• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    1. Method of treating carbon black for depolarization masses of dry batteries obtained by thermal decomposition of liquid or gaseous hydrocarbons in the presence of oxygen-containing gas and water vapor at 1200-2000 ° C and pressure
    公开号:SU1061699A3
    申请号:SU792831601
    申请日:1979-10-22
    公开日:1983-12-15
    发明作者:Дорн Фридрих-Вильгельм；Вольтер Манфред；Неймер Геро
    申请人:Хехст Аг (Фирма)；
    IPC主号:
    专利说明:

    2. A device for treating soot containing a vertical case with a cylindrical lined chamber for heating soot, means for feeding and removing bends located on opposite ends of the case, nozzles for supplying gas with countercurrent and waste gases, a nozzle for supplying the reaction gas installed below nozzles exhaust gases, and graphite electrodes, differing in that, in order to increase the inertness of soot, one of the electrodes is made in the form of a tube forming the chamber, and the other is vertically cial movement.
    The present invention relates to a method for treating carbon blacks for depolarization masses of dry batteries and a device for its implementation. J A known method for producing carbon black for depolarization masses of dry batteries involves thermal decomposition of liquid or gaseous coal hydrocarbons in the presence of oxygen-containing gas and water vapor. 1200 - 2POO ° C and pressure (1-80) -U release of soot and the subsequent heating of soot by electric current (indirect to a temperature not lower than 1200 ° C when applying hydrogen chloride gas and / or nitrogen. However, the resulting special soot in contact with an oxidizing agent, for example, pyrolusite, is not sufficiently inert, but when partially decomposed, pyrolusite is oxidized to form CO2.The formation of a gaseous reaction product is especially harmful, since soot with pyrolusite is used as a depolarization mass in dry batteries, t in a closed space. The resulting CO2 causes an increase in internal pressure in it, which can lead to deformation of the body of the element with an electrical break. As a result of the reaction between the soot and pyrolusite, the content of Mn (IV) and, consequently, the capacity of the dry cell are inevitably reduced, which results in a decrease in the discharge power of the dry battery. A device for treating soot is known, comprising a vertical housing with a cylindrical lined chamber for heating soot, means for supplying and removing soot located in opposite ends of the case, nozzles for supplying gases with countercurrent and waste gases, a nozzle for supplying the reaction gas installed below the patra for removal of exhaust gases, and graphite electrodes fixed in the chamber. However, in this device, the duration of carbon black treatment depends on the throughput, since the carbon black processing zone cannot be changed, which negatively affects the properties of the carbon black (its inertness). The aim of the invention is to increase the battery discharge time by increasing the inertness of soot to pyrolusite. This goal is achieved by the fact that according to the method of treating carbon black, obtained by thermal decomposition of liquid or gaseous hydrocarbons in the presence of oxygen-containing gas and water vapor at 12 Fo - 2000 ° C and a pressure of (1-80) x, including heating soot with an electric current to a temperature not lower than With the supply of gaseous hydrogen chloride and / or nitrogen, the treatment of soot is carried out with a countercurrent supply of gas with the formation of a fluidized moving bed for 1–5 hours and the passage of electric current through soot. . . This goal is also achieved by the fact that, in a soot processing device, comprising a vertical body with a cylindrical lined chamber for heating soot, means for supplying and removing soot located at opposite ends of the body, branch pipes for supplying countercurrent gases and flue gases, branch pipe the reaction gas, installed below the nozzles for removal of exhaust gases, and graphite electrodes, one of the electrodes is made in the form of a pipe forming the chamber, and the other is vertically moving the ceiling elements. The advantage of the proposed method .ba. The fact is that CCrA constantly passes through the treatment zone, therefore, upon thermal exposure, no soot sintering into large pieces occurs. Thanks to this in
    the soot structure is largely preserved, more; suitable for adsorption, and graphitic has only a single place. soot particles. In addition, this method has a positive effect on the stability of the structure and the inertness of soot that. is of particular importance when mixing carbon black with pyrolusite and. increase the discharge time of dry batteries.
    Another advantage is the purification effect, which is caused by the prolonged treatment of soot in the high-temperature zone, while the oxygen-containing surface soot groups decompose and the non-volatile aromatic and nonaromas; the lower-grade atomic components are removed, therefore the soot processed by the proposed method contains less 0.01% toluene extractable fraction. In the proposed device, a constant level of soot filling in the graphite tube is achieved by setting the graphite electrode at a certain height. Since an electric current is passed through the soot, the resistance value of the pseudo-liquid soot layer is different from the immersion value of the graphite electrode in the soot. As soot is unloaded from a graphite tube, the amount of graphite electrode immersion in soot decreases and resistance increases. Thus, electrical resistance can serve as a criterion for the metering of soot in a graphite pipe. By raising or lowering a graphite electrode, it is possible to determine the level of soot filling in a graphite pipe and, consequently, the time of processing soot in a pseudo-liquid layer for a given unloading volume and its properties.
    The drawing shows the proposed device, a partial section.
    A cylindrical graphite bottom pipe 1 is installed on the receiving pipe 2 in the cooled screw 3, the discharge pipe 4 of which serves to unload the treated soot. At the upper end of the graphite pipe 1 is closed with a cap 5. In the upper part of pipe 1 there is a nozzle b for exhaust gases, and in the middle part below latrubka 6 there are several pipes 7 for feeding the reaction gas. In the receiving pipe 2 of the screw 3 is installed: a pipe 8 for supplying nitrogen. Con; centrally with a graphite pipe 1 there is a cylindrical steel case 9, lined with extruded material 10, at the upper end of the chamber.
    Through krgoku 5, the metering nozzle (pipe) 11 is passed, to the top 4y
    the end of which is connected to the metering screw 12 for feeding soot. A graphite electrode 13, which ends inside the graphite pipe 1, is also passed through the cover 5, the electrode 13 is provided with a supporting and {Regulatory device 14. A contact block 15 is provided at the upper end of the graphite electrode 13 and equipped with a flexible conductor 16. At the lower end of the graphite pipe 1 contact block 17, provided with a conductor 18.
    The device works as follows.
    To be treated soot through
    5 the metering screw 12 and the metering tube 1 1 enter the graphite tube 1, while the amount of soot loaded into the graphite tube must be such that the lower end of the metering tube
    0 pipe 11 was above the filling level. Nitrogen is blown through pipe 8 down into graphite pipe 1, with the result that soot is in the pseudo-liquid phase. Additionally, according to pipe 7, carbon dioxide 1 can be fed to graphite pipe 1. The resulting waste gases are removed through pipe 6. A lead wire 18 is attached to the graphite pipe 1,
    0, while the graphite electrode 13 provided with the conductor 16 has a lower end immersed in carbon black. As a result, the carbon black is included in the circuit as a heating
    5 and is heated in accordance with the applied voltage. The current at a constant voltage depends on the depth only of the immersion of the electrode in the soot. The deeper the electrode is immersed in soot, the more intense the current. Using this relationship, it is possible to fill the graphite pipe 1 with soot at a stationary electrode 13 so that a current sufficient to heat the loaded soot flows.
    five
    The screw 3 is turned on, and the soot is discharged through pipe 4, as a result of which the level of soot in the g {afit pipe is lowered. To prevent current decline, the dosing screw is turned on.
    0 12 and increase the filling level so that the amperage reaches its original value. Due to this, the filling level remains approximately constant.
    five
    P. And measure 1 (getting soot). Heavy fuel oil containing,%: carbon 8.1,4; hydrogen 9.0; oxygen 0.4; nitrogen 0.3; sulfur ash 2.4, is subjected to reaction with oxygen (0.75 m at normal
    0 pressure per 1 kg of oil fuel) .. and water vapor (0.5 kg per 1 kg of oil fuel) at 1250 С and 30 at. Soot containing reaction gas is washed with water, while
    5 get approximately 1% aqueous suspension of soot, 200 l / h of this suspension and 9 l / h of gasoline (boiling area 60 - continuously. Pumped from the bottom into the stirred tank, in which intensive mixing of the soot suspension and benzi is obtained by mixing -on. Processing time in the tank for 15 minutes at a pH of 9.1; a temperature of 30 s and a pressure of 1.1 at. After the joint removal of water and carbon black and the upper part of the container, a bulk material is obtained which consists of 25% carbon black and 50% gasoline and 25% water. Then from a bulging material, by heating in a rotating tubing Externally heated lakes remove water and gasoline at 200 ° C, resulting in a dried soot, which is characterized by a number, AS 48; a BET surface of 100.0 and an average value of zones with a graphite structure of 27-10 m. e p 2 (according to a known method). The carbon black obtained by Example 1 is loaded into a furnace that is heated by electrical resistive heating, heated in the furnace for 20 minutes in the presence of nitrogen to. The soot unloaded from the furnace is characterized by the number AS 26; WET surface 285 and the average size of the zones with a graphite structure of 60 -10- "m. Example 3 (according to the invention). The carbon black obtained in Example 1 is loaded through a dispenser into a graphite vessel with thermal insulation 70 cm in diameter, equipped with a vertically movable graphite electrode, and unloaded at its lower end using a water-cooled screw. At the same time, the graphite electrode is lowered so that in order to prevent material loss with waste flow, the soot surface is lower than the pipe version for waste gases. 500 l / h of nitrogen are fed from the bottom of the graphite vessel to create a pseudo-liquid layer of carbon black. The loading and unloading of soot is regulated in such a way that the throughput is approximately 10 kg / h. The constant load of soot is ensured by fixing the graphite electrode in a certain position, while the conductive soot itself is a heating resistance, time The treatment time is 1.5 hours. The graphite vessel is maintained at a temperature of 1500 ° C. The discharged carbon black is characterized by the number AS 17, 5i; BET-surface 120 and the average size of the zones with a graphite structure 110-10 m, Example 4- (according to the invention). Analogously to Example 3, but the graphite electrode is set so that, when the level of carbon black achieved as a result, a processing time of about 3 hours is ensured. In addition, a temperature of 1800 ° C is maintained in the graphite capacity. Unloaded soot is characterized by the number of AZ 15; BET-surface 80 with an average size of zones with a graphite structure of 13510 ° m Example 5 (according to the invention). Analogously to example 3, but in addition to nitrogen, hydrogen chloride gas in the amount of 500 l / h is additionally supplied to the graphite tank in countercurrent with respect to soot. The graphite electrode is set to Tick so that the processing time is about 4 hours. Unloaded soot is characterized by the number AS 18; The WET surface is 145 mVr and the average size of the zones with a graphite structure is 105-10 ° m. The content of nickel in soot is reduced to less than 10 ppm, iron and vanadium to less than 50 ppm of each, and the content of chloride in soot is less than 100 ppm. The improved properties of carbon black obtained by the proposed method, when used in dry batteries, have been proven by testing. For this purpose, zinc pyrolusite elements of type R 20 have been manufactured using such carbon black (according to the standard 86 of the International Electrotechnical Commission). In this case, the depolarization mixture (cathode mass) contains, by weight parts: pyrolusite 55; ammonium chloride 14; zinc oxide 1; water 5; carbon black 9 (prepared according to examples 1 and 5) and a 30% w / w aqueous solution of zinc chloride as an internal electrolyte 16. By 6 cells were stored at room temperature for 5-7 days (usual storage - n); at 45 ° C for 30 days (storage in tropical conditions - T) and then discharged under the following conditions: transistor discharge (4 hours per day after 40 ohms to 0.9 V); bit through a tape recorder (2 hours per day in 5 ohms to 1.1 volts); LiSt -g: discharge (4 minutes per hour at 8 cycles per day in Ohm to 0.9 V). In addition, a short-circuit current was determined. In order to qualitatively assess the preservation of elements according to their appearance, after storage in tropical conditions (T), defectiveness scores have been developed, depending on the size and degree of the deformed outside of the element closure made of i-containing asphalt.
    : At the same time, an especially large number of I / IPB points (poor condition) was charged to the leaked out element, while the element in which So much bubble formation was detected was attached to a smaller number of points. In accordance with this element, the coping for which no change was detected was estimated to be zero k: a person with 4 points of defectiveness.
    The table shows the results of the storage and discharge test.
     - 6 days at T - 30 days at,
    : It follows from the above data that the soot preamble is so inert that it does not react with pyrolusite in the case of storage at high temperature, it is known in thermograms time as known. The sediment reacts with pyro-exclusive when stored under conditions of high temperatures. The positive effect consists precisely in increasing the inertization of soot relative to 10 pyrolusite and is achieved by implementing the proposed method and device.
    权利要求:
    Claims (2)
    [1]
    METHOD OF PROCESSING SOOT AND DEVICE FOR ITS IMPLEMENTATION.
    (57) 1. A method of processing carbon black for depolarizing masses of dry baht. thermal decomposition of liquid or gaseous hydrocarbons in the presence of an oxygen containing gas and water vapor at 1200–2000 ° С. and pressure (1-80) Ю ^ ^ Pa, including heating the soot by electric current to a temperature not lower than 1200 ° C with the supply of gaseous hydrogen chloride and / or nitrogen, which is different in that, in order to increase the battery discharge time by increasing the inertness of soot to pyrolusite, soot treatment is carried out with countercurrent gas supply and the formation of a fluidized moving layer of soot for 1-5 hours and the passage of electric current through the soot.
    [2]
    2. A soot treatment device, comprising a vertical body with a cylindrical lined chamber for heating soot, means for supplying and removing soot located on opposite ends of the body, nozzles for supplying gas with countercurrent and exhaust gases, a nozzle for supplying reaction gas mounted below the nozzles off-gases, and graphite electrodes, about τη, which is characterized by the fact that, in order to increase the inertness of soot, one of the electrodes is made in the form of a pipe forming a chamber, and the other is vertically located in it moving ceiling elements.
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    法律状态:
    优先权:
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