Chemical synthesis comprising heat treatment by intermittent dielectric heating, combined with a recycling system

Abstract

This invention relates to the design of a process by intermittent dielectric heating combined with a recycling system. This process consists in subjecting reagents to electromagnetic waves selected in the frequencies ranging between 300 GHz and 3 MHz intermittently using a recycling system. This process enables the treatment of oils that are hardly absorbent as well as great investment savings. This process enables operation on different scales, whether in laboratories, on a semi-industrial or industrial scale, without forfeiting the advantages of continuous dielectric heating.

1 . A process of heat treatment in a chemical synthesis comprising circulating one or more reagents in a recycling system;
 subjecting said reagent(s) to electromagnetic waves intermittently, wherein the reagent(s) is/are subjected to said electromagnetic waves in one part of the recycling system and not in another part of the recycling system;   wherein said heating is intermittent dielectric heating.   
     
     
         2 . The process according to  claim 1 , wherein the electromagnetic waves are selected in the frequencies ranging between 300 GHz and 3 MHz. 
     
     
         3 . The process according to  claim 2 , wherein the frequencies are microwave frequencies (MW) from about 300 MHz to about 30 GHz; or high frequencies (HF) from about 3 MHz to about 300 MHz. 
     
     
         4 . The process according to  claim 1 , wherein the reagent(s) are not continuously exposed to dielectric heating but wherein all reaction mixture molecules are intermittently subjected to dielectric heating. 
     
     
         5 . The process according to  claim 1 , wherein the reagent(s) are selected from the group consisting of products that hardly absorb electromagnetic waves, products that are highly absorbent of said electromagnetic waves and a mixture of both, wherein said process is either not enhanced or enhanced with one or more hardly or highly absorbent catalysts or additives and/or process gas. 
     
     
         6 . The process according to  claim 5 , wherein the reagent(s) is/are selected from the group consisting of vegetable oils, animal fats or oils, compounds of animal or vegetable oils, hydrocarbons, saturated alkanes, saturated and/or unsaturated esters, saturated and/or unsaturated acids; alcohols; epoxides; amino alcohols; and amines. 
     
     
         7 . The process according to  claim 6 , wherein
 said vegetable oils are selected from the group consisting of rapeseed oil, sunflower oil, peanut oil, olive oil, walnut oil, corn oil, soy oil, linseed oil, safflower oil, apricot kernel oil, sweet almond oil, hemp oil, grassed oil, copra oil, palm oil, cottonseed oil, Babes oil, jujube oil, sesame oil, argon oil, milk-thistle oil, gourds oil, raspberry oil, Carnage oil, enema oil, poppies oil, Brazil nut oil, castor oil, dehydrated castor oil, hazelnut oil, wheat germ oil, borage oil, oenothera oil, Tung oil, and tall oil;   said animal fats or oils are selected from the group consisting of sperm-whale oil, dolphin oil, whale oil, seal oil, sardine oil, herring oil, shark (dog-fish) oil, cod-liver oil, neatsfoot oil, as well as beef, pork, horse, and mutton tallow (marrow);   said compounds of animal or vegetable oils are selected from the group consisting of squalene extracted from non-saponifiable fats of vegetable oils: olive oil, peanut oil, rapeseed oil, corn germ oil, cottonseed oil, linseed oil, wheat germ oil, rice bran oil, and squalene contained in large amounts in shark (dog-fish) oil;   said hydrocarbons are unsaturated, alone or in a mixture, alkene, or a saturated or unsaturated alkane;   said saturated and/or unsaturated esters are selected from the group consisting of alone or in a mixture, one or several esters obtained by esterification between a monoalcohol and/or polyol and at least one saturated and/or unsaturated fatty acid; waxes; butters, phospholipids; spingolipids; and glucolipids;   said saturated and/or unsaturated acids are selected from the group consisting of alone or in a mixture, one or several saturated acids, one or several monounsaturated fatty acids; one or several polyunsaturated fatty acids, one or several acids comprising conjugated dienes or conjugated trienes, and one or several acids comprising one or several hydroxyl groups;   said alcohols are selected from the group consisting of glycerol, sorbitol, sucrose, mannitol, xylitol, neopentylglycol, pentaerythritol, saccharose, galactose, glucose, maltose, maltotriose, fructose, maltitol, lactitol, lactose, ribose, mellibiose, cellobiose, gentiobiose, altrose, gulose, polyalkyleneglycols, polyglycerols, polyphenols, alkylpolyglucosides, polyglucosides, glycol, pentaerythritol, 1,2-ethanediol, 1,4-butanediol; 1,6-hexanediol, aminoalcohols, epoxyalcohols, saturated or unsaturated fatty alcohols, linear or branched alcohols, vitamins (for example, tocopherol, ascorbic acid, retinol), sterols (including phytosterols), hemiacetals, aminoalcohols, epoxyalcohols, propanol, ethanol, methanol, tetradecyl alcohol and their analogs;   said epoxides are selected from the group consisting of alone or in a mixture, vernolic acid, coronaric acid, 1,2-epoxy-9-decene, 3-4-epoxy-1-butene, 2-3-epoxy-1-propanol, and fatty esters obtained by esterification between 2-3-epoxy-1-propanol and a fatty acid;   said amino alcohols are selected from the group consisting of alone or in a mixture, monoethanol amine (MEA), diethanol amine (DEA), triethanol amine (TEA), 3-amino-1,2-propanediol, 1-amino-2-propanol; and 2-2′-aminoethoxy ethanol; and   said amines are selected from the group consisting of ammonia, primary, secondary and tertiary alkyl amines, fatty amines, amino alcohols, triethanol amine (TEA), 3-amino-1,2-propanediol, 1-amino-2-propanol), and ethoxylated amines, wherein said amines can be saturated or unsaturated, linear or branched.   
     
     
         8 . The process according to  claim 6 , wherein the animal or vegetable fats and oils undergo a prior treatment intended to make them more reactive or less reactive. 
     
     
         9 . The process according to  claim 6 , wherein the alcohols undergo a prior treatment to make them more reactive or less reactive. 
     
     
         10 . The process according to  claim 1 , wherein said process uses a catalyst or additive selected from the group consisting of the common acid catalysts, the common basic catalysts, acid and/or basic resins, zeolithes and enzymes, carbon blacks, and activated carbon fibers. 
     
     
         11 . The process according to  claim 1 , wherein the heat treatments are carried out under a normal atmosphere, an oxygen-rich atmosphere, or an inert atmosphere. 
     
     
         12 . The process according to  claim 1  wherein said chemical synthesis includes a heat treatment and the use of a single reagent, or a mixture of reagents, in variable proportions, with or without catalysts, with or without process gas. 
     
     
         13 . The process according to  claim 12 , wherein said chemical synthesis is selected from the group consisting of esterification, transesterification, epoxidation, sulfation, phosphatation, hydrogenation, peroxidation, isomerization, dehydration, quaternization, amidation, polymerization, polycondensation, decolorizing, deodorizing, and systems for eliminating volatile compounds. 
     
     
         14 . The process according to  claim 1 , wherein said chemical synthesis is a lipochemistry reaction. 
     
     
         15 . The process according to  claim 1 , wherein said chemical synthesis is selected from the group consisting of manufacturing polymers of unsaturated fatty acids, manufacturing polymers of unsaturated fatty acid esters, manufacturing polymers of unsaturated hydrocarbons and manufacturing derivatives of these products using intermittent dielectric heating under microwaves. 
     
     
         16 . The process according to  claim 1 , wherein said chemical synthesis results in the synthesis of polyglycerol, polyglycerol esters, polyglycerol-6 dioleate, and/or polyglycerol-2 tristearate. 
     
     
         17 . The process according to  claim 3 , wherein said microwave frequency is a standing frequency at 915 MHz (authorized frequency with a tolerance of 1.4%) or at 2.45 GHz (authorized frequency with a tolerance of 2%). 
     
     
         18 . The process according to  claim 3 , wherein said high frequency is a standing frequency at 13.56 MHz with a tolerance of 0.05% or at 27.12 MHz with a tolerance of 0.6%. 
     
     
         19 . The process according to  claim 8 , wherein the prior treatment is selected from the group consisting of hydrogenation, hydroxylation, epoxidation, phosphatation, sulfonation reactions or combinations thereof. 
     
     
         20 . The process according to  claim 10 , wherein said common acid catalyst is selected from the group consisting of para toluene sulfonic acid, sulfuric acid, phosphoric acid, perchloric acid and combinations thereof. 
     
     
         21 . The process according to  claim 10 , wherein said common basic catalyst is selected from the group consisting of soda, potash, alcoholate of alkaline metals, alcoholate of alkaline-earth metals, sodium acetate, triethyl amines, pyridine derivatives and combinations thereof. 
     
     
         22 . The process according to  claim 11 , wherein the heat treatments are carried out in an inert atmosphere. 
     
     
         23 . The process according to  claim 1 , wherein the reagent(s) are exposed to electromagnetic waves generated with:
 one (1) 6 kW magnetron generator operating at a frequency of about 2450 MHz for laboratory treatments, or   one (1) 60 kW magnetron generator operating at a frequency of about 915 MHz for industrial treatments,   
       
         
           
                 
                 
                 
                 
                 
                 
               
                     
                 
                     
                     
                     
                     
                   Number of 
                     
                 
                     
                   D (mm) 
                   H (mm) 
                   Unit Vexp 
                   reactors 
                   Total Vexp 
                 
                     
                 
                     
                 
                 
                 
                 
                 
                 
                 
                 
                 
               
                   Pilot 
                   30 
                   45 
                   32 
                   mL 
                   1 
                   32 
                   mL 
                 
                   Industrial 
                   100 
                   124 
                   1 
                   L 
                   4 
                   4 
                   L 
                 
                     
                 
             
                
                
                
                
               
               
                
               
            
             
                
                
                
               
            
           
         
         wherein: 
         D=diameter of cylindrical reactors=2R, 
         H=height of waveguide, 
         Unit Vexp=volume exposed to waves on a continuous basis for one reactor, 
         Total Vexp=volume exposed to waves on a continuous basis for both reactors,
     V  (exposed to the field)=π* R   2   *H.  
 
 
       
     
     
         24 . A device for the implementation of the process as claimed in  claim 1 , wherein it comprises or consists of:
 A)
 pumps 
 reactors subjected to the electromagnetic field 
 a dielectric system: chimney applicators, generator waveguides, iris, short-circuit piston, cooling systems 
 buffer reactors 
 tanks 
 a gas circuit, preferably for an inert gas such as nitrogen 
 condensers 
 measuring devices 
   and in particular B)
 pumps 
   The pump(s) is/are of the variable flow type.   It can be a feeder dosing pump and/or a recycling pump and/or a vacuum pump. The outflow of the recycling pump influences the time required for a molecule to transit under the waves.   The pumps can be selected, for purpose of indication, from among vane pumps or piston pumps.
 one or several reactors subjected to electromagnetic waves 
   a) The reactors subjected to the electromagnetic field do not absorb waves (pyrex, quartz, etc.).   b) They are typically cylindrical in shape.   c) They are positioned inside the applicators.
 a dielectric system: energy applicators, chimneys, waveguides, generator, iris, and short-circuit piston, cooling systems. 
   a) The applicators are formed by singlemode cavities that resonate at the transmission frequency according to a radiation in the direction of the waveguide.   b) The chimneys prevent wave leakage to the outside of the waveguide. They are preferably of a conical cylindrical shape, as indicated in Application FR No. 0108906 filed by this Applicant for limiting the presence of electric arcs.   c) The waveguide(s) carries/carry the electromagnetic waves. Each waveguide can be subdivided into two—and only two—waveguides.   d) The generators used are microwave or high-frequency generators.   e) The microwave (MW) frequencies range from about 300 MHz to about 30 GHz, preferably standing at 915 MHz (authorized frequency with a tolerance of 1.4%) or at 2.45 GHz (authorized frequency with a tolerance of 2%).   f) The high frequencies (HF) range from about 3 MHz to about 300 MHz, preferably standing at 13.56 MHz (authorized frequency with a tolerance of 0.05%) or at 27.12 MHz (authorized frequency with a tolerance of 0.6%).   g) The generators are outfitted with a safety feature that allows the incident waves to pass through and that diverts the reflected waves to a water load in which the waves are absorbed.   h) These generators also require the use of iris, of a shortcircuit piston in order to decrease the reflected power and to promote absorption of the generator-transmitted power by the reaction mixture.   i) The system is outfitted with cooling systems in order to avoid any overheating.
 buffer reactors 
   The buffer reactors permit treating a larger amount of reaction mixture.
 tanks 
   The system is outfitted with one or several feeder tank(s), receiver tank(s), filtration tank(s).
 gas circuits 
   The heat treatments are carried out under a normal atmosphere, or an oxygen-rich atmosphere or, preferably, an inert atmosphere.
 measuring devices 
   The system is outfitted with measuring devices such as manometers, thermocouples, flowmeters.   
     
     
         25 . The device according to  claim 24 , wherein the process can be used in dynamics or in continuum. 
     
     
         26 . The device according to  claim 24 , wherein it uses as energy applicator:
 type of energy applicators   As regards high frequency applicators, they consist mainly in:
 applicators of the capacitive type formed by two condenser armatures between which the generator's high-frequency voltage is applied. They are used for the heat treatment of materials whose volume constitutes a parallelepiped, one side of which is sufficiently thick (>10 mm). 
 applicators with rods for planar materials. These applicators are made up of tubular or rod-shaped electrodes. They are used for the heat treatment of materials whose volume constitutes a parallelepiped, one side of which is insufficiently thick (<10 mm). 
 applicators for filiform materials, formed by loops. 
   As regards microwave applicators, we can cite:
 the localized-field applicators: singlemode cavity 
 the diffuse-field applicators: multimode cavity 
 the near-field applicators: waveguide with radiating antennas 
   
     
     
         27 . The device according to  claim 24 , wherein:
 The “singlemode” system (localized field) which is formed by singlemode cavities resonating at the transmission frequency according to a radiation in the direction of the waveguide, is preferable to the “multimode” (diffuse field).   The applicator is outfitted with regular cylindrical chimneys.   The device includes good venting with humid air or with some other comparable gas as regards its dielectric constants (for example, sulfur hexafluoride SF6 under 1 bar) or chimneys with specially adapted shapes so as to eliminate static electricity formed on the outside wall of the reactor.   
     
     
         28 . The device according to  claim 24 , wherein a specific chimney geometry is used. 
     
     
         29 . The device according to  claim 24 , wherein the reactor is typically cylindrical in shape, and its diameter may not exceed the width of the waveguide. 
     
     
         30 . The device according to  claim 24 , wherein in the case of singlemode microwave applicators, under 2450 MHz, the waveguide width recommended in order to remain in the TE 0.1 (Transverse Electric) mode stands between about 70 and 100 mm, and more specifically at 90 mm. 
     
     
         31 . The device according to  claim 24 , wherein in the case of single mode microwave applicators, under 915 MHz, the waveguide width recommended to remain in the TE 0.1 (Transverse Electric) mode is about 250 mm. 
     
     
         32 . The device according to  claim 24 , wherein the dielectric system comprises applicators, chimneys, waveguides, a generator, iris, a shortcircuit piston, cooling systems, as follows:
 The applicators are formed by singlemode cavities that resonate at the transmission frequency according to a radiation in the direction of the waveguide.   The chimneys prevent wave leakage to the outside of the waveguide. They are preferably of a conical cylindrical shape, as indicated in Patent Application FR No. 0108906 filed by this Applicant for limiting the presence of electric arcs.   The waveguide(s) carries/carry the electromagnetic waves. Each waveguide can be subdivided into two—and only two—waveguides.   The device also uses iris, short-circuit piston in order to lower the reflected power and to promote absorption of the generated-transmitted power by the reaction mixture.   
     
     
         33 . The process according to  claim 7 , wherein the fats, oils, or their derivatives are an isolated reagent, or a reaction mixture comprising two or more compounds; which reaction mixture can comprise equivalent proportions of each compound, or some compounds can be majority compounds. 
     
     
         34 . The device according to  claim 28 , wherein said chimneys have a conical or cylindrical shape. 
     
     
         35 . A process of heat treatment in a chemical synthesis, comprising
 circulating one or more reagents in a recycling system;   subjecting said reagent(s) to electromagnetic waves intermittently, wherein the reagent(s) is/are subjected to said electromagnetic waves continuously in one part of the recycling system and not in another part of the recycling system;   wherein said electromagnetic waves are selected in the frequencies ranging between 300 GHz and 3 MHz.   
     
     
         36 . A process of heat treatment in a chemical synthesis comprising
 circulating one or more reagents in a recycling system; and   subjecting said reagents to electromagnetic waves intermittently, wherein the reagents are subjected to said electromagnetic waves in one part of the recycling system and not in another part of the recycling system;   wherein said heat treatment is intermittent dielectric heating, wherein at least one of said reagents is a compound which hardly absorbs electromagnetic waves, and wherein the reagents are exposed to electromagnetic waves selected in the frequencies ranging between 300 GHz and 3 MHz.   
     
     
         37 . The process according to  claim 1 , wherein said process is carried out on a production scale using a 915 MHz generator.