Powder dosing process

Abstract

The invention relates to a method for dosing non-flowable powders (P). The method comprises the following steps: a) introduction of a cryogenic fluid (FC), powders (P) to be dosed and carbon dioxide in solid form (CO2(s)), the average particle size diameter of which is between 0.1 and 10 times that of the powders (P); b) mixing and suspending the powders (P) with the cryogenic fluid (FC) and carbon dioxide in solid form (CO2(s)), to obtain a cryogenic suspension (SC), the proportion by volume of the powders (P) verifying 10% < [powders]vol < 80%; c) evacuation of the cryogenic suspension (SC); d) controlling the dosing of the powders (P) as a function of one or more parameters (Co) linked to step b) of mixing and suspending; e) dosing of the powders (P). Figure for short: Figure 2

Description

Title of the invention: Method for dosing powders Technical field

[0001] The invention relates to the field of powder dosing, and specifically non-flowable powders which may be of any known type, in particular of high density and / or cohesive.

[0002] It applies to any industrial process using powders, particularly non-flowable powders. It relates to a method for dosing non-flowable powders and an associated device. PRIOR ART

[0003] Conventionally, different ways make it possible to accomplish the function of dosing powders which are presented below according to four concepts.

[0004] Firstly, bucket dosing systems are composed of buckets or dosing forms such as rotating shutters, powder locks, among others. This type of solution is for example described in the article entitled "Continuous mechanical handling of bulk products", Claude SAUDEMONT, Techniques de l'ingénieur, Reference AG7511 vl, July 10, 2002. These systems also have several disadvantages. They can induce a dosage dependent on the granular state of the powders to be dosed, in particular the level of agglomeration, the apparent density, among others. In addition, they lead to a dosage in bursts.

[0005] Furthermore, screw dosing systems are composed of endless screws or also called Archimedean screws which, due to their rotary movement, allow a volume of granular medium to be pushed between each screw pitch. These systems nevertheless have several disadvantages. On the one hand, they are only effective for powders with minimal flowability. On the other hand, they cause a modification of the granular medium due to impacts at pipe bends. In addition, they can lead to a risk of blockage and only allow dosing in bursts, i.e. at each screw pitch.

[0006] In addition, vibrating floor dosing systems are composed of mobiles most often subjected to oscillating vibrational movements to sample the granular medium as continuously as possible. This type of solution is for example described in the thesis “Modeling the dynamic behavior of a vibrating floor: interaction with the granular medium, Benoît GELY, Thesis of the University Sigma Clermont Auvergne, September 2017. These systems also have several disadvantages. They can induce segregation and are sensitive to the granular medium.

[0007] Finally, conveyed or fluidized bed dosing systems are systems in which the powder to be dosed is subjected to a gas flow allowing a gas suspension to be formed with the granular medium which is then withdrawn. These systems also have disadvantages. Indeed, they can lead to non-functional dosing for a non-fluidizable medium and can also cause the segregation of the powders. By "fluidizable" is meant the fact that a powder belongs to class A or B of the GELDART classification as for example described in the article "Characterization and analysis of powders - Physical properties of divided solids", K. Saleh, P. Guigon, Techniques de l'Ingénieur, March 10, 2009.

[0008] Thus, the four types of solutions to the problem of powder dosing are not entirely satisfactory, or even not at all, for the dosing of non-flowable powders.

[0009] In particular, when using powders that are difficult to pour, or even impossible to pour, most of the dosing devices known from the prior art, in particular locks, buckets, and endless screws, induce "staircase" material distribution curves. These distributions are discontinuous and proceed in bursts. For a certain number of applications, such as the dosing of active ingredients in medicines, the dosing of sensitive reagents such as explosives, among others, discontinuous dosing is not acceptable, in particular due to the existence of too many impacts in the event of heterogeneity of the material concentrations in the products to be produced.

[0010] It is thus noted that there remains specifically a need to accomplish the dosing function of a non-flowable, or at least poorly flowable, granular medium, with in particular the following requirements: quickly, continuously, precisely in terms of distributed flow rate, even with granular media known to be non-flowable or fluidizable; without risk of dispersion of fine particles constituting the granular medium to be dosed; whatever the flowability or fluidizable nature of the powder to be dosed; without inducing segregation of the granular medium to be dosed; without compaction of the granular medium.

[0011] Other cryogenic grinding methods and devices are also known from French patent applications FR 3 072 307 A1 and FR 3 072 308 A1 for which the operating parameters are not satisfactory with regard to the stated needs. Statement of the invention

[0012] Consequently, the invention aims to meet at least partially the needs mentioned above and to remedy the drawbacks relating to the embodiments of the prior art.

[0013] Specifically, the invention aims in particular to be able to dose a granular medium as precisely as if it were a fluid but without inducing liquid effluent to be treated and without then having to separate in a manner expensive and / or time-consuming the powder of the vector fluid that could be used for this. It also aims to be able to dose any type of powder, with a particle size ranging from a few nanometers to a few centimeters, and for variable densities without limitation, which can be very low density or on the contrary very dense. Similarly, the invention aims to limit any risk of introducing impurities at the end of the dosage and to allow inerting of the granular medium.

[0014] Also, the invention relates, according to one of its aspects, to a method for dosing non-flowable powders, characterized in that it comprises the following steps:

[0015] a) introduction of a cryogenic fluid, powders to be dosed and carbon dioxide in solid form into a mixing and suspending system, the average diameter of the particle size of the carbon dioxide in solid form being between 0.1 and 10 times that of the particle size of the powders to be dosed,

[0016] b) mixing and suspending the powders with the cryogenic fluid and carbon dioxide in solid form, to obtain a cryogenic suspension, the proportion by volume of the powders satisfying the following equation (i):

[0017] (i): 10% < [powders]voi < 80%,

[0018] where:

[0019] [powders]voi is the proportion in volumetric mass of the powders,

[0020] c) evacuation of the cryogenic suspension, comprising the withdrawal of the cryogenic suspension, in particular under conditions of temperature greater than or equal to ambient temperature and pressure less than or equal to atmospheric pressure,

[0021] d) control of the dosage of the powders as a function of one or more parameters linked to step b) of mixing and suspension,

[0022] e) dosage of the powders.

[0023] The dosing method according to the invention is thus suitable for powders described as “non-flowable”. The concept of “flowability” corresponds to the property of a granular medium to flow naturally. It can be characterized by several methods. One of them can be derived from a Carr index type measurement. By definition, this index is determined as the ratio between the difference between the apparent volume occupied by a given quantity of powders and the packed volume of the same quantity of powders, all normalized to the apparent volume. Above a Carr index of 25, the granular medium is conventionally considered to be very poorly flowable. Below a Carr index of 15, the granular medium is considered to be relatively well flowable. Thus, within the meaning of the invention, non-flowable powders are understood to mean powders whose Carr index is strictly greater than 15, and preferably greater than or equal to 25.

[0024] Furthermore, the notion of “average diameter” of a granular medium is used to the extent that the granular medium considered is not made up of solid particles having all the same size and not generally strictly spherical. The particle size is in this case a distribution of size, surface area, or even equivalent volume. To this static distribution, it is possible to associate a notion of average dimension also called "average diameter". Such a notion is for example described in the article "Characterization of particle size", John DODDS, Gérard BALUAIS, Sciences Géologiques, bulletins and memoirs, 46-1-4 pages 79-104, 1993.

[0025] The choice of the range of values ​​of the average diameter of the particle size of carbon dioxide in solid form compared to that of the particle size of the powders to be dosed is advantageous in that it results from the taking into account of a significant number of factors and physical phenomena, concomitantly integrating rheological criteria, stability to sedimentation and energy efficiency.

[0026] As regards the rheological aspect, it must be taken into account in particular in terms of viscosity and overall flow behavior. As regards viscosity, it is correlated with the particle size but also with the incorporation rate (quantity of solid matter in a given volume of liquid). While there may be a link between particle size and viscosity, this link is not, however, direct when the suspended solids are not strictly monomodal (monomodal case only when the powders are called model powders, which is not the case in real cases of industrial use). However, the real powders to be transported are not monomodal and solid carbon dioxide cannot, moreover, have strictly the same particle size as the powder to be transported (in average diameter and / or in particle size range).Therefore, it is important to be able to adjust the average diameter of the carbon dioxide to obtain a suspension that is of acceptable viscosity to be circulated through a hydraulic system without spending too much energy for this. This adjustment cannot be known a priori and must be adjusted on a case-by-case basis. Furthermore, the incorporation rate, the polydispersity of the solids, and even their morphologies, also affect the overall behavior of the suspension in flow. There is no direct correlation between all these parameters and the behavior of the suspension, which can be either Newtonian, rheo-thickening, rheo-thinning, or even thixotropic. Ideally, we will seek Newtonian behavior, but some systems cannot easily approach it.

[0027] As regards stability to sedimentation, the behavior of suspension in a liquefied gas medium is not known to those skilled in the art. Indeed, this type of suspension does not induce an electric charge interaction between the liquid and the solid (the liquefied gas liquid being totally anionic and free from a charge inversion layer as in conventional liquids). In the case of very fine solids (less than a micron, or even a few hundred nanometers), atypical behaviors can be created (impact of Brownian motion for example). It is also possible that there may be agglomeration of aggregates of solid matter which then leads to accelerated sedimentation of the solid phase. If the carbon dioxide used instead of being very fine is relatively coarse compared to the powder transported, this can help avoid these phenomena but in return the mixture will lose its homogeneity, which is not favorable for the intended transport function. It should also be noted that if the average diameter of the solid carbon dioxide is too large, this phase will be impacted (for example mixing, high pressure losses induced, etc.) by the narrow passages of the hydraulic circuits used to transport the suspension.

[0028] To take into account all of these parameters and phenomena, the average diameter of the particle size of carbon dioxide in solid form is between 0.1 and 10 times that of the particle size of the powders to be dosed. More preferably, to have a more optimized compromise, in particular between rheology and stability to decantation, the average diameter of the particle size of carbon dioxide in solid form may be between 1 and 8 times that of the particle size of the powders to be dosed, in particular between 2 and 6 times that of the particle size of the powders to be dosed.

[0029] Furthermore, the conditions of equation (i) given above advantageously allow the production of a stable and pumpable cryogenic suspension. Also, advantageously, the cryogenic suspension is stable and pumpable thanks to the conditions laid down in the invention concerning the average diameter of the particle size of the carbon dioxide in solid form and the proportion by volume of the powders.

[0030] It should be noted that by "stable" is meant that a suspension is considered stable when the time required for complete settling of the suspension is at least ten times greater than the time of the transport, or transfer, operation thereof. Typically, in the context of the invention, the transport, or transfer, time of powders may be of the order of a few minutes while the stability time may be of the order of one hour.

[0031] Advantageously, the presence of carbon dioxide in solid form in the cryogenic suspension can act as a steric stabilizer for the powders in order to prevent their sedimentation.

[0032] It should be noted that by "pumpable" is meant the ability of a formulation to be implemented by means of a conventional pumping system, such as a piston or rotor pump. It should be noted, however, that a suspension characterized as "pumpable" is not necessarily intended to be pumped but is capable of being so if necessary. This notion of "pumpable" appears for example in the presentation entitled "Formulation, homogeneity and pumpability", François DE LARRARD, Bé-tonlabPro 3, Lesson No. 13, Laboratoire Central des Ponts et Chaussées - Centre de Nantes (LCPC). More intrinsically, a suspension is considered as "pumpable" to the extent that the driving force accessible by conventional pumping systems (particularly piston or rotor pumps) to enable its movement in a given circuit is greater than the braking force induced by the viscosity of the suspension. Conventionally, a suspension with a viscosity of around 100,000 mPa.s is considered non-pumpable. A suspension with a viscosity of less than 20,000 mPa.s is considered pumpable.

[0033] The method according to the invention may further comprise one or more of the following characteristics taken in isolation or in any possible technical combination.

[0034] Advantageously, the cryogenic fluid is a liquefied gas at ambient temperature and pressure. It may in particular be liquid nitrogen (N2). However, this choice is not limiting. The cryogenic fluid makes it possible to define the fluidic behavior, in particular liquid, of the cryogenic suspension and makes it possible, where appropriate, to maintain the carbon dioxide (CO2) in solid form.

[0035] Furthermore, solid carbon dioxide, also called dry ice, can be in the form of granules and / or powders. This dry ice, due to its size or occupancy rate in the cryogenic suspension, makes it possible to stabilize the powders to be dosed.

[0036] The first step a) may advantageously comprise the following successive sub-steps:

[0037] al) introduction of the cryogenic fluid and carbon dioxide in solid form into the mixing and suspending system, then

[0038] a2) introduction of powders to be dosed into the mixing and setting system suspension.

[0039] Advantageously, the introduction of the cryogenic fluid and the carbon dioxide, preferably carried out simultaneously, precedes the introduction of the powders to be dosed.

[0040] The duration between the two sub-steps a1) and a2) can be very short, in particular of the order of a few seconds, and thus the second sub-step a2) can be carried out almost immediately after the first sub-step a1).

[0041] Nevertheless, in general, the duration between the two sub-steps a1) and a2) may depend on the time taken to obtain a homogenized and good quality suspension between the cryogenic fluid and the carbon dioxide. In particular, the second sub-step a2) may be implemented when the stirring torque of the mixture between the cryogenic fluid and the carbon dioxide is substantially constant, in particular with a variability of less than 10%, better still 5%.

[0042] The evacuation of the cryogenic suspension advantageously corresponds to a movement of the cryogenic suspension to allow its evacuation. It can thus understand the withdrawal of the cryogenic suspension and also the volatilization of the cryogenic suspension. Volatilization can be induced by the temperature and pressure conditions established during evacuation or can be obtained by means of volatilization means provided for this purpose.

[0043] Furthermore, the carbon dioxide loading rate in solid form can be between 0.1 and 10 times that of powders to be transported.

[0044] Step d) of controlling the dosage of the powders can allow the acquisition and processing of the measurement of the stirring torque of the cryogenic suspension, to allow one or more control actions on one or more controllable members.

[0045] Furthermore, the invention also relates, according to another of its aspects, to a device for dosing non-flowable powders for implementing the method for dosing non-flowable powders as defined above, characterized in that it comprises:

[0046] - a system for supplying powders, carbon dioxide in solid form and in cryogenic fluid, comprising means for controlled introduction of the powders to be dosed and means for controlled introduction of carbon dioxide in solid form,

[0047] - a system for mixing and suspending the powders, the carbon dioxide carbon in solid form and cryogenic fluid to obtain a cryogenic suspension,

[0048] - a system for evacuating the cryogenic suspension, comprising a device for withdrawal of the cryogenic suspension associated with a mass flow meter,

[0049] - a powder dosing control system.

[0050] The mixing and suspending system may further comprise: a mixing tank; a mixing and stirring device, located inside the mixing tank; a means for measuring the level of the cryogenic suspension formed, at least partly located inside the mixing tank.

[0051] Furthermore, the mixing and suspending system may include an optical monitoring system for controlling the concentration homogeneity in the cryogenic suspension. DESCRIPTION OF FIGURES

[0052] The invention may be better understood by reading the detailed description of the non-limiting examples of its implementation and by examining the schematic and partial figures, in which:

[0053] [Fig.l] represents a simplified flowchart of the dosing principle with a dosing device for implementing a dosing method according to the invention,

[0054] [Fig.2] schematically illustrates an example of a device for dosing non-powders castable for implementing a dosing method in accordance with the invention,

[0055] [Fig.3A] is a schematic view along a section plane along the Z axis of [Fig.2]

[0056] and [Fig.3B] is a schematic view to the left of the sectional view of [Fig.3A], illustrating the principle of volatization and evaporation of the cryogenic suspension,

[0057] [Fig.4A],

[0058] [Fig.4B]

[0059] and [Fig.4C] illustrate, in sectional views, possible variants of mixing and stirring devices for the mixing and suspending system of a dosing device for implementing a dosing method according to the invention,

[0060] [Fig.5] graphically illustrates the evolution of the agitation torque of the suspension cryogenic as a function of stirring time and three solid charge introductions,

[0061] [Fig.6] represents the evolution of viscosity as a function of shear rate for suspensions of alumina and dry ice in liquid nitrogen, and

[0062] [Fig.7] represents the evolution of the viscosity as a function of the shear rate for different concentrations of dry ice suspensions in liquid nitrogen.

[0063] Throughout these figures, identical references may designate identical or similar elements.

[0064] Furthermore, the different parts represented in the figures are not necessarily on a uniform scale, in order to make the figures more readable. PRESENTATION OF IMPLEMENTATION METHODS

[0065] The cryogenic fluid FC here is liquefied nitrogen (N2) but this choice is not limiting.

[0066] [Fig. 1] is a simplified flowchart of the control necessary for the proper conduct of the dosage to specify the sequence of measurements and input and output data necessary for controlling the dosage of a dosage device for the implementation of a dosage method according to the invention.

[0067] [Fig. 2] represents an example of a device 30 for dosing non-flowable powders P for implementing a dosing method according to the invention. This firstly comprises a system SI for supplying powders P and cryogenic fluid FC, which comprises means 43a for controlled introduction of the powders P to be dosed and, in this example, means 43b for controlled introduction of carbon dioxide in solid form CO2(s).

[0068] Furthermore, the device 30 comprises a system S2 for mixing and suspending the powders P, the cryogenic fluid FC and the carbon dioxide in solid form CO2(s) to obtain a cryogenic suspension SC. It also comprises a system S3 for discharging the cryogenic suspension SC, and finally a system S4 for controlling the dosage of the powders P.

[0069] Furthermore, the evacuation system S3 of the cryogenic suspension SC comprises a device for withdrawing and, in this example, for volatilizing 91, 92 the cryogenic suspension SC associated with a mass flow meter 90. It is necessary that, as a variant, the volatilization can be obtained spontaneously without the use of dedicated volatilization means by the temperature and pressure conditions applied. In particular, the temperature can be greater than or equal to ambient temperature and the pressure can be less than or equal to atmospheric pressure.

[0070] The control system S4 is configured to allow the acquisition and processing of the measurement of the stirring torque Co of the cryogenic suspension SC.

[0071] Such a device 30 makes it possible to implement the method according to the invention. Thus, a step a) allows the introduction of the cryogenic fluid FC, the powders P to be dosed and the carbon dioxide in solid form CO2(s) into the mixing and suspension system S2.

[0072] This step a) can be carried out with simultaneous introduction of the constituents. However, advantageously, step a) comprises two successive sub-steps: a step a1) of introducing the cryogenic fluid FC and carbon dioxide in solid form CO2(s) into the mixing and suspension system S2, then a step a2) of introducing powders P to be dosed into the mixing and suspension system S2.

[0073] Advantageously, the average diameter of the particle size of the carbon dioxide in solid form CO2(s) is between 0.1 and 10 times that of the particle size of the powders P to be dosed, and the proportion by volume mass of the powders P verifies the following equation (i):

[0074] (i): 10% < [powders]vol < 80%,

[0075] in which [powders]voi is the proportion in volumetric mass of the powders P.

[0076] A step b) is then implemented for mixing and suspending the powders. P with the cryogenic fluid FC and carbon dioxide in solid form CO2(s), followed by a step c) of evacuation of the cryogenic suspension SC, comprising the withdrawal of the cryogenic suspension SC, under conditions of temperature greater than or equal to ambient temperature and pressure less than or equal to atmospheric pressure.

[0077] A step d) allows the control of the dosage of the powders P as a function of one or more parameters Co linked to step b) of mixing and suspension, and a step e) ensures the dosage of the powders P.

[0078] The system for mixing and suspending S2 the powders P, the cryogenic fluid FC and the carbon dioxide in solid form CO2(s) to obtain a cryogenic suspension SC may in particular comprise at least in part the elements of the devices described in French patent applications FR 3 042 985 A1 and FR 3 042 986 A1

[0079] This system S2 comprises a mixing tank 41. The mixing tank 41 is heat-insulated, thermally insulated, to allow the liquefied gas to be stored in the form of liquid nitrogen without excessive volatilization. Ideally, heat losses would be of the order of 2% per day or even less.

[0080] Also, the system S2 comprises a mixing and stirring device 42, located inside the mixing tank 41. This mixing and stirring device 42 may in particular be a stirring device, for example of the blade, propeller, turbine, anchor, attritor or other type, chosen in particular according to the viscosity of the cryogenic suspension SC envisaged. It may be any other profile possibly assisted by one or more acoustic stirring systems, such as ultrasonic stirring rods for example. The mixing and stirring device 42 may for example be a blade-type stirring device as shown in [Fig.4A], or a turbine-type stirring device as shown in [Fig.4B], or a porous distribution element with an injection of liquefied nitrogen N2(l) as shown in [Fig.4C].

[0081] The mixing and stirring device 42 is driven in rotation to generate stirring by means of a drive motor 45. This motor 45 incorporates a means for measuring the torque Co of the cryogenic suspension SC in order to identify whether the suspension is homogeneous, the torque Co then being substantially constant with a variability of less than 10%, or even 5%, and the loading rate being adapted. This mixing and stirring device 42 may also be supplemented by an ultrasonic stirring system 98, for example a stirring sonotrode, to avoid possible accumulation at the bottom of the tank 41, and / or by the use of an upward flow of chemical inert gas, such as nitrogen, to promote stirring depending on the granular medium to be dosed.

[0082] The means 43a, 43b for controlled introduction of the powders P to be dosed and of the carbon dioxide in solid form CO2(s) into the mixing tank 41 particularly comprise a first feed hopper 43a for introducing the powders P to be dosed and a second feed hopper 43b for introducing the carbon dioxide in solid form CO2(s). The controlled introduction is carried out by weighing or dosing. To do this, the feed hoppers 43a, 43b are used in conjunction with weighing systems 46a, 46b corresponding to suspended scales or load cells. It is thus possible to monitor the mass introduced as a function of time.

[0083] Furthermore, the supply system SI comprises a first insulated liquid nitrogen supply tank 71 and a second compressed gas nitrogen supply tank 72. In addition, a mass flow meter 74 is present at the mixing tank 41, for example of the Coriolis or ultrasonic type.

[0084] It should be noted that depending on the specificity of the granular medium to be transported, namely the cryogenic suspension, in particular depending on its particle size and density, the proportions of powders P, possibly carbon dioxide in solid form CO2(s) and liquid nitrogen may vary. However, in order to obtain a cryogenic suspension SC which is stable and pumpable within the meaning of the definitions given above, the proportion by density of the powders P verifies the following equation (i): (i): 10% < [powders]voi < 80%, in which [powders]voi is the proportion by density of the powders P.

[0085] In [Fig.2], it should also be noted the presence of a valve 101 for overpressure and allowing the supply of gaseous nitrogen for pressurizing the tank 41; and the presence of a three-way valve 102 allowing online sampling for granulometric diagnosis.

[0086] With a view to obtaining a cryogenic suspension SC which is pumpable and stable within the meaning of the invention, the major parameters to be determined and / or monitored are:

[0087] - the powder loading rate P, namely the volume of solid over the total volume of the SC suspension: we will advantageously seek to increase this rate to the highest possible value to optimize the quantity of P powders dosed for a given volume of displaced cryogenic SC suspension;

[0088] - possibly, the loading rate of carbon dioxide in solid form CO2(s): this rate is classically a function of the quantity of powders P to be introduced into the cryogenic suspension SC;

[0089] - the density of the powders P to be dosed: generally speaking, the more the powders P will be dense and with a high granulometry, the more we will seek to constitute viscous suspensions incorporating significant quantities of carbon dioxide CO2(s) to limit the risks of decantation of the P powders to be dosed within the cryogenic suspension SC;

[0090] - possibly the particle size of carbon dioxide in solid form CO2(s), given in particular by the average diameter of the particle size distribution of carbon dioxide available to formulate the cryogenic suspension SC;

[0091] - the particle size of the powders P given in particular by the average diameter of the dis granulometric distribution of the granular medium to be transported.

[0092] Also, advantageously:

[0093] - the granulometry of carbon dioxide in solid form CO2(s) is linked to that of P powders to be dosed: the average diameter being approximately between 0.1 and 10 times the particle size of the P powders to be dosed, or even between 1 and 8 times, or even between 2 and 6 times the particle size of the P powders to be dosed;

[0094] - the rate of carbon dioxide loading in solid form CO2(s) is linked to that of the P powders to be dosed: more precisely, it is roughly of the same order of magnitude, the value being between approximately 0.1 and 10 times the content of powders to be dosed;

[0095] - the liquid nitrogen content is limited as much as possible: it is advantageously less than 70% by volume; this liquid nitrogen content must nevertheless make the suspension flowable and cannot be less than 5% by volume;

[0096] - the particle size of the solid phase, comprising the powders P to be dosed and here the carbon dioxide in solid form CO2(s), is less than 10 times the diameter of the transport pipe, otherwise segregation could occur and cause the integrity of the granular medium to be dosed to be lost.

[0097] Advantageously, the particle size of the dry ice can be between 500 and 900 μm.

[0098] Regarding the suspension of powders P in the cryogenic fluid FC, it is necessary to control the homogeneity of distribution of the powders P because this corresponds to controlling the dosed mass. Indeed, the uncertainty of the dosed flow rate can be expressed as follows as a function of the uncertainty on the homogeneity, or more precisely on the variance by equation (ii):

[0099] dM / M = dQ / Q + dV / V + dt / t (ii),

[0100] where:

[0101] M represents the measured mass,

[0102] Q represents the mass flow rate,

[0103] V represents the variance, and

[0104] t represents the dosing time.

[0105] In order to guarantee good homogeneity, i.e. a low variance V, ideally even close to zero, it is necessary to ensure perfectly stirred reactor type agitation within the tank 41 for forming the cryogenic suspension. In other words, at each point in the volume of the tank 41, ideally, there is the same concentration of powders P. Thus at the outlet of the tank 41, the concentration of powders P corresponds to the average concentration in the tank 41 and the mass of powders P dosed is thus controlled by controlling the dosing time by means of this equation (ii).

[0106] Furthermore, the system S2 comprises a means 44 for measuring the level of the cryogenic suspension SC formed, at least partly located inside the mixing tank 41. More particularly, this measuring means 44 can take the form of a bubbling rod or an ultrasonic probe.

[0107] Advantageously, the system S2 also comprises an optical monitoring system 94 for controlling the homogeneity of concentration in the cryogenic suspension SC. This may correspond to a flowmeter coupled to a laser diode or a camera with image analysis for identifying the homogeneity of particle concentration online. It is associated with a peristaltic pump 95 allowing the circulation of the suspension towards the optical monitoring system 94.

[0108] Furthermore, the evacuation system S3 comprises a heat-insulated pipe 53 which allows the transport of the formulated suspension while limiting thermal losses to the arrival point. The length of the insulated pipe 53 must be chosen such that the travel time must be much less than the stability time of the solution, in particular of the order of at least a factor of 10. The pipe 53 is associated with a mass flow meter 90, of the Coriolis or ultrasonic type for example.

[0109] The withdrawal and volatilization device 91, 92 of the evacuation system S3 also comprises an exchanger and evaporator device 92 which allows the exchange and evaporation of the liquefied nitrogen phase N2(l). The cryogenic suspension SC is thus continuously evacuated by means of pressurization within the production tank 41 to ensure easy and controlled withdrawal. It also comprises a porous element, called poral, 92 which corresponds to a nitrogen vapor evacuation tube while allowing the inerting or sheathing of the outlet to avoid the formation of a frost plug at the outlet.

[0110] Figures 3A and 3B illustrate the principle of volatization and evaporation of the cryogenic suspension SC. In these figures, the references Sp, A, X and Sp represent respectively the surface of the cryogenic suspension, the air circulating nearby, the axis of symmetry and a heating resistor. In addition, a seal 110 is provided.

[0111] To stabilize the cryogenic suspension SC, it is also possible to electrostatically charge the powders P to be dosed. To do this, the powders P can be previously subjected to a significant electrical potential difference or can be charged by induced friction in a container whose oscillation will create wall friction against powders charging the latter depending on the nature of the wall of the container used.

[0112] Furthermore, to ensure good mixing by mechanical effect, it is necessary to rotate the stirring rotor 42 in such a way that it does not leave powders in contact with the wall of the bottom of the 4L tank. The minimum rotation speed of the rotor 42 must at least induce turbulence whose speed is greater than the detachment speed. By "detachment speed", we mean a speed of the liquid phase of a suspension for which the detachment phenomenon occurs. To summarize, the detachment phenomenon is a phenomenon that applies to a laminar boundary layer and which is often the origin of the turbulence because it produces potentially unstable zones. During detachment, the zero speed point that was initially stuck to the wall is found in volume: this is the detachment, and a new return speed boundary layer appears on the wall.It is recommended by Mersmann, in the article “Theoretical prediction of the minimum stirrer speed in mechanically agitated suspensions”, Mersmann A., Wemer F., Maurer S., Bartosch K., Chem. Eng. Process., vol. 37, pp. 503-510, 1998, to impose a speed . of rotation (Nmin) of the stirring mobile 42 at least equal to a value which can be expressed by the following relation:

[0113] in which:

[0114] Nmin represents the minimum stirring speed;

[0115] Np represents the power number (parameter evaluable according to the type of stirring mobile);

[0116] Dt represents the diameter of the stirring wheel;

[0117] D represents the diameter of the stirring tank;

[0118] dp represents the diameter of the powder particles;

[0119] g represents the unit of gravity;

[0120] ps represents the density of the powders; and

[0121] pL represents the density of the liquefied gas.

[0122] To ensure good mixing by fluidization, the liquefied gas phase must have a sufficient superficial velocity, compared to that of the powders P, which depends on the particle size of the granular medium to be fluidized and in particular on the physicochemical properties of the liquefied gas. More precisely, the minimum superficial velocity to be ensured must have the minimum fluidization value umF. This velocity is expressed using the following relationship linking the Reynolds number to that of Archimedes:

[0123] with:

[0124] emF represents the porosity of the powder bed to be fluidized; and

[0125] hk and hB are coefficients corresponding to the configuration of the system to be considered.

[0126] Thus, for example, for a powder bed which can be considered spherical: e,Hi ~ 0.4, with hK ~ 4.2 and hB ~ 0.3, we have Cl ~ 25 and C2 ~ 0.04.

[0127] In addition, the suspension can be stabilized by the use of solid carbon dioxide CO2(s) or by the application of electrostatic charges. The powders P are then charged by charge carriers of the same sign and the liquefied gas being neutral, the Powder grains, approaching naturally through sedimentation, will repel each other due to electrostatic repulsion and therefore maintain a state of equilibrium at the dispersion level.

[0128] Also, the electrostatic charging of the powders P can be done by triboelectricity or charging by discharge. As regards electrostatic charging by tribology, the powders are placed in a reservoir whose nature is chosen so that a transfer of electrons can take place between the powders P and the walls of the reservoir coming into contact with the latter. The transfer is possible and more or less easy depending on the charging potential of each of the materials coming into friction with each other.

[0129] Furthermore, the control system S4 for the evacuation of the cryogenic suspension SC allows in particular the evacuation of the cryogenic suspension SC as a function of at least one parameter linked to the mixing and suspension system S2, in particular the couple Co. The control system S4 makes it possible to compile all of the measurements carried out on the powder dosing device 30 P, and allows the control actions or feedback on the controllable members, such as valves, pump, stirring motor, etc.

[0130] Thus, the S4 control system integrates the acquisition and processing of several data:

[0131] - the measurement of the quantity of materials of dry ice MC02 and powders Powder, as well as cryogenic fluid FC, so as to evaluate the volume and / or mass contents of the constituents of the cryogenic suspension SC;

[0132] - measuring the level of the mixing tank 41 to avoid its clogging and evaluate the density of the formed cryogenic SC suspension;

[0133] - the measurement of the stirring torque Co allowing the viscosity of the cryogenic suspension SC and allowing to check that it is homogeneous and sufficiently agitated;

[0134] - the optical measurement for the solid concentration within the tank 41;

[0135] - pressure measurement to adjust the measured suspension movement rate by mass flow meter.

[0136] Furthermore, in order to achieve a homogeneous suspension and allow precise dosing of the powders to be distributed, it is possible to distinguish three possible strategies.

[0137] Firstly, the preparation of dilute suspension. This is the preferred case for powders of small particle size and low density. The volume concentration threshold of powders to be dosed in the cryogenic fluid FC can be in the interval ]0; 10%] for this type of suspension. Stabilization of the suspension by electrostatic charge is possible for these cases of dilute solution.

[0138] Secondly, the development of dense suspension. This is the preferred case for powders with a larger particle size and high density. The volume concentration threshold for powders to be dosed in the cryogenic fluid FC can be in the range ]20%; 80%] for this type of suspension. Stabilization of the suspension by electrostatic stability becomes difficult from 20% of the solid incorporation rate in the suspension. To stabilize the suspension, from these thresholds (order of magnitude since they depend not only on the concentration but also on the particle size and density of the powders in particular), it is possible to stabilize the suspensions by steric hindrance and increasing the viscosity of the suspension by introducing solid carbon dioxide CO2(s).

[0139] Thirdly, the development of intermediate density suspension. The volume concentration threshold of powders to be dosed in the cryogenic fluid FC can be in the range ]10%; 20%] for this type of suspension. In this case, a combination of mechanical and / or ultrasonic and / or convective flow stirring means should be considered.

[0140] It should be noted that the stirring speed must allow a sufficient level of turbulence to be achieved. It should be noted that when the particles are detached from the bottom of the tank 41, the aim is to avoid stagnation of particles at the bottom of the tank and with an even higher level of turbulence, the aim is to obtain a homogeneous distribution of the particles in the volume of the suspension. It is this homogeneity of distribution of particles in the suspension that the present invention makes it possible to obtain.

[0141] Also, for complete suspension, namely when no particles remain at the bottom of the stirred tank 41, all the particles must be detached and redeposition must be made impossible.

[0142] However, to obtain a homogeneous suspension, it is necessary to increase the stirring speed, knowing however that the ideal homogeneity of the solid phase placed in the suspension constitutes an asymptote. Note that in practice, a suspension with an Archimedes number greater than 10 cannot achieve complete homogeneity.

[0143] Generally, there is a compromise between homogeneity and energy to be introduced into the suspension in the form of turbulence. The optimal stirring speed corresponding to this compromise is of the order of 1.8 to 2 times the value of the minimum stirring speed.

[0144] All of these requirements must make it possible to optimize the homogeneity of the P powders for a given and optimized volume of cryogenic suspension, while guaranteeing the possibility of implementing the suspension by pressurization. This results in a limited viscosity, of the order of 100,000 mPa.s, and the formulation of a suspension adapted to the evacuation piping at the metering device.

[0145] Concerning the stirring torque parameter Co, [Fig.5] represents gra phically the value of the stirring torque Co as a function of time t. The references AO, Al, A2 and A3 correspond respectively to the no-load torque, to a first addition of solid charge, to a second addition of solid charge and to a third addition of solid charge. Thus, with each introduction of material Al, A2 and A3, the torque Co increases for a given stirring speed. However, after a certain stirring time, the torque Co tends to stabilize as shown by the levels in [Fig.5]. This then makes it possible to possibly introduce an additional quantity of powders P into the cryogenic suspension SC if the transport flow rate setpoint requires it, for example.

[0146] By means of figures 6 and 7, the rheological behavior of several SC cryogenic suspensions that can be envisaged within the framework of the invention is described.

[0147] Specifically, [Fig.6] represents the evolution of the viscosity v, expressed in mPa.s, as a function of the shear rate te, expressed in s1, for suspensions of alumina (Al 2O3), dry ice in liquid nitrogen.

[0148] [Fig.6] illustrates the rheological behavior of three systems: A12O3 / CO2: liquid nitrogen suspension containing nearly 10% (volume) of A12O3 and 48% (volume) of solid CO2; CO2: liquid nitrogen suspension containing 48% of solid CO2; and A12O3: liquid nitrogen suspension containing 10% of A12O3.

[0149] This experimental curve makes it possible to indicate that the viscosities of the suspensions considered show manageable rheological properties in terms of circulation and agitation, namely that the viscosity is not too high to be pumpable or that it is possible to agitate without excessive energy expenditure. Furthermore, these experimental elements acquired by the inventors show that the behaviors of the suspensions considered can be similar in the experimental range considered to Newtonian fluids.

[0150] [Fig.7] also represents the evolution of the viscosity v, expressed in mPa.s, as a function of the shear rate te, expressed in s1, for different concentrations of dry ice suspensions in liquid nitrogen.

[0151] Specifically, [Fig.7] illustrates the rheological behavior of five systems: 34%: liquid nitrogen suspension containing nearly 34% (mass) of solid CO2; 48%: liquid nitrogen suspension containing nearly 48% (mass) of solid CO2; 51.8%: liquid nitrogen suspension containing nearly 51.8% (mass) of solid CO2; 64%: liquid nitrogen suspension containing nearly 64% (mass) of solid CO2; 77.6%: liquid nitrogen suspension containing nearly 77.6% (mass) of solid CO2.

[0152] This experimental curve makes it possible to indicate that the viscosities of the suspensions considered show manageable rheological properties in terms of circulation and agitation, namely a viscosity not too high to be pumpable or that one can agitate without too much energy expenditure. This aspect is not trivial at in particular given the significant proportion of solids constituting these suspensions. Furthermore, these experimental elements acquired by the inventors show that the behavior of the suspensions considered can be similar in the experimental range considered to Newtonian fluids, which allows for more consolidated control and management of the process.

[0153] Consequently, Figures 6 and 7 illustrate the viscosities of cryogenic suspensions and show the influence of the dry ice content on the viscosity of the fluid to be transferred.

[0154] Generally, the rheological behavior of SC cryogenic suspensions can be approached by semi-empirical laws. As an example, an expression of the suspension viscosity as a function of the loading rate and the particle size of the solid constituting this suspension can be given below by equation (ii):

[0155] (ii): p / po = (1 + ^[N] <D / (l-<D / <Dm)2,

[0156] where:

[0157] p is the viscosity of the suspension;

[0158] po is the viscosity of the liquid phase;

[0159] [N] is a constant;

[0160] <!----> is the volume of solid in the volume of the suspension;

[0161] Om is the maximum volume of solid in the volume of the suspension.

[0162] Knowing the viscosity of the suspensions, it is then possible to deduce the flow rate of possible distribution Qv of the doser as a function of the overpressure to be applied within the tank to ensure a flow rate in accordance with the powder dosing instruction. We can thus obtain equation (iii) given below:

[0163] (iii): AP = (8-pL) -Qv / Or-R4),

[0164] where:

[0165] AP is the pressure difference between upstream and downstream of the flow meter;

[0166] p is the viscosity of the suspension;

[0167] Qv is the volume flow rate;

[0168] R is the radius of the fluid transport pipe;

[0169] L is the length of the transport pipe.

[0170] The invention is of course not limited to the embodiments which have just been described. Various modifications can be made thereto by those skilled in the art.

Claims

Claims

1. Method for dosing non-flowable powders (P), characterized in that it comprises the following steps: a) introduction of a cryogenic fluid (FC), powders (P) to be dosed and carbon dioxide in solid form (CO2(s)) into a mixing and suspension system (S2), the average diameter of the particle size of the carbon dioxide in solid form (CO2(s)) being between 0.1 and 10 times that of the particle size of the powders (P) to be dosed, b) mixing and suspending the powders (P) with the cryogenic fluid (FC) and the carbon dioxide in solid form (CO2(s)), to obtain a cryogenic suspension (SC), the proportion by volume of the powders (P) satisfying the following equation (i): (i): 10% < [powders]voi < 80%, where: [powders]voi is the proportion by mass volume of powders (P), c) evacuation of the cryogenic suspension (SC), including the withdrawal of the cryogenic suspension (SC),under conditions of temperature greater than or equal to ambient temperature and pressure less than or equal to atmospheric pressure, d) controlling the dosage of powders (P) as a function of one or more parameters (Co) linked to step b) of mixing and suspending, e) dosage of powders (P).,

2. Method according to claim 1, characterized in that the first step a) comprises the following successive sub-steps: a1) introduction of the cryogenic fluid (FC) and carbon dioxide in solid form (CO2(s)) into the mixing and suspension system (S2), then a2) introduction of powders (P) to be dosed into the mixing and suspension system (S2).

3. Method according to claim 1 or 2, characterized in that the average diameter of the particle size of the carbon dioxide in solid form (CO2(s)) is between 1 and 8 times that of the particle size of the powders (P) to be dosed, in particular between 2 and 6 times that of the particle size of the powders (P) to be dosed.

4. Method according to one of the preceding claims, characterized in that the rate of loading of carbon dioxide in solid form (CO2(s))

5.

6.

7.

8. is between 0.1 and 10 times that of powders (P) to be dosed. Method according to any one of the preceding claims, characterized in that step d) of controlling the dosage of the powders (P) allows the acquisition and processing of the measurement of the stirring torque (Co) of the cryogenic suspension (SC), to allow one or more control actions on one or more controllable members. Method according to any one of the preceding claims, characterized in that the cryogenic fluid (FC) is liquid nitrogen. Method according to any one of the preceding claims, characterized in that the solid carbon dioxide (CO2(s)) is in the form of granules and / or powders. Device (30) for dosing non-flowable powders (P) for implementing the method for dosing non-flowable powders (P) according to any one of the preceding claims, characterized in that it comprises: - a supply system (SI) for powders (P), carbon dioxide in solid form (CO2(s)) and cryogenic fluid (FC), comprising means for controlled introduction (43a) of the powders (P) to be dosed and means for controlled introduction (43b) of carbon dioxide in solid form (CO2(s)), - a system for mixing and suspending (S2) the powders (P), the carbon dioxide in solid form (CO2(s)) and the cryogenic fluid (FC) to obtain a cryogenic suspension (SC), - a system for discharging (S3) the cryogenic suspension (SC), comprising a device for withdrawing (91, 92) the cryogenic suspension (SC) associated with a mass flow meter (90), which withdrawal device is configured to withdraw the cryogenic solution under conditions of temperature greater than or equal to ambient temperature and pressure less than or equal to atmospheric pressure, - a system for controlling (S4) the dosage of the powders (P), configured to, on the one hand, control the system (SI) for supplying powders, carbon dioxide in solid form and cryogenic fluid so that the proportion ([powders]vol) in density of the powders (P) satisfies the following equation (i): 10% < [powders]voi < 80%, and on the other hand control the dosage of powders (P) according to one or more parameters (Co) linked to step b) of mixing and suspension.

9. Device according to claim 8, characterized in that the mixing and suspending system (S2) comprises: - a mixing tank (41), - a mixing and stirring device (42), located inside the mixing tank (41), - a means (44) for measuring the level of the cryogenic suspension (SC) formed, at least partly located inside the mixing tank (41).

10. Device according to claim 8 or 9, characterized in that the mixing and suspending system (S2) comprises an optical monitoring system (94) for controlling the homogeneity of concentration in the cryogenic suspension (SC).

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