• 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:
    A method for coking high-aromatic aromatic hydrocarbons, including the coking of hydrocarbons in a thin layer, characterized in that, in order to reduce the content of volatile substances to 4-8% and the coefficient of thermal expansion 10 K to
    公开号:SU1138034A3
    申请号:SU813340898
    申请日:1981-09-18
    公开日:1985-01-30
    发明作者:Глазер Херберт；Кох Карл-Хейнц；Марретт Рольф；Мейнбрекксе Манфред
    申请人:Рютгерсверке Аг (Фирма)；
    IPC主号:
    专利说明:

    W
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    CO 00
    ABOUT
    with
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    t, CC 11 The invention relates to methods of coking hydrocarbons to produce high-quality coke and can be used in the petrochemical industry. The known method of coking high boiling aromatic hydrocarbons, including the coking of hydrocarbons in a thin layer of 15-30 mm at 475-515 C for 35 min. M. The disadvantage of the known method is the low quality of the produced coke g high content of volatile substances and high value of thermal expansion coefficient. (KTR). The purpose of the invention is to reduce the content of volatile substances to 4-8% and the coefficient of thermal expansion to (2-4). This goal is achieved by the fact that according to the method of coking high boiling aromatic hydrocarbons, including the coking of hydrocarbons in a thin layer, the rate of heating t | (K / min) during coking is maintained depending on the thickness of the S layer (mm) by the equation Bt 500 5g S and the coking time C (min) is determined depending on the thickness of the S layer (mm) by the equation q q, b, and the factor proportions a are calculated from the time of coking in a preliminary experiment on a heated microscope stage and it is in the order of 3-9 minutes, and depending on the temperature of the exponents x is determined based on the final coking temperature tg established during the preliminary experiment and from the diagram . Anisotropic cokes are obtained from petroleum fractions or from susceptible pretreatment of coal tar pit by coking in a temperature range of about 500 ° C under pressure. At the same time, it is important that coking in the range of from 370,500 ° C with the formation of the corresponding structure of coke is carried out with a minimum temperature gradient. According to the proposed method, suitable mixtures of high-boiling aromatic hydrocarbons are coked according to a well-defined temperature and time program with thin layers 4, preferably under atmospheric pressure, and the functional relationship between the layer thickness and the optimal coking time for this type of loading essential for this program is set using a simple preliminary experience. To do this, a small amount of the starting product under standard conditions is coked on a heated microscope stage. The heated product to the S50s on the heated table is slowly heated (15 K / min) until the first mesophases appear in the pitch, which can be observed through a microscope. The temperature indicates the lowest coking temperature t. After that, the table temperature is increased at approximately the same rate to, and the time until the mesophase solidifies to produce cf coke is determined. According to experiments carried out with different mixtures of aromatic hydrocarbons at different thicknesses of layers, it has been established that there is a following dependence of the coking time on the thickness of the layer S а.8, where X is temperature dependent on the exponents; C (- proportionality factor. The temperature dependence of the exponent as a function of the final coking temperature is shown in the attached diagram (see drawing). The proportionality factor corrects the product effects and differences in the thermodynamic conditions of the production plant in relation to the heated table, it is It is in the order of 3–9 minutes when calculating the coking time t in minutes. As a first approximation, it is determined on the basis of preliminary experience. and x are slightly corrected by the equation. It has been established that the preliminary mesophonic state necessary for obtaining anisotropic cokes, leading to the formation of large textures, should have high current and appear already in layers a few millimeters thick at the time of coking for several minutes. This allows coking in layers with a thickness of up to 100 mm, preferably 5-50 mm, in a relatively short time and in the case of producing highly anisotropic coke. The heating rate may vary over a wide range. In the case of thin layers, it can be very high (e.g. 150 C / min), while in the case of thick layers it should be lower in order to provide a dense structure of coke with thick struts. , Especially beneficial was the heating rate of the equation dt 500 -. dS min 5 mm dt 500 The heating rate indicates the maximum value. The quality of coke deteriorates only if this value is exceeded. A slower heating rate is possible, but it requires a longer heating time, and therefore the method is less economical. The coke burden C O S is the shortest coking time. Longer coking times are possible without sacrificing quality, but the method will be less economical. The coking process can be carried out periodically, for example in a kiln with grid nozzles and an adjustable temperature program, or continuously, for example in a tonn furnace with a steel belt conveyor, the individual zones of which are maintained at a certain temperature according to the calculated conveyor speed and the selected heating rate. . By mixtures of high-boiling aromatic hydrocarbons, I mean residues from the processing of coal or mineral oils, with a boiling point of over 350 ° C and aromatic compounds of more than 70%, such as residues from coal processing, coal tar, residual oils obtained in the result is catalytic and thermal cracking of mineral oil fractions. It is especially advisable to apply the proposed method to pecks and peck-like substances, the initial boiling point of which is above their coking temperature. Example 1. A coal tar pitch with a softening point (T.R.) of 90 ° C (according to Kremer and Sarnov) and a quinoline-insoluble component (HX) content of 0.3% is pre-heated to, then it is applied in a layer 2 mm thick. a microscope stage warmed to 350 ° C and the table temperature are slowly increased (15 K / min). At a temperature of up to 390 ° C under the microscope, the appearance of mesophases can be observed. Then turn the table temperature up to 550 ° C; After 9 min the mesophases harden to form a char. The final coking temperature tg is 500 ° C. Based on the exponent x (0.8 according to the diagram), layer thickness 8 (2 mm) and coking time (9 min), the proportionality factor can be calculated by the following equation: 5.17. The pitch is coked in layers of 10 mm in thickness on the grid nozzles in a gas heated kiln in an atmosphere of flue gases under normal pressure. The coking time can be calculated from the data of preliminary experience: a. S 5.17-10 ° 32.6 min. Nozzles filled with pitch are fed into the preheated to 350 ° C kiln, and then the temperature is maintained for 29.6 minutes. The yield of the obtained semi-coke is 45%, the content of volatile substances +, 5%. The coke calcined at 1300 ° C has a volumetric analytical coefficient of thermal expansion. rhenium 3, 210 K in the temperature range from 20 to 200 ° C. The coking time can be reduced up to 30 minutes with the volatile matter content increasing to 6%, but without changing the coefficient of thermal expansion. The proportionality factor of the snik-ets by 9% (up to 4.75).
    PRI mme R 2. Use solid tar tar pitch with TR (K .. and C.) and the value of HHO, Coking temperature 500 C and time, 4 {4I coking min. The proportionality factor is therefore 4.59.
    Pitch is continuously coked with a layer of 5 # 1 thickness in a stream of inert gas under normal pressure on a steel belt conveyor heated from below using a gas-jet apparatus up to 500 ° C. The conveyor speed is calculated so that the pitch coke after the calculated coking time expires 16.6 minutes left the heating zone.
    The yield of pitch coke produced is 79%, the content of volatile substances is 7.6%. The coke calcined at 1300 ° C has a volumetric-analytical coefficient of heat, an expansion of 3.010.2 хÜ IT in the temperature range from 20 to.
    Froze Residue for residual oil distillation resulting from pyrolysis of naphtha to ethylene, with TP 120 ° C and an HX value of 0.15% are considered and coked as in example 1 at a final temperature in a layer 50 mm thick. The proportionality factor a, calculated from preliminary experience, is 6.3. Coking time 162 minutes with a layer thickness of 50 mm. The kiln is heated at a rate of 10 K / min.
    The yield of coke 68%, the content of volatile substances 6%. In the calcined state, coke has a volumetric analytical coefficient of thermal expansion of 4.0 ± 0.2.
    Example 4. Aromatic residue of carbon hydrogenation with the content of aromatic compounds 89% TR and HX 0.1% is considered and coked, analogously to example 1, in a layer 100 mm thick at a final temperature of 480 ° C. The proportionality factor is 4.0, and the coking time, therefore, 220 min at a layer thickness of 100 mm. The kiln is heated at a rate of 0.6 K / min. The yield of semi-coke is 89% with a volatile content of 6.5%. In the calcined state, coke has a volumetric analytical coefficient of thermal expansion of 3, 2-10 K.
    PRI me R 5. Obtained by distillation of hard coal tar pitch with TR 2.10 ° C (according to K. and C.) and HX below 0.1% are treated similarly to example 1. The final coking temperature is, and the proportionality factor is 9.0. The pitch is coated with a layer of 15 mm thick for 100 minutes. The heating rate of the calciner is 20 K / min. Get semi-coke with a volatile content of 7%. Yield 92%. The volumetric analytical coefficient of heat, expansion of calcined coke is 2.7 ± 0.2. H 0 in the temperature range from 20 to.
    PRI m e R 6. Solid pitch of coal tar with TR (according to K. and C.) and HX 0.2%, for which, according to example 2, with a layer thickness of 5 mm, the coking time of 16.6 minutes is preliminarily determined when heated to 500 ° C, must be heated in 10 minutes to a temperature of 500 ° C .
    The acceleration of coking causes not only a decrease in the coke yield to 80.2% with a content of volatile components of 9.6%, but also a sharp increase in the volume-analytical coefficient of thermal expansion of coke calcined to 1300 ° C to 5.3 ± 0.4 10 g - temperature limits from 20 to 200 C.
    Example 7. The hard pitch of coal tar in example 2 with a layer thickness of 5 mm should be heated and coked in 60 minutes to 500 C. Sharp delayed coking of the load causes more complex instrumentation and a significant increase in the quality of coke.
    The pitch coke obtained in 78% yield contains 6.2% of volatile substances. After calcination at 1300 ° C, the resulting coke has a volume-analytical coefficient of thermal expansion of 2.9 ± 0.2 10 K in the temperature range of 20-200 ° C.
    PRI me R 8. According to example 3, the residue from the distillation of residual mass, la, resulting from the pyrolysis of naphtha in ethylene, with TR 120 C and the value of HX 0.15% is coked for 80 minutes at a final temperature of 490 ° C. 7 The yield of coke produced is 80.4%, the content of volatile substances is 14.8%. In the calcined state, coke has a volume-analytical coefficient of thermal expansion of 6.44 (10 K in the temperature range 20–200 ° C. EXAMPLE 9. The hard tar coal tar pitch in example 2 is coked at a final temperature of 800 ° C. doing differently than according to the conditions indicated in example 2. Due to the higher coking rate, a lower coke yield is obtained, of a weight of 67% by weight, with a volatile content of 2.9% by weight. The analytical volume deteriorates coefficient of thermal expansion calcined to 1300 ° C oxa (7.8 ± 0.8–10) in the temperature range of 20–200 ° C. Example 10. The residue from the distillation of residual oil crawled as a result of the pyrolysis of naphtha V. et flax, as indicated in example 3, is coke at a final temperature of 750 ° C, otherwise than according to the conditions specified in Example 3. The coke yield is 57 wt.% with a substance content of 2.6 wt.%. The volumetric-analytical coefficient of thermal expansion of the calcined coke depends on condition (9 ,,five . EXAMPLE 11 The residue from the distillation of the residual oil obtained from the pyrolysis of naphtha into this flax, as indicated in Example 3, is coked, according to the conditions specified in the example. 3, but with cokeback 50 K / min. As a result of the rapid distillation of their substances, the coke yield decreases by 52% by weight. % The content of volatile substances and coke is 5.9 wt.%. Calcined coke shows a higher coefficient of thermal expansion and inhomogeneity: 5.4 ± 0.4 ... The table summarizes the modes in the preliminary experiment and the conditions of the coking parameters (where S is the thickness of the euro. Is the coking time; t is the final coking temperature; t ,, is the pitch application temperature; S max is the calculated maximum temperature gradient; - the selected temperature gradient) .
    11113803412
    Compared to a very vigorous and had a high
    measures (prototype). Coke the specified volumetric analytical coefficient
    in example 2, solid pitch of coal-thermal expansion (, 0
    resin in a thin layer (30 mm) in those., which means that the subsidence is 35 minutes at a temperature of 515 C. The irradiated raw coke is not suitable
    Green coke, obtained from the output of high-load production of 85 wt.%, And containing a content of fly-by-wire electrodes of steel industrial substances, is 14.8 Kb.% Of content.
    权利要求:
    Claims (1)
    [1]
    METHOD FOR COKING HIGH-BOILING AROMATIC HYDROCARBONS, including the coking of hydrocarbons in a thin layer, characterized in that in order to reduce the content of volatiles to 4-8% and the thermal expansion coefficient to ^ (2-4) -10 6 K ' speed heating (K / min) during coking support depending on the layer thickness S (mm) according to the equation dt = 500 d
    and the coking time £ (min) is determined depending on the thickness of the layer 8 (mm) according to the equation C = c. S and the proportionality factor a is calculated from the coking time in the preliminary experiment on a heated microscope stage and it is about 3-9 minutes, and the temperature-dependent exponents x are determined based on the final coking temperature ί ε established during the preliminary experiment and from the diagram.
    SU .... 1138034
    450
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    同族专利:
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    DE442355C|1923-11-17|1927-03-30|Patentaktiebolaget Groendal Ra|Process and device for the extraction of oil and other products from bituminous materials such as slate, coal and like|
    US1794542A|1927-01-20|1931-03-03|Piron Emil|Distilling hydrocarbons|
    GB311689A|1928-05-14|1930-03-21|Tar And Petroleum Process Comp|Improvements in methods for treatment of hydrocarbons|
    US2140276A|1936-11-18|1938-12-13|Universal Oil Prod Co|Continuous coking of hydrocarbon oils|
    US2427589A|1945-12-28|1947-09-16|Atlantic Refining Co|Method of refining hydrocarbon oil with a sludge-forming reagent|
    GB770368A|1955-03-18|1957-03-20|Fernando Mario Mora|Improvements in and relating to cracking equipment for heavy liquid compounds of high distilling point|
    DE1189517B|1957-04-03|1965-03-25|Verkaufsvereinigung Fuer Teere|Process for the production of a special coke from coal tar products|
    FR1195625A|1958-05-05|1959-11-18|Atomic Energy Authority Uk|Carbon manufacturing process|
    US3274097A|1965-10-04|1966-09-20|Marathon Oil Co|Method and apparatus for controlling carbon crystallization|
    US4066532A|1975-06-30|1978-01-03|Petroleo Brasileiro S.A. Petrobras|Process for producing premium coke and aromatic residues for the manufacture of carbon black|DE3432887A1|1984-09-07|1986-03-20|Rütgerswerke AG, 6000 Frankfurt|METHOD FOR PRODUCING HIGH-PERFORMANCE GRAPHITE ELECTRODES|
    US5034116A|1990-08-15|1991-07-23|Conoco Inc.|Process for reducing the coarse-grain CTE of premium coke|
    JP1576659S|2016-11-29|2018-07-02|
    JP1576658S|2016-11-29|2018-07-02|
    US11060033B2|2017-06-23|2021-07-13|The United States Of America, As Represented By The Secretary Of Agriculture|Compositions and methods for producing calcined coke from biorenewable sources|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    DE19803035593|DE3035593C2|1980-09-20|1980-09-20|Process for coking high-boiling, aromatic hydrocarbon mixtures to carbon materials with consistent properties|
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