![]() Rotary kiln and insufflator before.
专利摘要:
公开号:NL2015089A 申请号:NL2015089 申请日:2015-07-06 公开日:2016-04-04 发明作者:Brueck Gernot 申请人:Fuenix Ecogy B V; IPC主号:
专利说明:
Brief indication: Rotary drum oven and blower device therefor The invention relates to a rotary drum oven, comprising at least one indirectly heatable oven housing, which is rotatably held about a longitudinal axis of the oven and can be closed at one end by means of a fixed oven lid, an entrance opening provided for in the fixed oven lid solids to be prepared, as well as an exit device located at an end opposite the entry device. The invention furthermore relates to a blower device for use in a rotary drum furnace as well as a method for homogeneous heating, in particular evaporation of, in particular, particulate material in a rotary drum furnace. In the rotary kilns known hitherto, material is guided by means of a passage opening present in the fixed oven cover of the rotary kiln oven. The material transport is effected by means of a supply worm, the supply worm and the passage opening being thermally insulated from each other. On this basis, the supply worm heats by the infrared radiation (IR radiation) produced in the oven. IR radiation is heat radiation and is produced by heating the rotary kiln. In the heated feed worm, the temperature of the material to be supplied to the furnace is likewise raised. For materials comprising biogenic masses, this heating is usually not critical, since these materials do not change their state of aggregation at such temperatures created in the feed worm. Rotary kilns are also used for heating, in particular evaporation of plastics, in particular of thermoplastics. Many thermoplastics have melting temperatures that are already reached within a feedworm in the rotary drum oven, so that such materials melt in the feedworm and obtain a mass with an increased viscosity. Masses with high viscosities are slow-flowing and can stick to the supply worm or adjoining outlet openings. This has the consequence that the mass forms a blockage in the feed worm and reduces the amount of material supplied to the furnace. A further disadvantage in the processing of viscous masses is that they are transported at a relatively small speed. Furthermore, a syrupy mass adheres in such a way that it is difficult to portion. In general, effective heating of a mass is achieved by a homogeneous, that is to say, the same everywhere. In this context, it is practically practical to use masses with the largest possible total surface area. The total surface area of a mass is considered to be the sum of all (particle) surfaces contained in the mass. With a mass with a relatively small total surface area, partial areas of the mass are heated, so that the total time for heating the mass to a desired temperature becomes larger. Furthermore, the heating of masses with a smaller total area can lead to high temperature fluctuations inside the mass. For processing, however, it is often desirable that the materials comprise a homogeneous temperature distribution, so that products can be reliably manufactured from these materials with a constant goodness. A further drawback in the heating of materials with a relatively low melting point is that a relatively small furnace wall area is active in the heating of liquid materials. It is an object of the present invention to provide a rotary drum furnace of the above-mentioned type, an entry device for use in such a rotary drum furnace and a method with which a material introduced into the furnace is homogeneously and effectively brought to a desired speed as quickly as possible. temperature is heated, in particular is evaporated. In view of solving this object, the invention, starting from the rotary kiln as mentioned above, provides that the entry device consists of a tubular lance inserted into the furnace housing with a lance housing and an inner lance channel and that the lance housing consists of a material which comprises a surface which has IR radiation of at least 90%, in particular at least 95%, and which has exit openings extending from the inner lance channel to the outside through a wall of the lance, which are arranged one behind the other in the longitudinal direction of the lance, and that the lance is mounted outside the oven housing by means of a support. Furthermore, the invention provides for the use of the lance according to the present invention in a rotary drum furnace for blowing in material. According to the invention, a method is further provided in which an inner wall of the rotary drum oven facing the inner space of the oven with the blown-out material is uniformly provided by a blower device. In a rotary drum furnace according to the present invention, a material heating in the lance is prevented by IR radiation produced in the furnace, so that the material with a temperature below its melting or evaporating temperature is led from the blower device into the interior of the furnace. This prevents the material from melting inside the blower designed as a lance, so that neither the lance nor its exit openings are stuck by molten material. As a result, the rotary kiln oven can be operated with a constant mass flow rate, so that in any case the frequency of the maintenance work, which was previously still high due to adhered rotary kiln components, can be reduced. Moreover, the oven volume effectively used for heating is increased by the invention. In particular, supply quantities greater than 100 kg / h and per m3 of oven volume are achievable. Compared to the conventional feeder, the 5- to 10-fold of the material can thus be supplied. In an advantageous embodiment of the invention, the lance housing is surrounded by a casing tube, so that a circumferential gap is formed between the lance housing and the casing tube, and the exit openings are led outwards through tubular projections of the lance housing extending through the circumferential gap. The protrusions serve for this purpose that the material fed into the inner lance channel can be transported through the circumference gap to the inner space of the oven. Furthermore, the tubular protrusions serve for a purposeful bending of the material supplied to the inner wall of the oven. Deposits on the surface of the lance are prevented through the casing and also heat transfer through convection. For the invention it can be advantageous if the peripheral gap is / is flowed through a cooled gas stream of an inert gas which can be introduced into the peripheral gap at the end of the lance outside the oven housing and which is blown at the opposite end of the lance exits through a lance exit opening into an interior space of the oven. The circumferential gap that can be flowed through with an inert gas serves to dissipate heat from the surface of the inner lance channel and prevents oxidation of the lance surface. In this way heating of the lance and of the material transported in the inner lance channel is prevented and the IR-reflecting property of the lance surface is retained. In a measure improving the invention, the inner lance channel is connectable at its end outside the furnace housing or connected to a material blowing device for blowing in particulate material by means of an inert gas. Advantageous embodiments of the invention are included in the dependent claims and are further elucidated with reference to the drawing. Showing: FIG. 1 a longitudinal section of a rotary drum oven according to the present invention, FIG. 2 is an enlarged view of FIG. 1 in the portion of the oven cover. In the various figures of the drawing, the same parts are always marked with the same reference numeral. In the subsequent description, it is noted that the invention is not limited to the exemplary embodiments and is thereby not limited to all or more features of the feature combinations described. Rather, each individual feature of each exemplary embodiment is also independent of the other individual features described in conjunction therewith and also in combination with one or more of the features of another exemplary embodiment subject of the invention. FIG. 1 shows a rotary drum oven 1 according to the present invention, which comprises at least one indirectly heatable oven housing 2, which is rotatably held about a longitudinal oven axis XX and a fixed oven cover 3 that can be closed at least at one end, preferably a fixed oven cover 3 that can be closed on both sides , possession. Hereby, a penetration opening 4 provided in the fixed oven lid 3 proceeds an entry device 5, and in particular particulate material, such as, for example, particulate solids. Furthermore, an exit device 6 is provided on an end side opposite to the entry device 5. The entry device 5 comprises a tubular lance 7 protruding into the furnace housing 2 with a lance housing 8 and an inner lance channel 9. According to the present invention, the lance housing 8 consists of a material, comprising a reflecting surface that reflects the IR radiation by at least 90%, in particular 95%. In a feature improving the invention, the material of the lance housing consists of aluminum, in particular unalloyed, pure aluminum. In this context, it is defined that pure aluminum has a degree of purity of at least 95%, preferably a degree of purity of greater than 95% or particularly preferably a degree of purity of between 99.0% and 99.9%. Ultra-pure aluminum is also particularly suitable as a material of the lance housing, in which it comprises in particular a degree of purity of at least 99.99% for semi-finished products and 99.99% for aluminum blocks. In particular, only that surface of the inner lance channel 9 comprises aluminum in the form of pure aluminum or ultra-pure aluminum. The measure of the use of aluminum as a material for the lance housing 8 is based on the insight that ultrapure aluminum almost completely reflects IR radiation on its surface. According to the present invention, the lance 7 of the inner lance channel 9 comprises exit openings 10 extending outwardly through a wall of the lance 7 and provided in the longitudinal direction of the lance 7. Furthermore, the lance 7 is outside the furnace housing 2 by means of a support. 7 bearing. In particular, the lance 7 has a length of 2 m to 8 m, preferably a length of 4 m with a furnace length of 7 m or analogously with a different furnace length. The inner diameter of the inner lance channel 9 is preferably 5 cm to 20 cm, in particular 10 cm. In a further embodiment of the invention it can be advantageous if the lance 7 extends up to an oven post-processing portion 11 provided in the furnace housing 2 on the exit device 6. In particular with this measure it is desirable that, if possible, the entire inner wall of the oven 24 is used for heating and in particular for evaporation of material blown into the oven 1. In a possible embodiment of the invention, the size of the exit openings 10 increases in the direction towards the end of the lance 7 located inside the furnace housing 2. This measure is based on the fact that from the fixed oven lid 3 to the oven after-treatment section 11, the back pressure along the inner lance channel 9 becomes smaller. As a result, if large exit openings 10 remain constant along the inner lance channel 9, the quantity of the blown-out material would decrease. If the outlet openings 10 from the fixed oven lid 3 up to the oven post-processing section 11 become larger, the pressure drop within the lance 7 can be counteracted, and a uniform heating, in particular evaporation, of the material can be effected within the oven 1. . A further embodiment of the invention provides that oblique deflection surfaces 13 projecting into the inner lance channel 9, opposite the exit openings 10, are formed inside the inner lance channel 9. These oblique deflection surfaces 13 cause a bending of the material flow in the lance 7 to the corresponding opposite outlet opening 10. The purpose of the embodiment of the lance 7 is that the material is, if possible, only at the inner wall of the oven 24 within the shortest possible heated to a desired temperature. For the embodiment of the oblique deflection surfaces 13 this means that they are preferably designed in such a way that the flow of material exiting from the exit opening 10 is deflected in a targeted manner towards the oven inner wall 24. In particular, the exit openings 10 are designed and removed from the oven inner wall 24 such that the average path length between the exit opening 10 and the oven inner wall 24 is short, for example, a distance of 20 cm to 50 cm is effective. In this way, heating up to a material-specific melting temperature on the way to the oven inner wall 24 can be counteracted. A possible embodiment of the oblique deflection surfaces 13 may be that the surface of the oblique deflection surfaces 13 facing the passage opening 4 is concave. Furthermore, the oblique deflection surfaces 13 could be designed as a cone. In particular, the lance housing 8 is surrounded by a casing tube 14, so that a circumferential gap 15 is formed between the lance housing 8 and the casing tube 14 and the exit openings 10 are guided outwards by means of tubular projections 16 of the lance housing 8 running through the circumferential gap 15. . Such tubular protrusions 16 serve to promote material fed through the inner lance channel 9 through the peripheral gap 15 in the oven interior space 18. Moreover, the tubular protrusions 16 ensure a directed deflection of the material flow to the oven interior wall 24. For the invention it may be advantageous, that thermal insulation is provided between the tubular projections 16 and the casing tube 14 surrounding this. For example, a gap may be formed in the gap. A possible other further embodiment of the invention provides that an insulating material is provided between the casing tube 14 and the tubular protrusions 16, which comprises, for example, ceramic. In particular, the width of the circumferential gap 15 is between 0.5 cm and 5 cm, preferably between 1 cm and 2 cm. The casing tube 14 can be made of a heat-resistant material. However, the casing tube 14 is in particular made of metal, preferably steel. In particular, it protects the inner lance channel 9 against dust from the oven interior space 18 and against substances that could chemically react and / or form a layer with the surface of the inner lance channel 9. A further embodiment of the invention provides that the circumference gap 15 is / is flowed through a cooled gas stream of an inert gas which can be introduced into the circumference gap 15 at the end of the lance 7 outside the furnace housing 2 and can be fed to a blower the opposite end of the lance 7 exits from a lance exit opening 17 into an oven interior 18. In particular, the lance 7 is bent in front of its lance exit opening 17 at its end such that it is inclined towards the oven inner wall 24. As a result of this inert gas flow in the circumference gap 15, the heat radiated through the casing tube 14 is transported away and the surface of the lance 7 is prevented from heating because the hot gas reaches the lance. Inert gas is particularly suitable for this purpose, since it does not react with the wall material of the lance 7. This is particularly important in embodiments of the lance 7 made of a material comprising aluminum, since the formation of such layers, in particular the formation of an oxide layer can be inhibited on the aluminum. In particular, this also prevents particles from depositing on the aluminum surface. Along the lance 7, the inert gas heats from the passage opening 4 to the lance exit opening 17 by the IR radiation and the transfer of convection heat. Efficiently, an exit opening is provided on the lance exit opening 17 for the inert gas passing through the circumference gap 15. In particular, the inert gas outside the oven 1 can be produced from dry ice by evaporation and consist of CO 2. Advantageously, the inner lance channel 9 can be connected or connected at its end outside the furnace housing 2 to a material blowing device for blowing in particulate material by means of an inert gas. In particular, the mixture of particulate material and inert gas, such as, for example, CO2 in the inner lance channel 9 and the inert gas in the peripheral gap 15, is sucked in at the lance outlet opening 17 by means of a suction device. The material blow-in device is efficiently arranged for a blow-in amount of 500 kg / h and 1 m3 of oven volume. In a measure improving the invention, the furnace housing 2 is, for example, adapted for an inner wall temperature of 300 ° C to 1,200 ° C, in particular for an inner wall temperature of 600 ° C to 1,000 ° C. Preferably, an inner wall temperature of about 600 ° C is used for the processing of, for example, polyethylene, and an inner wall temperature of 1,000 ° C is used for biogenic masses, such as dried slurry. Furthermore, a one-sided, annular contact surface 20 is preferably formed between the oven housing 2 and the fixed oven cover, wherein a seal of the oven housing 2 with respect to the fixed oven cover 3 can be provided in the portion of the annular contact surface 20. An enlarged view of the relevant area in the rotary drum oven 1 is shown in Fig. 2. The seal of the oven housing 2 must in particular be designed such that, despite the rotation of the oven and the temperatures occurring in the oven 1, it the contact surface is reliably sealing. Moreover, it is effective if the casing tube 14 is sealed with respect to the passage opening 4. Hereby, a transfer of the heat from the inner wall of the oven 24 to the inner lance channel 9 is effectively inhibited. In a possible embodiment of the invention, a meander-shaped channel 21 is provided in the furnace post-processing part 11, wherein the channel entrance 22 is opposite to the lance exit opening 17 and the channel exit 23 opens into the exit device 6. This meander-shaped channel 21 ensures subsequent splitting of vapor-like molecular chains held in material in shorter molecular chains. In particular, the material to be blown in is a recyclable plastic made, for example, from used agricultural films. For this purpose plastic foils are shredded and made dry with the aid of dry ice in such a way that they can easily be ground into particles in a mill. The particles used comprise in particular a core size of 10 µm to 10 cm, preferably from 100 µm to 200 µm or from 200 mm to 1 cm. The particles can also be in the form of a flake. Upon entry into the inner lance channel 9, such particulate material comprises, for example, an average temperature of -10 ° C to 10 ° C, temperature of 0 ° C. In particular, the oven is arranged for an average blow-in amount of 100 kg / h to 800 kg / h per 1 m3 of oven volume, in particular for an blow-in quantity of 300 kg / h to 500 kg / h per 1 m3 of oven volume. The rotary kiln 1 comprises in particular a length of 5 m to 9 m, in particular a length of 7 m. The diameter of the oven is in particular from 50 cm to 1 m, in particular the inner diameter of the oven approximately 10% of the length of the oven, this being 72 cm in this exemplary embodiment. In particular, the particle-containing material used is preferably polyethylene and / or other aliphates. The evaporation of the supplied material is preferably effected by contact heat on the inner wall of the oven 24 and a heating effected immediately therethrough. At least one oven 1 is required for vaporizing the material; however, in a possible embodiment of the invention, a plurality of furnaces 1 can also be connected to each other. In this way, molecules split in the first furnace 1 could be split in a connecting furnace 1 into molecules with shorter chains. By evaporation and any further fission of the molecular chains, carbon and other solids are released as by-products, which are discharged therefrom by a suction device which is provided at the end of the furnace after-treatment section 11 in the furnace interior space 18. In order to support the transport of the solids to the extraction device, the rotary drum oven 1 is inclined such that the passage opening 4 is provided higher than the exit device 6. Furthermore, the rotary drum oven 1 rotates, for example, at a speed of 1 to 20 revolutions per minute, in particular at a rotation speed of 3 to 10 revolutions per minute. The invention is not limited to the illustrated and described exemplary embodiments, but it also comprises all embodiments that work in the same way within the meaning of the invention. It is expressly emphasized that the exemplary embodiments are not limited to all features and combinations, rather each individual sub-attribute can also have an inventive significance apart from all other sub-attributes. Furthermore, the invention is thus far not limited to the characteristic combination defined in the associated independent claim, but it can, however, also be defined by any desired other combination of certain characteristics of all individual characteristics that are generally public. This means that in principle practically any individual feature of the respective independent claim can be omitted or can be replaced by at least one individual feature disclosed to another position of the application. In this respect the claims can only be understood as a first formulation attempt for an invention.
权利要求:
Claims (19) [1] A rotary drum oven (1), comprising at least one indirectly heatable oven housing (2), which is rotatably held about a longitudinal axis of the oven and can be closed at one end with at least one fixed oven cover (3), (3) provided with a passage opening (4), an inlet device (5) for preparing solids runs, as well as an outlet device (6) located at an end opposite the inlet device (5), characterized in that the inlet device (5) tubular lance (7) projecting into the furnace housing comprising a lance housing (8) and an inner lance channel (9), and that the lance housing (8) consists of a material comprising a surface which has at least 90% IR radiation, preferably reflects at least 95% and has exit openings (10) extending from the inner lance channel (9) to the outside through a wall of the lance (7) and provided in the longitudinal direction of the lance (7), and that the lance (7) shower the oven housing (2) is supported by means of a support (7a). [2] Rotary drum oven (1) according to claim 1, characterized in that the material of the lance housing (2) comprises aluminum, in particular with a degree of purity of at least 95.0%. [3] Rotary drum oven (1) according to claim 1 or 2, characterized in that the lance (7) extends as far as an oven post-processing part (11) provided in the oven housing (2) for the exit device (6). [4] Rotary drum oven (1) according to one of claims 1 to 3, characterized in that the size of the exit openings (10) increases in the direction of the end of the lance (7) located inside the oven housing (2), in particular that the size of the exit openings is designed such that the supply pressure along the inner lance channel (9) is constant. [5] Rotary drum furnace (1) according to one of claims 1 to 4, characterized in that oblique deflection surfaces (13) formed into the inner lance channel (9) are formed inside the inner lance channel (9), opposite to the exit openings . [6] Rotary drum oven (1) according to one of claims 1 to 5, characterized in that the lance housing (8) is enclosed by a casing tube (14) such that a circumferential gap between the lance housing (8) and the casing tube (14) (15) is formed, and that the exit openings (10) are led out through tubular projections (16) of the lance housing (8) extending through the peripheral gap (15). [7] Rotary drum oven (1) according to claim 6, characterized in that the circumferential gap (15) is / is flowed through a cooled gas stream of an inert gas which is fed to the end of the lance (7) located outside the furnace housing (2) is introduced into the peripheral gap (15) with a blower and that a lance exit opening (17) is present at the opposite end of the lance (7). [8] Rotary drum furnace (1) according to one of claims 1 to 7, characterized in that the inner lance channel (9) is connected at its end outside the furnace housing (2) to a material blower for blowing in particulate material by means of of an inert gas. [9] Rotary drum oven (1) according to claim 8, characterized in that the material blow-in device is arranged for a blow-in amount of 100 kg / h to 800 kg / h per 1 m3 of oven volume, in particular for a blow-in amount of 300 kg / h to 500 kg / h per 1 m3 of oven volume. [10] Rotary drum oven (1) according to one of claims 1 to 9, characterized in that the oven housing (2) is designed for an inner wall temperature of 300 ° C to 1200 ° C, in particular for an inner wall temperature of 600 ° C to 1000 ° C. [11] Rotary drum oven (1) according to one of claims 1 to 10, characterized in that a one-sided, ring-shaped contact surface (20) is formed between the oven housing (2) and the fixed oven cover (3), wherein in the area of the ring-shaped contact surface (20) a seal of the oven housing (2) with respect to the fixed oven cover (3) is formed. [12] Rotary drum oven (1) according to one of claims 6 to 11, characterized in that the casing tube (14) is sealed with respect to the passage opening (4). [13] A rotary drum furnace (1) according to one of claims 7 to 12, characterized in that a meander-shaped channel (21) is formed in an oven after-treatment area (11), a channel entrance (22) opposite the lance exit opening (22) 17), and that a channel output (23) opens into the area of the exit device (6). [14] A lance (7) for use in a rotary drum oven (1) with the features of the preamble of claim 1, and characterized by the features of claims 1 to 12. [15] Method for evaporating a particulate material in a rotary drum oven (1) according to one of claims 1 to 13, characterized in that a heated oven inner wall (24) pointing towards the interior of the furnace (18) is uniform with the particulate containing material is provided by means of at least one blower provided with a furnace shaft and on the basis of radiation, convection and by contact on the inner wall of the furnace (24) at a temperature of the inner wall of the furnace (24) from 300 ° C to 1200 ° C evaporated. [16] Method according to claim 15, characterized in that plastic particles or biogenic mass, preferably slurry, are used as the particulate material. [17] A method according to claim 15 or 16, characterized in that the temperature of the particulate material in the blower device is kept below a critical temperature at which a change in the state of aggregation of the material takes place. [18] Method according to one of claims 15 to 17, characterized in that after the evaporation of the particulate material, an after-treatment of the molecules produced is achieved by further splitting. [19] The method according to any of claims 15 to 18, characterized in that the particulate material is blown in by means of an inert gas.
类似技术:
公开号 | 公开日 | 专利标题 NL2015089A|2016-04-04|Rotary kiln and insufflator before. TWI683082B|2020-01-21|Processed object drying method and horizontal rotary dryer WO2017075892A1|2017-05-11|Cold firework eruption device US8485815B2|2013-07-16|Overhung rotary tube furnace EP1793187B1|2011-11-23|Method and machine for the sintering and/or drying of powder materials using infrared radiation KR101914366B1|2018-11-01|Transfer device with double screw structure and waste plastic emulsification system using the same JP3564012B2|2004-09-08|Rotary kiln EP1742002A1|2007-01-10|Method and device for pulse heat treatment of bulk materials US20170297031A1|2017-10-19|Disc pulverizing mill JP6469995B2|2019-02-13|Rotary kiln JP2004232966A|2004-08-19|Rotary kiln device JP2017087105A|2017-05-25|Aerosol generating device and aerosol generating method JP2000161859A|2000-06-16|External heating rotary kiln furnace and its operation control method JP2006336994A|2006-12-14|Rotary kiln KR20020042655A|2002-06-05|Device for heating a meltable material NL2023475B1|2021-02-03|Rotary kiln for evaporating thermoplastic waste US5906483A|1999-05-25|Rotary film calciner US7033167B2|2006-04-25|Device for purifying and/or decontaminating polyester US10746467B2|2020-08-18|Rotary bed-type electric furnace FR2956125A1|2011-08-12|INSTALLATION FOR THE PRODUCTION OF BITUMINOUS COATED PRODUCTS. WO2017075893A1|2017-05-11|Material-feeding apparatus used for cold-firework eruption device, and cold-firework eruption device JP2015108474A|2015-06-11|Rotary kiln NL8201275A|1982-10-18|METHOD AND APPARATUS FOR GENERATING HEAT CN114008386A|2022-02-01|Rotary kiln for the evaporation of thermoplastic waste JP2011083773A|2011-04-28|Collected ash heating device for waste gasifying/melting equipment
同族专利:
公开号 | 公开日 DE102014109579A1|2016-01-14|
引用文献:
公开号 | 申请日 | 公开日 | 申请人 | 专利标题 WO2020197395A1|2019-03-26|2020-10-01|Fuenix Ecogy Ii B.V.|Rotary kiln for the evaporation of thermoplastic waste| WO2020261241A1|2019-06-28|2020-12-30|Fuenix Ecogy Ii B.V.|Method of feeding molten plastic into a reactor and device|
法律状态:
2019-10-02| PD| Change of ownership|Owner name: PLASMA POWER B.V.; NL Free format text: DETAILS ASSIGNMENT: CHANGE OF OWNER(S), ASSIGNMENT; FORMER OWNER NAME: FUENIX ECOGY I B.V. Effective date: 20190919 | 2021-07-14| QB| Registration of licences with regard to patents|Free format text: DETAILS LICENCE OR PLEDGE: LICENCE, NEW LICENCE REGISTRATION Name of requester: FUENIX HOLDING B.V. Effective date: 20210630 |
优先权:
[返回顶部]
申请号 | 申请日 | 专利标题 DE102014109579.0A|DE102014109579A1|2014-07-09|2014-07-09|"Rotary drum oven and blowing device for this purpose"| 相关专利
Sulfonates, polymers, resist compositions and patterning process
Washing machine
Washing machine
Device for fixture finishing and tension adjusting of membrane
Structure for Equipping Band in a Plane Cathode Ray Tube
Process for preparation of 7 alpha-carboxyl 9, 11-epoxy steroids and intermediates useful therein an
国家/地区
|