EP3618966A1 - Three-dimensional grinder, method for implementing same and uses thereof - Google Patents
Three-dimensional grinder, method for implementing same and uses thereofInfo
- Publication number
- EP3618966A1 EP3618966A1 EP19725763.7A EP19725763A EP3618966A1 EP 3618966 A1 EP3618966 A1 EP 3618966A1 EP 19725763 A EP19725763 A EP 19725763A EP 3618966 A1 EP3618966 A1 EP 3618966A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- grinding chamber
- stationary
- stationary grinding
- chamber
- mill
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims description 17
- 238000000227 grinding Methods 0.000 claims abstract description 112
- 238000010438 heat treatment Methods 0.000 claims abstract description 68
- 238000002156 mixing Methods 0.000 claims abstract description 58
- 239000011325 microbead Substances 0.000 claims abstract description 51
- 239000000203 mixture Substances 0.000 claims abstract description 49
- 230000006698 induction Effects 0.000 claims abstract description 35
- 239000007858 starting material Substances 0.000 claims abstract description 34
- 239000007788 liquid Substances 0.000 claims abstract description 27
- 239000012467 final product Substances 0.000 claims description 20
- 238000003786 synthesis reaction Methods 0.000 claims description 17
- 238000001816 cooling Methods 0.000 claims description 11
- 238000011144 upstream manufacturing Methods 0.000 claims description 4
- 230000004913 activation Effects 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 210000000056 organ Anatomy 0.000 claims 1
- 239000007795 chemical reaction product Substances 0.000 abstract description 2
- 238000007599 discharging Methods 0.000 abstract description 2
- 239000000725 suspension Substances 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 14
- 238000012360 testing method Methods 0.000 description 13
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 12
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Substances CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 6
- LRGQZEKJTHEMOJ-UHFFFAOYSA-N propane-1,2,3-triol;zinc Chemical compound [Zn].OCC(O)CO LRGQZEKJTHEMOJ-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000011324 bead Substances 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 4
- 230000002572 peristaltic effect Effects 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- 229910001928 zirconium oxide Inorganic materials 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229910001018 Cast iron Inorganic materials 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000004246 zinc acetate Substances 0.000 description 2
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 101000694017 Homo sapiens Sodium channel protein type 5 subunit alpha Proteins 0.000 description 1
- 241000102542 Kara Species 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910006501 ZrSiO Inorganic materials 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004320 controlled atmosphere Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000133 mechanosynthesis reaction Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
- B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
- B02C17/00—Disintegrating by tumbling mills, i.e. mills having a container charged with the material to be disintegrated with or without special disintegrating members such as pebbles or balls
- B02C17/16—Mills in which a fixed container houses stirring means tumbling the charge
- B02C17/163—Stirring means
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
- B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
- B02C17/00—Disintegrating by tumbling mills, i.e. mills having a container charged with the material to be disintegrated with or without special disintegrating members such as pebbles or balls
- B02C17/18—Details
- B02C17/1815—Cooling or heating devices
Definitions
- the present invention relates to the field of three-dimensional mills capable of allowing a micro-grinding of at least one raw material.
- the present application relates to a three-dimensional mill having therein a heating device, and in particular an induction heating device.
- the invention relates to a method of implementation of the abovementioned mill, as well as to its uses in particular for performing synthesis reactions of organic or inorganic chemistry.
- This mill comprises in particular a cylindrical or conical grinding chamber, extending along a longitudinal axis, which serves to receive the microbeads and the liquid medium.
- the chamber has at one end: a product inlet and at its other end, opposite the first, a product outlet.
- the mill also includes a mixer that is coaxial with the axis of the chamber and is pivotable to move the liquid medium and the microbeads.
- the mixer further has several mixing members distributed along its length to promote grinding.
- This type of mill is particularly used in the pharmaceutical field to reduce the diameter of a product, for example of the order of one micrometer to one nanometer.
- the object of the present invention is thus to provide a novel three-dimensional crusher capable in particular of improving the dispersion or the bringing into contact of at least one starting compound, preferably at least two, which is industrially exploitable and which is simple to use. artwork.
- the present invention relates to a three-dimensional mill comprising at least:
- a stationary grinding chamber having a wall of generally cylindrical shape extending along a longitudinal axis XX and delimiting an interior space, said grinding chamber being adapted to receive and mix at least one starting compound, generally at least two, in a liquid medium, so as to form an initial mixture, said chamber being intended to be partially filled with at least one grinding body , preferably microbeads,
- stationary grinding chamber comprises, at a first end, at least one inlet serving to introduce at least said at least one starting compound and the liquid medium, and at a second end, an outlet capable of discharging a final product formed in said stationary grinding chamber;
- an agitator disposed in said stationary grinding chamber comprising an elongated rod along the longitudinal axis XX, said stirrer being able to pivot so as to set the whole grinding body / initial mixture in motion,
- the stationary grinding chamber integrates into said interior space at least one heating device which is implanted to heat at least one zone of said stationary grinding chamber.
- the heater is an induction heater.
- the mill according to the invention makes it possible to carry out mechano-synthesis reactions, in particular continuously, that are effective via the presence of the heating device, such as an induction heating device.
- the heating device such as an induction heating device.
- such a device makes it possible, for example, to activate synthesis reactions of organic chemistry or of inorganic chemistry requiring a certain reaction temperature, to be able to use starting compounds that can be in liquid form as a function of their melting temperature. or to use starting compounds whose viscosity is not adequate at ambient temperature.
- the mill according to the invention is no longer intended for the starting compound in powder form, which is the general use of a three-dimensional micro-bead mill.
- the mill according to the invention has the advantage of forming a reactor for the efficient synthesis of chemical compounds as able to operate in temperature, and further increase the yields of these chemical syntheses, while decreasing the times of usual reactions.
- the reaction times generally pass from 3 to 13 hours at a time of less than 1 hour, typically less than 1 minute (for example, transesterification reaction of dimethyl carbonate according to the degree of conversion. wish).
- the heating device such as an induction heating device, can heat the initial mixture in the form of a liquid flow, even if it has a high flow and without heat dissipation outside the mill.
- the heating device located in the heart of the room stationary allows to provide enough heat energy to the continuous flow, that is to say the continuous flow of the starting compound (s) in the liquid medium passing through the stationary chamber.
- a simple heating of the periphery of the stationary chamber would result in an overall loss because some of this energy would have been dissipated outside the bowl, which is not the case of the heating device according to the invention.
- the present invention has the advantage of allowing the positioning (at the entrance and / or the middle of the stationary chamber, etc.) and the adjustment (desired temperature) of the at least one heating device, such as a induction heating device, depending on the desired reaction.
- said induction heating device is carried by at least a part of said stirrer enabling rotary activation of said induction heating device
- said induction heating device comprises: at least one inductor capable of generating a magnetic field, and at least one susceptor, electrically conductive, which is coupled to said inductor and is able to be heated by it;
- the stationary grinding chamber incorporates a magnetic screen disposed between said inductor and said rod of the agitator, so as to direct the heating to the initial mixture;
- said magnetic screen comprises a first tubular portion which is fitted over at least a portion of the length of said rod of the stirrer and a second disk-shaped portion connected to the first portion, which is arranged in line with said rod;
- said at least one inductor is a coil or a solenoid having turns which surround a portion of said rod of the stirrer, advantageously an upstream section, said rod portion being optionally protected by said magnetic screen;
- At least one susceptor corresponds to a first mixing member, arranged in the right of the agitator, advantageously located at the first end of the stationary grinding chamber;
- the first mixing member comprises a base secured to the rod of the stirrer, said inductor being implanted at said base;
- the stationary grinding chamber comprises, arranged (s) right of the agitator, one or more other mixing members, different (s) of the first mixing member;
- said at least one induction heating device is located near the first end of the stationary grinding chamber; said at least one induction heating device is connected to an alternating electric current generator disposed outside said grinding chamber via at least one current feed means, which is preferably coaxial with the agitator shaft;
- the stationary grinding chamber comprises a pressure control means, such as a valve;
- the mill comprises cooling means, such as a heat exchanger, disposed outside said stationary grinding chamber on the side of the second end;
- the mill comprises at least one means for controlling the temperature and / or at least one means for controlling the pressure inside the stationary grinding chamber.
- the invention also proposes a method for implementing the three-dimensional crusher as defined above, characterized in that it comprises the following successive steps:
- the method comprises the following additional step:
- the present invention relates to the use of the three-dimensional mill as described above for carrying out synthesis reactions of organic and inorganic chemistry or for grinding at least one starting compound.
- starting compound any compound which may be in liquid, gas, solid (powder, etc.) form, the starting compound generally being a reagent making it possible to carry out a chemical synthesis reaction with another starting compound and / or the liquid medium according to the desired reaction.
- liquid medium any liquid medium for improving the mixture of the starting compound (s) with the grinding bodies, such as microbeads; depending on the desired reaction, this starting medium may also correspond to one of the excess reagents.
- “Final product” means the product obtained at the outlet of the mill including in particular also the intermediate reaction products.
- Figure 1 shows a sectional view, along a section plane passing through the longitudinal axis XX, of a three-dimensional mill according to a first embodiment of the invention including an induction heating device;
- FIG. 2 shows a sectional view along the longitudinal axis XX of a three-dimensional mill according to a second embodiment of the invention comprising in particular two induction heating devices;
- FIG. 3 represents, in sectional planes passing through the longitudinal axis XX and by the axis AA, various variants of three-dimensional mills according to the invention, each comprising a heating device and at least one stirrer possibly supporting another mixing member: (a) the agitator comprises several other mixing members according to the mill of FIG. 1, (b) the agitator further comprises fingers capable of cooperating with the other mixing members and (c) the agitator does not have mixing members and fingers; and
- FIG. 4 shows the X-ray diffractometry (XRD) spectra of zinc glycerolate crystals obtained using the mill according to the invention and its method of implementation associated with zinc acetate as a catalyst when the heating device is used (temperature 93 ° C): Example 4 for the diffractogram located in the upper part, or without heating device (temperature 23 ° C): Example 3 for the diffractogram in the lower part. Also presented are the identification diffractograms from ZX ICDD sheets No. 00-023-1975 of zinc glycerolate, and ICCD No. 04-007-1614 of zinc oxide. DETAILED DESCRIPTION OF AN EXEMPLARY EMBODIMENT
- the Applicant has devoted himself to the development of a new improved three-dimensional crusher, suitable for implementation on an industrial scale.
- the Applicant has developed a grinder for carrying out, usually in a single step, chemical synthesis reactions having a good to excellent conversion rate, in very short reaction times (generally in less than 10 minutes). one hour and typically in less than 10 minutes) at temperatures greater than or equal to 60 ° C and with a relatively low power consumption.
- the three-dimensional mill 100 comprises at least one stationary grinding chamber 1 having a wall 7 of generally cylindrical shape which surrounds an interior 8.
- the wall 7 extends along a longitudinal axis XX, advantageously horizontal.
- This stationary grinding chamber 1 is configured to receive and mix at least one starting compound, generally at least two, in a liquid medium, so as to form an initial mixture.
- the chamber 100 can receive a single starting compound.
- the chamber may receive at least two separate starting compounds. Generally, at least two starting compounds will be introduced into the stationary grinding chamber 1.
- this stationary grinding chamber 1 is also intended to be partially filled with at least grinding bodies 6, such as microbeads 6.
- the stationary chamber 1 comprises, at a first end 2 (upstream), an inlet 4 which opens into the stationary grinding chamber 1 and serves to introduce the starting compound (s) and the liquid medium.
- This inlet 4 can also serve to introduce the microbeads 6 before the implementation of the mill 100.
- the size and nature of the microbeads 6 depend on the desired synthesis reaction and can be adjusted accordingly.
- the grinding chamber 100 comprises, at a second end 3 (downstream), an outwardly directed outlet 5 which is configured to discharge a final product formed in the stationary grinding chamber 1.
- the outlet 5 generally comprises a separation means (not shown), such as a sieve or a grid, adapted to evacuate only the final product and to retain the microbeads 6 when the mill 100 is in operation.
- the inlet 4 is generally connected to at least one pump, for example peristaltic (not shown).
- This pump makes it possible to bring the starting compound or compounds or the initial mixture, if previously prepared, inside the stationary grinding chamber 1 via the inlet 4.
- the starting compound (s), or the initial mixture prepared beforehand may for example be contained in at least one container, such as a tank.
- the pump further allows, during operation of the three-dimensional mill 100, to bring the starting mixture to a certain flow rate that is adjustable, hereinafter called "flow rate". This flow rate also forms a current in the stationary chamber 1 for driving the starting mixture from the inlet 4 to the outlet 5.
- the three-dimensional mill 100 also comprises an agitator 10 which comprises an elongated rod 11 along the longitudinal axis XX and which extends mainly around the first end 2 to beyond the second end 3 of the stationary chamber 1.
- an agitator 10 which comprises an elongated rod 11 along the longitudinal axis XX and which extends mainly around the first end 2 to beyond the second end 3 of the stationary chamber 1.
- This elongated rod 11 advantageously extends coaxially with the longitudinal axis XX above.
- This stirrer 10 is in particular pivotable so as to set in motion, in addition to the aforementioned start of passage, the grinding body assembly 6 and initial mixing.
- the stirrer 10 is configured to turn on itself, along the longitudinal axis XX, via an elongated rod 11 (or rotating shaft), to impart within the stationary chamber 1 a swirling motion to the initial mixture and thus perform an intense mixing between this initial mixture and the microbeads 6 present in the chamber 1 along the inner surface of the wall 7 of this chamber 1.
- the stirrer 10 via its elongated rod 11 may have a speed of rotation greater than or equal to 100 revolutions per minute, advantageously greater than or equal to 1000 revolutions per minute (rpm), preferably greater than or equal to 2000 revolutions per minute and typically greater than or equal to 2500 revolutions per minute.
- rpm revolutions per minute
- a speed of rotation greater than or equal to 100 revolutions per minute comprises the following values: 100; 150; 200; 250; 300; 350; 400; 450, 500; 550; 600; 650, 700; 750; 800; 850; 900, 950, 1000, etc., or any interval between these values
- "a rotational speed greater than or equal to 1000 revolutions per minute” includes the following values: 1000; 1100; 1200; 1300; 1400; 1500; 1600; 1700; 1800; 1900; 2000; 2100; 2200; 2300; 2400; 2500; 2600; 2700; 2800; 2900; 3000; 3100; 3200; 3300; 3400; 3500; 3600; 3700; 3800; 3900; 4000, 4500; 5000; 5500; 6000; etc., or any intervals between these values.
- the agitator 10 has a rotation speed ranging from 1000 rpm to 5000 rpm, in particular from 1500 rpm to 4500 rpm, preferably from 2000 rpm to 4000 rpm, and typically from 2800 to 3200 rpm.
- stirrer 10 just like the inner surface of the inner wall 7 of the chamber 1, may have various possible configurations shown for example in FIG. 3.
- the stirrer 10 comprises, along its elongate rod 11, "rotatable" mixing members 22, 26, arranged perpendicular thereto.
- a mixing member 22 (called “first mixing member”) may also correspond to a susceptor of the heating means 20 according to the invention and is thus different from the other mixing members 26 (known as “Other mixing devices”).
- This first mixing member 22, as well as the other mixing members 26, may correspond to the mixing members described in US 5,597,126.
- they may comprise at least two circular disks parallel to each other, configured to move the grinding bodies 6 (microbeads).
- the number of these mixing members 22, 26 in the grinding chamber 1 can vary from 2 to 8, preferably from 2 to 5.
- mixing members 22, 26 make it possible, on the one hand, to improve the grinding of the initial suspension by further stirring the microbeads 6 and, on the other hand, to accelerate the reaction time.
- the stirrer 10 may also comprise, along its stem 11, one or more mixing members 22, 26 "rotating” and which are furthermore capable of cooperating with fingers 28 ". fixed “perpendicular to the inner wall 7 of the chamber 1.
- a finger 28 is in particular in the form of a ring which extends perpendicularly from the wall 7.
- the mixing members 22, 26 and the fingers 28 are staggered, namely the mixing members 22, 26 and the fingers 28 are alternately arranged in the chamber 1.
- the fingers 28 thus form counter-fingers, each disposed between two mixing members 22, 26.
- the thickness of the rod 1 1 is increased relative to the previous configuration ( Figure 3a) so that the periphery of the mixing members 22, 26 is close to the inner wall 7 and the fingers 28 is close of the periphery of the rod of the agitator 10.
- the volume of the chamber is reduced compared to the previous configuration, thus allowing better mixing between the initial suspension, the microbeads 6 and the inner wall 7 of the chamber 1.
- the volume of the chamber 1 can be further reduced as shown in FIG. 3c.
- the agitator 10 has an external diameter slightly smaller than the internal diameter of the chamber 1, thus forming an annular chamber 12 of small volume disposed between the outer wall of the stirrer 10 and the inner wall 7 of the chamber 1
- the microbeads (not shown) are arranged in this annular chamber 12.
- the starting suspension is introduced through the inlet 4 with a certain flow rate, which will then travel through the annular chamber 12 to the outlet 5, while being stirred by the microbeads 6.
- the geometry of the grinding chamber 1 and the stirrer 10 may be adjusted by those skilled in the art depending on the desired reaction, as well as the desired reaction time.
- the grinding chamber 1 comprises an accelerator to improve the grinding of the initial mixture. This accelerator being known to those skilled in the art, it will not be detailed below.
- the stationary chamber has a diameter of 75 mm to 300 mm for a length of 80 mm to 900 mm and a stirrer 10 having a size ranging from 65 mm to 260 mm.
- the volume of the grinding chamber can vary from 0.35 L to 600 L, preferably from 0.35 L to 400 L, and typically from 0.35 L to 62 L.
- a volume of the stationary chamber 1 ranging from 0.35 L to 600 L comprises the following values: 0.35; 0.5; 0.8; 1; 2; 3; 4; 5; 6; 7; 8; 9; 10; 15; 20; 25; 30 ; 35; 40; 45; 50; 55; 60; 65; 70; 80; 85; 90, 100; 110; 120; 130; 140; 150; 160; 170; 180; 190; 200; 210; 220; 230; 240; 250; 260; 270; 280; 290; 300; 350; 400; 450; 500; 550; 600 etc., or any interval between these values.
- the microbeads 6 housed in the grinding chamber 3 of the mill 1 during its operation are substantially spherical in shape and have an average diameter of less than or equal to 5 mm, generally ranging from 0.05 mm to 4 mm, preferably from 0.2 to 3 mm, in particular from 0.3 to 2 mm, and typically of the order of 0.5 to 1 mm.
- the diameter of the microbeads is less than or equal to 1 mm and is typically of the order of 0.05 mm to 1 mm. They are preferably selected from microbeads having a high hardness and relatively resistant to abrasion.
- the microbeads 6 have a Vickers hardness measured according to the EN ISO 6507-1 (2005) standard greater than or equal to 900 HV1, preferably ranging from 900 HV1 to 1600 HV1, typically ranging from 1000 to 1400 HV1 and especially ranging from from 1 10 to 1300 HV1.
- HV1 "includes the following values: 900; 910; 920; 930; 940; 950; 960; 970; 980;
- the microbeads according to the invention have a high real density.
- the microbeads according to the invention have a real density greater than or equal to 2 g / cm 3 , in particular ranging from 2 to 15 g / cm 3 , preferably from 3 to 12 g / cm 3 , and typically from 4 to at 10 g / cm 3 .
- the microbeads according to the invention may be ceramic microspheres, (zirconium oxide Zr0 2 , zirconium silicate ZrSiO 4 ); steel microbeads, tungsten carbide microbeads, glass microbeads or a combination thereof.
- the microbeads are ceramic because they do not generate pollution by their wear.
- the microbeads are made of zirconium oxide.
- the zirconium oxide microbeads may be stabilized by another oxide, such as cerium oxide, yttrium oxide and / or silicon.
- compositions are suitable for forming the microbeads according to the invention:
- microbeads 6 that are suitable for the invention are not made of glass or exclusively of glass.
- the microbeads 6 represent, in volume, relative to the total volume of the stationary chamber 2 from 50% to 85%, preferably from 55% to 70%.
- a volume of 50 to 85% comprises the following values: 50; 55; 60; 65; 70; 75; 80; 85; etc., or any intervals between these values.
- the mill 100 comprises at least one heating device, such as, for example, an induction heating device 20 which is illustrated in particular in FIGS. 1 and 2.
- an induction heating device 20 which is illustrated in particular in FIGS. 1 and 2.
- the induction heating device (s) 20 are integrated inside the stationary grinding chamber (1) and make it possible to heat at least one zone of said stationary grinding chamber (1).
- the inductive heating device (s) 20 are located at the entrance of the chamber 1, that is to say around the first end 2 so as to be able to heat the flow of initial mixture from its introduction and allow and / or activate therefore the chemical synthesis.
- the induction heating device 20 is carried by at least a portion of said agitator 10, allowing the induction heating device 20 to be rotated about the longitudinal axis XX.
- This characteristic has the advantage of allowing better heating of the flow forming the initial mixture.
- At least one susceptor 22 electrically conductive, which is coupled to said inductor 21 and is adapted to be heated by it 21.
- the inductor 21 is a coil or solenoid having turns that surround a portion of said rod 11 of the stirrer 10, advantageously an upstream section located on the side of the first end 2 as shown in FIG. .
- the inductor 21 is particularly capable of generating a magnetic field which will allow the heating of the conducting materials of its environment, and in particular of the susceptor 22 to which it is coupled. Indeed, the susceptor, which is electrically conductive, is able to capture the magnetic field emitted by the inductor.
- the inductor 21 is made of stranded Litz wire and is thus wound on the rod 11 of the mill 100.
- a cable of IDPArtner 300 strands Litz Cu 9.425 mm 2 6x50x0.2 mm is suitable for the invention.
- the three-dimensional mill 100 does not comprise the grinding members 22 or 26, the stirring of the initial mixture being carried out in the annular chamber 12 of small volume.
- the induction heating device 20 is preferably disposed at the inlet of the chamber 1, at the junction between the rod 1 1 and the stirrer 10 of larger diameter.
- the inductor 21, such as a coil, can surround the rod 1 1; the susceptor 22 may have the shape of a disk perpendicular to the rod 1 1 which surrounds said coil.
- the coil and susceptor assembly can be rotated by the rod 11.
- the three-dimensional mill 100 comprises mixing members 22 or 26.
- the susceptor 22 may correspond to the first mixing member implanted at the first end 2, namely to the mixing member closest to the end 2 of the stationary grinding chamber 1.
- This first mixing member 22 is thus made of a material which is electrically conductive in order to form the susceptor.
- this first mixing member may be made of a carbon steel type resistive material in order to have a maximum coupling with respect to the magnetic field emitted by the inductor.
- the choice of this material is also indicated in that it preferably has a high temperature creep resistance, such as 800 ° C.
- the first mixing member 22 may be made of stainless steel Phyterm ® 260 equivalent Kara ferric stainless steel from ArcelorMittal grade K44. This material can be heated up to 700 ° C which allows the liquid flow therethrough to go from room temperature to the desired temperature.
- the other mixing members 26 which are different from the first mixing member 22, namely they are not necessarily electrically conductive, may in particular be made of chromium cast iron or zirconia type ceramic.
- the first mixing member 22 generally comprises a base secured to the rod 1 1 of the stirrer 10.
- the inductor 21 is located at this base.
- the induction heating device 20 is connected to an alternating electric current generator disposed outside said grinding chamber 1 via at least one current supply means 27 which is coaxial with the rod 1 1 of the agitator 10.
- the generator may have a power ranging from 5 to 15KW and preferably 10kW with a frequency ranging for example from 17 to 200 kHz. It has a capacity box that can be in parallel or in series.
- a serial generator ID Partner reference IX3600 model PO8010 is suitable for producing the mill according to the invention.
- the current supplying means 27 may for example correspond to copper strands, preferably a current supply strand going towards the coil and a return current supplying strand to the generator. These strands can be connected to the generator via a contactor 29.
- This supply means can modify the center of gravity of the rod 11 of the stirrer 10. It can however be balanced by compensating for it by the insertion screw for example in tungsten
- the contactor 29 is also coaxial with the rod 11 of the agitator 10. This arrangement has the advantage of supplying current to the coil when the stirrer 10 is rotating.
- the generator supplies a sinusoidal alternating current whose frequency is defined by the oscillation of the system constituted by the assembly: the generator capacity box, the inductor 21 and the current supply 27.
- the generator current is then delivered to the inductor 21 by the contactor 29 connected thereto via the current supply means 27.
- the inductor 21, supplied with current will then be able to generate a magnetic field which will be picked up by the first mixing member 22 and allow it to be heated.
- This first mixing member 22, which is rotated by the rod 11 of the stirrer 10 will then be able to heat efficiently the initial mixture (flow) passing through the grinding chamber 1 by thermal conduction.
- the stationary grinding chamber 1 includes a magnetic screen 23 disposed between said inductor 21 and said rod 1 1 of the stirrer 10, so as to direct the heating to the initial mixture.
- stirrer 10 or its rod 1 1 is made of electrically conductive material and thus, in order to avoid overheating of the stirrer 10, it is preferable to protect the stirrer 10 or minus the rod portion 1 1 which is surrounded by the inductor 21.
- the magnetic screen 23 (with an L-shaped section) has a first tubular portion 24 which is fitted over at least a portion of the length of said rod 1 1 of the stirrer 1, generally the portion of the rod which is surrounded by the coil 21, and a second disk-shaped portion 25 or crown, connected to the first portion 24, which is arranged at the right of said rod 11.
- This magnetic screen 23 also has the advantage of directing the magnetic field emitted by the coil 21 to the first mixing member 22 so that all the power is concentrated outside the inductor and in particular is not directed towards the rod. 1 1.
- the heating zone is restricted to the outer periphery of the rod 1 1 and particularly concentrated on the first mixing member 22.
- the magnetic screen may be a cylindrical torus Fluxtrol ® .
- the mill 100 may comprise an induction heating device 20.
- the mill 100 comprises, as shown in FIG. 2, two induction heating devices 20.
- the two heating devices 20 are generally assembled in series, ie a first heating device identical to the heating device described above is connected to a second heating device.
- the second heater is also similar to the first heater, except that it is connected to the same generator and contactor as the first heater.
- the means for supplying current to the second heating device is arranged between the first mixing member and the second mixing member, this second mixing member acting as a susceptor for the second heating means 20.
- This is disposed in line with the rod 1 1 and comprises a base secured therewith.
- the coil of the second heating means also surrounds the rod 11 at this base.
- the second heater also comprises a magnetic screen having two parts: a first tubular portion which is fitted on a portion of the rod 11 from the disc 25 of the magnetic screen of the first heater to the coil of the second device heating including the stretch surrounded by the coil, and a second portion also in the form of a disk connected to the first part and which is arranged at the right of the rod.
- This second part makes it possible in particular to orient the magnetic field emitted by the coil towards the second mixing member.
- the mill 100 may include more induction heaters 20. However, in general, one or two induction heaters suffice. to achieve the desired synthesis reactions.
- the stationary grinding chamber 1 may include a pressure control means, such as at least one valve (not shown). It is thus possible to work under a controlled atmosphere.
- the mill 100 may comprise at least one means for controlling the temperature, such as one or more thermocouples disposed on the surface of the grinding chamber 1. For example, they may be integrated into the inlet as well as at the outlet of the grinding chamber.
- the mill also comprises a means of cooling the final product, such as a heat exchanger, disposed outside said stationary milling chamber 1 on the side of the second end 3.
- a means of cooling the final product such as a heat exchanger, disposed outside said stationary milling chamber 1 on the side of the second end 3.
- This cooling means 30 has the advantage of lowering the temperature of the final product so as to avoid any possible thermal runaway.
- the cooling means is able to lower the temperature of the final product to a temperature up to ambient temperature (i.e. 15 and 30 ° C) or at least at a temperature to end the desired synthesis reaction.
- the present invention also relates to a method for implementing the three-dimensional mill 100 as described above, in particular a three-dimensional mill 100 comprising at least:
- a stationary grinding chamber (1) having a generally cylindrical wall extending along a longitudinal axis XX and defining an interior space, said chamber being adapted to receive and mix at least one starting compound, generally at least two, in a liquid medium, so as to form an initial mixture, said stationary grinding chamber (1) being intended to be partially filled with at least one grinding body (6), preferably microbeads,
- stationary grinding chamber (1) comprises, at a first end (2), at least one inlet (4) for introducing said at least one starting compound and said liquid medium and, at a second end (3), a outlet (5) adapted to discharge a final product formed in said stationary grinding chamber (1);
- the stationary grinding chamber (1) incorporating in said interior space at least one heating device (20) which is implanted to heat at least one zone of said stationary grinding chamber (1).
- the method is characterized in that it comprises the following successive steps:
- the method comprises the following additional step:
- the method according to the invention comprises step (i) comprising in particular the start of the heating device, such as induction heating device 20.
- the generator is operated to emit an alternating current that will be transmitted by the contactor and the current supply means to the coil 21.
- the coil will then emit a variable magnetic field that will be captured by the first mixing member 22.
- This first mixing member 22 which is electrically conductive, will be immersed in this magnetic field thanks in particular to the magnetic screen which on the one hand protects the stirrer 10 and the other hand directs the magnetic field towards this one.
- This will form at this first mixing member an induced electric current, also called eddy current.
- the displacement of the electrons forming this induced current dissipates heat by Joule effect at the first mixing member.
- the rod 11 of the stirrer 10 is also rotated.
- the initial mixture is prepared, it is fed to the three-dimensional mill 100 through, generally, the peristaltic pump adjustable flow via the inlet 4.
- the peristaltic pump allows to continue mixing the initial mixture before In addition, as indicated above, this pump makes it possible to introduce the starting suspension into the chamber 1 with a controlled flow rate.
- the initial mixture is introduced at a flow rate greater than or equal to 10 L / h.
- a flow rate greater than or equal to 10 L / h comprises the following values: 10 L / h; L / h; 20 L / h; L / h; L / hr; L / h; 40 L / h; 45 L / h; 55 L / h; 60 L / h; 65 L / h; 70 L / h; 80 L / h; 85 L / h; 90 L / h; 95 L / h; 100 L / h; 110 L / h; 120 L / h; 130 L / h; 140 L / h; 150 L / h; 50 L / h; 55 L / h; 60 L / h; 65 L / h; 70 L / h; 75 L / h; 80 L / h; 85 L / h; 90 L / h; 95 L / h; 100 L / h;
- the initial mixture is introduced at a flow rate ranging from 10 to 130 L / h, preferably from 20 to 100 L / h and typically from 30 to 90 L / h.
- the flow rates may vary depending on the size of the three-dimensional micro-bead mill used to carry out the process.
- the flow rate may be of the order of 40 to 150L / h, such as about 45 L / h; while for larger mills having in particular a stationary chamber 2 of 60L, the flow rate may be of the order of 2 to 15 m 3 / h, such as about 4 m 3 / h.
- the starting suspension travels the stationary chamber 1 of the inlet 4 to the outlet 5, while being set in motion by the stirrer 10 which allows intense mixing of this suspension with the microbeads 6 and, if appropriate, with the mixing members 26, the fingers 28, etc., along the inner wall 7 of the chamber 1.
- the induction heating means 20 makes it possible to heat the flows passing through the chamber 1 at a temperature of at least 60 ° C., preferably from 60 to 800 ° C., in particular from 60 to 400 ° C. for a residence time. less than or equal to 30 minutes, preferably less than or equal to 15 minutes, in particular less than or equal to 1 minute and in particular ranging from 5 to 25 seconds.
- a temperature of at least 60 ° C comprises the following values: 60; 61; 62; 63; 64; 65; 66; 67; 68; 69; 70; 71; 72; 73; 75; 75; 80; 81; 82; 83; 84; 85; 86; 87; 88; 89; 90; 100; 110; 120; 130; 140; 150; 160; 170; 180;
- a residence time of less than or equal to 30 minutes comprises the following values: 30 min, 29 min, 28 min; 27 min; 26 min; 25 min; 20 min; 15 min; 14 min; 13 min; 12 min; 11 min; 10 minutes ; 9 min; 8 min; 7 min; 6 min; 5 minutes ; 4 min; 3 min; 2 min ; 1 min; 55 sec; 50 sec; 45 sec; 40 sec; 35 sec; 30 sec; 25 sec; 20 sec; 15 sec; 10 sec; 5 sec; etc. or any intervals between these values.
- the residence time is generally inherent to the apparent volume of the balls and the flow rate.
- the residence time of the suspension in the chamber 2 is estimated at about 20 seconds. Therefore, the residence time can be advantageously adjusted, for example by controlling the apparent density of the microbeads, as well as the flow rate.
- Appent volume is meant the volume of microbeads including interstitial air between the beads.
- Bulk density is the ratio of microbead mass to apparent volume.
- the rotational speed of the stirrer may for example vary from 4 to 20 pi rad / s, preferably from 4 to 8 pi rad / s.
- the grinding step can be carried out in continuous mode or discontinuous mode in one or more passes (pendulum or recirculation mode).
- the number of passages of the initial mixture and / or of the final product which is reintroduced into the grinding chamber can range from 1 to 50, preferably from 1 to 10, in particular from 1 to 5 (ie, after a first pass, the product obtained at exit 5 is recovered and reinjected again, thanks to the pump, in the chamber 1 via the inlet 4 to allow a second passage).
- a number of passages ranging from 1 to 50 comprises the following values: 50; 49; 48; 47; 45; 40; 35; 30 ; 25; 20; 15; 10; 9; 8; 7; 6; 5; 4; 3; 2; 1.
- the number of passages of the starting suspension is 1 to 2, and preferably 1.
- this grinding step will preferably be performed in continuous mode.
- the final mixture is recovered (iv) at the outlet 5 of the mill 100.
- the final mixture is cooled by the heat exchanger.
- This cooling makes it possible in particular to avoid, if necessary, a runaway of the chemical reaction carried out in the mill.
- the cooling means is able to lower the temperature of the final product to a temperature up to ambient temperature (i.e. 15 and 30 ° C) or at least at a temperature to end the desired synthesis reaction.
- the cooling of the final product is carried out so that it has a temperature of less than or equal to 60 ° C, preferably less than or equal to 50 ° C and typically less than or equal to 30 ° C.
- the final mixture is washed, dried and / or calcined.
- the present invention also relates to the use of the three-dimensional mill 100 as described above for carrying out synthesis reactions of organic and inorganic chemistry or for grinding at least one starting compound.
- XRD X-ray diffractometry
- the detector used is an X'Celerator detector.
- the XRD measurements were performed between 5 ° and 70 ° (scale 2Q) with a pitch of 0.017 °.
- the suspensions of zinc glycerolate crystals were previously dried in air at 50 ° C., so as to obtain a powder.
- Dynomill ECM AP 2L from Willy A. Bachofen AG which contains 1 kg of microbeads, and which has been adapted to include a heating device 20 according to the invention as shown in FIG. 1.
- the mill includes a heater positioned at the inlet of the stationary chamber, and the first mixing member acts as a susceptor.
- the heating device has the following characteristics:
- microbeads are made of zirconium oxide and have a diameter of 0.45 / 0.55 mm.
- the characteristics of the microbeads used for the tests are summarized in Table 3 below:
- Microbeads of 0.45 / 0.55 mm are sold under the brand name Zirmil® Y Ceramic Beads by Saint-Gobain.
- the grinding chamber of the mill has a capacity of 2000 ml and is filled, by volume, relative to its total volume and depending on the tests, 80% of the microbeads described above.
- the microbeads are agitated by an agitator at a speed of rotation of 2890 cm / min.
- the agitator further comprises mixer discs made of chromium cast iron.
- the starting raw materials are: zinc oxide (ZnO) having a purity of 99% marketed by Ampère Industries, and glycerol of 99.5% purity, marketed by Reactolab.
- a starting slurry is prepared in a beaker from zinc oxide and glycerol, according to a weight ratio of glycerol to zinc oxide of 5.5, and a catalyst (acetic acid or zinc acetate), then the starting suspension is stirred with a magnetic stirrer; - It is then fed via a peristaltic pump adjustable flow mill Dynomill ECM AP 2L modified described above: the throughput rate in the mill can reach several hundred L / h. In this test, it was set at 150L / h corresponding to a residence time of about 20s;
- the starting suspension is then passed through the mill having microbeads 0.45-0.55 mm in diameter for a period of time (which depends on the flow rate of the starting suspension) at room temperature (20-25 ° C), allowing thus, at the outlet of the mill, obtaining a suspension of zinc glycerolate crystals;
- a comparative trial was also conducted. This test was carried out using a zinc glycerolate manufacturing method according to the prior art. This test consists in heating in a Z-shaped mixer capable of being heated (2L) zinc hydrozincite (1692 gr) with glycerol (428 gr), a wetting agent Solsperse 21000 (38 gr) and acetic acid as catalyst (3.6 g) for 4-5 hours at 120-130 ° C (Example 1 of US 7,074,949).
- the mill according to the invention makes it possible to carry out the desired chemical synthesis reaction in very short residence times.
- Example 2 carried out with the same catalyst as that described in the prior art and with a residence time of 20 seconds against 4-5 hours for the art previous, the yield obtained is 38%, against 10% without the use of a heating device according to the invention.
- the 38% yield could be improved by increasing the residence time of the initial mixture, for example with several passages in the stationary chamber or with a residence time of 1 to 2 minutes, always well below 4-5 hours of the prior art.
- Example 4 carried out with a catalyst different from that described in the prior art and with a residence time of only 20 seconds, a yield of 100% is obtained as compared with 4 to 5 hours of the prior art, FIG. In addition, the efficiency is 100% with the heating device against only 50% without it: indeed, the residual presence of the ZnO reagent is observed on the diffractrogram, FIG. 4.
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Abstract
Description
Claims
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PL19725763T PL3618966T3 (en) | 2018-05-29 | 2019-05-27 | Three-dimensional grinder, method for implementing same and uses thereof |
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FR1854592A FR3081732B1 (en) | 2018-05-29 | 2018-05-29 | THREE-DIMENSIONAL CRUSHER, ITS IMPLEMENTATION PROCESS AND ITS USES |
PCT/EP2019/063656 WO2019228983A1 (en) | 2018-05-29 | 2019-05-27 | Three-dimensional grinder, method for implementing same and uses thereof |
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EP3618966B1 EP3618966B1 (en) | 2020-08-05 |
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US (1) | US11969734B2 (en) |
EP (1) | EP3618966B1 (en) |
JP (1) | JP7461303B2 (en) |
KR (1) | KR102661290B1 (en) |
CN (1) | CN112512694B (en) |
DK (1) | DK3618966T3 (en) |
ES (1) | ES2827282T3 (en) |
FR (1) | FR3081732B1 (en) |
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2019
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US11919007B2 (en) | 2020-11-18 | 2024-03-05 | Willy A. Bachofen Ag | Agitator ball mill |
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KR20210013568A (en) | 2021-02-04 |
US11969734B2 (en) | 2024-04-30 |
EP3618966B1 (en) | 2020-08-05 |
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JP7461303B2 (en) | 2024-04-03 |
PL3618966T3 (en) | 2021-01-25 |
CN112512694A (en) | 2021-03-16 |
ES2827282T3 (en) | 2021-05-20 |
FR3081732A1 (en) | 2019-12-06 |
CN112512694B (en) | 2022-12-06 |
US20210213459A1 (en) | 2021-07-15 |
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