catalytic agents are required and no residues such as glycerol are produced.
El proceso de la presente invención, comprende en su modalidad más general, mezclar y emulsionar la biomasa con agua y alimentarla de manera continua bajo condiciones de presión y temperatura supercríticas a un reactor continuo en donde se mantienen condiciones isotérmicas de alta energía térmica a lo largo de una trayectoria interna para lograr una reacción de hidrotermólisis y lograr la conversión de la biomasa en condiciones estables a biopetróleo.  The process of the present invention, comprises in its most general modality, mixing and emulsifying the biomass with water and feeding it continuously under supercritical pressure and temperature conditions to a continuous reactor where high thermal energy isothermal conditions are maintained throughout of an internal trajectory to achieve a hydrothermolysis reaction and achieve the conversion of biomass under stable conditions to bio-oil.
Así mismo, el proceso de la presente invención provee etapas posteriores de fraccionamiento para obtener vahos tipos de biocombustibles tales como biodiesel y bioturbosina  Likewise, the process of the present invention provides subsequent stages of fractionation to obtain various types of biofuels such as biodiesel and bioturbosin.
SUMARIO DE LA INVENCION SUMMARY OF THE INVENTION
Es por lo tanto un objetivo principal de la presente invención, el proporcionar un proceso hidrotermolítico continuo para transformar biomasa de microalgas con sus triglicéridos en productos de refinación, bajo condiciones de presión y temperaturas sub y supercríticas. Es otro objetivo principal de la presente invención, el proporcionar un proceso hidrotermolítico continuo para transformar biomasa de microalgas con sus triglicéridos en productos de refinación de la naturaleza anteriormente descrita, el cual es capaz de procesar biomasa cruda sin necesitar de ningún tipo de pre-procesamiento, incluyendo alga entera, la cual se mezcla con agua, que no necesita ser destilada. It is therefore a main objective of the present invention, to provide a continuous hydrothermolytic process to transform biomass of microalgae with their triglycerides into refining products, under conditions of pressure and sub and supercritical temperatures. It is another main objective of the present invention, to provide a continuous hydrotermolytic process to transform microalgae biomass with its triglycerides into refining products of the nature described above, which is capable of processing raw biomass without requiring any pre-processing. , including whole seaweed, which is mixed with water, which does not need to be distilled.
Es aún un objetivo principal de la presente invención, el proporcionar un proceso hidrotermolítico continuo para transformar biomasa de microalgas con sus triglicéridos en productos de refinación de la naturaleza anteriormente descrita el cual no requiere agentes catalíticos y no produce residuos como el glicerol.  It is still a main objective of the present invention, to provide a continuous hydrotermolytic process to transform microalgae biomass with its triglycerides into refining products of the nature described above which does not require catalytic agents and does not produce residues such as glycerol.
Es todavía un objetivo principal de la presente invención, el proporcionar un proceso hidrotermolítico continuo para transformar biomasa de microalgas con sus triglicéridos en productos de refinación de la naturaleza anteriormente descrita el cual comprende en su modalidad más general, mezclar y emulsionar la biomasa con agua y alimentarla de manera continua bajo condiciones de presión y temperatura supercríticas a un reactor continuo en donde se mantienen condiciones isotérmicas de alta energía térmica a lo largo de una trayectoria interna para lograr una reacción de hidrotermólisis y lograr la conversión de la biomasa en condiciones estables a biopetróleo.  It is still a main objective of the present invention, to provide a continuous hydrothermolytic process to transform microalgae biomass with its triglycerides into refining products of the nature described above which comprises in its most general modality, mixing and emulsifying the biomass with water and continuously feed it under supercritical pressure and temperature conditions to a continuous reactor where high thermal energy isothermal conditions are maintained along an internal path to achieve a hydrotermolysis reaction and achieve the conversion of biomass under stable conditions to bio-oil .
Es un objetivo adicional de la presente invención, el proveer etapas posteriores de fraccionamiento para obtener vahos tipos de biocombustibles tales como biodiesel, bioturbosina.  It is a further objective of the present invention, to provide subsequent fractionation steps to obtain various types of biofuels such as biodiesel, bioturbosin.
Estos y otros objetivos y ventajas de la presente invención se harán aparentes a las personas con conocimientos normales en el ramo, de la siguiente descripción detallada de la invención.  These and other objectives and advantages of the present invention will become apparent to persons with normal knowledge in the field of the following detailed description of the invention.
BREVE DESCRIPCION DE LOS DIBUJOS. BRIEF DESCRIPTION OF THE DRAWINGS.
La Figura 1 es un diagrama del proceso de la presente invención.  Figure 1 is a diagram of the process of the present invention.
La Figura 2 es un diagrama del perfil de reformado del reactor.  Figure 2 is a diagram of the reforming profile of the reactor.
La Figura 3 es una vista en perspectiva del reactor de flujo continuo del método de la presente invención mostrando sus componentes internos.  Figure 3 is a perspective view of the continuous flow reactor of the method of the present invention showing its internal components.
La Figura 4 es una vista frontal del núcleo tubular interno del reactor de la presente invención. DESCRIPCION DETALLADA DE LA INVENCION Figure 4 is a front view of the internal tubular core of the reactor of the present invention. DETAILED DESCRIPTION OF THE INVENTION
El proceso hidrotermolítico continuo para transformar triglicéridos en productos de refinación será ahora descrito haciendo referencia primeramente a una modalidad general del mismo y posteriormente a modalidades específicas del mismo.  The continuous hydrotermolytic process for transforming triglycerides into refining products will now be described by referring first to a general modality thereof and then to specific modalities thereof.
En una modalidad general, el proceso de la presente invención utiliza como materia prima biomasa cruda y agua y comprende las etapas de:  In a general embodiment, the process of the present invention uses raw biomass and water as raw material and comprises the steps of:
a) mezclar y emulsionar una corriente de biomasa y agua en una proporción de 35 % (pudiendo operarse en un rango de 10 a 50 %) con respecto al volumen en donde la desviación de la proporción en peso biomasa agua es de -25%+15% a temperatura ambiente para crear una corriente de mezcla homogénea y emulsificada de biomasa y agua mediante el envío de la mezcla a un emulsificador de alta velocidad;  a) mix and emulsify a stream of biomass and water in a proportion of 35% (being able to operate in a range of 10 to 50%) with respect to the volume where the deviation of the proportion in weight of biomass water is -25% + 15% at room temperature to create a homogeneous and emulsified mixture stream of biomass and water by sending the mixture to a high-speed emulsifier;
b) procesar de manera continua la corriente de mezcla homogénea y emulsificada de aceite de microalgas con sus triglicéridos y agua por hidrotermólisis dentro de un reactor de flujo continuo a una presión de entre 150 a 350 atm (preferentemente 280 atm, y a una temperatura estable de entre 380 a 450°C preferentemente 400 C, en donde la corriente de la mezcla homogénea y emulsificada entra al reactor a temperatura ambiente, a una presión de entre 150 a 350 atm (preferentemente 280 atm) y con un flujo másico de 7Kg/hr (pudiéndose ajustar entre 2 a 8 kg/hr lo cual puede vahar dependiendo del reactor) con el fin de obtener una mezcla rica en hidrocarburos ligeros y definas además de compuestos aromáticos derivados de la biomasa alimentada que sale del rector a una presión de entre 150 a 350 atm (preferentemente 280atm), una temperatura de 400 C y con un flujo másico de 7Kg/Hr, el cual puede variar dependiendo del reactor. La alimentación de biomasa al reactor se realiza en condiciones ligeramente alcalinas 9 a 11 el cual solo será ajustado con respecto al pH natural de la suspensión, alcalinidades superiores pueden favorecer la formación de espumas en las etapas de fraccionamiento limitando la eficiencia de las mismas;  b) continuously process the homogeneous and emulsified mixture stream of microalgae oil with its triglycerides and water by hydrotermolysis within a continuous flow reactor at a pressure of between 150 to 350 atm (preferably 280 atm, and at a stable temperature of between 380 to 450 ° C preferably 400 C, where the stream of the homogeneous and emulsified mixture enters the reactor at room temperature, at a pressure of between 150 to 350 atm (preferably 280 atm) and with a mass flow of 7Kg / hr (It can be adjusted between 2 to 8 kg / hr which may vary depending on the reactor) in order to obtain a mixture rich in light and defined hydrocarbons in addition to aromatic compounds derived from the fed biomass that leaves the rector at a pressure of between 150 at 350 atm (preferably 280atm), a temperature of 400 C and with a mass flow of 7Kg / Hr, which can vary depending on the reactor.The biomass feed to the reactor is carried out in co Slightly alkaline editions 9 to 11 which will only be adjusted with respect to the natural pH of the suspension, higher alkalities may favor the formation of foams in the fractionation stages by limiting their efficiency;
c) despresurizar la mezcla rica en hidrocarburos ligeros y definas además de compuestos aromáticos que sale del reactor en donde la mezcla se expande de forma isoentálpica en cuatro pasos hasta una presión subcrítica del orden de 1 atm con el descenso respectivo de la temperatura hasta 345 C por el efecto Joule-Thompson; d) fraccionar la corriente de efluente del reactor en un fraccionador primario de columna en dos cortes generales, domo y fondos obteniéndose respectivamente: • por domo: una corriente de hidrocarburos ligeros, incondensables y agua en fase gas, que comprende nonenos, metil y dimetil pirazino, ciclopentanonas, fenoles, cresoles, propano, propileno, C17, C18 insaturados, C02, así como CO. Los gases en un proceso productivo masivo son susceptibles de licuefacción y fraccionamiento como precursores petroquímicos o en procesos de menor escala como fuentes de energía calorífica a calentadores (ambos escenarios no descritos).c) depressurize the mixture rich in light and defined hydrocarbons in addition to aromatic compounds leaving the reactor where the mixture expands in an isoscopic manner in four steps to a subcritical pressure of the order of 1 atm with the respective temperature decrease to 345 C by the Joule-Thompson effect; d) fractionating the reactor effluent stream into a primary column splitter into two general cuts, dome and bottoms, respectively obtaining: • by dome: a stream of light, incondensable hydrocarbons and water in the gas phase, comprising nonenos, methyl and dimethyl pyrazine, cyclopentanones, phenols, cresols, propane, propylene, C17, C18 unsaturated, C02, as well as CO. The gases in a massive production process are susceptible to liquefaction and fractionation as petrochemical precursors or in smaller-scale processes as sources of heat energy to heaters (both scenarios not described).
• por fondo: aromáticos policíclicos, tetradecenos, naftalenos, Índoles, indenos, aminas y amidas de cadena larga, derivados cumarilicos y coniferilicos. Estos compuestos ricos en aromáticos e insaturados deben ser canalizados a separación trifásica para recuperación de hidrocarburos ligeros y pesados solubles y enviar una fracción de ambos a reprocesamiento al reactor de Hidrotermólisis para permitir la hidrólisis de los componentes no fragmentados en el primer ciclo. La kerosina es resultado de la mezcla de estos aromáticos. • by background: polycyclic aromatics, tetradecenes, naphthalenes, idols, indennes, long chain amines and amides, coumaryl and coniferyl derivatives. These aromatic and unsaturated rich compounds must be channeled to three-phase separation for recovery of soluble light and heavy hydrocarbons and send a fraction of both to reprocessing to the Hydrotermolysis reactor to allow hydrolysis of the non-fragmented components in the first cycle. Kerosene is a result of the mixture of these aromatics.
e) producir bioturbosina a partir de la kerosina obtenida en el paso d) mediante la alimentación de la kerosina un reactor secundario empacado con níquel utilizando agua como fuente de hidrogeno para permitir la saturación de la cadena y la formación de una corriente de bioturbosina y trazas de bionafta;  e) produce bioturbosin from the kerosene obtained in step d) by feeding the kerosene a secondary reactor packed with nickel using water as a source of hydrogen to allow saturation of the chain and the formation of a stream of bioturbosin and traces of bionafta;
f) purificar la bioturbosina producida en la etapa e) mediante la alimentación de la corriente de bioturbosina y trazas de bionafta a un fraccionador secundario donde se separa la bionafta y se obtiene bioturbosina.  f) purify the bioturbosin produced in step e) by feeding the bioturbosin and traces of bionafta stream to a secondary fractionator where the bionaphta is separated and bioturbosin is obtained.
La corriente de hidrocarburos de la etapa d) es hidro desoxigenada e hidrogenada en un reactor empacado de múltiples cuerpos con Níquel Molibdeno y Níquel Cobalto, con enfriadores de interpaso para reducir el riesgo de coquización, a la salida del primer par de cuerpos, la corriente efluente del reactor se enrique con toluenos, etilbencenos, C8, C9, C11 , C12 y pesados como cresoles y C14 a C16 así como nitrilos de cadena larga superiores a C18.  The hydrocarbon stream of step d) is hydroxy deoxygenated and hydrogenated in a multi-body packed reactor with Nickel Molybdenum and Nickel Cobalt, with interpass chillers to reduce the risk of coking, at the exit of the first pair of bodies, the stream The reactor effluent is enriched with toluenes, ethylbenzenes, C8, C9, C11, C12 and heavy as cresols and C14 to C16 as well as long chain nitriles greater than C18.
En el último par de cuerpos la hidrogenación lleva a la formación de dimetil hexanos y compuestos C9 a C8 alifáticos.  In the last pair of bodies hydrogenation leads to the formation of dimethyl hexanes and C9 to C8 aliphatic compounds.
Adicionalmente, en dicha modalidad general, el proceso de la presente invención comprende adicionalmente condensar los hidrocarburos ligeros (bionafta ligera) de la corriente superior del fraccionador primario obtenida en el paso d) y separar incondensables y agua, mediante la alimentación de dicha corriente superior a un condensador para su posterior almacenamiento y disposición; Additionally, in said general embodiment, the process of the present invention further comprises condensing the light hydrocarbons (light bionate) from the upper stream of the primary fractionator obtained in step d) and separate incondensables and water, by feeding said higher current to a condenser for later storage and disposal;
En una modalidad específica el proceso hidrotermolítico continuo transforma biomasa de microalgas con sus triglicéridos en productos de refinación. La presente invención utiliza como materia prima agua y biomasa de microalgas con sus triglicéridos.  In a specific modality, the continuous hydrotermolytic process transforms biomass of microalgae with its triglycerides into refining products. The present invention uses microalgae water and biomass with its triglycerides as raw material.
Dicha modalidad específica del proceso hidrotermolítico continuo para transformar biomasa de microalgas con sus triglicéridos en productos de refinación de la presente invención comprende las etapas de:  Said specific modality of the continuous hydrotermolytic process to transform microalgae biomass with its triglycerides into refining products of the present invention comprises the steps of:
a) producir una corriente de agua + KOH (3) mediante una bomba centrifuga a) produce a stream of water + KOH (3) by means of a centrifugal pump
(P-101 ) que succiona el agua de un tanque de almacenamiento (TQ-AGUA) con un porcentaje máximo del 1 % de hidróxido de potasio (no es catalizador) para favorecer el rompimiento de las cadenas de celulosa y al mismo tiempo como medida preventiva para evitar la coquización en el reactor y crear una corriente (4) de biomasa de microalgas con sus triglicéridos mediante una bomba centrifuga (P-100) que succiona dicha biomasa de microalgas con sus triglicéridos de un tanque de almacenamiento (TQ-BIOMASA), en donde la proporción de agua a biomasa de microalgas con sus triglicéridos es de entre 10 a 50 %, preferentemente 35 % con respecto al volumen de agua y en donde las condiciones de ambas corrientes es la siguiente: (P-101) that sucks the water from a storage tank (TQ-WATER) with a maximum percentage of 1% potassium hydroxide (not a catalyst) to favor the breakdown of cellulose chains and at the same time as a measure preventive to prevent coking in the reactor and create a stream (4) of microalgae biomass with its triglycerides by means of a centrifugal pump (P-100) that sucks said microalgae biomass with its triglycerides from a storage tank (TQ-BIOMASS) , where the proportion of water to biomass of microalgae with their triglycerides is between 10 to 50%, preferably 35% with respect to the volume of water and where the conditions of both streams are as follows:
Figure imgf000009_0001
b) mezclar y emulsificar las corrientes de agua (3) y biomasa de microalgas con sus triglicéridos (4) mediante la alimentación continua de dichas corrientes de manera continua a un mezclador lineal (MIX-100) y posteriormente alimentar la corriente de mezcla (7) a un tanque emulsificador de alta velocidad (TQ-MEZCLADOR) para producir una mezcla homogenizada de agua y biomasa algal con sus triglicéridos, en donde el tiempo de permanencia del agua y biomasa de microalgas con sus triglicéridos en el tanque emulsificador de alta velocidad es de preferentemente 3 a 5 minutos a temperatura ambiente. La presencia de sales disueltas y minerales que usualmente se encuentran en el agua favorecen las reacciones por radicales libres, no siendo necesario tener agua desmineralizada;
Figure imgf000009_0001
b) mixing and emulsifying the streams of water (3) and biomass of microalgae with their triglycerides (4) by continuously feeding said streams continuously to a linear mixer (MIX-100) and subsequently feeding the mixing stream (7 ) to a high speed emulsifier tank (TQ-MIXER) to produce a homogenized mixture of water and algal biomass with its triglycerides, where the residence time of the microalgae water and biomass with its triglycerides in the high speed emulsifier tank is preferably 3 to 5 minutes at room temperature. The presence of dissolved salts and minerals that are usually found in water favor reactions by free radicals, and it is not necessary to have demineralized water;
c) crear una corriente presurizada (11 ) de la mezcla homogenizada y emulsificada de agua y biomasa de microalgas con sus triglicéridos obtenida en la etapa b) mediante la succión de dicha mezcla del tanque emulsificador representada por la corriente (9) por medio de una bomba de alta presión (P-102) que eleva la presión de la mezcla desde 0 kg/cm2g hasta alcanzar una presión de entre 150 a 350 atm, preferentemente 280 atm, en donde las condiciones de la corriente presurizada (11 ) creada son las siguientes: c) creating a pressurized stream (11) of the homogenized and emulsified mixture of water and biomass of microalgae with their triglycerides obtained in step b) by suctioning said mixture from the emulsifying tank represented by the stream (9) by means of a high pressure pump (P-102) that raises the pressure of the mixture from 0 kg / cm 2 g to a pressure of between 150 and 350 atm, preferably 280 atm, where the conditions of the pressurized stream (11) created They are as follows:
Figure imgf000010_0001
Figure imgf000010_0001
La corriente presurizada se envía a un tanque de capacitancia (TQ-CAP) para garantizar un flujo continuo y estable a la siguiente etapa  Pressurized current is sent to a capacitance tank (TQ-CAP) to ensure a continuous and stable flow to the next stage
d) procesar continuamente la corriente presurizada de la mezcla homogenizada y emulsificada de agua y biomasa de microalgas con sus triglicéridos (11 ) por medio de hidrotermólisis mediante la alimentación continua de la corriente presurizada de la mezcla homogenizada y emulsificada de agua y biomasa de microalgas con sus triglicéridos (11 ) creada en la etapa c) y que sale del tanque de capacitancia a un reactor presurizado de flujo continuo calentado (CRV-100, CRV-101 , CRV-102) cuyas condiciones de operación son una temperatura de entre 300° C a 500° C preferentemente 400° C y una presión de entre 150 a 350 atm, preferentemente 280 atm, en donde se realiza la conversión de la mezcla de agua y biomasa de microalgas con sus triglicéridos en una corriente continua (20) de una mezcla rica en hidrocarburos ligeros y definas además de compuestos aromáticos derivados de la biomasa alimentada (biopetróleo). El tiempo de residencia de la corriente presurizada continua dentro del reactor es de 13 minutos a 28 minutos, preferentemente 15 minutos y varía en función de la temperatura del reactor de conformidad con la gráfica presentada en la figura 2. d) continuously process the pressurized stream of the homogenized and emulsified mixture of water and biomass of microalgae with its triglycerides (11) by means of hydrotermolysis by continuously feeding the pressurized stream of the homogenized and emulsified mixture of water and microalgae biomass with its triglycerides (11) created in stage c) and leaving the capacitance tank to a pressurized heated continuous flow reactor (CRV-100, CRV-101, CRV-102) whose operating conditions are between 300 ° C C at 500 ° C preferably 400 ° C and a pressure between 150 to 350 atm, preferably 280 atm, where the conversion of the mixture of water and biomass of microalgae with its triglycerides into a direct current (20) of a mixture rich in light and defined hydrocarbons in addition to aromatic compounds derived from the fed biomass (bio-oil). The residence time of the continuous pressurized stream inside the reactor is 13 minutes to 28 minutes, preferably 15 minutes and varies depending on the reactor temperature in accordance with the graph presented in Figure 2.
A la salida del reactor se produce una corriente continua (20) de una mezcla específica de derivados de hidrocarburos Nonenos, metil y dimetil pirazino, ciclopentanonas, fenoles, cresoles, propano, propileno, C17, C18 insaturados, C02, asi como CO más aromáticos, policíclicos, tetradecenos, naftalenos, Índoles, indenos, aminas y amidas de cadena larga, derivados cumarilicos y coniferilicos con las siguientes condiciones:  At the exit of the reactor a direct current (20) of a specific mixture of nonenos, methyl and dimethyl pyrazine hydrocarbons derivatives, cyclopentanones, phenols, cresols, propane, propylene, C17, C18 unsaturated, C02, as well as more aromatic COs is produced. , polycyclic, tetradecene, naphthalene, indole, indenos, amines and long chain amides, coumaryl and coniferyl derivatives with the following conditions:
Figure imgf000011_0001
Figure imgf000011_0001
De manera específica, los componentes de la mezcla de derivados de hidrocarburos ligeros, kerosina rica en insaturados y biodiesel son los siguientes: Specifically, the components of the mixture of light hydrocarbon derivatives, unsaturated kerosene and biodiesel are the following:
BIOCRUDO BIOCRUDO BIOCRUDOBIOCRUDE BIOCRUDE BIOCRUDE
COMPONENTE HTL NiMo300°-400 CoMo 180-300 HTL COMPONENT NiMo300 ° -400 CoMo 180-300
1 LIGEROS 1 % 2% 4%  1 LIGHTWEIGHT 1% 2% 4%
2 GASOLINA (kerosina) 3% 6% 22%  2 GASOLINE (kerosene) 3% 6% 22%
3 TURBOSINA (ligero) 7% 18% 35%  3 TURBOSINE (light) 7% 18% 35%
4 DIESEL(biodiesel) 16% 11 % 12%  4 DIESEL (biodiesel) 16% 11% 12%
5 GASOLEO 40% 40% 16%  5 GASOLEO 40% 40% 16%
6 RESIDUO (carbonoso) 33% 23% 11 %  6 RESIDUE (carbonaceous) 33% 23% 11%
100% 100% 100%  100% 100% 100%
e) despresurizar la corriente de salida del reactor (20) obtenida en la etapa d) hasta una presión subcrítica del orden de 1 atm con el descenso respectivo de la temperatura hasta 345 C por efecto Joule-Thompson mediante un tren regulador de válvulas de presión (VLV-100, VLV-101 , VLV-102) para producir una corriente despresurizada (23) que comprende una mezcla de Nonenos, metil y dimetil pirazino, ciclopentanonas, fenoles, cresoles, propano, propileno, C17, C18 insaturados, C02, así como CO más aromáticos policíclicos, tetradecenos, naftalenos, índoles, indenos, aminas y amidas de cadena larga, derivados cumarilicos y coniferilicos; e) depressurize the reactor output current (20) obtained in step d) to a subcritical pressure of the order of 1 atm with the respective temperature drop to 345 C by Joule-Thompson effect by a pressure valve regulator train (VLV-100, VLV-101, VLV-102) to produce a depressurized stream (23) comprising a mixture of Nonenos, methyl and dimethyl pyrazine, cyclopentanones, phenols, cresols, propane, propylene, C17, C18 unsaturated, C02, as well as CO plus polycyclic aromatics, tetradecenes, naphthalenes, idols, indennes, amines and long chain amides, coumaryl and coniferyl derivatives;
f) separar cada uno de los cortes de hidrocarburos de la corriente despresurizada (23) obtenida en la etapa e) mediante su alimentación a un fraccionador primario T-100, que comprende una columna con calentador (COLUMNA), un rehervidor (REHERVIDOR 101 ) y un rehervidor trifásico (REHERVIDOR TRIFASICO) en donde se separan dos corrientes:  f) separating each of the hydrocarbon cuts from the depressurized stream (23) obtained in step e) by feeding it to a primary fractionator T-100, comprising a column with heater (COLUMN), a reboiler (REHERVER 101) and a three-phase reboiler (THREE PHASE REHERVIDER) where two streams are separated:
• por el domo: una corriente (25) de hidrocarburos ligeros, incondensables y agua en fase gas, que comprende nonenos, metil y dimetil pirazino, ciclopentanonas, fenoles, cresoles, propano, propileno, C17, C18 insaturados, C02, así como CO;  • by the dome: a stream (25) of light, incondensable hydrocarbons and water in the gas phase, comprising nonenos, methyl and dimethyl pyrazine, cyclopentanones, phenols, cresols, propane, propylene, C17, C18 unsaturated, C02, as well as CO ;
• por el fondo: una corriente (39) que comprende aromáticos policíclicos, tetradecenos, naftalenos, índoles, indenos, aminas y amidas de cadena larga, derivados cumarilicos y coniferilicos estos últimos subproductos de la despolimerización de la pared celular de la biomasa de microalgas. g) alimentar la corriente (25) obtenida por el domo del fraccionador primario obtenida en la etapa f) a un condensador (V-103) en donde se separa:  • at the bottom: a stream (39) comprising polycyclic aromatics, tetradecenes, naphthalenes, idols, indennes, amines and long chain amides, coumaryl and coniferyl derivatives these latter by-products of the depolymerization of the cell wall of the microalgae biomass. g) feed the current (25) obtained by the dome of the primary fractionator obtained in step f) to a capacitor (V-103) where it separates:
una corriente superior de venteo (VENTEO. ATM) que comprende aproximadamente: 11 % de furfurales, 70% de CO2, 19% de propano a un flujo de aproximadamente 0.20 Kg/hr;  an upper vent stream (VENTEO. ATM) comprising approximately: 11% furfural, 70% CO2, 19% propane at a flow rate of approximately 0.20 Kg / hr;
una corriente intermedia (31 ) que comprende hidrocarburos HCO, C9 a C12, Bencenos, C8-C6 cíclicos;  an intermediate stream (31) comprising hydrocarbons HCO, C9 to C12, Benzenes, C8-C6 cyclic;
una corriente inferior (AGUA-01 ) que comprende condensados ligeros y agua la cual se manda a un tanque de agua recuperada para su reinyección al proceso, ya que dicha agua contiene algunos hidrocarburos;  a lower stream (WATER-01) comprising light condensates and water which is sent to a recovered water tank for re-injection into the process, since said water contains some hydrocarbons;
h) dividir la corriente intermedia (31 ) en una primera corriente (27) y una segunda corriente (33) de hidrocarburos HCO, C9 a C12, Bencenos, C8-C6 cíclicos, mediante un derivador (TEE-100), en donde la corriente (27) es reciclada al fraccionador primario T-100 con el fin de realizar la rectificación de la corriente con los gases y vapores que se dirigen al domo;  h) divide the intermediate stream (31) into a first stream (27) and a second stream (33) of hydrocarbons HCO, C9 to C12, Benzenes, C8-C6 cyclic, by a shunt (TEE-100), where the current (27) is recycled to the primary fractionator T-100 in order to rectify the current with the gases and vapors that are directed to the dome;
i) mezclar la corriente (33) con una corriente (49) que comprende lignina, celulosa, agua y triglicéridos y con una corriente (43) que comprende dióxido de carbono, ciclohexano, propano, lignina, ácido fórmico, agua, metanol y furfurales, mediante un mezclador MIX-106 para crear una corriente mezclada de hidrocarburos (51 ) con todos los componentes de las corrientes (33), (49) y (43), es decir: noneno, dióxido de carbono, ciclohexano, propano, lignina, benceno, ácido fórmico, celulosa, agua, triglicéridos, metanol, y furfurales. El origen de las corrientes (49) y (43) será descrito más adelante. i) mixing the stream (33) with a stream (49) comprising lignin, cellulose, water and triglycerides and with a stream (43) comprising carbon dioxide, cyclohexane, propane, lignin, formic acid, water, methanol and furfurals , by means of a MIX-106 mixer to create a mixed hydrocarbon stream (51) with all the components of the streams (33), (49) and (43), that is: noneno, carbon dioxide, cyclohexane, propane, lignin, benzene, formic acid, cellulose, water, triglycerides, methanol, and furfurals. The origin of the currents (49) and (43) will be described later.
j) impulsar la corriente de hidrocarburos (51 ) por medio de una bomba (P-107) y a través de un mezclador (MIX-107), que agrega a la corriente de hidrocarburos (51 ), hidrógeno (HIDROGENO) en una cantidad de entre 50 gr/hr a 200 gr/h, preferentemente 100 gr/h para mantener la emulsificación dispersión de la corriente hidrogeno antes del precalentador de reacción primario, de esta manera creando una corriente (54) que comprende: los componentes de la corriente de hidrocarburos HCO (51 ) más hidrógeno;  j) boosting the hydrocarbon stream (51) by means of a pump (P-107) and through a mixer (MIX-107), which adds hydrogen (HYDROGEN) to the stream of hydrocarbons (51) between 50 gr / hr at 200 gr / h, preferably 100 gr / h to keep the emulsification dispersion of the hydrogen stream before the primary reaction preheater, thus creating a stream (54) comprising: the components of the stream of HCO hydrocarbons (51) plus hydrogen;
k) pasar la corriente de hidrocarburos HCO mezclada con hidrógeno (54) obtenida en el paso j) a través de un precalentador (E-104) que calienta la mezcla a temperaturas de 180 a 300°C dependiendo de la bioquímica de la biomasa con el fin de reducir la carga térmica integral y acondicionar la carga previo a la entrada a la siguiente etapa de hidrodesoxigenar e hidrogenar (solo en la fase de arranque ya que la hidrogenación es inestable en el lecho del reactor de dicha etapa) una vez alcanzadas las condiciones estacionarias, aproximadamente después de 10 o 15 minutos realizando un ajuste de condiciones hasta 180-200°C”. La corriente precalentada se denomina como (55);  k) passing the HCO hydrocarbon stream mixed with hydrogen (54) obtained in step j) through a preheater (E-104) that heats the mixture at temperatures of 180 to 300 ° C depending on the biochemistry of the biomass with in order to reduce the integral thermal load and condition the load prior to the entry to the next stage of hydrodeoxygenating and hydrogenating (only in the start-up phase since hydrogenation is unstable in the reactor bed of said stage) once the stationary conditions, approximately after 10 or 15 minutes by adjusting conditions up to 180-200 ° C ”. The preheated current is referred to as (55);
L) hidrodesoxigenar e hidrogenar la corriente de hidrocarburos mezclada con hidrógeno precalentada (55) obtenida en la etapa k) mediante su alimentación a un reactor empacado de múltiples cuerpos con níquel molibdeno y níquel cobalto (CRV- 103, CRV-104, CRV-105), trabajando a: 49 Kg/cm2 y 190°C utilizando agua como fuente de hidrogeno, con enfriadores de interpaso (E105, E-106) para reducir el riesgo de coquización, en donde a la salida del primer par de cuerpos, la corriente efluente del reactor se ha enriquecido con toluenos, etilbencenos, C8, C9, C11 , C12 y pesados como cresoles y C14 a C16 así como nitrilos de cadena larga superiores a C18. En el ultimo par de cuerpos la hidrogenación lleva a la formación de dimetil hexanos y compuestos C9 a C8 alifáticos y biodiesel. La corriente de salida (66) del reactor empacado comprende específicamente: noneno, dióxido de carbono, ciclohexano, propano, lignina, benzeno, ácido fórmico, celulosa, agua, triglicéridos, HDC-CELHDR- 01 , furfurales, hidrogeno, glicerol, ALC-C18-PARAF, metano, HYD-CEL-C5-OL, PM- grupo-Ciclohexano, PM-arom-OL, HDC-CEL-HDR-02. L) hydrodeoxygenate and hydrogenate the hydrocarbon stream mixed with preheated hydrogen (55) obtained in step k) by feeding it to a multi-body packed reactor with molybdenum nickel and cobalt nickel (CRV-103, CRV-104, CRV-105 ), working at: 49 Kg / cm 2 and 190 ° C using water as a source of hydrogen, with intercoolers (E105, E-106) to reduce the risk of coking, where at the exit of the first pair of bodies, The reactor effluent stream has been enriched with toluenes, ethylbenzenes, C8, C9, C11, C12 and heavy as cresols and C14 to C16 as well as long chain nitriles greater than C18. In the last pair of bodies hydrogenation leads to the formation of dimethyl hexanes and C9 to C8 aliphatic compounds and biodiesel. The output stream (66) of the packed reactor specifically comprises: noneno, carbon dioxide, cyclohexane, propane, lignin, benzene, formic acid, cellulose, water, triglycerides, HDC-CELHDR- 01, furfurals, hydrogen, glycerol, ALC-C18-PARAF, methane, HYD-CEL-C5-OL, PM- cyclohexane-group, PM-arom-OL, HDC-CEL-HDR-02.
m) enfriar la corriente (66) producida en la etapa I) mediante su paso por un enfriador primario que enfría la corriente a una temperatura de entre 180-200°C” produciéndose una corriente enfriada (67);  m) cooling the current (66) produced in stage I) by passing through a primary cooler that cools the current to a temperature between 180-200 ° C ”producing a cooled current (67);
n) alimentar la corriente enfriada (67) obtenida en la etapa m) a un separador trifásico (V-100) en donde se obtiene una corriente (69) de Hidrogeno, Propano y Metano que comprende los hidrocarburos volátiles, una corriente (71 ) de hidrocarburos líquidos C8, C9, C12, C16 y C18 y algunos aromáticos que comprende los cortes objetivo y una corriente (70) de anillos aromáticos densos, residuos de polimerización de celulosa que comprende condensados pesados más agua;  n) feeding the cooled stream (67) obtained in step m) to a three-phase separator (V-100) where a stream (69) of Hydrogen, Propane and Methane comprising volatile hydrocarbons, a stream (71) is obtained of liquid hydrocarbons C8, C9, C12, C16 and C18 and some aromatics comprising the target cuts and a stream (70) of dense aromatic rings, cellulose polymerization residues comprising heavy condensates plus water;
o) enviar la corriente (71 ) de hidrocarburos líquidos C8, C9, C12, C16 y C18 y algunos aromáticos a una columna secundaria (T-101 ) que funciona a una temperatura de 400 C y que incluye un calentador y un rehervidor (V-102), en donde se separa por el domo de la columna secundaria (T-101 ) una corriente (73) de nafta más ligeros más incondensables los cuales pueden ser aprovechados como combustibles (como los hidrocarburos de la corriente de venteo de la etapa g)); por la zona intermedia de la columna secundaria se crea una corriente (75) de Bioturbosina y por el fondo se crea una corriente (78) de biodiesel y pesados.  o) send the stream (71) of liquid hydrocarbons C8, C9, C12, C16 and C18 and some aromatics to a secondary column (T-101) that operates at a temperature of 400 C and that includes a heater and a reboiler (V -102), where a lighter stream (73) of lighter naphtha is separated by the dome of the secondary column (T-101) which can be used as fuels (such as hydrocarbons from the vent current of the stage g)); A stream (75) of Bioturbosin is created in the middle of the secondary column and a stream (78) of biodiesel and heavy is created in the bottom.
La corriente de fondo de la etapa f) (39) se envía al rehervidor trifásico, The background current of step f) (39) is sent to the three-phase reboiler,
(REHERVIDOR TRIFASICO) en donde se crea: una corriente de gases (35) que comprenden noneno, CO2, ciclohexano, propano, lignina, benceno, ácido fórmico, agua, metanol, y furfurales, la cual se regresa a la columna de fraccionamiento primario (T-100) para un nuevo proceso de rectificación; una corriente intermedia (37) que comprende ciclohexano, lignina, celulosa, agua y triglicéridos, la cual se condensa mediante un condensador de interfases (E-102) y se envía a un tanque de capacitancia (V-101 , TQ CAPACITANCIA DE INTERMEDIOS) donde se reciben dichos intermedios en forma líquida. La corriente de fondo (53) del rehervidor trifásico (REHERVIDOR TRIFASICO) que comprende: dióxido de carbono, ciclohexano, propano, lignina, ácido fórmico, agua, metanol, y furfurales, la cual sale a una temperatura de 147.1 grados, es impulsada por una bomba (P-105) hacia un enfriador (E-103) el cual baja la temperatura de la corriente a una temperatura de 60° C, creándose la corriente enfriada (41 ) que tiene los mismos componentes que la corriente (53). Del tanque de capacitancia (v-101 , TQ CAPACITANCIA DE INTERMEDIOS) sale una corriente (47) (que comprende ciclohexano, lignina, celulosa, agua y triglicéridos), creada por una bomba (P-100), la cual se divide mediante un derivador (TEE-102), en las corrientes (48) y (49) que tiene los mismos componentes que la corriente (47), en donde la corriente (49) es a la que se hace referencia en la etapa(THREE PHASE REHERVIDER) where it is created: a stream of gases (35) comprising noneno, CO2, cyclohexane, propane, lignin, benzene, formic acid, water, methanol, and furfural, which returns to the primary fractionation column (T-100) for a new rectification process; an intermediate stream (37) comprising cyclohexane, lignin, cellulose, water and triglycerides, which is condensed by an interface capacitor (E-102) and sent to a capacitance tank (V-101, TQ INTERMEDIATE CAPACITANCE) where said intermediates are received in liquid form. The bottom stream (53) of the three-phase reboiler (THREE-PHASE REHERVIDER) comprising: carbon dioxide, cyclohexane, propane, lignin, formic acid, water, methanol, and furfural, which leaves at a temperature of 147.1 degrees, is driven by a pump (P-105) to a cooler (E-103) which lowers the temperature of the current to a temperature of 60 ° C, creating the cooled current (41) that has the same components as the current (53). A current (47) (comprising cyclohexane, lignin, cellulose, water and triglycerides) is created from the capacitance tank (v-101, TQ INTERMEDIATE CAPACITANCE), created by a pump (P-100), which is divided by a shunt (TEE-102), in the currents (48) and (49) having the same components as the current (47), where the current (49) is referred to in the step
(i). (i).
La corriente enfriada (41 ) que proviene del fondo del rehervidor trifásico, se divide en las corrientes (42) y (43) mediante un derivador (TEE-101 ), en donde la corriente (43) es a la que se hace referencia en la etapa (i)  The cooled current (41) that comes from the bottom of the three-phase reboiler is divided into the currents (42) and (43) by a shunt (TEE-101), where the current (43) is referred to in the stage (i)
Las corrientes (42) y (48) se mezclan mediante el mezclador (MIX-105) en donde se crea la corriente (50) que comprende recirculación de intermedios y pesados (ciclohexano, grupo lignina, PM-lignina-1 , celulosa, agua y triglicéridos), la cual se regresa al mezclador lineal (MIX-100) y al tanque emulsificador de alta velocidad (TQ- MEZCLADOR) para su reproceso, para asegurar una formación adecuada de componentes ligeros e intermedios y reducir la formación de pesados y para para no tener material fuera de especificación que destruya el catalizador el cual se encuentra en los reactores de cuerpos múltiples para llevar a cabo la hidrodesoxigenación y la hidrogenación (CRV-103 CRV-104 CRV-105).  The streams (42) and (48) are mixed by the mixer (MIX-105) where the stream (50) is created comprising intermediate and heavy recirculation (cyclohexane, lignin group, PM-lignin-1, cellulose, water and triglycerides), which is returned to the linear mixer (MIX-100) and the high-speed emulsifier tank (TQ-MIXER) for reprocessing, to ensure adequate formation of light and intermediate components and to reduce the formation of heavy and in order not to have material outside the specification that destroys the catalyst which is found in the multi-body reactors to carry out hydrodeoxygenation and hydrogenation (CRV-103 CRV-104 CRV-105).
A la corriente (33) de hidrocarburos HCO obtenida en la etapa h) se le agrega la corriente (49) que proviene del tanque de capacitancia y la corriente (43) que proviene del fondo del rehervidor trifásico, mediante un mezclador MIX-106 dando inicio al paso (k), con el fin de orientar el proceso hacia la producción de los productos que se desean (ligeros, pesados o intermedios) cuando el proceso ya está estabilizado.  To the stream (33) of HCO hydrocarbons obtained in step h) is added the stream (49) that comes from the capacitance tank and the stream (43) that comes from the bottom of the three-phase reboiler, using a MIX-106 mixer giving Start to step (k), in order to guide the process towards the production of the desired products (light, heavy or intermediate) when the process is already stabilized.
A este respecto, si se cierran las llaves o válvulas (VAL-A), (VAL-B) que controlan el paso de las corrientes (43) y (49) respectivamente al mezclador (MIX-106) y se envían dichas corrientes a la recirculación de intermedios y pesados (50) a través del mezclador (MIX-105) todas estas corrientes al reprocesarse en el reactor se van convirtiendo en hidrocarburos más ligeros.  In this regard, if the keys or valves (VAL-A), (VAL-B) that control the passage of the streams (43) and (49) respectively to the mixer (MIX-106) are closed and said streams are sent to the recirculation of intermediate and heavy (50) through the mixer (MIX-105) all these currents when reprocessed in the reactor become lighter hydrocarbons.
Es necesario producir una mezcla adecuada de productos finales que tengan hidrocarburos pesados (los menos), medios (bioturbosina) y ligeros (gasolinas) dependiendo del mercado o de contratos de venta (por ejemplo, a gasolineras), abriendo y permitiendo el paso de las corrientes (43) y (49) hacia el mezclador (MIX- 106). En el caso de que en el proceso se encuentre circulando muchos pesados (es decir, contenidos excesivos de la corriente (43), en donde“muchos pesados” implica un desbalance de la producción de las corrientes (73) y (78)) es necesario interrumpir el flujo de la corriente (43) hacia el mezclador (MIX-106). Por otro lado, en caso de estar produciéndose un desbalance hacia ligeros, es necesario cerrar el mezclador (MIX-105). No se trata de cerrar en su totalidad el paso hacia ninguno de los mezcladores, se trata de crear un balance hacia donde lo requiera el mercado o el contrato de venta, en caso extremo si se puede cerrar en su totalidad. It is necessary to produce an adequate mixture of final products that have heavy hydrocarbons (the least), medium (bioturbosine) and light hydrocarbons (gasoline) depending on the market or sales contracts (for example, gas stations), opening and allowing the passage of currents (43) and (49) towards the mixer (MIX-106). In the event that many heavy ones are circulating in the process (that is, excessive contents of the current (43), where “many heavy ones” implies an imbalance in the production of the currents (73) and (78)) it is It is necessary to interrupt the flow of the current (43) to the mixer (MIX-106). On the other hand, if there is an imbalance towards light, it is necessary to close the mixer (MIX-105). It is not about closing the passage towards any of the mixers, it is about creating a balance sheet where the market or the sales contract requires it, in the extreme case if it can be closed in its entirety.
El reactor presurizado de flujo continuo donde se realiza la hidrotermólisis de la mezcla homogenizada y emulsificada de agua y biomasa de microalgas con sus triglicéridos cuenta con una trayectoria por la cual fluye la corriente presurizada, la cual es calentada en su totalidad de manera equitativa por medios de calentamiento.  The pressurized continuous flow reactor where the hydrotermolysis of the homogenized and emulsified mixture of water and biomass of microalgae with its triglycerides is carried out has a path through which the pressurized stream flows, which is heated in its entirety equally by means heating
A continuación de dan los componentes generales de cada una de las corrientes mencionadas:  Following are the general components of each of the currents mentioned:
Figure imgf000016_0001
Figure imgf000016_0001
Figure imgf000017_0001
Figure imgf000018_0001
Figure imgf000019_0001
Figure imgf000020_0001
Figure imgf000017_0001
Figure imgf000018_0001
Figure imgf000019_0001
Figure imgf000020_0001
Figure imgf000021_0001
Figure imgf000022_0001
Figure imgf000023_0001
Figure imgf000021_0001
Figure imgf000022_0001
Figure imgf000023_0001
En la modalidad específica del proceso de la presente invención, el reactor de flujo continuo comprende: In the specific embodiment of the process of the present invention, the continuous flow reactor comprises:
una carcasa externa de forma tubular (100), teniendo: un espacio interior (101 ), una pared interna (102), un primer extremo abierto (103) que cuenta con un anillo de acoplamiento (104) que rodea la apertura; un segundo extremo (105) que termina en una extensión tubular abierta (106) que tiene un diámetro menor que la carcasa externa (100), en donde dicha extensión tubular (106) cuenta con una apertura (no mostrada) rodeada por uña anillo de acoplamiento externo (107) y en donde la carcasa externa (100) cuenta con una primera (108) y segunda (109) aperturas superiores separadas, dispuestas de manera longitudinal en la porción superior de la carcasa externa (100); an external tubular shaped housing (100), having: an interior space (101), an internal wall (102), a first open end (103) having a coupling ring (104) surrounding the opening; a second end (105) ending in an open tubular extension (106) having a diameter smaller than the outer shell (100), wherein said tubular extension (106) has an opening (not shown) surrounded by an external coupling ring (107) and where the external housing (100) has a first (108) and second (109) separate upper openings, arranged longitudinally in the upper portion of the external housing (100);
una tapa (110) que se ajusta herméticamente al primer extremo abierto (103) de la carcasa externa (100) y la cual se une al anillo de acoplamiento (104) del primer extremo abierto (103) por medio de pernos, dicha tapa (110) teniendo una primera (112) y una segunda (113) aperturas separadas coliniales dispuestas a lo largo de un eje horizontal en una porción superior de dicha tapa (110);  a cover (110) tightly fitting to the first open end (103) of the outer housing (100) and which is attached to the coupling ring (104) of the first open end (103) by means of bolts, said cover ( 110) having a first (112) and a second (113) separate colinial openings arranged along a horizontal axis in an upper portion of said cover (110);
un elemento calentador (114) que comprende un miembro de forma tubular que cuenta con un primer extremo cerrado (no mostrado) y un segundo extremo cerrado (115) que tiene un disco de acoplamiento (116), en donde el elemento calentador (114) se encuentra alojado dentro del espacio interior (101 ) de la carcasa externa (100), dispuesto de manera longitudinal a lo largo de la longitud interna de la carcasa externa (100) y de manera concéntrica con dicha carcasa externa (100), teniendo un diámetro tal que le permite extenderse a lo largo de la extensión tubular abierta (106) de manera ajustada, de tal forma que el disco de acoplamiento (1 16) cubre la extensión tubular abierta (106) y se acopla al anillo de acoplamiento externo (107) de dicha extensión tubular abierta (106) por medio de pernos. El elemento calentador (1 14) incluye medios de calentamiento internos que en una modalidad específica comprenden una resistencia eléctrica, aunque en otras modalidades puede comprender un quemador de gas;  a heating element (114) comprising a tubular shaped member having a first closed end (not shown) and a second closed end (115) having a coupling disk (116), wherein the heating element (114) it is housed inside the inner space (101) of the outer shell (100), arranged longitudinally along the inner length of the outer shell (100) and concentrically with said outer shell (100), having a diameter such that it allows it to extend along the open tubular extension (106) in a tight manner, such that the coupling disc (1 16) covers the open tubular extension (106) and is coupled to the external coupling ring ( 107) of said open tubular extension (106) by means of bolts. The heating element (1 14) includes internal heating means which in a specific embodiment comprise an electrical resistance, although in other embodiments it may comprise a gas burner;
una pluralidad de anillos de soporte (117) dispuestos de manera equidistante, concéntrica y transversal dentro de la carcasa interna y sujetos a la pared interna de la misma, en donde cada anillo de soporte (117) sujeta de manera ajustada una porción de la sección transversal del elemento calentador (114), el cual pasa a través de cada apertura de dicha pluralidad de anillos de soporte (117);  a plurality of support rings (117) arranged in an equidistant, concentric and transverse manner within the internal housing and attached to the internal wall thereof, wherein each support ring (117) tightly holds a portion of the section transverse of the heating element (114), which passes through each opening of said plurality of support rings (117);
un núcleo tubular interno (1 18), compuesto por una o más tuberías que forman un circuito, dicho núcleo tubular interno (118) dispuesto dentro de la carcasa externa (100), rodeando el elemento calentador (114) y pasando a través de aperturas localizadas en los anillos de soporte (no mostradas) los cuales sirven de soporte al núcleo tubular interno (118), dicho núcleo tubular interno (118) teniendo un primer extremo (1 19) que tiene una entrada de flujo y un segundo extremo (120) que tiene una salida de flujo procesado, en donde el primer extremo (119) sale a través de la primera apertura (112) de la tapa (110) de manera hermética y en donde el segundo extremo (120) sale a través de la segunda apertura (1 13) de la tapa (110) de manera hermética; an internal tubular core (1 18), composed of one or more pipes forming a circuit, said internal tubular core (118) disposed within the outer casing (100), surrounding the heating element (114) and passing through openings located in the support rings (not shown) which support the inner tubular core (118), said inner tubular core (118) having a first end (1 19) having a flow inlet and a second end (120) having a processed flow outlet, where the first end (119) exits through the first opening (112) of the cover (110) tightly and where the second end (120) exits through the second opening (1 13) of the lid (110) tightly;
un tanque de expansión superior (121 ), ubicado sobre la carcasa externa (100) y conectado a la misma por medio de un par de tuberías con válvula (122), (123), conectadas a la primera y segunda aperturas superiores de la carcasa externa.  an upper expansion tank (121), located on the external housing (100) and connected to it by means of a pair of pipes with valve (122), (123), connected to the first and second upper openings of the housing external
De conformidad con la modalidad específica del proceso descrita anteriormente, la entrada del núcleo tubular interno se encuentra conectado a la bomba de alta presión (P-102), y la salida del núcleo tubular interno se encuentra conectado al tren regulador de válvulas de presión (VLV-100, VLV-101 , VLV-102).  In accordance with the specific modality of the process described above, the internal tubular core inlet is connected to the high pressure pump (P-102), and the inner tubular core outlet is connected to the pressure valve regulator train ( VLV-100, VLV-101, VLV-102).
El interior (101 ) de la carcasa externa (100) se encuentra lleno de un fluido térmico, el cual en una modalidad preferida comprende mezcla nitrato de sodio y potasio que permita la transferencia de calor, a una presión de 1.5 kg/cm2g, de tal forma que tanto el elemento calentador y el núcleo tubular interno se encuentran sumergidos en el mismo. The interior (101) of the outer shell (100) is filled with a thermal fluid, which in a preferred embodiment comprises a mixture of sodium and potassium nitrate that allows heat transfer, at a pressure of 1.5 kg / cm 2 g , so that both the heating element and the inner tubular core are submerged therein.
De conformidad con la modalidad específica del proceso descrita anteriormente, el elemento calentador (114) calienta el fluido térmico hasta una temperatura de 400 C, el cual a su vez calienta el núcleo tubular interno (118). El proceso supercrítico por reacción de hidrotermólisis se lleva a cabo de manera continua dentro del núcleo tubular interno (118) al cual ingresa la corriente de la mezcla homogenizada y emulsificada de agua y biomasa de microalgas con sus triglicéridos (11 ) la cual ingresa por la entrada del núcleo tubular interno. El fluido térmico lleva a la corriente presurizada desde una temperatura de 32 C hasta una temperatura de activación de 400 °C conforme la mezcla va circulando por el núcleo tubular interno (1 18). Una vez que la mezcla alcanza la temperatura de activación dentro del núcleo tubular interno (118), la reacción de hidrotermólisis procede y se lleva a cabo la conversión de la mezcla a una mezcla rica en hidrocarburos ligeros y definas además de compuestos aromáticos derivados de la biomasa alimentada en un tiempo de 15 minutos permanencia que depende de la temperatura dentro del reactor de conformidad con la gráfica de la Figura 2, el cual es el tiempo que le toma a una porción de la mezcla recorrer todo el circuito del núcleo tubular interno de tal forma que conforme la mezcla se acerca al segundo extremo (120) del circuito del núcleo tubular interno (118), la reacción de hidrotermólisis y por lo tanto la conversión de reactivos a una mezcla rica en hidrocarburos ligeros y olefinas además de compuestos aromáticos se completa totalmente. In accordance with the specific modality of the process described above, the heating element (114) heats the thermal fluid to a temperature of 400 C, which in turn heats the internal tubular core (118). The supercritical process by hydrotermolysis reaction is carried out continuously within the internal tubular core (118) to which the current of the homogenized and emulsified mixture of water and biomass of microalgae with its triglycerides (11) enters which enters through the Inner tubular core inlet. The thermal fluid carries the pressurized current from a temperature of 32 C to an activation temperature of 400 ° C as the mixture circulates through the inner tubular core (1 18). Once the mixture reaches the activation temperature inside the inner tubular core (118), the hydrotermolysis reaction proceeds and the conversion of the mixture into a mixture rich in light and defined hydrocarbons is carried out in addition to aromatic compounds derived from the biomass fed in a time of 15 minutes permanence that depends on the temperature inside the reactor in accordance with the graph of Figure 2, which is the time it takes for a portion of the mixture to travel the entire internal tubular core circuit of such that as the mixture approaches the second end (120) of the circuit of the Internal tubular core (118), the hydrotermolysis reaction and therefore the conversion of reagents to a mixture rich in light hydrocarbons and olefins in addition to aromatic compounds is completely completed.
La función del tanque de expansión (112) es la de recibir el fluido térmico que se ha expandido en el interior (101 ) de la carcasa externa (100) y mantenerlo durante la operación a la misma temperatura del reactor gracias a un segundo elemento de calentamiento interno (124) que se extiende dentro del tanque de expansión.  The function of the expansion tank (112) is to receive the thermal fluid that has expanded inside (101) of the outer casing (100) and keep it during operation at the same reactor temperature thanks to a second element of internal heating (124) that extends into the expansion tank.
Se deberá entender que el proceso de la presente invención puede hacer uso de reactores de flujo continuo que tengan otros diseños, siempre y cuando permita que la corriente presurizada logre alcanzar la temperatura de activación y que mantenga la presión necesaria para llevar a cabo la reacción de hidrotermólisis de manera continua.  It should be understood that the process of the present invention can make use of continuous flow reactors that have other designs, as long as it allows the pressurized current to reach the activation temperature and that it maintains the pressure necessary to carry out the reaction of hydrotermolysis continuously.
Por ejemplo, la trayectoria de flujo interno puede comprender una espiral que puede ser calentada por cualquier medio adecuado diferente a un medio térmico.  For example, the internal flow path may comprise a spiral that can be heated by any suitable means other than a thermal medium.
Así mismo, las etapas de mezclado y homogenizado, despresurizaron, separación y purificación pueden ser llevadas a cabo utilizando cualquier equipo disponible diseñado para tal efecto y para funcionar de manera continua en conjunto con el reactor de flujo continuo.  Likewise, the mixing and homogenizing, depressurizing, separation and purification steps can be carried out using any available equipment designed for this purpose and to operate continuously in conjunction with the continuous flow reactor.
Deberá finalmente entenderse que el proceso hidrotermolítico continuo para transformar biomasa de microalgas con sus triglicéridos en productos de refinación de la presente invención no se limita a la modalidad descrita anteriormente y que los expertos en el ramo quedarán capacitados, por las enseñanzas que aquí se establecen, para efectuar cambios en el proceso hidrotermolítico continuo para transformar biomasa de microalgas con sus triglicéridos en productos de refinación de la presente invención, cuyo alcance quedará establecido exclusivamente por las siguientes reivindicaciones.  It should finally be understood that the continuous hydrotermolytic process to transform microalgae biomass with its triglycerides into refining products of the present invention is not limited to the modality described above and that experts in the field will be trained, by the teachings set forth herein, to effect changes in the continuous hydrotermolytic process to transform microalgae biomass with its triglycerides into refining products of the present invention, the scope of which will be established exclusively by the following claims.

Claims

REIVINDICACIONES
1. Un proceso hidrotermolítico continuo para para transformar triglicéridos en productos de refinación bajo condiciones de presión y temperaturas supercríticas comprendiendo el procesar de manera continua una corriente presurizada (11 ) de una mezcla homogenizada y emulsificada de biomasa de microalgas con sus triglicéridos, por medio de hidrotermólisis dentro de un reactor presurizado de flujo continuo a una presión de entre 150 atm a 350 atm y a una temperatura de activación entre 300° C a 500° C, con el fin de obtener una corriente continua (20) de una mezcla rica en hidrocarburos ligeros y definas además de compuestos aromáticos derivados de la biomasa alimentada. 1. A continuous hydrotermolytic process to transform triglycerides into refining products under supercritical pressure and temperature conditions comprising continuously processing a pressurized stream (11) of a homogenized and emulsified mixture of microalgae biomass with its triglycerides, by means of hydrotermolysis within a pressurized continuous flow reactor at a pressure between 150 atm to 350 atm and an activation temperature between 300 ° C to 500 ° C, in order to obtain a continuous current (20) of a hydrocarbon-rich mixture light and defined in addition to aromatic compounds derived from the fed biomass.
2. Un proceso hidrotermolítico continuo de conformidad con la reivindicación 1 , en donde el reactor se encuentra presurizado a una presión de 280 atm. 2. A continuous hydrotermolytic process according to claim 1, wherein the reactor is pressurized at a pressure of 280 atm.
3. Un proceso hidrotermolítico continuo de conformidad con la reivindicación 1 , en donde la temperatura de activación dentro del reactor es de 400° C. 3. A continuous hydrotermolytic process according to claim 1, wherein the activation temperature within the reactor is 400 ° C.
4. Un proceso hidrotermolítico continuo de conformidad con la reivindicación 1 , en donde el tiempo de residencia de la corriente presurizada continua dentro del reactor es de 13 minutos a 28 minutos, preferentemente 15 minutos. 4. A continuous hydrotermolytic process according to claim 1, wherein the residence time of the continuous pressurized stream within the reactor is 13 minutes to 28 minutes, preferably 15 minutes.
5. Un proceso hidrotermolítico continuo de conformidad con la reivindicación 1 , en donde la corriente continua (20) que sale del reactor comprende una mezcla específica de derivados de hidrocarburos Nonenos, metil y dimetil pirazino, ciclopentanonas, fenoles, cresoles, propano, propileno, C17, C18 insaturados, C02, así como CO más aromáticos, policíclicos, tetradecenos, naftalenos, Índoles, indenos, aminas y amidas de cadena larga, derivados cumarilicos y coniferilicos 5. A continuous hydrothermolytic process according to claim 1, wherein the direct current (20) leaving the reactor comprises a specific mixture of nonenos, methyl and dimethyl pyrazine hydrocarbon derivatives, cyclopentanones, phenols, cresols, propane, propylene, C17, C18 unsaturated, C02, as well as more aromatic, polycyclic, tetradecene, naphthalene, Idoles, indenos, amines and long chain amides, coumaryl and coniferyl derivatives
6. Un proceso hidrotermolítico continuo de conformidad con la reivindicación 1 , en donde la corriente continua (20) sale del rector a una presión de 150 a 350 Atm preferentemente 280 atm, una temperatura de entre 300° C a 500° C, preferentemente 400° C y con un flujo másico de entre 2 y 8 kg/hr, preferentemente 7 Kg/hr. 6. A continuous hydrotermolytic process according to claim 1, wherein the direct current (20) leaves the rector at a pressure of 150 to 350 Atm preferably 280 atm, a temperature between 300 ° C to 500 ° C, preferably 400 ° C and with a mass flow of between 2 and 8 kg / hr, preferably 7 Kg / hr.
7. Un proceso hidrotermolítico continuo de conformidad con la reivindicación 1 , en donde la hidrotermólisis de la corriente presurizada (11 ) de una mezcla homogénea de biomasa de microalgas con sus triglicéridos, es llevada a cabo dentro de un reactor de flujo continuo que comprende: una trayectoria por la cual fluye la corriente presurizada de la mezcla homogénea de biomasa de microalgas con sus triglicéridos (11 ), la cual es calentada en su totalidad de manera equitativa por medios de calentamiento. 7. A continuous hydrotermolytic process according to claim 1, wherein the hydrothermolysis of the pressurized stream (11) of a homogeneous mixture of microalgae biomass with its triglycerides, is carried out within a continuous flow reactor comprising: a path through which the pressurized stream of the homogeneous mixture of microalgae biomass with its triglycerides (11) flows, which is heated in its entirety equally by heating means.
8. Un proceso hidrotermolítico continuo de conformidad con la reivindicación 7, en donde una vez que la mezcla alcanza la temperatura de activación dentro de la trayectoria, la reacción de hidrotermólisis procede y se lleva a cabo la conversión de reactivos a una mezcla específica de derivados de hidrocarburos Nonenos, metil y dimetil pirazino, ciclopentanonas, fenoles, cresoles, propano, propileno, C17, C18 insaturados, C02, así como CO mas aromáticos policíclicos, tetradecenos, naftalenos, Índoles, indenos, aminas y amidas de cadena larga, derivados cumarilicos y coniferilicos en un tiempo de permanencia dentro del reactor de entre 13 a 28 minutos, preferentemente 15 minutos, el cual es el tiempo que le toma a una porción de la corriente presurizada (11 ) recorrer toda la trayectoria de tal forma que conforme la corriente presurizada se acerca al segundo extremo de la trayectoria, la reacción de hidrotermólisis procede y por lo tanto la conversión de los reactivos se completa totalmente. 8. A continuous hydrotermolytic process according to claim 7, wherein once the mixture reaches the activation temperature within the path, the hydrotermolysis reaction proceeds and the conversion of reagents to a specific mixture of derivatives is carried out. of nonenos, methyl and dimethyl pyrazine hydrocarbons, cyclopentanones, phenols, cresols, propane, propylene, C17, unsaturated C18, C02, as well as more aromatic polycyclic COs, tetradecenes, naphthalenes, ions, indenos, amines and long chain amides, coumaryl derivatives and coniferilics in a residence time within the reactor of between 13 to 28 minutes, preferably 15 minutes, which is the time it takes for a portion of the pressurized stream (11) to travel the entire path such that it conforms to the current Pressurized approaches the second end of the path, the hydrotermolysis reaction proceeds and therefore the conversion of the reagents is c completely complete.
9. Un proceso hidrotermolítico continuo de conformidad con la reivindicación 1 , en donde la corriente presurizada de la mezcla homogenizada y emulsificada de agua y biomasa de microalgas con sus triglicéridos (11 ) entra al reactor con una presión de entre 150 atm a 350 atm preferentemente 280 kg/cm2g. 9. A continuous hydrotermolytic process according to claim 1, wherein the pressurized stream of the homogenized and emulsified mixture of water and biomass of microalgae with their triglycerides (11) enters the reactor with a pressure of between 150 atm to 350 atm preferably 280 kg / cm 2 g.
10. Un proceso hidrotermolítico continuo de conformidad con la reivindicación 1 , en donde la corriente presurizada de la mezcla homogenizada y emulsificada de agua y biomasa de microalgas con sus triglicéridos (11 ) entra al reactor con un flujo másico de entre 2 y 8 Kg/hr preferentemente 7 Kg/hr. 10. A continuous hydrotermolytic process according to claim 1, wherein the pressurized stream of the homogenized and emulsified mixture of water and biomass of microalgae with its triglycerides (11) enters the reactor with a mass flow of between 2 and 8 Kg / preferably 7 Kg / hr.
11. Un proceso hidrotermolítico continuo de conformidad con la reivindicación 1 , en donde la corriente presurizada de la mezcla homogenizada y emulsificada de agua y biomasa de microalgas con sus triglicéridos (11 ) que entra al reactor tiene una proporción de agua a biomasa de microalgas con sus triglicéridos es de entre 10 a 50%, preferentemente 35% con respecto al volumen de agua. 11. A continuous hydrotermolytic process according to claim 1, wherein the pressurized stream of the homogenized and emulsified mixture of water and biomass of microalgae with their triglycerides (11) entering the reactor has a The proportion of water to biomass of microalgae with their triglycerides is between 10 to 50%, preferably 35% with respect to the volume of water.
12. Un proceso hidrotermolítico continuo de conformidad con la reivindicación 1 , en donde la corriente presurizada de la mezcla homogenizada y emulsificada de agua y biomasa de microalgas con sus triglicéridos (1 1 ) es generada mediante la succión de dicha mezcla, de un medio contenedor por medio de una bomba de alta presión que eleva la presión de la mezcla desde 0 kg/cm2g hasta alcanzar entre 150 a 350 atm (preferentemente 280 kg/cm2g), en donde la proporción de agua a biomasa de microalgas con sus triglicéridos es de entre 10 a 50 %, preferentemente 35 % con respecto al volumen de agua y en donde las condiciones de la corriente presurizada creada son las siguientes: 12. A continuous hydrotermolytic process according to claim 1, wherein the pressurized stream of the homogenized and emulsified mixture of water and biomass of microalgae with their triglycerides (1 1) is generated by suctioning said mixture from a container medium by means of a high pressure pump that raises the pressure of the mixture from 0 kg / cm 2 g to reach 150 to 350 atm (preferably 280 kg / cm 2 g), where the proportion of water to microalgae biomass with its triglycerides are between 10 and 50%, preferably 35% with respect to the volume of water and where the conditions of the pressurized current created are the following:
Figure imgf000029_0001
13. Un proceso hidrotermolítico continuo de conformidad con la reivindicación 11 , en donde: la corriente presurizada de la mezcla homogenizada y emulsificada de agua y biomasa de microalgas con sus triglicéridos (11 ) es producida mediante la creación de una corriente de agua + KOH (3) y una corriente de biomasa de microalgas con sus triglicéridos (4) las cuales son mezcladas y emulsificadas de manera continua en un mezclador lineal y una vez mezcladas, la corriente de mezcla (7) es posteriormente alimentada a un tanque emulsificador de alta velocidad desde donde es succionada por la bomba de alta presión.
Figure imgf000029_0001
13. A continuous hydrotermolytic process according to claim 11, wherein: the pressurized stream of the homogenized and emulsified mixture of water and biomass of microalgae with their triglycerides (11) is produced by creating a stream of water + KOH ( 3) and a microalgae biomass stream with its triglycerides (4) which are continuously mixed and emulsified in a linear mixer and once mixed, the mixing stream (7) is subsequently fed to a high speed emulsifier tank from where it is sucked by the high pressure pump.
14. Un proceso hidrotermolítico continuo de conformidad con la reivindicación 1 , comprendiendo las etapas subsecuentes de: 14. A continuous hydrotermolytic process according to claim 1, comprising the subsequent steps of:
despresurizar la corriente de salida del reactor (20) hasta una presión subcrítica del orden de 1 atm con el descenso respectivo de la temperatura hasta 345 C por efecto Joule-Thompson para producir una corriente despresurizada (23) que comprende una mezcla de nonenos, metil y dimetil pirazino, ciclopentanonas, fenoles, cresoles, propano, propileno, C17, C18 insaturados, C02, así como CO mas aromáticos policíclicos, tetradecenos, naftalenos, índoles, indenos, aminas y amidas de cadena larga, derivados cumarilicos y coniferilicos; depressurize the reactor outlet stream (20) to a subcritical pressure of the order of 1 atm with the respective temperature drop to 345 C by Joule-Thompson effect to produce a depressurized stream (23) comprising a mixture of nonenos, methyl and dimethyl pyrazine, cyclopentanones, phenols, cresols, propane, propylene, C17, C18 unsaturated, C02, as well as CO more aromatic polycyclic, tetradecene, naphthalene, indole, indenos, amines and long chain amides, coumaryl and coniferyl derivatives;
fraccionar cada uno de los cortes de hidrocarburos de la corriente despresurizada (23) en dos cortes generales, domo y fondos obteniéndose respectivamente: por domo: una corriente (25) de hidrocarburos ligeros, incondensables y agua en fase gas, que comprende nonenos, metil y dimetil pirazino, ciclopentanonas, fenoles, cresoles, propano, propileno, C17, C18 insaturados, C02, así como CO, y por fondo, una corriente (39) que comprende: aromáticos policíclicos, tetradecenos, naftalenos, índoles, indenos, aminas y amidas de cadena larga, derivados cumarilicos y coniferilicos estos últimos subproductos de la despolimerización de la pared celular de la biomasa de microalgas.  to divide each one of the hydrocarbon cuts of the depressurized stream (23) into two general cuts, dome and bottoms respectively obtaining: by dome: a stream (25) of light, non-condensable hydrocarbons and water in gas phase, comprising nonenos, methyl and dimethyl pyrazine, cyclopentanones, phenols, cresols, propane, propylene, C17, C18 unsaturated, C02, as well as CO, and in the background, a stream (39) comprising: polycyclic aromatics, tetradecenes, naphthalenes, ions, indennes, amines and long chain amides, coumaryl and coniferyl derivatives these latter by-products of the depolymerization of the cell wall of the microalgae biomass.
15. Un proceso hidrotermolítico continuo de conformidad con la reivindicación 14, en donde la corriente de domo es alimentada a un a un condensador en donde se separa: 15. A continuous hydrotermolytic process according to claim 14, wherein the dome current is fed to a capacitor where it separates:
una corriente superior de venteo que comprende aproximadamente: 11 % de furfurales, 70% de CO2, 19% de propano a un flujo de aproximadamente 0.20 Kg/hr; una corriente intermedia (31 ) que comprende hidrocarburos HCO, C9 a C12, Bencenos, C8-C6 cíclicos;  an upper vent stream comprising approximately: 11% furfural, 70% CO2, 19% propane at a flow of approximately 0.20 Kg / hr; an intermediate stream (31) comprising hydrocarbons HCO, C9 to C12, Benzenes, C8-C6 cyclic;
una corriente inferior que comprende condensados ligeros y agua la cual se manda a un tanque de agua recuperada para su reinyección al proceso, ya que dicha agua contiene algunos hidrocarburos.  a lower stream comprising light condensates and water which is sent to a recovered water tank for re-injection into the process, since said water contains some hydrocarbons.
16. Un proceso hidrotermolítico continuo de conformidad con la reivindicación 15, en donde: la corriente intermedia es dividida en una primera corriente y una segunda corriente similares, mediante un derivador, en donde la primera corriente es reciclada al fraccionador primario con el fin de realizar la rectificación de la corriente con los gases y vapores que se dirigen al domo y en donde la segunda corriente es mezclada con una corriente (49) que comprende lignina, celulosa, agua y triglicéridos y con una corriente (43) que comprende dióxido de carbono, ciclohexano, propano, lignina, ácido fórmico, agua, metanol y furfurales, mediante un mezclador para crear una corriente mezclada de hidrocarburos (51 ) con todos los componentes de las corrientes (33), (49) y (43), es decir: noneno, dióxido de carbono, ciclohexano, propano, lignina, benceno, ácido fórmico, celulosa, agua, triglicéridos, metanol, y furfurales. 16. A continuous hydrotermolytic process according to claim 15, wherein: the intermediate stream is divided into a similar first and second stream, by a shunt, wherein the first stream is recycled to the primary fractionator in order to perform the rectification of the stream with the gases and vapors that go to the dome and where the second stream is mixed with a stream (49) comprising lignin, cellulose, water and triglycerides and with a stream (43) comprising carbon dioxide , cyclohexane, propane, lignin, formic acid, water, methanol and furfurals, using a mixer to create a mixed hydrocarbon stream (51) with all the components of the streams (33), (49) and (43), that is : noneno, dioxide carbon, cyclohexane, propane, lignin, benzene, formic acid, cellulose, water, triglycerides, methanol, and furfurals.
17. Un proceso hidrotermolítico continuo de conformidad con todas las reivindicaciones anteriores en donde la corriente de hidrocarburos (51 ) es impulsada por una bomba a través de un mezclador, que agrega a la corriente de hidrocarburos (51 ), hidrógeno en una cantidad de entre 50 gr/hr a 200 gr/h, preferentemente 100 gr/h para mantener la emulsificación dispersión de la corriente hidrogeno antes de un precalentador de reacción primario, de esta manera creando una corriente (54) que comprende: los componentes de la corriente de hidrocarburos HCO (51 ) más hidrógeno. 17. A continuous hydrotermolytic process according to all the preceding claims wherein the hydrocarbon stream (51) is driven by a pump through a mixer, which adds hydrogen to the stream of hydrocarbons (51) in an amount between 50 gr / hr at 200 gr / h, preferably 100 gr / h to keep the emulsification dispersion of the hydrogen stream before a primary reaction preheater, thus creating a stream (54) comprising: the components of the stream of HCO hydrocarbons (51) plus hydrogen.
18. Un proceso hidrotermolítico continuo de conformidad con todas las reivindicaciones anteriores comprendiendo adicionalmente hidrodesoxigenar e hidrogenar la corriente de hidrocarburos mezclada con hidrógeno precalentada (55) mediante su alimentación a un reactor empacado de múltiples cuerpos con níquel molibdeno y níquel cobalto, trabajando a: 49 Kg/cm2 y 190°C utilizando agua como fuente de hidrogeno, con enfriadores de interpaso para reducir el riesgo de coquización, en donde a la salida del primer par de cuerpos, la corriente efluente del reactor se ha enriquecido con toluenos, etilbencenos, C8, C9, C1 1 , C12 y pesados como cresoles y C14 a C16 así como nitrilos de cadena larga superiores a C18, en donde en el último par de cuerpos la hidrogenación lleva a la formación de dimetil hexanos y compuestos C9 a C8 alifáticos y biodiesel y en donde la corriente de salida (66) del reactor empacado comprende específicamente: noneno, dióxido de carbono, ciclohexano, propano, lignina, benzeno, ácido fórmico, celulosa, agua, triglicéridos, HDC-CELHDR-01 , furfurales, hidrogeno, glicerol, ALC-C18-PARAF, metano, HYD-CEL-C5-OL, PM-grupo-C¡clohexano, PM-arom-OL, HDC-CEL-HDR-02. 18. A continuous hydrotermolytic process in accordance with all the preceding claims further comprising hydrodeoxygenating and hydrogenating the hydrocarbon stream mixed with preheated hydrogen (55) by feeding it into a multi-body packed reactor with molybdenum nickel and cobalt nickel, working at: 49 Kg / cm2 and 190 ° C using water as a source of hydrogen, with intercoolers to reduce the risk of coking, where at the exit of the first pair of bodies, the reactor effluent stream has been enriched with toluenes, ethylbenzenes, C8 , C9, C1 1, C12 and heavy as cresols and C14 to C16 as well as long chain nitriles higher than C18, where in the last pair of bodies hydrogenation leads to the formation of dimethyl hexanes and C9 to C8 aliphatic compounds and biodiesel and wherein the output stream (66) of the packed reactor specifically comprises: noneno, carbon dioxide, cyclohexane, propane , lignin, benzene, formic acid, cellulose, water, triglycerides, HDC-CELHDR-01, furfurals, hydrogen, glycerol, ALC-C18-PARAF, methane, HYD-CEL-C5-OL, PM-group-C-chlorhexane, PM-arom-OL, HDC-CEL-HDR-02.
19. Un proceso hidrotermolítico continuo de conformidad con todas las reivindicaciones anteriores comprendiendo adicionalmente las etapas de: 19. A continuous hydrotermolytic process in accordance with all of the preceding claims further comprising the steps of:
enfriar la corriente (66) mediante su paso por un enfriador primario que enfría la corriente a una temperatura de entre 180-200°C” produciéndose una corriente enfriada (67); alimentar la corriente enfriada (67) a un separador trifásico en donde se obtiene una corriente (69) de Hidrogeno, Propano y Metano que comprende los hidrocarburos volátiles, una corriente (71 ) de hidrocarburos líquidos C8, C9, C12, C16 y C18 y algunos aromáticos que comprende los cortes objetivo y una corriente (70) de anillos aromáticos densos, residuos de polimerización de celulosa que comprende condensados pesados más agua; cooling the current (66) by passing through a primary cooler that cools the current to a temperature between 180-200 ° C ”producing a cooled current (67); feeding the cooled stream (67) to a three-phase separator where a stream (69) of Hydrogen, Propane and Methane comprising volatile hydrocarbons, a stream (71) of liquid hydrocarbons C8, C9, C12, C16 and C18 is obtained and some aromatics comprising the target cuts and a stream (70) of dense aromatic rings, cellulose polymerization residues comprising heavy condensates plus water;
enviar la corriente (71 ) de hidrocarburos líquidos C8, C9, C12, C16 y C18 y algunos aromáticos a una columna secundaria que funciona a una temperatura de 400 C y que incluye un calentador y un rehervidor, en donde se separa por el domo de la columna secundaria una corriente (73) de nafta más ligeros más incondensables los cuales pueden ser aprovechados como combustibles; por la zona intermedia de la columna secundaria se crea una corriente (75) de Bioturbosina y por el fondo se crea una corriente (78) de biodiesel y pesados.  send the stream (71) of liquid hydrocarbons C8, C9, C12, C16 and C18 and some aromatics to a secondary column that operates at a temperature of 400 C and that includes a heater and a reboiler, where it is separated by the dome of the secondary column is a stream (73) of lighter gasoline, more tireless which can be used as fuels; A stream (75) of Bioturbosin is created in the middle of the secondary column and a stream (78) of biodiesel and heavy is created in the bottom.
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