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    • 专利摘要:
    1503007 Treatment of pitch; carbonization; graphitization KUREHA KAGAKU KOGYO KK 20 June 1975 [24 June 1974] 26400/75 Heading C1A [Also in Division C5] Crystalloidal pitch is produced by (1) treating solid pitch particles having a maximum dimension of the minimum projected area of not more than 5 mm. to render them resistant to mutual fusion and then (2) contacting the particles with a non- oxidative gas at 350-550‹ C. while maintaining a void ratio of not less than 30% by volume. The treatment (1) can be carried out by (a) coating the particles with a metal (e.g. Cu, Cr, Ni or Ag), or a metal salt (e.g. a chloride of Ni, Fe or Al) or with a phenol, furan or epoxy resin; (b) forming an oxidized coat on the particles by immersing the particles in a solution of hydrogen peroxide, a chlorate, a hypochlorite, a perchlorate, nitric acid, ferric chloride, a dichromate, a mixed acid, a permanganate or a peracetate or by treating the particles with an oxidizing gas (e.g. oxygen, ozone, an oxide of sulphur or nitrogen or a halogen) which can be diluted with an inert gas (e.g. nitrogen, argon, hydrogen, steam or combustion gas) or (c) removing low boiling point or low melting point components by extracting the particles with a solvent such as acetone, methylethyl ketone, benzene, toluene, hexane, heptane, cyclohexane, methanol, chloroform or carbon tetrachloride. The softening point of the particles treated by extraction can be increased by heating between the softening and flow points of the pitch. The particles can be globular, filamentary or other shapes and can be composed of petroleum pitch, coal pitch (optionally containing 3 wt. per cent iron chloride) or pitch derived from by-product tars produced by thermal cracking of crude oil or naphtha. The heating can be carried out in a fluidized bed, fixed bed or rotary kiln. The crystalloidal pitch can be carbonized and graphitized, e.g. by heating in argon at up to 2400‹ C.
    公开号:SU999980A3
    申请号:SU752150208
    申请日:1975-06-24
    公开日:1983-02-23
    发明作者:Каваи Есио；Асано Киро；Тамура Хумио；Сайто Цуеси
    申请人:Куреха Кагаку Когио Кабусики Кайся (Фирма)；
    IPC主号:
    专利说明:

    (-54) METHOD OF OBTAINING A MESOPHASE PITCH FOR CARBON
    one
    The invention relates to the transformation of simple pitch into meophase pitch, in particular, to a method for producing the so-called mesophase (cr-5) pitch, used as a starting material for carbon products.
    There is a known method of treating solid particles of a pitch with a solvent and then heating at 170–470 ° C in an oxidizing medium 1j.
    This method produces superhard pitch, but it is not mesophase.
    The closest to the proposed technical solution is the method of obtaining mesophase pitch for carbon products, including heating of high-temperature pitch to 350-20 in an inert / free oxygen-free medium, followed by exposure, while the pitch molecules polycondense mutually due to the condensation reaction and orientate Soz-25 giving inside the pitch is a kind of optically isothermal liquid crystal. Such a liquid crystal is also called a mesophase. The mesophase consists of pekoobrazukhtsih molecules with aromatics- jg
    PRODUCTS
    chesky properties; orienteering and interlinked thanks to their own interaction. In a polarization microscope, the mesophase can be observed as anisotropic garyar. a pitch containing such a mesophase is referred to as crystalloid pitch 23.
    However, carbon-graphite products from such a pitch do not have sufficiently high density and strength, since by a known method it is difficult to obtain a pitch in a homogeneous mesophase state with sufficient reproducibility.
    The purpose of the invention is to improve the physico-mechanical characteristics of carbon products.
    This goal is achieved in that according to the method including extraction from a pitch with a particle size equivalent to a diameter of less than 5 mm, low-boiling components with a solvent and heating the high-temperature pitch to 350-500 ° C in a gaseous medium not containing free oxygen, followed by exposure to a volume of gas in a layer of pitch particles, equal to 3099% of the volume of the layers. The solvent is selected from the group consisting of acetone, methyl ethyl ketone, benzene, hexane, heptane, cyclohexane, methanol, chloroform, and carbon tetrachloride. As a gaseous medium, water vapor or combustion products are used; Thus, a homogeneous mesophase of the pitch is obtained, which ensures the improvement of the physicomechanical characteristics of the products obtained from such a pack. The term equivalent diameter. It is based on the assumption that the particles of a pitch have a certain shape, for example spheres, cubes and rectangular parallelepipeds, and the areas and volumes of particles of a variety of forms are equivalent to the corresponding parameters of real particles. The term is used to indicate the diameter of the central cross section of the intended particles. As the source material, it is possible to use different types of pitches, for example, coal tar pitch, oil pitch or any pitch, is a major byproduct in chemical production. For ease of handling and continuity of processing, in order to prevent alloying and heat treatment, it is desirable to use a pitch with a softening temperature of at least 70 ° C. The term “softening temperature” means the temperature at which 1 g of a pitch sample placed in a cylinder 10 mm in diameter, equipped with a nozzle 1 mm in diameter at the bottom, begins to flow out of the nozzle when | 10 kg / cm load is applied to the sample while the cylinder is heated externally sample temperature at a rate of 5 - 15 C / min. Usually, the softening temperature is measured with a flow-measuring apparatus manufactured by Shimazu Seisacuso. Peck is converted into solid particles with an equivalent cross-sectional diameter of not more than 5 mm for the production of crystalloid pitch. The preparation of pitch particles is accomplished by grinding or pouring pitch. It is very important that the particles of the pitch have an equivalent cross-section diameter of not more than 5 mm, preferably not more than 3 mm. Particles with an equivalent diameter of 5 mm or more do not pass, because gas is violently released and deformed during the heat treatment to which they are converted into a crystalloid. The shape of the pitch particles is not particularly limited with and may be spherical, fibrous, cylindrical, or even indefinite. When preparing pitch particles with a low softening temperature, it is desirable to cast in the form of spheres, from grinding with a high softening temperature, grinding is desirable. The pitch used is melted in the mold. fibers for the final production of carbon fibers. Processing of pitch particles is then required in order to prevent the interfusion of individual pitch particles. This treatment is carried out by removing low-boiling or low-melting components from pitch particles using extraction, in which case the treatment can be carried out by extracting solid pitch particles at room temperature, using a solvent that can effectively and selectively dissolve low-boiling or low-melting components of pitch particles. and essentially unsuitable for dissolving other pitch components. As examples of solvent solutions meeting these requirements, acetone, methyl ethyl ketone, benzene, toluene, hexane, heptane, cyclohexane, methanol, chloroform and carbon tetrachloride can be given. They can be used alone or as a mixture of two or more solvents. When choosing a suitable solvent from the above group, one should follow the rule of selecting that solvent, which is suitable in properties to the bake itself with the formation of a larger number of particles than other solvents of this group. With the help of extraction, solid pitch particles can be obtained, made of residual components, possessing a softening temperature of 340-400Pc and not amenable to interfusion. Upon receipt of pitch particles with a softening temperature, no more than individual pitch particles will be unstable to mutual fusion. In this case, it is necessary that the pitch particles obtained after extraction be subjected to treatment, carried out by extracting pitch particles in an atmosphere of non-oxidizing gas at a temperature between the softening point and the pour point temperature of the pitch particles for a time from several minutes to twenty or more (further called preheating.The preheating serves to soften and compress the surface of pitch particles by a small amount without any Particle sizes, therefore, close the pores on the surface and make it homogeneous. Thanks to it, the pitch particles retain their shape when the food is cooked at a regular, heat treatment. The pitch particles that have been processed from reciprocal fusion are subjected to tello processing, which by keeping the particles in contact with a non-oxidizing gas of 350-550 ° C, while maintaining the volume of the particles in a volume ratio of at least 30%. The term volume ratio used here means the fraction occupied by the hot (non-oxidative) gas in a given volume of a dispersed system consisting of solid particles and ne postglacial hot gas stream. Since the volume ratio is at least 30%, heat treatment can be performed continuously and evenly in a short period of time. As an example of the non-oxidizing gas used for this purpose, one can mention nitrogen, argon, hydrogen, water, steam, and incompletely burned exhaust gases. The resulting direct contact of the solid of the pitch bed with a non-oxidizing gas dispersed medium takes the form of a fluidized bed; layer, fixed bed or fully movable layer. The temperature at which this heat treatment is carried out is in the range of 350 -, the conversion of solid pitch particles into crystal pitch is essentially unattainable if the temperature is below the lower limit, and when the temperature exceeds the upper limit of 5 ° C, abruptly carbonized, it is difficult to achieve proper conversion to crystalloidal pitch. The heat treatment time may be selected based on its relationship with the applied temperature. So, for example, at high temperatures, time can | (very slow. Usually, at 380-450, time is needed for a few hours. When heat treatment is applied to the particles of the pitch, the mesophase occurs and the growth of the particles occurs, resulting in crystalline pitch The pitch particles are heat treated with the influence of the current of the heated gas. The time and temperature of the heat treatment can be arbitrarily changed so quickly that the degree of conversion to cryschloid pitch can be easily adjusted. This invention also includes the possibility of fairly fast processing to significantly increase productivity due to the small size of the processed pitch particles.In addition, due to the peculiarities of changing the shape of the original pitch particles, it is possible to obtain the desired substances of various types suitable for isotropic and heterotropic carbon products If solid pitch particles have the form of globules and, accordingly, are isometric, the emergence and growth of the crystalloidal components (mesophases occur it is isotropic. If the pitch particles are in the form of fibers, the crystalloid components grow mainly in the direction of the main axis. You can get a high-density and high-strength carbon material by making a carbon starting material by adjusting the degree of crystalloid transformation, finely grinding the resulting raw material, press the resulting powder without using bonded zukhtsiy and speca extruded material. Obtaining the 1st crystal-like pitch can be used in the production of carbon products and graphite products of very high quality, therefore it can be used in the field of electrotechnical products, in the field of mechanical products, for example, seals and bearings, in the field of atomic energy and in the field of household goods. as impermeable and corrosion resistant containers, etc. An example. Oil pitch with a softening temperature of 100 C and with a benzene insoluble LM content of 40% was molded into globules with an average diameter of 0.5 mm. Pitch globules were extracted with hexane at room temperature for 5 hours and additional; extraction using benzene at room temperature for 3 hours, after which they are dried in air; about 25% by weight of the low-boiling components are removed from them. After processing the extraction of the body of the pitch globules. Then, the pitch globules are heated to 350 ° C while in the form of a fluidized bed with a 65% volume assignment in a stream of non-oxidizing, hot gas, combustion (gas from incomplete combustion of a mixture of methane and hydrogen without oxygen, supplied at a linear velocity of 30 cm / s At the moment of time when the temperature of the globules reaches the level, air is blown into the system to bring the oxygen content to 4% in the mountain gas flow in order to oxidize the surface of the pitch globules for 10 minutes. After that, the air supply is stopped and the system The mu is heated to at a temperature rise rate of lOOC / h. When the system is defended for 4 hours, it is not
    stopping the flow of combustion gas. As a result, crystalloidal pitch globules are obtained with a content of quinoline soluble components of 8%, a fixed 93% carbon value, which is capable of agglomeration. Globules crushed to. average diameter of 10 microns, pressed under pressure of 1 t / cm, and, finally, graphitize.
    The resulting graphite has a bulk density of 2.05 g / cm, specific gravity 2.14 g / cm, flexural strength 1100 kg / cm and porosity 5%.
    Example 2. From tar, obtained during thermal cracking of crude oil at elevated temperature, a pitch with a softening temperature of 150 ° C is prepared. The pitch is extruded through filters with a diameter of 0.1 mm and collected onto a spool to produce filaments with a diameter of 20 microns. The filaments are immersed in methanol at 40 ° C for 5 hours, then dried in air to raise the softening temperature to 280 ° C. The filaments are then heated in the form of a fixed bed with a volume ratio of 80% by volume to 285 seconds with a flow of combustion gas at a speed of 10 liters. / min and stand at for 30 min. Then, the air supply is started to regulate the total oxygen content of the mixed system to 4 vol.% So that the filaments are subjected to oxidative treatment for 5 minutes. Upon completion of the oxidation treatment, the air supply is stopped and the filaments are heated to 400 ° C at the rate of temperature increase with the combustion gas flow and stand at this temperature for 2 hours, as a result of which the crystalloid content is formed. The threads are woven together, oriented, and reheated to 1000 ° C at a rate of temperature increase. X-ray analysis showed that the yarn obtained in the result showed an orientation degree of 80%. With the help of additional heat treatment (carried out at 2400 ° C., The degree of orientation of the threads is increased to 90%. By this time, the unit weight of the threads is 2.15 g / C1 g
    PRI me R 3. The tar produced during the thermal cracking of crude oil at elevated temperatures prepares a pitch with a softening temperature. Using the method of melting izpeka papuch fibers with an average diameter of 10 microns
    The pitch fibers are extracted with acetone at 40 ° C for 5 hours to eliminate low melting components. As a result, fibers with a softening temperature of 370 ° C are obtained. In a boiler-type heater, fibers are heated in the form of a fixed bed with a volume ratio of 80 vol.% To 4) 0 ° C using a combustion gas at a rate of temperature increase of 100 s / h. The fibers have no mutual fusion, the average diameter is 7 microns. A study of the fibers under a polarization microscope showed that the crystals are located in the direction of the major axis relative to the direction of length in the form of concentric circles relative to the cross section made in the diametrical direction.
    Example 4. With the help of extrusion of the melt of the pitch used in Example 1, through a filler plate
    2mm and cutting extruded pitch into 5 / IM pieces, cylindrical pellets are obtained. Cylindrical pitch particles are subjected to extraction according to the conditions and under the action of the solvents listed in Table. 1 to remove low boiling point components from these particles. The particles obtained have a softening point of more. The particles are then subjected to surface oxidation and crystallization under the same conditions as in Example 1, except that they are processed in a rotary oven at a volume ratio of 93% by volume instead of treatment in a pseudo-liquefied layer with a volume ratio of 60% .
    The properties of the obtained crystalline pitch particles are given in Table. 1, all particles contain less than 8% of quinoline-soluble substances and exhibit a degree of carbonation of more than 93%.
    The graphitized products obtained by crushing the mentioned cryocholed pitch particles, followed by carbonization and graphitization in Example 1, have a bulk density of more than 2.0 g / cm, a bending strength of more than 1,100 kg / cm, and a porosity of less than 5% (Table i).
    PRI me R 5. Extracted pitch obtained in Example 4 with a softening temperature is subjected to crystallization in a rotary kiln at a volume ratio of 80% for 5 hours at 420 s in the exhaust gas stream from burning propane (containing 0.01% residual oxygen). The resulting product has a degree of carbonization of 95% and contains
    3 wt.% Substances, insoluble in quinoline.
    PRI me R 6. Extracted pitch obtained in Example 4 with a softening temperature of 3K is placed as a fixed layer in a chamber made of a steel plate with a volume ratio of 39% and crystallized at 420 ° C by introducing water vapor into the chamber layer for 5 hours. The resulting product has a degree of carbonization of 94.9% and contains 7.8% by weight of substances insoluble in quinoline.
    P p: and measures. Extracted pitch obtained according to example 4 with a softening temperature of 328 ° C, is subjected to crystallization at 410 ° C for 8 hours in a rotary kiln at a volume ratio of 80% and by passing a stream of argon into the furnace. The next time, the same procedure is carried out at. the same conditions, except for replacing the argon flux with a hydrogen flux.
    The first product has a degree of carbonization of 95% and contains 7.9% by weight of substances that are insoluble in the quinoline; the second product has a degree of carbrene 94, 9% and contains 8.0% of quinoline insoluble. Example 8 (comparative. The oil pitch used in Example 1, having a softening temperature of 10 and a content of 40% benzene-soluble substances, is treated for 16 hours by a known method in a flask in an atmosphere of gaseous nitrogen at 435 ° C to obtain a mesophase After grinding and sifting the obtained pitch, sample B is obtained — powder pitch with an average particle diameter of 10 µm.
    When used as the starting material of the same pitch, the procedures of example 1 are performed and the sample A of a crystalloid pitch with an average particle diameter of 10 microns is obtained.
    From the Liv samples, five plates with a diameter of 100 m and, approximately 10 mm thick at rooms at a temperature and pressure of 1 t / cm using a cylindrical metal mold with a diameter of 100 m, are pressed. The resulting products (plates) are heat treated in an electric furnace in an atmosphere of gaseous nitrogen. when the temperature increases at a rate of 5 C / min before and within 2 hours after reaching it. The resulting products showed in testing the results presented in table. 2
    Products from sample A. All five samples are a round plate without any cracks. Products from sample B. Only one round p.pastin without any defects. There are many cracks in the other plate, and the remaining samples collapsed into many pieces when removed from the mold.
    It should be noted that the numerical data is determined for only one sample of a round plate made from sample B.
    Control pans 50x20x5 mm in size, burned in an electric furnace at. The resulting samples have the properties shown in table. 3
    As follows from the presented examples and data, carbon-graphite products from mesophase pitch by the proposed method have higher physical and mechanical characteristics than by a known method.
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    1.78 - 1.83
    Specific weight, .g / ml
    Strength on
    1000-1200 bending, kg / cm
    Specific weight, g / mp
    权利要求:
    Claims (2)
    [1]
    Flexural strength, kg / cm. Formula of the invention. 1 A method for producing a mesophilic pitch in dp carbon products, including heating of high-temperature pitch to ZBO-ZOO C in a gaseous medium that does not contain free oxygen, followed by exposure, and that, for the purpose of improving the physicomechanical characteristics of carbon products, pitch with a particle size equivalent to a diameter of less than 5 mm and | Preah is used; low boiling components are extracted from it with a solvent, heating and holding are carried out at the volume of gas in an hour egg pitch Nome equal to 30-99% of the bed volume.
    Table 2
    1.5 (At the solid plate)
    810 (At the solid plate /)
    T a b l and c a .3
    2.03
    1.70
    650
    1000 2. A method according to claim 1, wherein the solvent is selected from the group consisting of acetone, methylstilketone, benzene, hexane, heptane, cyclohexane, methanol, chloroform and carbon tetrachloride. 3. Method 1 -2, from whether it is the fact that water vapor or products of combustion of fuel are used as the gaseous medium. Information sources,. 1 taken into account in the examination 1. UK patent number 1295765, cl. C 10 C 3/08, 1972.
    [2]
    2. French Patent 2204571, 1КЛ. From 01 to 31/07, May 24, 1974 Spro: toyp).
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    同族专利:
    公开号 | 公开日
    SE397363B|1977-10-31|
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    DE2559874C2|1982-02-04|
    DE2559537A1|1977-02-03|
    DE2559537C2|1981-10-08|
    FR2276366B1|1979-05-25|
    SE7507144L|1975-12-29|
    JPS5238855B2|1977-10-01|
    FR2276366A1|1976-01-23|
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    DE2527943C2|1982-03-11|
    DE2559536A1|1977-02-03|
    JPS51521A|1976-01-06|
    GB1503007A|1978-03-08|
    CA1051806A|1979-04-03|
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    CN113046109B|2021-03-11|2021-12-07|山西中科化美科技有限责任公司|Preparation method and application of low-sulfur low-nitrogen environment-friendly asphalt|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    JP49071257A|JPS5238855B2|1974-06-24|1974-06-24|
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