TREATMENT METHOD AND DEVICE USING A SUPERCRITICAL FLUID AND INJECTION OF ADDITIVE
20170182523 · 2017-06-29
Inventors
Cpc classification
B08B3/045
PERFORMING OPERATIONS; TRANSPORTING
B08B7/0021
PERFORMING OPERATIONS; TRANSPORTING
B08B3/08
PERFORMING OPERATIONS; TRANSPORTING
B08B3/02
PERFORMING OPERATIONS; TRANSPORTING
B08B3/04
PERFORMING OPERATIONS; TRANSPORTING
International classification
B08B7/00
PERFORMING OPERATIONS; TRANSPORTING
B08B3/02
PERFORMING OPERATIONS; TRANSPORTING
B08B3/08
PERFORMING OPERATIONS; TRANSPORTING
H01L21/02
ELECTRICITY
B08B3/04
PERFORMING OPERATIONS; TRANSPORTING
H01L21/67
ELECTRICITY
Abstract
A treatment device using a supercritical fluid comprises: a chamber (14) for receiving the parts to be treated, provided with an opening and closing door (15), means (6, 8) for supplying a supercritical fluid to the chamber (14), comprising first fluid storage means (6) and means (10,12) for bringing the fluid to the supercritical state, second storage means (30), for storing a second fluid, such as an additive, for example a solvent, means (34, 36, 38) for injecting into the chamber the second fluid stored in the second storage means (30), at atmospheric pressure or at a pressure substantially close to atmospheric pressure, or together with the supercritical fluid, after the door is closed and the parts to be cleaned are loaded into the chamber.
Claims
1-17. (canceled)
18. Treatment device using a supercritical fluid comprising: a) a main chamber for receiving the parts to be treated, provided with a door for establishing fluid communication between the inside of the chamber and the outer atmosphere, b) a first circuit for supplying a supercritical fluid to said chamber, comprising a fluid storage chamber, c) a first reservoir, for storing a second fluid, such as an additive, d) a second circuit to inject into the main chamber the second fluid stored in said reservoir, at atmospheric pressure or at a pressure substantially close to atmospheric pressure, after the parts to be cleaned are loaded in the main chamber and the door for establishing fluid communication between the inside of the main chamber and the outer atmosphere is closed.
19. Device according to claim 18, said second circuit comprising a low pressure pump or instead enabling an injection by gravity.
20. Device according to claim 18, further comprising: a second intermediate reservoir arranged on the path of the fluid that comes out of said first reservoir, between the latter and said main chamber, a circuit for filling this second intermediate reservoir from said first reservoir, and at least a valve for injecting or introducing, into said main chamber, or the inlet thereof, at least some of the contents of said second intermediate reservoir.
21. Device according to claim 20, said second intermediate reservoir being able to store a quantity of second fluid independent of the quantity of fluid contained in the first reservoir.
22. Device according to claim 20, said second intermediate reservoir being able to maintain a fluid in gaseous form.
23. Device according to claim 20, said valve for introducing, into said main chamber, or to the inlet thereof, a mixture of this pressurised fluid and the second fluid, comprising a check valve that only opens if the pressure is greater than a given set pressure.
24. Treatment device using a supercritical fluid, comprising: a) a main chamber for receiving the parts to be treated, provided with a door to establish fluid communication between the inside of the chamber and the outer atmosphere, b) a first circuit for supplying said main chamber with fluid, in the supercritical state, comprising a fluid storage chamber, c) a first reservoir for storing a second fluid, such as an additive, d) a second circuit for injecting into the main chamber, with the supercritical fluid, after loading the parts to be cleaned and closing the door, the second fluid from said first reservoir, said second circuit comprising: d1)a second intermediate reservoir arranged on the path of the fluid that comes out of said first reservoir, between the latter and said main chamber, said second intermediate reservoir comprising: a first orifice, for introducing therein, on the one hand, the second fluid at atmospheric pressure or at a pressure substantially close to atmospheric pressure and, on the other hand, the pressurised fluid, in the supercritical state, a second orifice, different to the first, for injecting or for introducing a mixture of pressurised fluid and the second fluid into the chamber or at the inlet thereof.
25. Device according to claim 24, said second intermediate reservoir being able to store a quantity of second fluid independent of the quantity of fluid contained in the first reservoir.
26. Device according to claim 24, said intermediate reservoir being able to maintain a fluid in gaseous form.
27. Device according to claim 24, said valve for introducing, into said main chamber, or to the inlet thereof, a mixture of this pressurised fluid and the second fluid, comprising a check valve that only opens if the pressure is greater than a given set pressure.
28. Method of cleaning using a supercritical fluid comprising, in this order: a) the introduction of at least one first part to be cleaned into a chamber, provided with a door for establishing fluid communication between the inside of the chamber and the outer atmosphere, then closing said door, b) then the injection into said chamber, at atmospheric pressure or at a pressure substantially close to atmospheric pressure, of at least one co-solvent, c) then the supply of said chamber with supercritical fluid and the cleaning of said part.
29. Method according to claim 28, the co-solvent being injected into the chamber using a low pressure pump or instead uniquely by gravity.
30. Method according to claim 28, the additive being firstly injected into an intermediate reservoir, then introduced into the chamber.
31. Method according to claim 28, the additive being: a solvent, for example selected from among water, aqueous solutions, alcohols, for example 1 to 5 C aliphatic alcohols, such as ethanol, methanol, butanol, ketones, such as acetone, and mixtures thereof, and/or a fragrance, and/or an impregnation product, for example a paint and/or a tanning product, and/or an oil, and/or a hydrophobic product.
32. Method according to claim 28, the dense fluid being nitrogen or oxygen, or a fluid selected from among methane, ethanol, propane, nitrogen protoxide, a fluorinated gas, ammonia, alcohol, ethanol, isopropanol, water.
33. Treatment method using a supercritical fluid comprising, in this order: a) the introduction of at least one first part to be cleaned, into a chamber, provided with a door for establishing fluid communication between the inside of the chamber and the outer atmosphere, then stopping or closing the communication between the inside of the chamber and the outer atmosphere, b) then: the introduction, into an intermediate reservoir, via a same first orifice, of an additive or a second fluid, at atmospheric pressure or at a pressure substantially close to atmospheric pressure, then pressurised fluid, in the supercritical state, the injection of a mixture of pressurised fluid, in the supercritical state, and the second fluid or the additive, into the chamber, or to the inlet thereof, via a second orifice, different to the first.
34. Method according to claim 33, said intermediate reservoir being arranged on the path of the fluid that comes out of another reservoir, between the latter and said main chamber, storing a quantity of second fluid independent of the quantity of fluid contained in said other reservoir.
35. Method according to claim 33, said intermediate reservoir being maintained at a temperature making it possible to maintain the second fluid in gaseous form.
36. Method according to claim 33, the additive being: a solvent, for example selected from among water, aqueous solutions, alcohols, for example 1 to 5 C aliphatic alcohols, such as ethanol, methanol, butanol, ketones, such as acetone, and mixtures thereof, and/or a fragrance, and/or an impregnation product, for example a paint and/or a tanning product, and/or an oil, and/or a hydrophobic product.
37. Method according to claim 33, the dense fluid being nitrogen or oxygen, or a fluid selected from among methane, ethanol, propane, nitrogen protoxide, a fluorinated gas, ammonia, alcohol, ethanol, isopropanol, water.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0072]
[0073]
[0074]
DETAILED DESCRIPTION OF PARTICULAR EMBODIMENTS
[0075] In
[0076] In particular, this machine comprises first storage means 6 (or storage chamber, called main storage chamber of the system), provided for storing liquefied gas, at several tens of bars, for example 60 bars. This chamber may be provided with means for measuring the temperature and/or the pressure and/or the level of liquid that it contains. It may be supplied by a reserve 2, which has for example a vat shape (which contains gas at, for example, 20 C. and 20 bars), to which the device may be connected. This reserve is placed in communication with the storage chamber 6 via the valve 6.sub.1, and a filling pump 3 or a compressor.
[0077] The initial filling of this chamber may be carried out in the following manner. Liquefied gas is introduced therein by pumping and opening of the inlet valve 6.sub.1, at the temperature of the reserve 2, for example 20 bars and 20 C. In the course of the treatment, this chamber could, moreover, be supplied by gas recycled from the treatment chamber 14.
[0078] The heating means 7 then make it possible to increase the temperature and pressure conditions in this chamber 6, for example, for CO.sub.2, to +20 C. and 60 bars, or, more generally, to a temperature comprised between 15 C. and 30 C., and a pressure comprised between 50 bars and 90 bars.
[0079] An autoclave 14, or treatment chamber, receives the parts to be treated. This chamber is provided with a door 15, through which the parts may be introduced into the chamber, then, after treatment, extracted from the chamber. It may also be provided with a vent, or a conduit forming a vent, and a valve 14.sub.2.
[0080] Means for, potentially, making this autoclave move, as well as means for receiving baskets that are going to contain the parts to be cleaned, are described in the document WO 02/32593.
[0081] Means 8, comprising for example a pump 10 and heating means 12 make it possible to convey the fluid, withdrawn from the chamber 6, under thermodynamic conditions enabling it to be used in the treatment chamber 14. In the case where the fluid is CO.sub.2, the pump 10 makes it possible to bring the fluid from the reserve 6 to a pressure greater than 73.85 bars, and the heating means 12 make it possible to bring the temperature of the fluid to a value greater than 31 C., these conditions then assuring that the fluid is in a so-called supercritical state. The fluid circulates in the conduit 27, the valve 14.sub.1 opening access of the flow of supercritical fluid to the autoclave 14.
[0082] Means 16 (in this example: a valve 16.sub.1 and a regulation valve 16.sub.2) make it possible to depressurise the gas at the outlet of the autoclave 14.
[0083] Means 18, forming a separator, make it possible to separate the gas from extracted impurities or products that it transports and which result from a preceding or underway treatment operation.
[0084] The whole of these means make it possible to carry out a treatment cycle, that is to say a series of steps, which mainly include:
[0085] a) the loading of the parts into the autoclave 14,
[0086] b) the closing of the door 15 and means 14.sub.2 (or, more generally, the stopping or the closing of the establishment of fluid communication, that is to say the impossibility of fluid exchange between the inside of the chamber and the outer atmosphere),
[0087] c) the treatment of the parts by action of the dense fluid on the parts to be treated; this step is carried out at high pressure P.sub.0, for example greater than 100 bars, again for example around 120 bars for supercritical CO.sub.2,
[0088] d) the reduction of the pressure in the chamber, from P.sub.0 to a value P.sub.1, substantially less than P.sub.0; P.sub.1 is for example of the order of several tens of bars, or even comprised between 50 bars and 90 bars, or instead between 60 and 70 bars.
[0089] e) the opening of the door (or, more generally, the establishment of fluid communication between the inside of the chamber and the outer atmosphere) and the unloading of the parts; the internal volume of the autoclave is then at atmospheric pressure.
[0090] It is sought to introduce an additive to the dense fluid, in order to carry out a specific treatment on the parts.
[0091] As explained in the patent application WO 02/32593, for example for a cleaning treatment, the addition of a co-solvent to the dense fluid, under pressure, makes it possible to obtain improved extraction of contaminating organic compounds, pollutants, in other words undesirable compounds, from the parts to be cleaned.
[0092] This co-solvent may be selected, for example, from among water, aqueous solutions, alcohols, for example 1 to 5 C aliphatic alcohols, such as ethanol, methanol, butanol, ketones, such as acetone, and mixtures thereof.
[0093] Among aqueous solutions may be cited detergents solutions such as anionic and/or cationic surfactants, solutions of complexing agents, chelating agents, buffer solutions, for example phosphate and/or hydrogen phosphate, etc.; antioxidant solutions, such as ascorbic acid, to stabilise the material.
[0094] Other types of additives may be added, instead of the solvent, or in combination therewith: [0095] an additive of fragrance type (added for example at the end of the cycle), [0096] an impregnation product, for example a paint and/or a tanning product (for example chromium VI or a plant tannin), and/or an oil, and/or a hydrophobic product.
[0097] Compared to the structure that has been described above, the embodiment of
[0098] In the structure represented in
[0099] As already explained above with reference to
[0100] The injection, according to the invention, of an additive at atmospheric pressure or at a pressure substantially close to atmospheric pressure makes it possible to dispense with, for the injection of additive, the use of a high pressure pump, which is costly, in particular in terms of maintenance.
[0101] The operation of this machine is then identical to that which has been described above.
[0102] The sequence of steps that take place at the start of a treatment cycle is for example the following:
[0103] aloading the parts and closing the door and the means 14.sub.2 (or, more generally, stopping or closing the establishment of fluid communication between the inside of the chamber and the outer atmosphere, that is to say the establishment of a state in which it is impossible to achieve any fluid exchange between the inside of the chamber and the outer atmosphere),
[0104] binjection of the additive at atmospheric pressure or close to atmospheric pressure,
[0105] cthen injection of gas into the autoclave, to bring it to a pressure of around 5 to 15 bars, in order to avoid the formation of dry ice.
[0106] A variant, with a view to injection of additive at a pressure identical to, or substantially close to, atmospheric pressure, is illustrated in
[0107] Preferably, in order not to use a pump, the cartridge 36 is situated below the reservoir 30 and above the autoclave 14.
[0108] In this device, the outlet of the reservoir 30 of additive may be controlled by a set of valves 32.sub.1, 32.sub.2, that are going to make it possible: [0109] first of all, by opening the valve 32.sub.2, after closing the valve 32.sub.1, to store temporarily the additive in the cartridge 36, of known volume. The liquid goes from the reservoir 30 to the cartridge 36 through simple action of gravity. The cartridge 36 is extended by a conduit 36.sub.1 rising higher than the reservoir 30 and of small section making it possible to have in the volume of the cartridge 36 a quantity approximately independent of the filling of the reserve 30; the valve 32.sub.2 may then be closed, [0110] then, by opening the valve 32.sub.1, the additive, stored in the cartridge 36, may be injected, via conduit 34, to the inlet of the autoclave 14.
[0111] This injection of additive thus takes place uniquely by action of gravity, without use of a pump or energy other than actuation of the valves.
[0112] The sequence of steps at the start of the treatment cycle may be identical to the sequence of steps a-c that have been described above.
[0113] Yet another variant, with a view to an injection of an additive to the inlet of the autoclave 14, is illustrated in
[0114] In a more precise manner, in this device, the outlet of the reservoir 30 of additive is controlled by the valve 32.sub.2.
[0115] First of all, by opening this same valve 32.sub.2, additive may be stored temporarily in the cartridge 36, of known volume. The storage pressure in the cartridge is atmospheric pressure or is close to atmospheric pressure. According to a variant illustrated in
[0116] Potentially, means 38.sub.1, forming a check valve, may be provided downstream of the cartridge 36, on the route 34. These means 38.sub.1, which can only open under a given pressure (to which the check valve is calibrated), greater than the pressure at which the additive is stored in the cartridge 36, then assure the closing of the route 34 for the additive. A conduit 38 makes it possible to withdraw dense fluid at the outlet of the means 8. If the dense fluid is carbon dioxide, it is then in the supercritical state. A valve 38.sub.2 is arranged on this conduit 38, and is going to make it possible to control the introduction of this fluid into the cartridge 36. When this valve is open, the fluid, arriving under high pressure, sweeps out the cartridge 36, taking along with it the additive, at a sufficient pressure to open the check valve 38.sub.1 (when it is present). The latter could be replaced by a valve synchronised with the opening of the valve 38.sub.2
[0117] In the embodiment that has just been explained, the additive enters into the cartridge 36, from the reservoir 30, and exits therefrom, to be injected into the autoclave 14, via a same orifice, which may be situated at a first end of the cartridge 36. This is different to it, which may be situated at a second end of the cartridge 36, opposite to the first end, through which the dense fluid enters into the cartridge 36. It is for example arranged in a manner opposite to that through which the dense fluid enters into the cartridge.
[0118] The sequence of steps that take place at the start of a cleaning cycle is for example the following:
[0119] aloading of the parts and closing the door and the means 14.sub.2 (or, more generally, stopping or closing the establishment of fluid communication between the inside of the chamber and the outer atmosphere, that is to say the establishment of a state in which it is impossible to achieve any fluid exchange between the inside of the chamber and the outer atmosphere),
[0120] bthen injection of gas into the autoclave, to bring it to a pressure of around 5 to 15 bars, in order to avoid the formation of dry ice.
[0121] In the course of the treatment cycle, at the desired moment, the opening of the valve 38.sub.2 and the closing of the valve 14.sub.1 enable the dense fluid to pass through the cartridge 36 and carry along the additive.
[0122] Yet another variant, with a view to injection of additive to the inlet of the autoclave 14, is illustrated in
[0123] Here again, the volume of the cartridge 36 may be placed in communication with the outlet of the means 8, in order to send, into the cartridge 36, a quantity of dense fluid, potentially supercritical, which is going to make it possible to sweep out the cartridge and to introduce the additive to the inlet of the autoclave 14.
[0124] More precisely, in this device, the outlet of the additive reservoir 30 may be controlled by the valve 32.sub.2.
[0125] First of all, by opening this same valve 32.sub.2, the additive may be stored temporarily in the cartridge 36, of known volume.
[0126] The conduit 38 makes it possible to withdraw dense fluid at the outlet of the means 8. But, here, the dense fluid enters into the cartridge 36 through the bottom and comes out through the top while bubbling through the additive, which makes it possible to carry along the additive progressively by dissolution; the dense fluid is going to dissolve the additive on its passage and to carry along a part thereof. There is thus an action of the additive extended over time and the dense fluid is not saturated with additive in one go.
[0127] Depending on the density of the additive compared to the dense fluid, a mounting according to
[0128] The sequence of steps at the start of the cleaning cycle may be identical to the sequence of steps a-b that has been described above.
[0129] In the two embodiments of
[0130] In the embodiments of
[0131] In the embodiments of
[0132] Whatever the envisaged embodiment, apart from the above means, a device according to the invention may comprise means 5, of electronic and/or computer type, for controlling and regulating the operation of each of the components of the machine, notably the pumps and the valves, according to a programmed sequence of steps.
[0133] These controller forming means 5 may comprise circuits, which make it possible to send to each of the components of the machine instructions and/or voltages enabling it to be run according to a predefined sequence. In particular, these means are going to make it possible to implement a cleaning preparation cycle and/or a cleaning cycle as described above, and notably to adjust the steps of transfer of gas between the means 2 and 6 on the one hand, and the storage means 20 on the other hand. More precisely, these means are going to control the opening or closing durations of the valves 32.sub.1, 32.sub.2, 38.sub.1, 38.sub.2, 38.sub.3, but also other valves of the system, and the operation, notably, of the pump 10, and the means 12.
[0134] This assembly 5 may moreover potentially receive signals corresponding to measurements carried out using one or more pressure sensors, for example arranged to measure the pressure in the autoclave 14, or in the storage means 20, and can process them and use them for the control of one or more components of the machine.
[0135] This controller assembly 5 may communicate with a user interface to inform a user of the status of the machine, in particular its operating cycle.
[0136] An example of embodiment of these means 5 is described below in a more precise manner with reference to
[0137] In this example, these means comprise means 53 for memorising instructions relative to the processing of data, for example to carry out a method of the type described above.
[0138] According to an example of embodiment, the controller 5 comprises a central unit, which itself includes a microprocessor 56, a set of non-volatile memories and RAM 57, peripheral circuits, all of these elements being coupled to a bus 55. Data may be stored in the memory zones, notably data for implementing a method according to the present invention or for controlling a machine according to the present invention. Means 59 are going to make it possible to manage the flow of input and output data, from other components of the machine, and in the direction thereof.
[0139] In a variant, this controller assembly 5 may be realised in the form of a FPGA (Field Programmable Gate Array) or an ASIC (Application Specific Integrated Circuit).
[0140] The means 54, which may comprise visualisation means, may potentially enable a user to interact with the operation of a machine according to the invention, for example by intervening on a particular step of an operating cycle.
[0141] A machine according to the invention, and a method for operating such a machine, as described above, makes it possible to achieve the saving of a high pressure pump such as one of the pumps 301 of
[0142] This saving may be obtained: [0143] either by injection of the additive at low pressure, as for example explained above with reference to
[0145] The invention has been described above within the scope of the implementation of a pressurised dense fluid, notably carbon dioxide in the supercritical state. It may apply to other fluids, in particular nitrogen or oxygen, under conditions enabling them to be in the supercritical state (for oxygen: beyond 119 C. and 50 bars; for nitrogen: beyond 147 C. and 34 bars)
[0146] In a variant, another fluid may be implemented, for example a fluid selected from among methane, ethanol, propane, nitrogen protoxide, a fluorinated gas, ammonia, alcohol, ethanol, isopropanol, water.
[0147] The invention has been described above for a cleaning method.
[0148] But other methods may be implemented using a device or a method according to the invention, the suitable fluid being used in the dense state, or even supercritical state. For each of the different examples cited below, CO.sub.2 may be used.
[0149] In all cases, the fluid, whether dense or super-critical, bathes the parts to be treated. The contact, more or less long, between the latter and the fluid brings about the sought after treatment.
[0150] This is the case, for example, of a debinding method or an extraction method (cleaning being a particular case of extraction).
[0151] A debinding method makes it possible to extract a binder from a part made of an alloy, for example from a powder such as a powder assembled in a paraffin, and/or to extract any binder adapted to the manufacture of the alloy.
[0152] Again for example, a method for extracting one or more natural substances may be implemented in particular in the pharmaceuticals or food processing industry.
[0153] An extraction method, or instead degreasing, may also be implemented for treating natural wool, in order to extract suint therefrom.
[0154] The invention also makes it possible to implement a sterilisation method (for example in the food-processing or medical field), at low temperature, based on the penetrability of the gas, at high pressure, which is going to be able to penetrate into the material to be treated and to neutralise, or to kill, infectious agents.
[0155] The invention may also be used in methods of impregnation or input of product transported by the supercritical fluid within the material to be treated.
[0156] More generally, any type of part may be treated by a method according to the invention.
[0157] The materials, which can be treated by a method according to the invention, are generally solid materials, for example: [0158] metals, [0159] metal alloys, potentially plated, such as aluminium, titanium, steel, stainless steel, copper, brass, and any other alloy, or plated metal, [0160] ceramic materials, polymer materials, powders, notably powders of the materials cited above, [0161] textile materials, natural or synthetic, or instead leather, [0162] rectification sludges, stemming for example from a bar turning method.
[0163] The treated parts may be, for example: [0164] parts from the aeronautics, or automobile, industry [0165] clock making and/or micromechanical parts, [0166] electric or electronic connectors, [0167] components made of semiconductor materials from the microelectronics industry, [0168] medical or surgical apparatus or tools, etc. [0169] clothes, or natural materials used in the textile industry, for example wool, or leather.