• 专利附录
  • 专利说明
  • 权利要求
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    • 专利摘要:
    The invention relates to a method for processing at least one capillary tube, wherein at least one capillary tube is flowed around with supercritical carbon dioxide so that the supercritical carbon dioxide flows along an outside and an inside of the at least one capillary tube, and the at least one capillary tube is processed by the action of supercritical carbon dioxide ,
    公开号:CH711764A2
    申请号:CH01489/16
    申请日:2016-11-10
    公开日:2017-05-15
    发明作者:Grimme Ralf；Zorn Christoph
    申请人:Fraunhofer-Gesellschaft Zur Förderung Der Angewandten Forschung E V；
    IPC主号:
    专利说明:

    Description: The invention relates to a method and a device for processing at least one capillary tube by rinsing with supercritical carbon dioxide.
    Capillary tubes and guide cannulas (also called capillaries hereinafter), as e.g. used in minimally invasive medicine as guide lines, have a small outer diameter and long lengths. In order to be able to introduce them into human veins to place drugs locally or to take samples, they must have a high purity.
    These guide cannulas often have an outer coating such as e.g. hydrophilic lubricious PTFE. It is chemically very stable, has a good biocompatibility and a low coefficient of friction, so that a sensitive handling by the surgeon is possible. However, these surfaces are prone to damage during handling and cleaning.
    By manufacturing the inner surfaces of the capillaries are contaminated with production aids.
    The industrial cleaning of the inner surfaces of the capillaries represents a major challenge. Capillaries with a small inner diameter and large lengths can currently be cleaned only very expensive by rinsing with solvent. Due to the high flow resistance of the capillaries only small amounts of the cleaning agent can be pressed through individual capillaries. Then it must be rinsed with water and dried consuming. The cleaning currently does not achieve high levels of purity and requires high production costs.
    In the prior art, capillaries are cleaned by rinsing with liquid solvents, possibly also several times with different media. For short capillaries with large diameters, wires can be used to remove coarse contaminants or conventional spray flushing systems. For long and thin capillaries, however, no other cleaning methods are known.
    A disadvantage of the solutions of the prior art is that the cleaning liquid can be pressed with high pressure through capillary difficult. The volume flow of the cleaning fluid remains very low, which requires very long flushing times. Only low viscosity cleaning fluids can be used. Also, the pressure can not be increased arbitrarily, otherwise the capillaries are damaged. High filling pressures require a special, high-pressure-resistant and tight connection of the capillaries. By such a connection there is a risk of damaging the capillary or the outer coating of the capillaries. Capillaries must be completed individually, which means a lot of time.
    For medical applications only biocompatible cleaning agents can be used, since it can not be excluded that residues remain in the capillaries. If flammable solvents are used, there is a risk of fire and explosion, so that explosion-proof systems and workplaces are necessary. Residues of the cleaning liquid must be removed by prolonged rinsing, e.g. be removed with water. After rinsing a drying of the capillaries is required, which is time consuming and energy consuming.
    The object of the present invention is to overcome the disadvantages described above and to provide a method and apparatus for processing capillaries, which achieves good results both inside and outside the capillary and reduces the cost of processing. The invention is to enable in this way economic internal production and external machining of capillary tubes.
    The object is achieved by the method for processing at least one capillary tube according to claim 1 and the apparatus for processing at least one capillary tube according to claim 13. The respective dependent claims indicate advantageous developments of the inventive method and the inventive device.
    According to the invention, a method for processing at least one capillary tube is first indicated. Under a capillary tube is understood here a thin, long tube. Other crude components, such as long coil springs, can be considered here as a capillary tube. It should be noted that although it is possible and advantageous for the invention, it is not necessary for the capillary tube to have a capillary action. The invention can also be used for other thin long tubes. The tube may advantageously be flexible. A possible outer diameter of a capillary tube can be, for example,> 0.4 mm, preferably> 0.6 mm, preferably> 0.64 mm and / or <10 mm, preferably <1.6 mm, preferably <1 mm, preferably <0 , 8 mm, preferably <0.7 mm, preferably <0.67 mm. An inner diameter of such a capillary tube may be, for example,> 0.3 mm, preferably> 0.4 mm, preferably> 0.45 mm and / or <9 mm, preferably <0.6 mm, preferably <0.52 mm. A length of a capillary tube may be, for example, preferably> 10 mm, preferably> 100 mm, preferably> 500 mm, preferably> 800 mm, preferably 1000 mm, preferably 1100 mm and / or <2000 mm, preferably <1500 mm, preferably <1300 mm, preferably <1060 mm.
    According to the invention, the at least one capillary tube is surrounded by supercritical carbon dioxide in such a way that the supercritical carbon dioxide flows along an outer side and an inner side of the at least one capillary tube. The supercritical carbon dioxide preferably wets the outside and the inside of the at least one
    Capillary tube. The inventive method can be carried out for individual capillary tubes, but it is also possible to process bundles of multiple capillary tubes simultaneously with the inventive method.
    According to the invention, the at least one capillary tube is processed by the action of supercritical carbon dioxide. The processing may be, for example, a cleaning or a coating of the corresponding surface. Other forms of processing are possible, for example by adding suitable substances to the supercritical carbon dioxide, as will be explained below.
    Carbon dioxide is supercritical from a pressure of about 74 bar and a temperature of about 31 ° C. The inventive method is therefore preferably carried out so that these conditions are maintained in the execution of the method. The conditions for the formation of supercritical carbon dioxide are material properties of carbon dioxide, which are well known and should not be discussed here.
    Preferably, the supercritical carbon dioxide is continuously fed to the at least one capillary tube during processing and is continuously removed from the at least one capillary tube. Most preferably, the carbon dioxide is then relaxed. In this way it can be achieved that the supercritical carbon dioxide is always moved on the surface of the capillary tubes. However, it is also possible to intermittently interrupt the supply and removal of supercritical carbon dioxide and to let the superficial carbon dioxide in contact with the capillary tube act for a while. Advantageous exposure times can be, for example, from a few seconds to hours.
    As already stated, it is advantageous if a plurality of bundled capillary tubes are processed simultaneously by means of the inventive method. All the capillary tubes of the bundle are then flowed around with supercritical carbon dioxide in such a way that the supercritical carbon dioxide flows along the outside and the inside of the capillary tubes and thereby processes the corresponding surfaces.
    Preferably, the inventive method is carried out in a pressure vessel. In this case, advantageously, the one or more capillary tubes can be clamped in a common clamping element. Advantageously, the clamping can be done so that openings of the capillary or the tubes are present at the end in the interior of the clamping element. It can then be passed through the clamping element to the at least one capillary tube, the supercritical carbon dioxide.
    In an advantageous embodiment of the invention, the clamping element can also be arranged in a closing element, which can be placed on an inlet opening of the pressure vessel. In this case, firstly the at least one capillary tube can be inserted into the clamping element of the terminating tube and subsequently the at least one capillary tube can be introduced into the inlet opening of the pressure vessel and the terminating element inserted into the inlet opening. In this embodiment, the at least one capillary tube can completely pass through the tensioning element. The closure member may have a port for supplying supercritical carbon dioxide, and more preferably it may contain all the elements necessary to distribute the carbon dioxide between the inside and outside of the capillary tube. This may optionally be the tensioning element and / or, for example, one or more flow barriers. In the latter case, the clamping element can optionally be designed without flow-forming properties.
    In an advantageous embodiment of the invention, the clamping element and / or an additional flow barrier can be designed so that a defined first portion of the flowing through the clamping element or the flow barrier supercritical carbon dioxide flows into the at least one capillary tube and a defined second portion of the flowing through the clamping element or the flow barrier supercritical carbon dioxide flows past the at least one capillary tube. Advantageously, the sum of the first and the second portion is the total amount of the carbon dioxide flowing around the capillary tubes.
    The division of the supercritical carbon dioxide by the clamping element or the flow barrier in the two said proportions can be effected by a predetermined and defined leakage or a predetermined distance between the inner wall of the clamping element and the flow barrier and the outer wall of the or the capillary tubes is adjusted. Alternatively or additionally, a distance between a plurality of the capillary tubes can also be predetermined. For example, a plurality of capillary tubes can be combined into a bundle so that the capillary tubes of the bundle touch each other. The inner wall of the clamping element or the flow barrier can then advantageously rest positively on the outer sides of the bundle to extremely lying capillary tubes.
    The inside of the clamping element and or or the flow barrier may alternatively have a polygonal cross-section, for example a hexagonal cross-section which is measured so that the capillary tubes of the capillary tube or the single capillary tube on the walls of the clamping element and / or or abut the flow barrier. In this case, gaps between the capillary tubes and the inner walls of the clamping element or the flow barrier, which can form the defined leakage described above arise.
    In an advantageous embodiment of the invention, the clamping element may be equipped so that it simplifies introduction of the capillary tubes in the pressure vessel. It is possible to first clamp the capillaries in the clamping element and then introduce together with the clamping element in the pressure vessel. This is particularly advantageous when the clamping element is part of said end element.
    In an advantageous embodiment of the invention, the introduction of the capillaries can be supported in the pressure vessel, that the capillary tube is brought with one end to an opening of the pressure vessel and at a different opening of the pressure vessel, a negative pressure is generated, for example by means of a vacuum pump , It then creates a negative pressure in the pressure vessel, through which the at least one capillary tube is sucked into the pressure vessel. This embodiment is particularly advantageous when the pressure vessel is cylindrical and the capillary or the tubes are to be arranged coaxially with the cylinder axis of the pressure vessel in this.
    In an advantageous embodiment of the invention, it is possible to introduce the supercritical carbon dioxide via a first valve in the at least one capillary or the plurality of capillary tubes and a second, different from the first valve, supercritical carbon dioxide on the outside of the at least one capillary tube or to supply the capillary tubes. In this embodiment of the invention, it is possible to adjust by means of the valves a pressure difference between the supercritical carbon dioxide inside the capillary tube or the capillary tubes and the supercritical carbon dioxide on the outside of the capillary tubes so that this pressure difference is smaller than a maximum pressure difference, when exceeded the capillary tube would be damaged.
    In an advantageous embodiment of the invention, it is possible that the at least one capillary tube is rolled up during processing on a spool. This simplifies the handling of long capillary tubes and allows a compact design of the device provided for the method.
    Advantageously, in this case a coil on which the capillary tube is rolled up, are introduced together with the capillary tube as a whole in the pressure vessel. As described, supercritical carbon dioxide is then introduced into the capillary tube and introduced into the region of the pressure vessel outside the capillary tube, so that supercritical CO 2 flows around the inner and outer surfaces of the capillary tube.
    In an advantageous embodiment of the invention, the processing is a cleaning. The supercritical carbon dioxide effectively removes contaminants.
    In an advantageous embodiment of the invention as a cleaning method, the supercritical carbon dioxide at least one abrasive and / or at least one detergent substance can be added.
    The inventive method can also be used for coating the surfaces of the capillary tube. It can be added to the supercritical carbon dioxide a substance to be deposited, such as oil. This solute can e.g. be introduced with the supercritical CO 2 in a reactor or the capillary tube. If one relaxes the supercritical carbon dioxide in the reactor or lowers the temperature, the solute precipitates very finely distributed and wets the component or the capillary tube. In this embodiment, the carbon dioxide can be introduced in the supercritical state in the pressure vessel and then cooled or expanded in the pressure vessel. The non-supercritical CO 2 is then removed from the pressure vessel. As a result, e.g. Capillary tubes are protected from corrosion. It is also possible to produce hydrophilic or hydrophobic surfaces in this way.
    In an advantageous embodiment of the invention, carbon dioxide, which is removed from the pressure vessel can be relaxed. When relaxing, impurities fall out and can be removed. The gaseous or liquid carbon dioxide can then be reused.
    The invention also relates to a device for processing at least one capillary tube. The inventive device has a pressure vessel into which at least one capillary tube is completely insertable. The pressure vessel is thus equipped so that in it the capillary tube to be processed can be arranged as a whole.
    According to the invention, the pressure vessel has at least one inlet, via which supercritical carbon dioxide can be introduced into the pressure vessel. In this case, the supercritical carbon dioxide can be introduced in such a way that it flows around an outside and an inside of the at least one capillary tube in the pressure vessel.
    Preferably, the capillary is not considered here as part of the inventive device, but the inventive device is designed so that one or more capillary tubes can be arranged in it.
    In an advantageous embodiment, the pressure vessel has at least one outlet for the carbon dioxide. The outlet may advantageously have a valve and / or a throttle, by means of which a pressure in the pressure vessel to a value is stable, so that the carbon dioxide in the pressure vessel remains supercritical.
    Advantageously, the device according to the invention also has a heating element, with which the supercritical CO 2 at a sufficiently high temperature, i. preferably greater than or equal to 31 ° C is stable. Preferably, a pressure of greater than or equal to 74 bar is adjustable in the pressure vessel.
    In an advantageous embodiment of the invention, the inventive device may comprise at least one hollow cylindrical clamping element which is arranged in the pressure vessel. Advantageously, the clamping element can be removed from the pressure vessel and used in this.
    Preferably, an interior of the clamping element is designed so that the at least one capillary tube, when it is introduced into the clamping element, in the interior of the clamping element bears against this. The capillary tube or the capillary tubes are then then against an inner wall of the clamping element. The contact between the
    However, it need not be internal wall of the clamping element and the capillary or (s) positively. Touching along a contact line is also possible.
    In an advantageous embodiment, the clamping element may be arranged in a closing element, which is insertable into the inlet opening of the pressure vessel. Advantageously, said inlet for CO2 then passes through this terminating element. Reference is made here to the preceding description of the terminating element.
    Advantageously, the tensioning element is configured such that, when the at least one capillary tube is arranged in the tensioning element, it has a predetermined leakage around the at least one capillary tube so that a predetermined first portion of the supercritical carbon dioxide flows past the at least one capillary tube and a predetermined second Share in the at least one capillary tube flows. The statements made above regarding the procedure apply here accordingly.
    In an advantageous embodiment of the invention, the pressure vessel may have a cylindrical interior, in which the at least one capillary tube or a bundle of capillary tubes with its or their longitudinal axis are coaxial with a longitudinal axis of the cylindrical interior can be arranged. The reactor can here, for example, have a long, pressure-resistant stainless steel tube. This is particularly preferably heat-insulated and / or heated.
    Preferably, the at least one inlet valve for supercritical carbon dioxide is disposed on an end face of the cylindrical interior of such a pressure vessel and thus opens into the interior via the end face.
    For loading, the reactor may be provided with a closable lid. This cover may have the said inlet or be arranged at the opposite end of the cylindrical interior. The lid can be formed in particular by said closing element.
    In the embodiment of a long cylindrical pressure vessel, the length of the interior of the pressure vessel is preferably equal to or slightly larger than the length of the capillaries to be processed. The interior space can in this case have a somewhat larger diameter than the outside diameter of the capillary tubes or the outside diameter of a bundle of capillary tubes to be processed.
    In the case of a long cylindrical pressure vessel, it is particularly preferred if said clamping element rests with an outer side of the clamping element on an inner side of the pressure vessel. In this way, the capillary tubes can be fixed by means of the clamping element in the pressure vessel in the radial direction. If an end element is provided in which the tensioning element is arranged, then the tensioning element can advantageously abut with its outside on an inner side of the end element.
    In an advantageous embodiment of the invention, at least one flow barrier may be provided in the interior of the pressure vessel and / or possibly in the interior of the closing element, which at least partially surrounds that area in which the capillary tube or tubes can be arranged. The flow barrier is designed such that it opposes supercritical carbon dioxide, which flows outside the capillary tube, a defined flow resistance. In this way it can be achieved that the pressure at the openings of the capillary tubes is sufficiently large, so that supercritical CO 2 flows into the capillary tubes in a sufficient amount.
    In an advantageous embodiment of the invention, said clamping element may comprise two parts which, when the at least one capillary tube is therein, are mutually entangled or wedged into each other. In order to effect a Verschränkbarkeit, the two parts may have facing surfaces over which they touch, these surfaces are at an angle of greater than 0 ° and less than 90 °, preferably 45 ° relative to the cylinder axis. If a pressure in the direction of the cylinder axis exerted on the two parts, they move against each other along said surfaces and thereby pinch the capillary tubes.
    In order to effect a Verkeilbarkeit of the two parts, an opening of the one part, which faces the other part, be conical and the other part engage in this conical opening. If a pressure in the direction of the cylinder axis exerted on the two parts, the conical opening of the one part presses the other part together, so that it presses on therein capillary tubes and clamps them so. Advantageously, the engaging part can be segmented along its circumference, wherein there is a gap between adjacent segments. In this way, the segments act as spring elements. A Einklemmbarkeit the capillary tubes is thereby improved.
    In an advantageous embodiment of the invention, the interior of the pressure vessel can be limited by two coaxial cylinders with different radius. In the direction of the cylinder axis of these cylinders, the pressure vessel can be limited by a bottom and a lid, wherein preferably the lid is removable. If the lid removed, so one or more capillary tubes can be introduced into the pressure vessel. The capillary tubes can then rotate spirally around the inner cylinder.
    In an advantageous embodiment of the invention, the inventive device may have a relief valve, via which the pressure vessel can be emptied. It can thereby reduce the pressure inside the pressure vessel to external pressure and the capillaries are removed.
    In an advantageous embodiment of the invention, the device may have an insertion device. As a result, the handling of long thin capillary tubes can be improved. The capillary tubes can be inserted into the insertion device and then introduced as a whole into the pressure vessel. The insertion device can be designed such that the capillary tubes lie straight therein. The length of the insertion device is thus in this case substantially equal to the length of the capillary tubes.
    Optionally, the loading device can also be designed cylindrical, wherein the capillary tube is wound on the cylinder, so this rotates about its cylinder axis. Such an insertion device is particularly advantageous when the pressure vessel has the above-described embodiments with two coaxial cylinder walls, since then the loading device around the inner cylinder, i. the cylinder with a smaller radius, can be inserted into the pressure vessel.
    Advantageously, the device according to the invention has a pressure sensor with which the pressure of the supercritical carbon dioxide in the interior of the pressure vessel can be measured. Based on the pressure, for example, the outlet valve or throttle valve can be controlled so that the pressure in the interior of the pressure vessel remains sufficiently large.
    Advantageously, the device according to the invention can also comprise a temperature sensor with which the temperature of the supercritical carbon dioxide in the interior of the pressure vessel can be measured. About the measurement result, for example, a heater can be controlled, with which the carbon dioxide in the interior of the pressure vessel is heated. In this way it can be ensured that the temperature is always sufficiently high so that the carbon dioxide remains supercritical.
    In the following, the invention will be explained by way of example with reference to some figures. In this case, the same reference numerals designate the same or corresponding features. The features shown in the examples can also be combined under different examples and realized independently of the specific example.
    It shows:
    1 shows a section through an exemplary device according to the invention,
    FIG. 2 shows a section of the capillary receptacle shown in FIG. 1, FIG.
    3 shows a closure or closure element,
    4 shows the clamping element shown in FIG. 3 with capillaries, FIG.
    5 shows another example of a tensioning element,
    6 shows another possible embodiment of a clamping element,
    FIG. 7 shows a section through the device shown in FIG. 3, FIG.
    8 shows a cross section through an exemplary embodiment of the invention,
    9 shows an exemplary schematic arrangement of a pressure vessel,
    10 is another exemplary embodiment of the invention in section,
    11 shows the embodiment shown in FIG. 10 as a whole,
    12 shows the schematic structure of the embodiment shown in FIGS. 10 and 11,
    13 shows an embodiment using high-pressure components, and FIG. 14 shows the effect of the method according to the invention when used for cleaning.
    Fig. 1 shows a detail of an inventive device for processing at least one capillary tube 1. The apparatus shown has a pressure vessel 2, in which in the example shown, a bundle of capillary tubes 1 is completely inserted. The pressure vessel is not fully shown here, but cut off to the right. The device shown in FIG. 1 itself continues to the right side as indicated and ends at the end of the capillaries with a pressure-tight closure or an outlet valve.
    The pressure vessel 2 has a cylindrical interior, in which the capillary tubes 1 are introduced parallel to the cylinder axis. In the example shown in FIG. 1, the capillary tubes 1 are inserted into a capillary receptacle 5, which in turn lies in the interior of the pressure vessel 2. In the example shown, the capillary receptacle 5 extends over the entire length of the capillaries 1 of the capillary bundle.
    Via a connection element 4 is introduced via an opening of the pressure vessel 2 at the end face of supercritical carbon dioxide. For this purpose, the C02 feed 4 can be introduced into a conical region 6 at the corresponding end of the pressure vessel 2. The connection is sealed by means of a seal 7 against the escape of supercritical CO2. The entire pressure vessel 2 is designed so that it withstands the pressure of supercritical carbon dioxide, ie pressures greater than or equal to 74 bar.
    If supercritical carbon dioxide is introduced through a channel 8 of the CO 2 supply 4 into the interior of the pressure vessel 2, this flows firstly into the capillaries 1 and secondly between the capillaries 1. The supercritical carbon dioxide then flows around an outside of the capillaries 1 and in each case the insides of the capillary tubes 1 in the pressure vessel. 2
    The supply of supercritical carbon dioxide through the channel 8 is controllable by means of an inlet valve, which is not shown in this figure.
    In the example shown in FIG. 1, the pressure vessel 2 has a vent 3, through which the interior of the pressure vessel 2 can be relaxed. Behind the opening 3, a drain valve may be provided, through which the passage of carbon dioxide through the opening 3 is controllable. The opening 3 extends in the example shown on the one hand through the wall of the pressure vessel 2 and the other through the wall of the capillary 5th
    The capillaries shown can, for example, have an outer diameter of 0.65 mm and an inner diameter of 0.45 mm at a length of 111 cm. For example, the capillaries may have an outer coating that contains or consists of hydrophilic, lubricious PTE.
    FIG. 2 shows a section of the capillary receptacle 5, which is arranged in FIG. 1 in the interior of the pressure vessel 2. The capillary receptacle 5 is elongated and extends over a length which is substantially equal to the length of the capillaries 1. The capillary receptacle 5 has an inner region into which the capillaries 1 can be inserted. The inner region can be cylindrical, for example, but a part of the cylindrical shape is cut out, so that an elongate opening over the part of the length or the entire length of the Kapillaraufnahme 5 results, through which the capillaries 1 can be inserted into the Kapillaraufnahme 5. After inserting the capillaries 1 in the capillary 5, the capillary can be closed by means of lid, which is held by a lock 50. The cover (not shown in FIG. 2) advantageously extends over the entire length of the capillary receptacle. After closing the capillary receptacle can be inserted through the frontal opening of the pressure vessel 2 in this direction in the direction coaxial with its longitudinal axis.
    In the example shown in FIG. 2, the capillary receptacle 5 has a region 10 with an outer diameter which is smaller than the rest of the capillary receptacle 5. Due to the reduced outer diameter in the region 10, as shown in FIG. 1, a Cö2 feed 4 can engage in the frontal opening of the pressure vessel 2 and at the same time comprise the region 10 of reduced diameter of the capillary receptacle 5. In this way, a conclusive connection of the capillaries 1 of the capillary bundle to the channel 8 of the CO 2 supply 4 is ensured.
    3 shows by way of example how a closure 11 or a closing element 11 of a pressure vessel 2 can be realized, which allows a closure of the pressure vessel 2 such that a carbon dioxide feed 4 can be connected to the pressure vessel 2 and thereby introduced carbon dioxide flows around the capillaries 1 in the desired manner.
    In Fig. 3, only the connection of the capillaries 1, of which three capillaries 1a, 1b and 1c are shown, is shown. The closing element 11 has on its right side a region of smaller diameter, with which it is insertable into an element 12 which surrounds this region of smaller diameter in the inserted state. The device shown in Fig. 3 comprises a tensioning element 13 which contains two parts, 13a and 13b. In this case, the second part 13 b is arranged in the element 12 so that it is supported by the element 12 to the right side. The first part 13 a of the clamping element is supported to the left in the closing element 11. The second (right-hand) part 13b of the clamping element 13 has a tapered region towards the left side, with which it engages in a conical region of the first (left) part 13a of the clamping element. The capillaries pass through both parts 13a and 13b of the clamping element. For this purpose, the parts 13a and 13b of the clamping element have a cylindrical inner region, to the cylinder axis parallel to the capillaries 1a, 1b, 1c extend. If now the closing element 11 is inserted into the element 12, the second part 13b of the clamping element pushes into the first part 13a. Characterized in that the second part tapers towards the left side, in this case a force in the radial direction is exerted on the second part 13b, whereby a contact pressure force is exerted on the fibers 1a, 1b, 1c.
    In the example shown, the capillaries 1 a, 1 b, 1 c to the left to a sieve 14, which covers the end openings of the capillaries 1 a, 1 b, 1 c.
    In the example shown, the capillaries 1a, 1b, 1c are additionally circulated to the left of the first part 13a of the clamping element 13 by a flow barrier 15.
    If now supercritical carbon dioxide is introduced from the left through a feed opening of the closing element 11 into the pressure vessel 2, then this first flows through the sieve 14 and then both through the capillaries 1a, 1b, 1c, as well as between the capillaries 1a, 1b, 1c through. According to the invention, the portion of the carbon dioxide flowing into the capillaries 1a, 1b, 1c can be adjusted relative to the portion of the passing carbon dioxide in that the flow barrier 15 and the parts 13a and 13b of the clamping element 13 have a defined leakage between their respective inner walls and the outer walls of the Capillaries 1a, 1b, 1c have.
    FIG. 4 shows in isolation the capillaries 1a, 1b, 1c and the clamping element 13 shown in FIG. 3. All other components can be designed as shown in FIG.
    As already shown in Fig. 3, the clamping element 13 has two parts 13a and 13b, wherein the part 13b tapers to the left and engages in a conical region at the right end of the first part 13a. The tensioning element 13 has a cylindrical channel through which the capillaries 1a, 1b, 1c pass through the tensioning element 13. The cylindrical shape of the inner region of the clamping element 13 does not have to be a circular cylindrical shape, but can basically be a cylindrical shape with an arbitrary cross section. Cylinders with a hexagonal cross-section or cylinders with a cross-section are particularly advantageous, so that the inner wall of the cylindrical shape extends in a form-fitting manner to the capillaries 1a, 1b, 1c.
    FIG. 5 shows another example of a tensioning element 13 which can be used as the tensioning element 13 shown in FIGS. 3 and 4. In Fig. 5, only the clamping element 13 is shown without the capillaries 1, the pressure vessel 2 or other components in cross section. The tensioning element 13 in turn has two parts 13a and 13b which, as shown in FIG. 4, engage in one another via a tapered or conical region. In the example shown in Fig. 5, the tapered second part 13b is cut along its circumference over part of its length. This results in the incised area two halves 13b1 and 13b2, which are elastically flexible against each other. When the second part 13b is inserted into the first part 13a, the two halves 13b1 and 13b2 are bent towards each other and thereby press against the capillaries 1 which pass through the tensioning element 13. It should be noted that Fig. 5 shows only one half of the clamping element 13. The clamping element 13 has in its complete form a further half, which is identical to the half shown, so in particular also has an incision as shown.
    6 shows an alternative embodiment of the tensioning element 13 with capillary tubes 1 arranged therein. In the example shown in FIG. 6, the tensioning device again has two parts 13a and 13b which, not shown here, have a cylindrical channel inside have, through which the capillaries 1 run. For the design of the channel can be made to the preceding embodiments. The parts 13a and 13b of the tensioning device 13 are chamfered at their ends facing each other, so that the cylinder axes of the channels are coaxial with each other, but the first part 13a and the second part 13b abut each other on the chamfered surfaces.
    Now, a force in the axial direction, i. is exerted in the direction of the cylinder axis of the channel or the longitudinal axis of the capillaries 1 on the parts 13a and 13b, which presses the parts 13a and 13b of the tensioning device towards each other, so clamp the parts 13a and 13b, the capillaries 1 between them. In this way, the clamping element allows the capillaries 1 to be fixed against displacement along their longitudinal direction.
    FIG. 7 shows a section through the closing element 11 shown in FIG. 3 on the left side of the flow barrier 15. A union nut 51 presses the clamping elements 13, 13a, 13b against the flow barrier 15. This is supported in the closing element 11, so that when tightening the nut 51, a clamping force is created. The flow barrier 15 is only loose in the closing element 11th
    While only three capillary tubes can be seen in Fig. 3, seven capillary tubes 1 are combined into a bundle in Fig. 7. In the example shown in FIG. 7, the clamping element 13 and the flow-limiting element 15 comprise a cylindrical interior 16 with a hexagonal cross-section.
    Fig. 8 shows a Fig. 7 corresponding cross-section through an exemplary embodiment of a device according to the invention. In contrast to FIG. 7, in the example shown in FIG. 8, the flow-limiting element 15 and optionally also the clamping element 13 are designed such that they enclose an inner space 16 whose wall follows the outer contour of the bundle of the capillary tubes 1. Preferably, the wall of the inner space 16 encloses the bundle of the capillary tubes 1 in a form-fitting manner.
    Fig. 9 shows an example of a possible arrangement of a pressure vessel in a schematic representation, which can be used to carry out the inventive method or may be part of the inventive device.
    The pressure vessel 2 in this case has an inlet 21 for supercritical carbon dioxide and an outlet 22 for carbon dioxide. With a temperature measuring device 25, a temperature T1 of the supercritical carbon dioxide at the inlet 21 of the pressure vessel 2 can be measured. With a further temperature measuring device 26, a temperature T3 at the outlet 22 of the pressure vessel 2 can be measured. Via an inlet valve 27, supercritical carbon dioxide can be introduced into the system and its flow rate can be controlled. With a pressure gauge 29, a pressure P at the inlet 21 of the pressure vessel 2 can be measured.
    From the outlet 22 effluent carbon dioxide flows through an outlet valve 28 and a throttle 30 to the outside. By adjusting the valve 28 and the throttle 30 can be set in the pressure vessel 2, a continuous flow of supercritical carbon dioxide between the inlet 21 and outlet 22 of the pressure vessel 2, wherein by the valve 28 and the throttle 30, the pressure in the interior of the pressure vessel 2 on a sufficient high value can be maintained to keep the carbon dioxide in the pressure vessel 2 supercritical.
    Between the inlet valve 27 and the inlet 21 of the pressure vessel 2, the arrangement shown in the example shown in FIG. 9 has an expansion valve 32, via which the pressure in the overall system can be reduced to atmospheric pressure or, optionally, the pressure P at the inlet 21 of FIG Pressure vessel 2 can be additionally adjusted. In normal machining operation, the valve 32 is preferably closed.
    The capillary tubes are not shown in FIG. 9. They are arranged here in the pressure vessel 2 and extend with their longitudinal axis parallel to the longitudinal axis of the pressure vessel 2. Supercritical carbon dioxide, which enters the pressure vessel 2 through the inlet 21, flows on the one hand through the interior of the capillaries 1 and on the other on the outside. The proportions of the carbon dioxide flowing through the capillaries 1 and flowing past them can be adjusted as shown in the other figures.
    The device shown in Fig. 9 also has an optional heater 23 which is connected to, for example, a heating coil in the interior of the pressure vessel 2. Instead of the heating coil 23, for example, a countercurrent heat exchanger 23 could be used. Between the heater 23 and the heat transfer spiral 24 here circulates a medium which transports heat generated by the heater 23 to the interior of the pressure vessel 2. In this way, the temperature T2 of the supercritical carbon dioxide in the pressure vessel 2, which can be measured with a temperature measuring device 43, be kept at a sufficiently high value, so that the carbon dioxide remains supercritical.
    In the example shown in FIG. 9, a vacuum pump 33 is also connected to the outlet 22 of the pressure vessel 2 via a valve 31. This vacuum pump 33 can be used to suck capillary tubes 1 into the pressure vessel. For this purpose, the capillary tubes 1 are arranged with one end near the inlet 21 and then the vacuum pump 33 is put into operation or the valve 31 is opened. It is thereby produced a suppression in the pressure vessel 2, through which the capillary tubes 1 are sucked into the pressure vessel 2. For flushing or processing operation, the valve 31 is then closed.
    10 shows a further exemplary embodiment of an inventive device in section. In the example shown in FIG. 10, the pressure vessel 2 is delimited by two coaxial circular-cylindrical walls, between which the capillary tube or the capillary tubes run wound on a coil 34. The coil 34 is designed in the example shown as a removable element, so that the capillary tube 1 can first be completely wound on it and then can be used as a whole in the pressure vessel 2. Down the pressure vessel 2 is closed by a solid floor. Upwards, it can be closed by a cover 35. The lid 35 and / or the pressure vessel 2 can advantageously have a heating device with which the interior of the pressure vessel 2 is heated so that it located supercritical carbon dioxide can be maintained at a temperature which is sufficiently high to ensure the supercritical state.
    When the capillary tube 1 wound up on the coil 34 is inserted into the pressure vessel 2, the interior of the capillary tube 1 is brought via a connection 37 with an inlet 21 of the pressure vessel into a compound permeable to supercritical carbon dioxide. Over the inlet 21 supercritical carbon dioxide is then introduced directly into the interior of the capillary tube.
    The device shown in FIG. 10 further has an additional inlet 36, via which supercritical carbon dioxide can be introduced into the interior of the pressure vessel 2, so that the latter flows around the capillary tube 1 on the outside thereof. The separate inlets 21 and 36 for supercritical carbon dioxide into the interior of the capillary 1 and the surrounding space, the pressure difference between the interior of the capillary 1 and the exterior can always be adjusted so that damage to the capillary 1 is avoided by excessive pressure differences.
    The additional supercritical carbon dioxide inlet 36 is optional in FIG. Alternatively, the element 37, via which supercritical carbon dioxide is conducted into the capillary 1, as described in FIGS. 1 to 9 may be formed with a defined leakage. By means of a suitable design of the leakage, it can be adjusted which proportion of the supercritical carbon dioxide flowing through the inlet 21 flows into the capillary tube 1 and which portion flows past it. In this way, a suitable pressure difference between the interior and exterior space of the capillary 1 can be maintained.
    The apparatus shown in Fig. 10 also has an outlet 22 for carbon dioxide; by which batchwise or continuously carbon dioxide can be discharged from the interior of the pressure vessel. The discharge through the outlet 22 may be via a valve and / or a throttle, so that in the interior of the pressure vessel 2, a sufficient pressure can be maintained to keep the supercritical carbon dioxide in the supercritical state.
    Fig. 11 shows the embodiment shown in Fig. 10 of the inventive device as a whole in a state in which the coil 34 is arranged with the capillary tube 1 completely inside the pressure vessel 2 and the lid 35 just before the closure of the interior of the pressure vessel 2 is arranged above this. For the details of Fig. 11 reference should be made to the description of FIG.
    Fig. 12 shows schematically the structure of the embodiment of the invention shown in Figs. 10 and 11. Via the inlet 21, supercritical carbon dioxide can be introduced into the interior of the capillary 1. With a pressure gauge 39, a pressure P1 of the introduced into the capillary 1 supercritical carbon dioxide can be determined.
    Via a further inlet 36, supercritical carbon dioxide can be introduced into the interior of the pressure vessel 2. A pressure P2 of the carbon dioxide which can be introduced into the interior of the pressure vessel can be measured with a pressure gauge 40. Preferably, the pressures P1 and P2 are controlled so that they are sufficiently large to ensure the supercritical state of the carbon dioxide inside the capillary 1 and the pressure vessel 2 and that their difference is sufficiently low to avoid damage to the capillary tube 1. In this case, the pressure P1 is adjustable via a first valve 41 and the pressure P2 via a second valve 42. As shown in Fig. 9, a relief valve 32 is provided, which is arranged in a line between the valve 41 and the Inlet 21 branches off and opens on the other side of the valve 32 to the outside.
    By means of a temperature measuring device 43, a temperature T2 in the interior of the pressure vessel 2 is measurable. This temperature T2 is regulated by heaters 23 and 38. The first heater 23 is arranged in the lid 35 of the pressure vessel, while the second heating device 38 is arranged in the pressure vessel itself.
    Carbon dioxide, which flows out of the pressure vessel 2 through the outlet 22, is passed through a valve 28 and a throttle 30 in the machining operation, which can ensure that the pressure inside the pressure vessel 2 is not below the pressure for maintaining the supercritical state of carbon dioxide decreases. Via a further valve 44, the pressure vessel 2 can also be relaxed, for example after the end of the machining process.
    The capillary 1 is open at its opposite end to the inlet 21 and opens into the interior of the pressure vessel 2. In this way, through the outlet 22, the supercritical carbon dioxide introduced through the inlet 21 as well as through the inlet 36 flows out.
    For example, a processing sequence in the device shown here may be as follows. First, the capillary tube 1 is provided with the element 37, for example a sealing piece 37, and inserted into the pressure vessel 2. It is then closed the lid. Next, the pressure vessel is flooded, in which the valve 41 and / or the valve 42 is opened. This is followed by rinsing of the capillary tube 1 and the pressure vessel by opening the valves 41, 42 and 28. Finally, the system is depressurized, in which the valves 41 and 42 are closed and the valves 32 and 44 are opened.
    In detail, with the arrangement shown in Fig. 12, the inventive method can be carried out as follows: After closing the lid 35, the pressure vessel (reactor) 2 via the flood valves 41 and 42 (V1 and V2) with supercritical C02 filled until the working pressure is applied. The temperature of the incoming supercritical CO 2 is monitored by means of a temperature sensor T1. The filling process can be regulated in the case of very thin-walled capillaries or very pure capillaries. That the inlet valves 41 and 42 are controlled by means of the measured pressure values P1 and P2 or volume flowmeters, not shown here so that no C02 from the pressure vessel 2 leinströmt backwards into the capillary and the differential pressure does not exceed the damage threshold of the capillary 1. The process temperature in the pressure vessel 2 is monitored by means of a further temperature sensor 43 (T2). Via the heaters 23 and 38 (H1, H2) of the pressure vessel and the temperature of the incoming supercritical CO2 (T1), the process temperature required for cleaning is set. After filling the reactor 2, it may be advantageous to let the supercritical CO 2 act for a certain time. Here, the pressure and the temperature are maintained or changed defined. After the reaction time, the purge valve 28 (V3) is opened, so that a defined amount of supercritical CO 2 can escape via the throttle 30 (D1). The escaping supercritical CO 2 is replaced by the still open inlet valve 41 and 42 (V1 and V2) regulated. The rinsing process starting with this ensures that the supercritical CO 2 inside the capillary 1 is continuously replaced by fresh (clean) supercritical CO 2. In order that the capillary 1 and the coil 34 also become clean, the reactor 2 can be rinsed with fresh supercritical CO 2 in the same way. In order to keep the required amount of CO 2 small, the coils are preferably designed so that the reactor 2 is filled as well as possible. If required, "positive displacement inserts" can be used.
    The flushing process ends, for example, when the required internal and external purity is reached by closing the flushing valve 28 (V3). The necessary rinsing time can be determined by tests or you can place a suitable inline measuring system in the rinsing outlet. With the help of such a measuring system, the flushing process can be controlled as needed. After cleaning, the pressure vessel 2 and the capillary 1 are emptied via the expansion valves (V4 and V5) and the coil 34 with the capillary 1 can be removed from the reactor 2.
    FIG. 13 shows an embodiment of the device according to the invention with high-pressure components. The capillary tubes 1 are arranged in a long tube 2 as a pressure vessel 2. Via an inlet 45 and an outlet 46, heating fluid can be conducted through the pressure vessel 2, which flows there separately from the supercritical carbon dioxide. Supercritical carbon dioxide can be supplied to the system via an inlet 21 and can be diverted via an outlet 22. The system shown in Fig. 13 also has a connection 47 for a vacuum pump 33, with which in the pressure vessel 2, a vacuum can be generated in order to simplify the loading of capillaries 1, as described above. The device shown in FIG. 13 may be connected, for example, as shown in FIG. 9.
    Fig. 14 shows the effect of the inventive method and the inventive device when cleaning capillary tubes. The editing is here so a cleaning of the capillary tube. The results shown were determined by means of a gas chromatograph. It can be seen that long chain hydrocarbon compounds are present in the capillaries before purification (upper diagrams). This is indicated by the numerous peaks in the right-hand area of the upper diagrams. After purification with supercritical carbon dioxide these peaks have completely disappeared. It can be seen that all contaminants could be removed by the invention.
    权利要求:
    Claims (24)
    [1]
    1. A method for processing at least one capillary tube, wherein at least one capillary tube with supercritical carbon dioxide is flowed around so that the supercritical carbon dioxide along an outside and an inside of the at least one capillary tube flows, and the at least one capillary tube is processed by the action of supercritical carbon dioxide.
    [2]
    2. The method according to any one of the preceding claims, wherein during the processing supercritical carbon dioxide is supplied to the at least one capillary tube continuously and continuously removed from the at least one capillary tube and relaxed.
    [3]
    3. The method according to any one of the preceding claims, wherein a plurality of bundled capillary tubes is processed simultaneously by the method.
    [4]
    4. The method according to any one of the preceding claims, wherein the method is carried out in a pressure vessel, wherein the at least one capillary tube is clamped in a clamping element, so that the clamping element surrounds the at least one capillary tube, wherein the supercritical carbon dioxide through the clamping element to the outside of the at least one capillary tube is passed, wherein the at least one tensioning element is configured such that it limits a flow of supercritical carbon dioxide past the at least one capillary tube, so that a defined first portion of the supplied supercritical carbon dioxide flows into the at least one capillary tube and a defined second Proportion of the guided supercritical carbon dioxide flows past at least one capillary tube.
    [5]
    5. The method according to the preceding claim, wherein the at least one capillary tube is first clamped in the clamping element and is then introduced together with the clamping element in the pressure vessel.
    [6]
    6. The method according to one of the two preceding claims, wherein the clamping element is arranged in a closing element, and wherein first the at least one capillary tube is clamped in the clamping element and then the closing element is inserted into an inlet opening of the pressure vessel.
    [7]
    7. The method according to any one of the preceding claims, wherein the supercritical carbon dioxide via a first valve in the at least one capillary tube and a second, different from the first valve, valve is passed to the outside of the at least one capillary tube, and that by means of the valves, a pressure difference is set between the supercritical carbon dioxide inside the capillary tube and the supercritical carbon dioxide on the outside of the capillary tube so that it is smaller than a maximum compressive strength of the at least one capillary tube.
    [8]
    8. The method according to any one of the preceding claims, wherein the at least one capillary tube is rolled up during processing by means of the method on a spool.
    [9]
    9. The method according to any one of the preceding claims, wherein the method is carried out in a pressure vessel, and wherein the at least one capillary tube is introduced into the pressure vessel by the at least one capillary tube is brought with one end to an opening of the pressure vessel and at another opening a pressure is generated in the pressure vessel, so that the at least one capillary tube is sucked into the pressure vessel.
    [10]
    10. The method according to any one of the preceding claims, wherein the supercritical carbon dioxide at least one abrasive and / or at least one detergent-active substance is added.
    [11]
    11. The method according to any one of the preceding claims, wherein the method is a method for cleaning the at least one capillary tube.
    [12]
    12. The method according to any one of claims 1 to 10, wherein the method is a method for coating the at least one capillary tube, wherein the supercritical carbon dioxide at least one substance is admixed, which is deposited on the at least one capillary tube.
    [13]
    13. Apparatus for processing at least one capillary tube, comprising a pressure vessel into which at least one capillary tube is completely insertable, wherein the pressure vessel has at least one inlet, via which supercritical carbon dioxide can be introduced into the pressure vessel, so that the supercritical carbon dioxide has an outside and an inside the at least one capillary tube flows around in the pressure vessel.
    [14]
    14. Device according to the preceding claim, wherein the pressure vessel has at least one outlet for the carbon dioxide, wherein the outlet has a valve and / or a throttle, by means of which a pressure in the pressure vessel to a value is durable, so that the carbon dioxide in the pressure vessel remains supercritical.
    [15]
    15. Device according to one of claims 13 to 14, comprising at least one hollow cylindrical clamping element, wherein an interior of the clamping element is designed so that the at least one capillary tube in the arranged in the clamping element state in the interior of the clamping element bears against the latter and wherein the clamping element designed in that, if the at least one capillary tube is arranged in the clamping element, it has a predetermined leakage around the at least one capillary tube, so that when supercritical carbon dioxide is introduced into the pressure vessel, a predetermined first portion of the supercritical carbon dioxide flows past the at least one capillary tube and a predetermined second portion flows into the at least one capillary tube.
    [16]
    16. Device according to claims 13 to 15, wherein the pressure vessel has a cylindrical interior, in which the at least one capillary tube with its longitudinal axis parallel to a longitudinal axis of the cylindrical interior can be arranged, and the at least one inlet valve on an end face of the cylindrical interior in the Pressure vessel opens.
    [17]
    17. Device according to one of the two preceding claims, wherein the clamping element rests with an outer side of the clamping element on an inner side of the pressure vessel.
    [18]
    18. Device according to one of claims 15 to 17, comprising a closing element which is arranged in the inlet of the pressure vessel, wherein the closing element has a cylindrical channel, in which the at least one capillary tube can be arranged, wherein the clamping element is arranged in the channel of the closing element in that it circulates around the at least one capillary tube when it is arranged in the terminating element.
    [19]
    19. Device according to one of claims 15 to 18, wherein the interior of the clamping element has a hexagonal cross-section in a plane perpendicular to the cylinder axis of the clamping element or the at least one capillary tube surrounds positively.
    [20]
    20. Device according to one of the two preceding claims, comprising at least one flow barrier, which surrounds the region in which the at least one capillary tube can be arranged in the interior of the pressure vessel or in the closing element, and which is designed so that they supercritical carbon dioxide, outside the at least one capillary tube flows, if this is arranged in the pressure vessel or in the connecting element, opposes a flow resistance.
    [21]
    21. Device according to one of claims 15 to 20, wherein the clamping element comprises two parts which, when the at least one capillary tube is therein, are verschränkbar against each other or wedged into one another, wherein preferably one of the parts has spring elements, which in a radial direction are flexible to the cylinder axis of the clamping element, wherein an end opening of the other part is conical, so that the spring elements are compressed during insertion of the first part in the end opening of the second part in the radial direction and pressed onto the at least one capillary tube.
    [22]
    22. Device according to one of claims 13 to 21, wherein an interior of the pressure vessel is limited by a cylinder or by two coaxial cylinders of different radius and by a bottom and a lid.
    [23]
    23. Device according to the preceding claim, wherein the lid has a heater.
    [24]
    24. Device according to one of claims 13 to 22, wherein with the device, a method according to any one of claims 1 to 12 is feasible.
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    同族专利:
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    DE102015222247A1|2017-05-11|
    DE102015222247B4|2017-10-26|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    WO2001060534A1|2000-02-18|2001-08-23|Eco2 Sa|Device and method for the precision cleaning of objects|
    DE102006015382A1|2006-04-03|2007-10-04|Robert Bosch Gmbh|Process to treat surgical implant having nano-scale pores with carbon dioxide in supercritical condition|
    US8658091B2|2011-09-15|2014-02-25|Novasterilis, Inc.|Using supercritical carbon dioxide to remove residual EtO from sutures|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    DE102015222247.0A|DE102015222247B4|2015-11-11|2015-11-11|Method and device for processing capillary tubes|
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