• 专利附录
  • 专利说明
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    • 专利摘要:
    At temperatures from 5 to 78 ° C., preferably at room temperature, and from 0.6 to 25 atm, preferably from 0.8 to 17 atm, the wet F32 stream is fed with a feedstock of a molecular sieve containing composition selected from a sieve of type 3A, 4A or 5A. Drying method of wet F32 consisting of continuous contact.
    公开号:KR20000047606A
    申请号:KR1019990049213
    申请日:1999-11-08
    公开日:2000-07-25
    发明作者:베르똑치오르네
    申请人:엘프 아토켐 소시에떼아노님；
    IPC主号:
    专利说明:

    Method for drying difluoromethane {PROCESS FOR DRYING DIFLUOROMETHANE}
    FIELD OF THE INVENTION The present invention relates to the field of fluorohydrocarbons, and more particularly, the subject of the present invention is wet difluoromethane (CH 2 F 2 ), using a molecular sieve of type A, which can be used in an industrial manufacturing plant. It relates to a method of drying continuously.
    Difluoromethane (also known in the art as abbreviation F32 or HFC-32) is one of the possible substitutes for chlorofluorocarbons (CFCs) associated with the Montreal Protocol. It more specifically tends to replace chloropentafluoroethane (F115, a very strong contributor to the greenhouse effect due to its action on ozone) and will replace F22 or chlorodifluoromethane in the near future. In this respect, it is either R407 C (a mixture of 50% / 50% by weight with HFC-125 or pentafluoroethane) or R410 A (23% / 25% / 52% by weight used in the refrigeration industry). Some of the composition of some azeotropic mixtures such as proportions of HFC-32 / HFC-125 or pentafluoroethane / HFC-134a or 1,1,1,2-tetrafluoroethane mixtures.
    F32 is fluorinated methylene chloride (CH 2 Cl 2 ) in the presence of a catalyst using hydrogen fluoride (HF), or by hydrolysis of dichlorodifluoromethane (F12) or chlorodifluoromethane (F22), Or alternatively can be obtained by decomposing the α-fluoro ether under the action of Lewis acid in the presence of HF.
    Some of these methods require acid or base cleaners, which introduce large or small amounts of water into the final product. As such, the product must undergo an additional drying process to satisfy the normally controlled specification for hydrogen fluoride (HFCs), ie less than 10 ppm of moisture.
    This is required to avoid corrosion problems in the refrigerator.
    Molecular sieves, also known as synthetic zeolites, are chemical compounds widely used industrially, in particular as adsorbents for drying gas or liquid. There is a metal aluminosilicate having a three-dimensional crystal structure composed of a set of tetrahedra. The tetrahedron is formed by four oxygen molecules located at the apex, and surrounds a silicon atom or an aluminum atom located at the center. The structure generally includes cations that make the system electrically neutral, derived from sodium, potassium or calcium.
    In the case of so-called A type molecular sieves, the tetrahedrons are assembled to form a truncated octahedron. The octahedron is arranged in a simple equiaxed crystal structure that itself forms a network having a cavity of about 11.5 mm 3 in diameter. The cavity is reachable through holes or pores that can be partially blocked by cations. When the cation is derived from sodium, the cavity has a hole of 4.1 mm 3 in diameter, and thus a so-called 4 A molecular sieve is obtained. The crystal structure of such a sieve can be represented by the formula:
    Na 12 [(AlO 2 ) 12 (SiO 2 ) 12 ] .XH 2 O
    [Wherein X (which represents the number of molecules of the water-forming portion of the structure (crystal water)) may be less than 27, which represents 28.5 wt% of anhydrous zeolite.
    After removing the crystal water by heating to a temperature of about 500 to 700 ° C., the cavities in the material allow for selective adsorption of various gases or liquids. As such, the pores in the various types of zeolites pass or adsorb only molecules whose effective diameter is less than or equal to the effective diameter of the pores in the corresponding cavity. In the case of drying of gas or liquid, the material to be dried itself is not adsorbed or is adsorbed only to a negligible extent, while it is water molecules that remain inside the above-mentioned cavities by selective adsorption.
    In addition, the size of the pores (or voids) can be modified for different types of molecular sieves. Thus, by replacing most of the sodium ions of the 4A molecular sieve with potassium ions, a 3A molecular sieve having a pore diameter of about 3 mm 3 is obtained. The 5A molecular sieve is prepared by replacing sodium ions with calcium ions, and the effective diameter of the pores is about 5 mm 3.
    Sieves of type 3A, 4A or 5A are widely commercially available.
    In practical use, the molecular sieve can be combined with other substances such as binders, in particular mud, and the resulting composition is molded into granules, beads or extrudates, for example.
    The molecular sieves thus adjusted are used industrially by loading them into a drying column which is dried when the wet gas is introduced.
    After a period of operation, depending on the operating conditions (flow rate of gas to be dried, amount of molecular sieves) in the drying column, an increase in the moisture content of the dried gas through the column is observed. The instant corresponds to the water-saturation of the sieve feedstock, i.e. the maximum amount of adsorbable water. The amount is generally about 20% by weight relative to the weight of the dry sieve.
    This sieve feedstock saturated with water must then be subjected to a so-called regeneration treatment, after which the initial water adsorption capacity of the sieve is restored. The treatment usually consists of passing an inert gas stream into the column at a temperature of 200 ° C to 300 ° C. In practical terms, the treatment of the saturated sieve feedstock is carried out in the same column in which the gas stream to be dried is introduced. This same drying column sometimes acts as a phase to dry out the wet gas and sometimes to regenerate the molecular sieve feedstock using an inert gas. However, after several dry-regeneration operations, if an irreversible reduction in the water-saturation capacity of the sieve feedstock is observed, it is necessary to shut down the column to replenish the sieve feedstock with fresh feedstock.
    By "new sieve feedstock" is meant herein a sieve feedstock that has not been used as a desiccant.
    Under the industrial practice of gas drying with molecular sieves, two drying columns which can alternately operate with each other are usually used, one is used in the drying phase and the other is used in the regenerating phase. .
    Drying F32 with molecular sieves poses specific problems due to the proximity of the effective diameters of the F32 molecule and water (0.33 nm and 0.21 nm, respectively).
    Thus, French patent application FR 2,705, 586 explicitly refers to a batch in which wet F32 is contacted with 3A type molecular sieve and ester oil at a temperature of 120 ° C. in a pressure vessel.
    However, the document teaches that under the above conditions, F32 is adsorbed to the sieve and undergoes a decomposition reaction, and as a result, the water-saturation capacity of the sieve is significantly reduced through deformation of the crystal state of the sieve.
    The document concludes that such a sieve is not suitable for F32 desiccants. The patent application concludes in the recommendation of molecular sieves obtained by replenishment of 3A type sieves for reducing the pore size for drying of F32 circulating as a refrigerant in a refrigerator.
    At this point it has been found that this drawback can be avoided by drying the continuously produced F32 air stream at a certain temperature range, and in particular by performing a specific process of regenerating the sieve feedstock.
    As such, one of the objects of the present invention is to provide a process for drying wet F32 using a simple, commercially available sieve that can be used in an industrial production plant of F32.
    It is a further object of the present invention to provide a continuous drying method of wet F32 which selectively separates water from sieve F32 with reduced F32 loss.
    It is a further object of the present invention to provide a process for continuous drying of wet F32 which comprises a step of regenerating a molecular sieve feedstock which generally maintains a constant water-saturation capacity.
    It is a further object of the present invention to provide a continuous method of drying of wet F32 which reduces the time to stop the drying column to replenish the molecular sieve feedstock.
    It has been found that the abovementioned objects are achieved in part or in whole by the process according to the invention described below.
    (1) represents a membrane pump,
    (3) represents a glass bead column,
    (4) represents a plunger,
    (5) represents a homogenization tank,
    (6) represents a drying tube,
    (7) represents the electrical conductivity measuring container,
    (8) represents the conductivity system,
    (9) represents a recorder,
    10 denotes an automatic stop device,
    11 represents a buffer tank,
    15 represents a buffer reservoir,
    18, 19, and 20 represent valves.
    As such, the present invention relates to a method for drying wet F32, which is used at a temperature of 5 to 78 ° C., preferably at room temperature, and at 0.6 to 25 atmospheres, preferably 0.8 to 17 atmospheres, for which the F32 stream is 3A, 4A. Or in continuous contact with a feedstock of a molecular sieve containing composition selected from a 5A type sieve.
    Contrary to the teachings of the prior art, it is thus possible according to the invention to continuously dry F32 using a commercially available type A sieve.
    The F32 stream to be dried can be a gas or liquid stream. If the F32 air stream to be dried is a liquid, the process is advantageously carried out at 9 to 25 atmospheres, preferably at 12 to 17 atmospheres.
    According to a preferred variant, when the F32 air stream to be dried is a gas, the process is carried out at a pressure of 0.6 to 10 atmospheres, preferably 0.8 to 5 atmospheres.
    The F32 air stream to be dried generally contains less than 10,000 ppm, preferably less than 6000 ppm.
    The wet F32 is preferably placed in contact with the sieve feedstock in a drying column located downstream of the F32 manufacturing plant.
    Prior to use for drying the F32 stream, fresh molecular sieve feedstock is activated. The purpose of the treatment is to remove the adsorbed water during storage and manipulation prior to installation of the material and prior to installation in a drying column. The treatment generally comprises heating to a temperature of 200 to 300 ° C. in the atmospheric pressure range.
    The flow rate of the F32 air stream to be dried and the amount of sieve feedstock suitable for the drying operation can be determined by a person skilled in the art capable of chemical engineering by calculating and testing as a function of plant size without great difficulty.
    According to a preferred variant according to the invention, the molecular sieve used is a sieve of type 3A. Such a sieve decreases the F32 adsorption capacity due to the effective pore diameter and improves the efficacy.
    According to a preferred variant of the process according to the invention, the molecular sieve feedstock used comprises 120 to 300 ° C, preferably 150 to 150 ° C, at an absolute pressure of less than 100 mm Hg, preferably less than 80 mm Hg. It is preferably regenerated (after reaching the water-saturation capacity) by a process consisting of heating to 250 ° C. The duration of the process is preferably determined so that substantially all amounts of adsorbed product (essentially water and a small amount of residual F32) can be desorbed after wet F32 drying. In the following, the amount is referred to by the term "initial amount".
    According to another preferred variant according to the invention, the molecular sieve feedstock used is firstly:
    (i) at a temperature of at least 70 ° C. to 170 ° C., preferably 80 ° C. to 165 ° C., for a time necessary to remove at least 80%, preferably at least 90%, of the initial amount of F32 adsorbed to the feedstock, And then
    (ii) at another temperature between 180 ° C. and 300 ° C., preferably between 190 ° C. and 250 ° C., for a period of time necessary to remove at least 90%, preferably at least 95%, of the initial amount of water adsorbed to the feedstock. Thereby being regenerated by a process consisting of passing an inert gas stream, such as helium, over the feedstock at a pressure within the atmospheric pressure range.
    The operating time required at temperature (i) is determined by monitoring the content profile of F32 in the inert gas leaving the regeneration column, with appropriate control methods such as chromatographic analysis. The operating time required for temperature (ii) is determined in a similar manner using, for example, a hygrometer. The time depends on the plant and is based on several parameters known to those skilled in the art: the flow rate of the inert flushing gas, the heat of desorption of water and F32, the thermal mass of the metal apparatus including sieves and sieves.
    The last two embodiments of the method according to the invention, relating to a sieve feedstock regeneration method, are particularly useful because it is possible to keep the water-saturation capacity of the molecular sieve feedstock substantially the same as before regeneration even after regeneration. This same industrially used sieve feedstock can be effectively used in several cycles of drying / regeneration of F32. Of the two variants, the use of an inert gas stream is more particularly preferred because it is simpler to implement and operate in a factory.
    When molecular sieve feedstock regeneration is carried out by the two-step process described above, first:
    -(i1) at a first temperature between 70 ° C and 130 ° C, preferably between 100 ° C and 125 ° C, for the time required to remove at least 60% (preferably at least 70%) of the initial amount of adsorbed F32, and next
    (i2) at a second temperature of 130 ° C. to 170 ° C., preferably 145 ° C. to 165 ° C., by operating for a time necessary to remove at least 80%, preferably at least 90% of the initial amount of adsorbed F32 Particular preference is given to carrying out (i).
    Such treatment more preferably maintains the water-saturating capacity of the sieve feedstock. It also recovers F32, which is significantly lower in moisture content than the wet F32 to be dried, especially after step (i1).
    The regeneration process for the sieve feedstock according to one of the two variants described above is preferably carried out in the same column as mentioned above. More preferably the drying process according to the invention is carried out in two parallel columns, one operating in a bed for substantial wet F32 drying and the other in a bed for regeneration of saturated molecular sieve feedstock.
    As described above, when the process for regeneration of the sieve feedstock is performed at a heating temperature of 200 to 300 ° C. (in the presence of an inert gas stream), a decrease in the water-saturation capacity of the molecular sieve feedstock is observed. . This degradation causes the plant to shut down to replenish the sieve feedstock, which is incompatible with the operation of the drying plant.
    In addition to molecular sieves, the compositions used in the process according to the invention contain additives customarily used in the art, in particular mud-based binders, which enable the molding zeolite products to maintain moldability and strength. The composition is generally in the form of pearls or granules. Regarding strength and effective drying power, it is preferable that the granules are essentially cylindrical with a diameter of 0.5 to 5 mm and a length of 3 to 15 mm, and for pearls, a diameter of 1 to 5 mm.
    The following examples are intended to illustrate the method according to the invention and are not limiting.
    Example 1 Drying of the F32 Airflow Using a Feedstock of 3A Type Molecular Sieves
    40.8 g of a feedstock of Ceca NK 30 (3 mm 3) sieves of granule form of about 1.5 mm in diameter and 5 to 10 mm in length are placed inside a stainless steel drying tube 6 having an inner diameter of 14 mm and a height of 750 mm. The dryer thus has an operating height of about 380 mm and is equipped with a jacket for heating the sieve feedstock.
    Feedstock preactivation is carried out by heating to 200 ° C.
    The F32 gas stream containing 4100 ppm of moisture was then circulated through the drying tube at a flow rate of 44 l / hr at a temperature of about 20 ° C. and 1 atmosphere, and the drying efficiency was monitored by measuring the moisture content, which itself Is performed using an electrical conductivity measuring vessel (7) coupled to a conductivity meter (8) connected to the recorder (9) and the automatic stop device (10).
    The desiccant is then passed through a 5 L volume buffer reservoir 15, from which the water with a flow rate of 0.4 ml / hour consists of a glass bead column 3 and a plunger 4 with the aid of a membrane pump 1 The dried F32 stream is thus humidified to a moisture value of 4100 ppm as mentioned above. After passing through the humidification and homogenization tank 5 above, the air flow returns to the dryer 6.
    The 10-L buffer tank 11 maintains the pressure of the F32 gas stream at a value of about 1 atmosphere.
    The assembly view described in FIG. 1 thus constitutes a gas-phase drying loop which stimulates the operation of the drying column for the continuous treatment of the wet F32 air stream.
    The moisture content of F32 below 10 ppm is measured at the outlet of the drying tube.
    Deviation from the output signal of the measuring vessel indicating that the sieve feedstock has reached the water-saturation capacity appears after 18 hours 30 minutes of operation, corresponding to a water saturation capacity of 19.9% by weight of the dry body.
    Example 2: Regeneration of 3A type molecular sieve feedstock by heating at 1 mm Hg atmosphere, 200 ° C .:
    The assembly diagram described in FIG. 1 also allows several cycles to be performed with the same molecular sieve feedstock; Each cycle consists of continuously drying the wet F32 to the sieve feedstock water-saturation point and then regenerating the feedstock. The cycle is performed with minimal consumption of F32.
    After 18 hours and 30 minutes of operation to reach the water-saturation capacity of the sieve feedstock as described in Example 1, the circulation of the wet F32 gas stream is stopped by closing the appropriate valve.
    This is followed by circulating a helium stream for 2 hours at room temperature in the drying tube 6, the purpose of which is to remove F32 remaining between the granules of the molecular sieve feedstock.
    In this way, the valve 18 and the valve 19 are locked, and the valve 22 is opened to connect the drying tube 6 to the vacuum pump through a metal trap submerged in liquid nitrogen.
    Thus the pressure in the tube goes down to 1 mm Hg. The temperature in the drying tube 6 is adjusted to 200 ° C. by circulating the heat-induced liquid in the jacket of the dryer.
    The temperature and pressure conditions are maintained for about 2 hours until complete removal of the small amount of F32 that is still adsorbed to the moisture and sieve feedstock. This desorbed water (and F32) remains in the liquid nitrogen trap and is weighed at regular time intervals. If the weight of the trap is substantially constant, the regeneration process is stopped.
    The drying test is then repeated as defined in Example 1 using the sieve feedstock thus regenerated.
    After 19 hours of operation, the water-saturation capacity of the sieve feedstock is reached. It is 18.4%, thus representing 92.5% of the water-saturation capacity measured at the end of Example 1.
    This example shows that the water-saturation capacity is maintained at a substantially constant value after this regeneration treatment, which is preferably included in the wet F32 drying process according to the present invention.
    Example 3 Regeneration of 3A Type Molecular Sieve Feedstock Performed at 3 Constant Temperature Regime Using Helium Airflow:
    Example 1 is repeated using 41.1 g of a fresh feedstock of Ceca NK 30 (3 mm 3) molecular sieves.
    Saturation is reached after 19 hours of operation. It is 18.5% by weight of the dry body.
    The sieve feedstock is then regenerated in a drying tube 6 by circulating a helium stream under normal atmospheric pressure and under the following conditions:
    2 hours at -120 ° C
    1 hour 30 minutes at -150 ° C, then
    2 hours at -200 ° C.
    Chromatographic monitoring 14 of desorbed F32 shows that the corresponding amount of F32 (expressed for the initial amount of adsorbed F32) is about 70% after the floating regime at 120 ° C. and about after the floating regime at 150 ° C. Indicates 90%.
    Chromatographic monitoring 14 of water in the helium stream indicates that at least 95% of the water adsorbed on the sieve feedstock desorbed after the immobilization regime at 200 ° C.
    The drying test is then repeated as defined in Example 1 using the sieve feedstock thus regenerated.
    A water-saturation capacity of 16.9% was measured. Such a value corresponds to 91.3% of the water-saturation capacity obtained at the end of the drying step of this example.
    This example shows that the water-saturation capacity is maintained at a substantially constant value after this regeneration treatment, which is preferably included in the wet F32 drying process according to the present invention.
    Example 4:
    In accordance with Example 1 40.3 g of an unfresh sieve feedstock were used, having a water-saturation capacity of 14.2%.
    The sieve feedstock is used to perform a series of drying / regeneration cycles: each cycle is a continuous drying of the wet F32 carried out to the water-saturation point of the feedstock according to Example 1, followed by the above Regeneration of feedstock consists of:
    3 hours at -120 ℃
    3 hours at -160 ℃
    2 hours at -200 ° C.
    After 3 hours at 160 ° C., 98% of the initial amount of adsorbed F32 was desorbed.
    The results are shown in the table below. The table below shows that the water-saturation capacity of the sieve feedstock remains largely constant.
    Cycle numberMoisture capacity (%) One14.2 214.3 314.5 413.0 515.3
    Comparative example:
    Example 1 is repeated using 40.8 g of fresh sieve feedstock.
    After 19 hours of operation, water-saturation is reached. It is 18.4% by weight of the dry sieve.
    Regeneration is carried out while flushing the bed of the sieve with preheated (oven 13) dry helium 12 to 150 ° C., where the bed of sieve is simultaneously heated through the jacket of the dryer 6: the purpose of the method is to actually take place in an industrial process. As such, all sieve feedstocks are to reach the 200 ° C. temperature very quickly.
    After the floating regime at the temperature of 200 ° C. for 2 hours, the sieve is cooled and 35.3 g of the feedstock are dry tested as defined in Example 1.
    For this example, the water-saturation capacity of the sieve feedstock is reached after 10 hours of operation and is only 11.2%. This value corresponds to a 40% reduction in initial saturation capacity before regeneration.
    The process according to the invention makes it possible to selectively separate water from sieve F32 with reduced F32 loss, and the water-saturation capacity of the molecular sieve feedstock recycled according to the invention remains largely constant. In addition, according to the method of the present invention, the wet F32 can be continuously dried while reducing the dry column downtime for replenishing the molecular sieve feedstock.
    权利要求:
    Claims (10)
    [1" claim-type="Currently amended] At temperatures from 5 to 78 ° C., preferably at room temperature, and from 0.6 to 25 atm, preferably from 0.8 to 17 atm, the wet F32 stream is fed with a feedstock of a molecular sieve containing composition selected from a sieve of type 3A, 4A or 5A. Drying method of wet F32 consisting of continuous contact.
    [2" claim-type="Currently amended] The method according to claim 1, wherein the F32 air stream to be dried is a gas stream and the pressure is 0.6 to 10 atmospheres, preferably 0.8 to 5 atmospheres.
    [3" claim-type="Currently amended] The process according to claim 1 or 2, characterized in that the F32 air stream contains less than 10,000 ppm, preferably less than 6000 ppm.
    [4" claim-type="Currently amended] The process according to claim 1, wherein the wet F32 is contacted with a sieve feedstock in a column located downstream of the F32 manufacturing plant.
    [5" claim-type="Currently amended] The method according to any one of claims 1 to 4, wherein the molecular sieve used is a 3A type chain.
    [6" claim-type="Currently amended] 6. The sieve feedstock according to claim 1, wherein the sieve feedstock is brought to a temperature of 120 ° C. to 300 ° C., preferably 150 ° C. to 250 ° C., at an absolute pressure of less than 100 mm Hg, preferably less than 80 mm Hg. Regeneration of the sieve feedstock by a method consisting of heating.
    [7" claim-type="Currently amended] The method of claim 1, wherein:
    (i) at a temperature of at least 70 ° C. to 170 ° C., preferably 80 ° C. to 165 ° C., for a time necessary to remove at least 80%, preferably at least 90%, of the initial amount of F32 adsorbed to the feedstock, And then
    (ii) at another temperature between 180 ° C. and 300 ° C., preferably between 190 ° C. and 250 ° C., for a period of time necessary to remove at least 90%, preferably at least 95%, of the initial amount of water adsorbed to the feedstock. Thereby regenerating the sieve feedstock by a process consisting of passing an inert gas stream, such as helium, over the sieve feedstock at a pressure of about atmospheric pressure.
    [8" claim-type="Currently amended] The method of claim 7 wherein first:
    -(i1) at a first temperature between 70 ° C and 130 ° C, preferably between 100 ° C and 125 ° C, for the time required to remove at least 60% (preferably at least 70%) of the initial amount of adsorbed F32, and next
    (i2) at a second temperature of 130 ° C. to 170 ° C., preferably 145 ° C. to 165 ° C., by operating for a time necessary to remove at least 80%, preferably at least 90% of the initial amount of adsorbed F32 method characterized by performing (i).
    [9" claim-type="Currently amended] 9. Process according to any one of claims 6 to 8, characterized in that the regeneration of the sieve feedstock is carried out in the same column as defined in claim 4.
    [10" claim-type="Currently amended] 10. The process of claim 9, wherein one is operated in two parallel columns operating in a phase for wet F32 drying and the other in a phase for regeneration of saturated molecular sieve feedstock.
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    同族专利:
    公开号 | 公开日
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    TW523502B|2003-03-11|
    US20030057157A1|2003-03-27|
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    DE69913473D1|2004-01-22|
    ES2213342T3|2004-08-16|
    JP2000169405A|2000-06-20|
    FR2786766B1|2001-01-26|
    FR2786766A1|2000-06-09|
    EP1008576B1|2003-12-10|
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    1998-12-08|Priority to FR98.15469
    1998-12-08|Priority to FR9815469A
    1999-11-08|Application filed by 엘프 아토켐 소시에떼아노님
    2000-07-25|Publication of KR20000047606A
    2002-07-24|Application granted
    2002-07-24|Publication of KR100346011B1
    优先权:
    申请号 | 申请日 | 专利标题
    FR98.15469|1998-12-08|
    FR9815469A|FR2786766B1|1998-12-08|1998-12-08|Difluoromethane drying process|
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