U.S. patent application number 10/540518 was filed with the patent office on 2006-10-12 for chemical synthesis comprising heat treatment by intrmittent dielectric heating combined with a recycling system.
This patent application is currently assigned to Aldivia SA. Invention is credited to Pierre Charlier De Chily, Mikaele Raynard.
Application Number | 20060228088 10/540518 |
Document ID | / |
Family ID | 32406540 |
Filed Date | 2006-10-12 |
United States Patent
Application |
20060228088 |
Kind Code |
A1 |
Charlier De Chily; Pierre ;
et al. |
October 12, 2006 |
Chemical synthesis comprising heat treatment by intrmittent
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.
Inventors: |
Charlier De Chily; Pierre;
(Irigny, FR) ; Raynard; Mikaele; (St Brevin Les
Pins, FR) |
Correspondence
Address: |
ROTHWELL, FIGG, ERNST & MANBECK, P.C.
1425 K STREET, N.W.
SUITE 800
WASHINGTON
DC
20005
US
|
Assignee: |
Aldivia SA
49, rue des Sources
Saint-Genis-Laval
FR
69230
|
Family ID: |
32406540 |
Appl. No.: |
10/540518 |
Filed: |
December 17, 2003 |
PCT Filed: |
December 17, 2003 |
PCT NO: |
PCT/FR03/03752 |
371 Date: |
April 13, 2006 |
Current U.S.
Class: |
385/147 |
Current CPC
Class: |
H05B 6/62 20130101; B01J
19/129 20130101; B01J 2219/00141 20130101; B01J 2219/0892 20130101;
H05B 6/806 20130101; B01J 19/2465 20130101; B01J 2219/0877
20130101; Y02P 20/582 20151101; H05B 6/10 20130101; B01J 19/126
20130101 |
Class at
Publication: |
385/147 |
International
Class: |
G02B 6/00 20060101
G02B006/00 |
Foreign Application Data
Date |
Code |
Application Number |
Dec 23, 2002 |
FR |
02/16743 |
Claims
1. A heat treatment process in a chemical synthesis, of the
dielectric type, characterized in that said dielectric heating is
carried out intermittently, that is to say, the reagent or reagents
is/are subjected to electromagnetic waves intermittently, in
combination with a recycling system.
2. A process as claimed in claim 1 wherein the electromagnetic
waves are selected in the frequencies ranging between 300 GHz and 3
MHz.
3. A process as claimed in claim 2 wherein the frequencies are
selected from among: MW frequencies and HF Those microwave
frequencies (MW) that 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%). Those high frequencies (HF) that 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%).
4. A process as claimed in claim 1, wherein the entire reaction
volume is not continuously exposed to dielectric waves but wherein
all reaction mixture molecules are intermittently subjected to the
field.
5. A process as claimed in claim 1, wherein the reagent(s) can be
selected from among those products that hardly absorb the
electromagnetic waves or those products that are highly absorbent
of said waves or a mixture of both, whether or not enhanced with
one or several hardly or highly absorbent catalysts or additives
and/or process gas.
6. A process as claimed in claim 5 wherein the reagent(s) is/are
selected from among: vegetable oils 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, Brazilnut oil, castor
oil, dehydrated castor oil, hazelnut oil, wheat germ oil, borage
oil, oenothera oil, Tung oil, or tall oil. animal fats or oils
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, mutton tallow (marrow). compounds of
animal or vegetable oils 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) or squalene contained in large amounts in shark (dog-fish)
oil. hydrocarbons unsaturated: alone or in a mixture, an alcene,
for example one or several terpenic hydrocarbons, that is to say,
one or several polymers of isoprene, or one or several polymers of
isobutene, of styrene, of ethylene, of butadiene, of isoprene, of
propene, or one or several copolymers of these alcenes. saturated:
alcanes, for example ethane, propane. saturated and/or unsaturated
esters 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; glucolipids. saturated and/or
unsaturated acids alone or in a mixture, one or several saturated
acids such as caprylic acid, lauric acid, myristic acid, palmitic
acid, stearic acid, arachidic acid, behenic acid, lignoceric acid,
cerotic acid, one or several monounsaturated fatty acids such as
oleic acid, palmitoleic acid, myristic acid, petroselenic acid,
erucic acid; one or several polyunsaturated fatty acids such as for
example linoleic acid, alpha and gamma linolenic acids, arachidonic
acid; 5c,8c, 11 c, 14c-eicosapentaenoic acid (EPA), 4c,7c, 10c,
13c, 16c, 19c-docosahexaenoic acid (DHA), one or several acids
comprising conjugated dienes or conjugated trienes such as licanic
acid, isomers of linoleic and linolenic acids; one or several acids
comprising one or several hydroxyl groups such as ricinoleic acid.
alcohols 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 (for
example, diethanol amine (DEA), triethanol amine (TEA),
3-amino-1,2-propanediol), epoxyalcohols, saturated or unsaturated
fatty alcohols (for example, myristyl alcohol, oleyl alcohol,
lauryl alcohol), linear or branched alcohols, vitamins (for
example, tocopherol, ascorbic acid, retinol), sterols (including
phytosterols), hemiacetals (for example, 1-ethoxy-1-ethanol),
aminoalcohols (for example, 2-2'-aminoethoxy ethanol),
epoxyalcohols (for example, 2-3-epoxy-1-propanol), propanol,
ethanol, methanol, tetradecyl alcohol and their analogs. epoxides
alone or in a mixture, vernolic acid, coronaric acid,
1,2-epoxy-9-decene, 3-4-epoxy-1-butene, 2-3-epoxy-1-propanol, fatty
esters obtained by esterification between 2-3-epoxy-1-propanol and
a fatty acid (for example, Cardura E10.RTM.)). amino alcohols alone
or in a mixture, monoethanol amine (MEA), diethanol amine (DEA),
triethanol amine (TEA), 3-amino-1,2-propanediol,
1-amino-2-propanol; 2-2'-aminoethoxy ethanol. amines ammonia,
primary, secondary and tertiary alkyl amines (for example, methyl
amine, dimethyl amine, trimethyl amine, diethyl amine), fatty
amines (for example, oleic amines, coconut alkyl amines), amino
alcohols (for example, monoethanol amine (MEA), diethanol amine
(DEA), triethanol amine (TEA), 3-amino-1,2-propanediol,
1-amino-2-propanol), ethoxylated amines (2-2'-aminoethoxy ethanol,
amino-1-methoxy-3-propane), which amines can be saturated or
unsaturated, linear or branched.
7. A process as claimed in claim 6, wherein the animal or vegetable
fats and oils, as well as their derivatives, can undergo a prior
treatment intended to make them on the one hand more reactive or on
the other hand less reactive (both an isolated reagent and a
reaction mixture comprising two or several compounds, which
reaction mixtures can comprise equivalent proportions of each
compound, or some compounds can be majority compounds).
8. A process as claimed in claim 6, wherein the alcohols as well as
their derivatives can undergo a prior treatment intended to make
them on the one hand more reactive or on the other hand less
reactive, such as for example hydrogenation, hydroxylation,
epoxidation, phosphitation, sulfonation.
9. A process as claimed in claim 1, wherein it uses as catalysts or
additives: catalysts the common acid catalysts (para toluene
sulfonic acid, sulfuric acid, phosphoric acid, perchloric acid,
etc.), the common basic catalysts (soda, potash, alcoholate of
alkaline metals and of alkaline-earth metals, sodium acetate,
triethyl amines, pyridine derivatives, etc.), acid and/or basic
resins of the Amberlite.TM., Amberlyst.TM., Purolite.TM.,
Dowex.TM., Lewatit.TM. types, zeolithes and enzymes, carbon blacks,
and activated carbon fibers.
10. A process as claimed in claim 1, wherein the volume exposed to
electromagnetic waves is with: one (1) 6 kW magnetron generator
operating at the 2450 MHz frequency for the laboratory treatments
one (1) 60 kW magnetron generator operating at the 915 MHz
frequency for the industrial treatments TABLE-US-00006 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)=.pi.*R.sup.2*H
11. 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.
12. A device as claimed in claim 11, wherein the process can be
used in dynamics or in continuum.
13. A device as claimed in claims 11 or 12, 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
14. A device as claimed in claim 11, 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.
15. A device as claimed in claim 11, wherein a specific chimney
geometry is used, in particular a conical chimney.
16. A device as claimed in claim 11, wherein the reactor is
typically cylindrical in shape, and its diameter may not exceed the
width of the waveguide.
17. A device as claimed in claim 11, 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.
18. A device as claimed in claim 11, wherein in the case of
singlemode microwave applicators, under 915 MHz, the waveguide
width recommended to remain in the TE 0.1 (Transverse Electric)
mode is about 250 mm.
19. A device as claimed in claim 11, 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.
20. A Process as claimed in claim 1, characterized in that the heat
treatments are carried out under a normal atmosphere, or an
oxygen-rich atmosphere, or preferably under an inert
atmosphere.
21. Applications of the process as claimed in claim 1 in all "heat
applications" chemical syntheses involving 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.
22. Applications as claimed in claim 21, wherein as "heat
applications" we can cite, as non-limitative examples, such
reactions as esterification, transesterification, epoxidation,
sulfatation, phosphitation, hydrogenation, peroxidation,
isomerization, dehydration, quaternization, amidation,
polymerization, polycondensation, and all the common treatments
such as decolorizing, deodorizing, and the other systems for
eliminating volatile compounds.
23. Applications of the process as claimed in claim 1 to all
"lipochemistry" reactions.
24. Applications of the process as claimed in claim 1 for
manufacturing polymers of unsaturated fatty acids, of unsaturated
fatty acid esters, of unsaturated hydrocarbons or of derivatives of
these products using intermittent dielectric heating under
microwaves.
25. Applications of the process as claimed in claim 1 specific to
the synthesis of: polyglycerol polyglycerol esters polyglycerol-6
dioleate polyglycerol-2 tristearate
Description
BACKGROUND OF THE INVENTION
[0001] Regardless of the complexity of the molecule to be
manufactured, chemists always try to find a way to reduce the
reaction time and the number of steps required for synthesizing a
molecule because of a constant concern regarding costs and
profitability.
[0002] Many studies have been conducted for the purpose of
controlling the various parameters capable of influencing the
unfolding and speed of a reaction. Additives, such as solvents,
catalysts, have been widely used. Although these compounds
stimulate the reaction medium, they are sometimes toxic to man and
the environment, and they require expensive post-treatments such as
neutralization, washing, drying, filtration.
[0003] Today, the trend is toward manufacturing processes that are
simple, low in cost, and respectful of man and his environment.
[0004] Some physical processes have been tested: the use of
ultrasounds, high frequencies, and recently, microwaves.
[0005] The various tests conducted using dielectric heating, that
is to say, heating under microwave frequencies or high frequencies,
have shown the potential value of this new technology: indeed,
dielectric heating permits considerable time and energy savings,
combined with lower investment costs; the reactions no longer
require the use of any solvent or catalyst; burn-up and unwanted
reactions are avoided.
[0006] Although today there are available many types of
high-frequency and microwave applicators, they are all nonetheless
configured in such a way that the reaction medium is continuously
exposed to electromagnetic waves in order to be able to benefit
from the advantages inherent in this new technology. The amount of
material processed in this manner is limited, because it depends on
the dimensions of the waveguides that are themselves
standardized.
SUMMARY OF THE INVENTION
[0007] The applicant has discovered a new heat treatment process
involved in a chemical synthesis: namely, intermittent dielectric
heating combined with a recycling system. The reagents are
subjected to electromagnetic waves on an intermittent basis using a
recycling system. The electromagnetic waves are selected among the
frequencies ranging from 300 GHz to 3 MHz.
[0008] This process is original and low in cost. Additionally, 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.
Applications:
[0009] The invention makes it possible to carry out efficient and
rapid heat treatments on different scales, whether in laboratories,
on a semi-industrial or on industrial scale.
[0010] This invention relates to all "heat applications," that is
to say, the chemical syntheses involving a heat treatment and
featuring a sole reagent, or a mixture of reagents, in variable
proportions, with or without catalysts, with or without process
gas.
[0011] As "heat applications," we can cite, as non-limitative
examples, such reactions as esterification, transesterification,
epoxydation, sulphatation, phosphitation, hydrogenation,
peroxydation, isomerization, dehydration, quaternization,
amidation, polymerization, polycondensation, and all the common
treatments such as decolorizing, deodorizing, and the other systems
for eliminating volatile compounds.
[0012] The invention in fact applies very specifically to all
"lipochemistry" reactions.
[0013] This innovative technique permits, for example,
manufacturing polymers of unsaturated fatty acids, esters of
unsaturated fatty acids, unsaturated hydrocarbons or derivatives of
these products using intermittent dielectric heating under
microwaves. In this connection, the applicant has filed a Patent
Application FR 98 13770 and a Patent Application PCT WO 00/26265
(PCT/FR 99/02646).
Prior Art:
[0014] The field of this invention relates to the use of microwave
(MW) or high frequency (HF) electromagnetic waves for any heat
treatment.
[0015] The MW and HF Frequencies
[0016] The MW microwave frequencies are comprised between about 300
MHz and about 30 GHz, preferably at 915 MHz (authorized frequency
with a tolerance of 1.4%) or at 2.45 GHz (authorized frequency with
a tolerance of 2%).
[0017] The HF high frequencies are comprised between about 3 MHz
and about 300 MHz, preferably 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%).
[0018] Absorbed Power
[0019] The Absorbed Power (AP) is a dependent variable of the
Incident Power (IP) and of system losses.
[0020] For a product that hardly absorbs electromagnetic waves, and
for a given Incident Power (IP), the Absorbed Power (AP) decreases
and the losses increase, in particular those losses due to static
electricity.
[0021] Indeed: IP=AP+losses Wherein: IP=Incident Power in Watts
AP=Absorbed Power in Watts Losses=heat losses+static
electricity
[0022] The Absorbed Power (in Watts) by a material under HF or MW
treatment is expressed by the following formula:
AP=kf.epsilon.''E.sup.2V with: AP: Absorbed Power in Watts E:
electric field created inside the material in V/cm f: frequency of
wave K: constant (M.K.S.A)=5.56.10.sup.-13 V: volume of material in
cm.sup.3 .epsilon.'': material loss factor=.epsilon.'tang .delta.
.epsilon.': actual relative permittivity of the
material=.epsilon..sub.0*.epsilon..sub..tau. .di-elect
cons..epsilon..sub.0: permittivity of vacuum .epsilon..sub.R:
dielectric constant tang .delta.: angle of losses .epsilon.'
translates the ability of a material to orient itself in the field,
and tang .delta. its ability to release heat.
[0023] Note: For air or vacuum, .epsilon.'=1 (lowest value for
.epsilon.') and tang .delta.=0, i.e., .epsilon.''=0.
[0024] Type of Energy Applicators
[0025] The type of energy applicator selected depends on the
technology used (high frequencies or microwaves), the dimensional
characteristics of the product to be treated and its mode of
treatment.
[0026] As regards high frequency applicators, these essentially
consist in: [0027] 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). [0028] 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). [0029] applicators for
filiform materials, formed by loops.
[0030] For the microwave applicators, we can cite: [0031]
localized-field applicators: singlemode cavity [0032] diffuse-field
applicators: multimode cavity [0033] near-field applicators: guide
with radiating antennas
[0034] Among these microwave applicators, there are available on
the market for example: [0035] the "synthewave 402" and the
"synthewave 1000" that are made up of 1 ml to 100 ml or 600 ml
reactors [0036] the "Discover" with 1 ml to 125 ml reactors [0037]
the "Ethos MR" with a capacity of less than 400 ml
[0038] Risks of Electrical Breakdown or Electric Arcs
[0039] The Applicant has filed a Patent Application FR No 0108906
concerning an improved apparatus for carrying out dielectric
heating. In said patent, the invention relates to a new shape or
geometry of a chimney, in particular a chimney with a conical shape
or geometry, which permits heating any type of product under
microwave frequencies or high frequencies, in statics or dynamics
with a sizeable power density without any risk of electric arcs or
electrical breakdown.
[0040] Any person skilled in the art may refer to said patent
application for further details. For his/her convenience, a summary
thereof is provided hereinbelow. [0041] In the case of hardly
absorbent molecules, the choice of applicators is complicated. The
applicator in fact has to transmit a great deal of electromagnetic
energy to the product in order to be able to provide heat while
avoiding electric arcs. [0042] Heating under microwave frequencies
is preferable to heating under high frequencies for which the risk
of electrical breakdown is greater. [0043] 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 guide is preferred to the "multimode" (diffuse
field). The singlemode system avoids a non-homogeneous distribution
of the electric field and the presence of hot points. Likewise,
this type of reactor creates stability in the products exposed.
[0044] The singlemode applicator outfitted with the usual
cylindrical chimneys, which is the most suitable one of all common
applicators with hardly absorbent molecules, does not permit
working with a high density of power without running the risk of
electrical breakdown. [0045] Nonetheless, the introducing into the
reaction medium of some polar compounds such as water, so as to
play the role of intermediary in energy transfer and thus reduce
the density of power needed, is still not satisfactory. Unwanted
side reactions can take place, making supplemental treatments such
as neutralization, washing, drying or filtration necessary to
purify the product at the end of the reaction. [0046] One
alternative to mitigate the problems related to the hardly
absorbent compounds is to eliminate the static electricity as it
forms on the outer wall of the reactor. In order to eliminate the
static electricity, one must either make for a good ventilation
using humid air or some other gas that is comparable from the
standpoint of its dielectric constants (for example: sulfur
hexafluoride SF6 under 1 bar) (1st solution), or adapt the shapes
of the chimneys so as to aerate them (2nd solution). The first
solution is not attractive due to the complexity of equipment,
safety issues, and cost reasons. [0047] The applicant has
discovered a new chimney shape or geometry, in particular a conical
chimney, that makes it possible to heat any type of products under
microwave frequencies or high frequencies, in statics or in
dynamics, with a sizeable power density without any risk of
electric arcs or electrical breakdown. Description of the
Invention
[0048] The applicant has discovered a new heat treatment process
that consists of submitting the reagent, either alone or in a
mixture, to electromagnetic waves in an intermittent manner, with
the help of a recycling system.
[0049] The electromagnetic waves are selected in the frequencies
ranging between 300 GHz and 3 MHz.
[0050] This process retains the advantages of continuous dielectric
heating while increasing production capacity.
[0051] Description of the Equipment
[0052] The intermittent heating process is simple and low-cost. It
consists of: [0053] pumps [0054] reactors subjected to the
electromagnetic field [0055] a dielectric system: chimney
applicators, generator waveguides, iris, shortcircuit piston,
cooling systems [0056] buffer reactors [0057] tanks [0058] a gas
circuit, preferably for an inert gas such as nitrogen [0059]
condensers [0060] measuring devices The Pumps
[0061] The pump(s) is (are) of the variable-flow type.
[0062] 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.
[0063] The pumps can be selected, for purposes of indication, from
among vane pumps or piston pumps.
Reactors subjected to the Electromagnetic Field
[0064] The reactors subjected to the electromagnetic field do not
absorb the waves (pyrex, quartz, etc.).
[0065] They are typically cylindrical in shape.
[0066] They are positioned inside applicators.
Dielectric system: Chimney Applicators, Generator Waveguides, Iris,
Shortcircuit Piston, Cooling Systems
[0067] The applicators are formed by singlemode cavities that
resonate at the transmission frequency according to a radiation in
the direction of the waveguide.
[0068] 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.
[0069] The waveguide(s) carries/carry the electromagnetic waves.
Each waveguide can be subdivided into two--and only
two--waveguides.
[0070] The generators used are microwave or high-frequency
generators.
[0071] 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%).
[0072] 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%).
[0073] 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.
[0074] 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.
[0075] The system is outfitted with cooling systems in order to
avoid any overheating.
The Buffer Reactors
[0076] The buffer reactors permit treating a larger amount of
reaction mixture.
The Tanks
[0077] The system is outfitted with one or several feeder tank(s),
receiver tank(s), filtration tank(s).
The Gas Circuits
[0078] The heat treatments are carried out under a normal
atmosphere, or an oxygen-rich atmosphere or, preferably, an inert
atmosphere.
The Measuring Devices
[0079] The system is outfitted with measuring devices such as
manometers, thermocouples, flowmeters.
[0080] This process can be used in dynamics or in continuum.
Principle of Intermittent Heating
[0081] The entire reaction volume is not continuously exposed to
the waves; however, all molecules of the reaction mixture are
intermittently subjected to the field.
[0082] Various configurations may be considered for carrying out an
intermittent dielectric heating.
[0083] The first configuration consists in subjecting several
reactors to the electromagnetic waves. See FIG. 1.
[0084] The second configuration consists in using several energy
applicators on a single reactor. See FIG. 2.
[0085] The number of applicators depends on the desired working
temperature, on the amount of product to be treated, on the
reaction temperature rise time, on the dielectric constants of the
reagents.
[0086] Any person skilled in the art will understand that other
configurations are possible besides these two and that the
invention relates to all other intermediate positions.
[0087] Furthermore, the applicant has discovered an original system
consisting in circulating the reaction mixture in a loop, thus
reducing investment costs for an equivalent production capacity.
Without this recycling system, it would indeed be necessary to use
a large-size reactor and a multitude of applicators in order to
succeed in heating the same amount of products and to achieve the
desired result, which would entail enormous costs.
[0088] See FIG. 3.
[0089] The intermittent dielectric heating combined with a
recycling system makes it possible to increase the production
capacities, which are limited under the continuous dielectric
heating system, represented in FIG. 4 or FIG. 3 if the applicators
cover the entire volume to be treated.
[0090] This process can be used in dynamics or in continuum.
[0091] According to this configuration, the entire reaction volume
is not continuously exposed to the waves; however, all molecules of
the reaction mixture are intermittently subjected to the field.
[0092] It should be noted that, according to this principle, the
invention logically should not have functioned, that is to say, it
should logically not have yielded any good results. As a matter of
fact, a molecule will only be subjected to the electromagnetic
waves for a fraction of its circulation time, for example, 1 sec
every 10 sec. Any person skilled in the art understands that this
should have produced either very poor results (inefficient process)
or zero results. Yet, surprisingly we obtain on the contrary very
good results (see hereinbelow) accompanied by the major advantages
also mentioned herein.
Volume Exposed to the Electromagnetic Field
[0093] The volume exposed to the electromagnetic field is
calculated according to the formula below: V(exposed to the
field)=.pi.*R.sup.2*H wherein:
[0094] R=radius of reactor exposed to the field
[0095] H=height of reactor exposed to the field
Parameter H:
[0096] The height of the reactor exposed to the field typically
corresponds to that of the waveguide in order to permit treating
the maximum amount of material all at once.
[0097] Let's take the case of heat treatments under singlemode
microwave, at 2450 MHz. The height of the waveguide in Mode TE 0.1
(Transverse Electric) is equal to 45 mm. The fundamental mode of
excitation TE 0.1 makes it possible for the wave to propagate as a
single arch, contrary to Mode TE 0.2 which presents two field
maxima, yielding a less homogenous heating.
[0098] Let's take the case of heat treatments under singlemode
microwave, at 915 Hz. In that case, the height of the waveguide is
equal to 124 mm.
Parameter R
[0099] Typically, the reactor is cylindrical in shape. Its diameter
may not exceed the width of the waveguide.
[0100] In the case of singlemode microwave applicators, under 2450
MHz, the recommended waveguide width in order to remain in Mode TE
0.1 (Transverse Electric) ranges from about 70 to 100 mm, standing
more specifically at 90 mm.
[0101] In the case of the singlemode microwave applicators, under
915 MHz, the recommended waveguide width in order to remain in Mode
TE 0.1 (Transverse Electric) stands at about 250 mm.
Advantages of the Intermittent Dielectric Heating
[0102] Contrary to the common dielectric systems this invention
surprisingly permits heating volumes of materials on an industrial
scale while keeping the process low-cost. Therefore, the Applicant
has devised a process involving intermittent dielectric heating
combined with a recycling system.
[0103] The Applicant demonstrates, by this invention that the
reagents benefit from the advantages inherent to the
electromagnetic wave technology without being continuously exposed
to the field. Indeed, the benefits of the dielectric heating are
preserved: [0104] 1. the reaction time is significantly reduced;
[0105] 2. the reaction is carried out in a single step [0106] 3.
non-use of solvent [0107] 4. energy savings (because the times are
significantly shorter) [0108] 5. absence of burn-up and side
reactions. Reagents:
[0109] For this invention, the reagent(s) can be selected from
among the products that are hardly absorbent of electromagnetic
waves or the products that are highly absorbent of said
electromagnetic waves, or a mixture of both, which may or may not
be enhanced by one or several hardly or highly absorbent catalysts
or additives and/or process gases.
[0110] Vegetable Oils
[0111] As vegetable oils, we may mention, among others, 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, grapeseed oil, copra oil, palm oil,
cottonseed oil, Babassu oil, jojoba oil, sesame oil, argan oil,
milk-thistle oil, gourdseed oil, raspberry oil, Karanja oil, neem
oil, poppyseed oil, Brazilnut oil, castor oil, dehydrated castor
oil, hazelnut oil, wheat germ oil, borage oil, oenothera oil, Tung
oil, or tall oil.
[0112] Animal Fats or Oils
[0113] As animal oils or fats, we can cite, among others,
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, mutton tallow (marrow).
[0114] Animal or Vegetable Oil Compounds
[0115] We can also use compounds of animal or vegetable oils such
as 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) or squalene
contained in massive amounts in shark (dog-fish) oil.
[0116] These animal or vegetable fats and oils, as well as their
derivatives, can undergo a prior treatment intended to make them on
the one hand more reactive or on the other hand less reactive. The
invention relates to both an isolated reagent and a reaction
mixture comprising two or more components. These reaction mixtures
can include equivalent proportions of each compound; or, certain
compounds can be the primary compounds.
[0117] Hydrocarbons
[0118] As unsaturated hydrocarbons, we can cite, alone or in a
mixture, and as non-limitative examples, an alcene, for example one
or several terpenic hydrocarbons, that is to say, one or several
polymers of isoprene, or one or several polymers of isobutene, of
styrene, of ethylene, of butadiene, of isoprene, of propene, or one
or several copolymers of these alcenes.
[0119] As saturated hydrocarbons, we can cite, among others, the
alcanes, for example ethane, propane.
[0120] Saturated and/or Unsaturated Esters
[0121] As for esters of saturated and/or unsaturated fatty acids,
we can use such acids either alone or as a mixture, and by way of
non-limitative examples, 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; glucolipids.
[0122] Saturated and/or Unsaturated Acids
[0123] As unsaturated fatty acids, we can use, either alone or in a
mixture, and as non-limitative examples, one or several saturated
acids such as caprylic acid, lauric acid, myristic acid, palmitic
acid, stearic acid, arachidic acid, behenic acid, lignoceric acid,
cerotic acid, one or several monounsaturated fatty acids such as
oleic acid, palmitoleic acid, myristic acid, petroselenic acid,
erucic acid; one or several polyunsaturated fatty acids such as for
example linoleic acid, alpha and gamma linolenic acids, arachidonic
acid; 5c,8c,11c,14c-eicosapentaenoic acid (EPA),
4c,7c,10c,13c,16c,19c-docosahexaenoic acid (DHA), one or several
acids comprising conjugated dienes or conjugated trienes such as
licanic acid, isomers of linoleic and linolenic acids; one or
several acids comprising one or several hydroxyl groups such as
ricinoleic acid.
[0124] Alcohols
[0125] As alcohols, we can mention, among others, 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 (for
example, diethanol amine (DEA), triethanol amine (TEA),
3-amino-1,2-propanediol), epoxyalcohols, saturated or unsaturated
fatty alcohols (for example, myristyl alcohol, oleyl alcohol,
lauryl alcohol), linear or branched alcohols, vitamins (for
example, tocopherol, ascorbic acid, retinol), sterols (including
phytosterols), hemiacetals (for example, 1-ethoxy-1-ethanol),
aminoalcohols (for example, 2-2'-aminoethoxy ethanol),
epoxyalcohols (for example, 2-3-epoxy-1-propanol), propanol,
ethanol, methanol, tetradecyl alcohol and their analogs.
[0126] The alcohols as well as their derivatives can undergo a
prior treatment intended to make them more reactive or, on the
contrary, less reactive, such as for example: hydrogenation,
hydroxylation, epoxydation, phosphitation, sulfonation.
[0127] Epoxides
[0128] As epoxydes, we can use, alone or in a mixture, and as
non-limitative examples, vemolic acid, coronaric acid;
1,2-epoxy-9-decene, 3-4-epoxy-1-butene, 2-3-epoxy-1-propanol, fatty
esters obtained by esterification between 2-3-epoxy-1-propanol and
a fatty acid (for example, Cardura E10.RTM.).
[0129] Amino Alcohols
[0130] As amino alcohols, we can use, alone or in a mixture, and as
non-limitative examples, monoethanol amine (MEA), diethanol amine
(DEA), triethanol amine (TEA), 3-amino-1,2-propanediol,
1-amino-2-propanol; 2-2'-aminoethoxy ethanol.
[0131] Amines
[0132] As amines, we can mention, among others, ammonia, primary,
secondary and tertiary alkyl amines (for example, methyl amine,
dimethyl amine, trimethyl amine, diethyl amine), fatty amines (for
example, oleic amines, coconut alkyl amines), amino alcohols (for
example, monoethanol amine (MEA), diethanol amine (DEA), triethanol
amine (TEA), 3-amino-1,2-propanediol, 1-amino-2-propanol),
ethoxylated amines (2-2'-aminoethoxy ethanol,
amino-1-methoxy-3-propane).
[0133] All these amines can be saturated or nonsaturated, linear or
branched.
[0134] Catalysts
[0135] Among the catalysts or additives, there shall be, as
non-limitative examples, the common acid catalysts (para toluene
sulfonic acid, sulfuric acid, phosphoric acid, perchloric acid,
etc.), the common basic catalysts (soda, potash, alcoholate of
alkaline metals and of alkaline-earth metals, sodium acetate,
triethyl amines, pyridine derivatives, etc.), acid and/or basic
resins of the Amberlite.TM., Amberlyst.TM., Purolite.TM.,
Dowex.TM., Lewatit.TM. types, zeolithes and enzymes, carbon blacks,
and activated carbon fibers.
[0136] The invention will be better understood upon reading the
following description and the non-limitative examples given
below.
EXAMPLES
[0137] The examples given below highlight the value of the
invention and will allow any person skilled in the art to easily
extrapolate to other dimensions and/or geometries without departing
from the true scope and spirits of the invention in its broader
aspects.
[0138] Additionally, the following examples, which are given solely
for purposes of description and in no way of limitation, illustrate
the value of the invention. These examples aim to demonstrate that
the intermittent dielectric heating process is low-in-cost and
permits heating reaction volumes on an industrial scale while still
benefiting from the advantages of this technology.
I. Volumes Exposed to Electromagnetic Waves
[0139] The tests were conducted on the laboratory and on industrial
scale using two (2) generators: [0140] one (1) 6 kW magnetron
generator operating at the 2450 MHz frequency for the laboratory
treatments
[0141] one (1) 60 kW magnetron generator operating at the 915 MHz
frequency for the industrial treatments TABLE-US-00001 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
[0142] wherein:
[0143] D=diameter of cylindrical reactors=2R
[0144] H=height of waveguide
[0145] Unit Vexp=volume exposed continually basis to waves for one
reactor
[0146] Total Vexp=volume exposed continually to waves for both
reactors V(exposed to the field)=.pi.*R.sup.2*H II. Comparison
between Conventional Heating and Intermittent Dielectric Heating a.
Polyglycerol Synthesis
[0147] The tests are conducted at 260.degree. C., in the presence
of 2% sodium acetate in order to obtain a polyglycerol with a
viscosity at 50.degree. C. equal to 3600 cP.
[0148] They make reference to Patent Application FR No 0108906.
TABLE-US-00002 Total V of Reaction glycerol V ratio Time
Intermittent Pilot 2,000 mL 1/62 3 h dielectric industrial 200 L
1/50 6 h 30 min heating Conventional Schou >72 h heating
[0149] wherein:
[0150] Total V of glycerol=total volume of glycerol treated
[0151] V ratio=ratio between the volume exposed to waves and the
total volume treated
b. Synthesis of Polyglycerol Esters
Synthesis of Polyglycerol-6 Dioleate
[0152] The tests are carried out in the presence of 0.25% sodium
acetate at 230.degree. C.
[0153] They make reference to Patent Application FR No 0108906.
TABLE-US-00003 Total V of Reaction mixture V ratio time
Intermittent 2000 mL 1/62 2 h 10 min dielectric heating
Conventional 4 h 30 min heating
[0154] wherein:
[0155] Total V of mixture=total volume treated
[0156] V ratio=ratio between the volume exposed to waves and the
total volume treated
Synthesis of polyglycerol-2 Tristearate
[0157] The tests are carried out in the presence of 0.25% sodium
acetate at 260.degree. C.
[0158] They make reference to Patent Application FR No 0108906.
TABLE-US-00004 Total V of Reaction mixture V ratio time
Intermittent 2000 mL 1/62 1 h 40 min dielectric heating
Conventional 4 to 5 h heating
[0159] wherein:
[0160] Total V of mixture=total volume treated
[0161] V Ratio=ratio between the volume exposed to waves and the
total volume treated
c. Conclusion
[0162] Even if the entire reaction volume is not exposed to
electromagnetic waves, the reaction times under intermittent
dielectric heating are considerably lower than those obtained with
conventional heating.
III. Comparison Between Intermittent Dielectric Heating and
Continuous Dielectric Heating
a. Efficiency of Intermittent Dielectric Heating
[0163] The table below shows the efficiency of intermittent
dielectric heating compared with continuous dielectric heating
which is typically used.
[0164] The tests are carried out under the same conditions
(composition of reaction mixtures, temperatures, catalysts, etc.)
[0165] at the laboratory scale (use of a Synthewave 402) which uses
continuous dielectric heating [0166] at the pilot scale, using a
2450 MHz generator that uses intermittent dielectric heating [0167]
and at the production scale using a 915 MHz generator that uses
intermittent dielectric heating
[0168] The synthesis tested consists in manufacturing unsaturated
fatty acid polymers, unsaturated fatty acid esters, unsaturated
hydrocarbons, unsaturated derivatives of these compounds, alone or
in a mixture. TABLE-US-00005 Pilot Industrial Extrap- Extrap-
Laboratory olated olated Mop MOi Mop MOi Mop V.sub.treated (mL) 25
2000 2000 200000 200000 V ratio 1/1 1/62 1/1 1/50 1/1
t.sub.reaction (h) 2 h 15 min 2 h 15 min .gtoreq.2 h 15** 2 h 15
.gtoreq.2 h 15**
[0169] wherein:
[0170] Mop=continuous microwave heating
[0171] Extrapolated Mop=continuous microwave heating in the case of
treatment of 200 kg of product
[0172] Moi=intermittent microwave heating
[0173] V.sub.treated=reaction volume treated
[0174] V ratio=ratio between the volume exposed to electromagnetic
waves and the total reaction volume
[0175] t.sub.reaction=reaction time
[0176] **: Treating a large amount of products requires a reaction
time greater than or equal to that for a lower amount. The reaction
time is 2 h15 for 25 mL of product. Thus, it can be asserted that
the reaction time needed to treat 200 kg of the same mixture will
be greater than or equal to 2 h15.
[0177] This table shows that the reaction times are unchanged,
whether one works on 25 mL, 2 kg, or 200 kg. However, in the case
of pilot and industrial tests (2 kg and 200 kg), the entire volume
is not subjected to dielectric heating: [0178] laboratory test
(continuous dielectric heating): the entire volume is exposed to
electromagnetic waves with Ratio=1/1 [0179] pilot test
(intermittent dielectric heating): only 1/62 of the volume is
exposed to the field [0180] industrial test (intermittent
dielectric heating): only 1/50 of the volume is exposed to the
field
[0181] b. Lowering of Investment Costs
[0182] If we had to treat 200 liters of product using continuous
dielectric heating, we would have to expose all 200 liters to the
electromagnetic waves.
[0183] By working at the 2450 MHz frequency, the maximum volume
exposed by applicator is 32 mL. Here this configuration is not
advantageous at all. In fact, we would need 6250 applicators.
[0184] By working at the 915 MHz frequency, the maximum volume
exposed by applicator is 1 L. We would then need 200
applicators.
[0185] For this invention, intermittent dielectric heating makes it
possible to use only four (4) applicators, that is to say, 50 times
less (a ratio consistent with that given in the preceding table)
for the same production capacity.
We can compare the investment costs:
[0186] X=investment cost of a system with intermittent dielectric
heating, 4 channels, recycling
[0187] Y=investment cost of a system with continuous dielectric
heating, 200 channels, without recycling
[0188] Y=10*X
[0189] The investment cost would then be 10 times higher in the
case of a continuous dielectric heating compared with intermittent
dielectric heating. This is essentially due to the cost of
applicators, which is much higher than the rest of the system
(buffer reactor, recycling pump, etc.).
* * * * *