• 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:
    1441675 Synthetic coking coal NIPPON MINING CO Ltd 1 Feb 1974 [3 Feb 1973] 04831/74 Heading C5E Synthetic coking coal is produced by coking at atmospheric pressure a heavy hydrocarbon composition having an "fa" of 0À4 or higher wherein and C/H is the ratio of carbon atoms to hydrogen atoms, Hα/H is the ratio of hydrogen atoms of aliphatic hydrocarbon groups in the a position to an aromatic ring to the total hydrogen atoms; and Ho/H is the ratio of hydrogen atoms of the aliphatic hydrocarbon groups in the # position or a more distant position from the nearest aromatic ring to the total hydrogen atoms. The coking can be carried out at 410-490‹ C. The feed can be (a) a raffinate produced from a residual oil by extraction with propane, butane, pentane or hexane, (b) an extract produced from a residual oil by extraction with dimethyl sulphoxide, diethylene glycol, sulpholane or methylcarbamate, (c) thermally or catalytically (e.g. using a silica catalyst) cracking a residual oil, or (d) blending a residual oil with a thermally cracked tar having an fa of 0À5-1À0. The residual oil can be an atmospheric or vacuum residue, natural asphalt, shale oil, coal tar or tar sand oil.
    公开号:SU950189A3
    申请号:SU741993358
    申请日:1974-02-01
    公开日:1982-08-07
    发明作者:Одзаки Хироми；Ямани Мамору；Есикаи Харуо
    申请人:Ниппон Майнинг Ко,Лтд (Фирма)；
    IPC主号:
    专利说明:

    This invention relates to the coke industry, specifically to methods for producing artificial sintering carbonaceous product used for the production of metallurgical coke.
    The closest to the present invention is a method for producing an artificial sintering carbon-containing product, including heat treating heavy hydrocarbons at a temperature that does not allow them to be cracked.
    The aim of the invention is to increase the yield of a product suitable for producing metallurgical coke-.
    This goal is achieved by the fact that according to the method of obtaining an artificial sintering carbon-containing product, which includes the heat treatment of heavy carbon / g of hydrogens at a temperature above the temperature at which their cracking began, heavy hydrocarbons have
    factor amomaticity viii 0.4, defined by the following formula
    c / tl: l / 2iH.i / H): l / iHQ / yl
    fa.
    with / and
    where C / H is the ratio of the number of carbon atoms to the number of hydrogen atoms;
    the ratio of the number of hydrogen atoms in the ot-order to the aromatic ring to the total number of hydrogen atoms;
    HO / H is the ratio of the number of hydrogen atoms in a position or higher position to the aromatic ring to the total number of hydrogen atoms.
    According to the proposed method, a distillation residue is subjected to pretreatment, for a key in extraction, thermal cracking, catalytic cracking, etc., in order to increase the aromaticity factor (fa) to a value greater than 0.4, or mixed with thermal resin. cracking, having a high content of arctic compounds, in order to increase the aromatic factor to a value exceeding 0.4, and then this composition is subjected to coking, resulting in an artificial sintering carbon-containing product with improved sintering capability. The aromaticity factor (fg) can be enhanced by various known methods, such as extraction, thermal cracking, catalytic cracking, etc. In the extraction process, carried out according to the proposed method, solvents can be used, which selectively extract hydrocarbons having a high content of aliphatic compounds, for example, can use light hydrocarbons, such as propane, butane, pental, hexane, etc. In this case, refined petroleum. obtained during the extraction process, the IC is used as a raw material for an artificial sintering carbon-containing product. However, in addition, solvents can be used that selectively extract hydrocarbons with a high content of aromatics, for example dimethyl sulfoxide, diethylene glycol, sulfolane, methylcarbamate, etc. In this case, the extracted product is used as a raw material for an artificial sintering carbon-based product. The cracking according to the proposed method is carried out mainly under conditions that reduce the intensity of the polycondensation reaction of the cracked oil. The product obtained by hermetic light cracking of the bottom residue of oil distillation under vacuum, or the bottom residue obtained as a result of a short thermal cracking of oil under vacuum, can be used as a raw material for artificial sintering carbon containing the product. During the initial processing, the aromatic factor of the hydrocarbon product is increased. It is desirable to increase the aromatic factor to a value greater than 0.4. The sintering ability of the artificial sintering carbon-containing product increases depending on the increase in the degree of hydrocarbon aromatization (fg) at a low intensity of the polycondensation reaction, under conditions of primary processing. It is also possible to obtain an artificial sintering carbon-containing product with high sintering ability by mixing the bottom residue of the distillation of oil from about 10-90% of thermal cracking resin containing high molecular weight aromatic hydrocarbons and having a fa 0.51.0, obtained by thermally cracking gas oil obtained in turn, as a result of coking heavy hydrocarbons, as a result of which the aromaticity factor of this composition is increased, and the subsequent coking of this composition. If a raw material with a high content of aromatic polycondensation is used in the preparation of an artificial sintering carbon-containing product with high sintering capacity, the primary processing of the raw material may be weakened. The aromatic factor (f) of the thermal cracking oil of the by-product of the naphtha cracking process (oil fraction with a boiling point exceeding 450 s) is 0.75. If, when producing an artificial sintering carbon-containing product with high sintering power, a naphtha cracking resin is used, then the first treatment can be omitted. However, the distillation residue under vacuum of Kuwait crude oil contains a small amount of aromatic polycondensation, so the aromatic factor (for) of this product is 0.3. In this case, the primary treatment gives an effective result, increasing the degree of aromatization to a value greater than 0.4. According to the proposed method, hydrocarbon fractions of oil, such as bottom residues of distillation of oil at atmospheric pressure and under vacuum, bottom residues of thermal and catalytic cracking, etc., can be used as a raw material product, other heavy hydrocarbons, such as natural asphalt, shale oil, coal tar, tar tar., etc. The temperature during the coking process is maintained in the range from 410 to 490 ° C, and the lower temperature limit can be extended to the initial cracking temperature of the raw product. This upper temperature limit is not critical and may be more than 500 ° C, although with increasing coking temperatures some drawbacks are found during the process, such as the deposition of coke on the pipe walls. According to the invention, an artificial sintering carbon-containing product is obtained, having a high free expansion coefficient (i.e., an increased sintering capacity), for example, equal to 6, as indicated in Example 2, compared with artificial carbon with a low free expansion coefficient (comparative sample 1) the free swelling ratio is determined according to Japanese Industrial Standard M8801-1972 (ASTM, O 720-67). The fluidity of the artificial sintering coal obtained by the proposed method is significantly higher than the fluidity of the natural sintering coal. For example, the artificial angle corresponding to example 1 has a softening temperature below 300 ° C and a curing temperature (determined according to ASTM, O 18112-69). Thanks to the proposed method, these advantages can be achieved, and the heavy oil obtained from the primary processing of the raw product can be used to prepare a lubricating oil fraction, and can also be used as a raw material for gas oil desulfurization. Example 1. VAT residue of distillation under vacuum of crude oil, having a specific weight of 1.01776 (at 25/25 ° C), softening temperature 3fC, permeation rate 315 (at 25c, Conradson coke residue 21.1 wt.% And aromaticity (fjj) 0.30, is fed to a countercurrent extractor having a length of 2100 mm and an internal diameter of 100 mm, in which hydrocarbons containing 34% by weight of aliphatic compounds are extracted, at a pressure of 30 kg / cm (pressure is generated with nitrogen) and when the ratio of butane to the bottom residue of the feedstock, is equal to 10. Extraction output 34% viscosity (98.9 ° C) 47.80 cSt, specific gravity (25/25 sec) 0.9397. 10 kg of the residual oil obtained as a result of this extraction, having a specific gravity of 1.0563 (at 25/25 ° C ), softening temperature 60 C, permeation index 15 (at 25 ° C) Conradson coke residue 29.6 wt.% and aromaticity factor (fg) 0.45, is loaded into a 20 l reactor and coked at 430 s for 3 h at atmospheric pressure. The yield of artificial cacacadic coal is 46%, the coefficient of free injection of this coal is 5- (the coefficient of free injections is determined according to Japanese Industrial Standard M8812-1972). When tested for fluidity (according to the Japanese Prohydrated Standard M8801-1972), it was found that this artificial specacade with carbon deposits the product has a softening-less tetrature and curing temperature. When testing samples in the box (in accordance with Japanese Industrial Standard M8801-1972), it was found that the drum index (defined according to Japanese Industrial Standard K2151-1972) of coke obtained from the standard mixture (0) is 93.1, and the drum index of coke obtained by replacing part of the artificial cacacadec of the carbon-containing product (10 wt.%) with natural Japanese sintering coal containing 15% in the standard mixture () is 92.9. The coking condition and the properties of the artificial sintering carbon are presented. in the table. Example 2. In the reactor corresponding to example 1, load 10 kg of the bottom residue of the distillation under vacuum Kuwait crude oil, corresponding to example 1, and this product is subjected to thermal hooking under a pressure of 50 mm Hg. (absolute) for 30 minutes, which is a primary treatment, resulting in a residual cracking oil with an aromatic factor (fg) of 0.65, the yield of this residual oil being 40%. The residual oil with a high degree of fo (0.65) is loaded into the reactor and subjected to coking at atmospheric pressure for 3 hours. The results obtained are presented in the table. Example 3. The bottom distillation residue under vacuum of crude oil corresponding to Example 1 is loaded into a continuously operating thermal cracking unit with a capacity of 6 kg / h, in which light cracking is carried out. The product obtained in this plant is subjected to distillation, as a result of which a fraction (7) with a boiling point above 450 ° C and an aromatic factor (%) of 0.42 is obtained. 100 g of this fraction is loaded into a 200 ml reactor and coked at 420 s for 5 hours at atmospheric pressure. The results obtained are presented in the table. Example 4. The bottom residue of the distillation under vacuum of Kuwalt crude oil, corresponding to Example 1, is injected into a fluidized bed catalytic cracking unit, in which the catalyst (silica) is fluidized in a fluidized state, thus providing high temperature cracking (temperature, residence time). the reaction zone. 0.5 s). The resulting cracking oil undergoes distillation, resulting in a fraction with a boiling point higher, an aromaticity factor (fj,) of 0.53 and a Conradsoy coke residue of 31.2% by weight. 100 g of this fraction are loaded into a 200 ml r reactor and subjected to coking at 3 h. The results obtained are presented in table. Example 5. The bottom distillation residue under vacuum Kuwait crude oil, corresponding to example 1, is subjected to coking, thermal cracking oil is obtained, which is subjected to distillation, and the fraction with boiling point above 200 s is separated. 3 liters of this FR is loaded into an autoclave with a capacity of 5 manufactured using stainless steel, and subjected to thermal cracking at 500 C for 1 h under pressure of 100 kg / cm. Properties of a thermal cracked resin with a fraction having a boiling point of more than 200 ° C: Specific gravity, 15 / 4s 1.0310 Initial boiling point, with 10% 30% 30% End point, C Analysis of the constituent components of the cracking resin, wt.%: Saturated compounds Ilf7 Aromatic compounds 74, 5 Resin component 13.8 30 g of a thermal cracking resin with a boiling point above 35 ° C and an aromatic factor () 0.72, which is a fraction of the said thermal cracking oil, is mixed with 70 g of the distillation residue under vacuum KuwaIt crude oil. The mixture is loaded into a 300 ml pieaKTop made of stainless steel and coked at 430 ° C for 3 hours at atmospheric pressure. The results obtained are presented in the table. Comparative Sample 1. 100 g of the bottom residue is distilled under vacuum of Kuwait crude oil, corresponding to example 1, is loaded into a 200 ml reactor and subjected to coking at atmospheric pressure for 4 hours. Results obtained. presented in taOLEYtse. ;. Comparative sample 2. The crude cracking oil of the by-product of the naphtha cracking process is subjected to interconnection and a fraction capable of boiling above 425 C and aromatic factor (f,) 0.75 is collected; ; 100 g of this fraction is loaded into a 200 ml reactor and subjected to coking at 420 ° C for 5 hours at atmospheric pressure. The results obtained are presented in the table.
    wow
    imageExtra- Lightweight Light Kata- No kCi cracking lithium butane KING KING is the product output with Tcmp more than 66 40 71 4500С, wt.% Aroma0, 45 0.65 0.42, f
    Condition coking temperature, ° С 430 420 420 pressure, mm Hg 760 760 760
    Not
    Not
    cracking
    100 0.75
    权利要求:
    Claims (1)
    [1]
    420 760 23 - 100 0.53 0.43 0.30 430 430 430 760 760 760 duration, h The properties of the artificial sintering product yield,% volatile yield,% 29.1 25.0 27.1 coefficient. free flash 5 Test of fluidity softening temperature, C Below 320 308 maximum flow temperature, 431 458 432 curing temperature, C 518 Coke strength (O}) 92.9 P The invention Formulation method for an artificial sintering carbon-containing product, including heat treatment of heavy hydrocarbons at a temperature higher than the temperature at which they are cracked, which is different from the fact that, in order to yield a product, heavy hydrocarbons have an aromaticity factor (fg) above 0.4, defined by the following formula
    Continuation of table 44
    Below 300 524 The coke strength is measured on coke obtained in the box test (according to Method J IS -M8801-1972) the partially artificial coking coal (10 wt.% In the tested mixture) is replaced with natural Japanese coke-chemical coal (15 wt.% standard mixture); and the distillation distillation residue under vacuum Kuwait crude oil; b - a mixture comprising 70 wt.% of the bottoms distillation under vacuum of Kuwait oil and 30 wt.% of the thermal cracking resin; c - legroin cracking resin. 37 33 30 30.1 24.8 20.6 Below Below Not pr1Em gcha300 300 eTS 428 435 Same 512 521 ".C / H-1 / 2Hqc / H-1 / 2iHo (Hi О С / Н С / Я - the ratio of the number of carbon atoms to the number of hydrogen atoms; n / H is the ratio of the number of hydrogen atoms in the a-position fe of the aromatic ring to the total number of hydrogen atoms; N. / H is the ratio of the number of hydrogen atoms in / - position or higher position to the aromatic ring, to the total number of hydrogen atoms.Sources of information taken into account in the examination 1. US Patent No. 2765602, C. 196-76, 18.09.56.
    类似技术:
    公开号 | 公开日 | 专利标题
    US4666585A|1987-05-19|Disposal of petroleum sludge
    RU2733847C2|2020-10-07|Integrated method for increasing production of olefins by reprocessing and treatment of a heavy residue of cracking
    US4079005A|1978-03-14|Method for separating undissolved solids from a coal liquefaction product
    SU950189A3|1982-08-07|Process for producing synthetic sintering carbonaceous product
    CA1210355A|1986-08-26|Low severity delayed coking
    SU719511A3|1980-02-29|Method of heavy oil raw material processing
    US3382084A|1968-05-07|Asphalt binder pitch
    US4389302A|1983-06-21|Process for vis-breaking asphaltenes
    US4429172A|1984-01-31|Process for the production of modified pitches and low boiling aromatics and olefins and use of said pitches
    US4725350A|1988-02-16|Process for extracting oil and hydrocarbons from crushed solids using hydrogen rich syn gas
    KR0148566B1|1998-11-02|Process for the conversion of a heavy hydrocarbonaceous feedstock
    US4207168A|1980-06-10|Treatment of pyrolysis fuel oil
    US4235702A|1980-11-25|Hydrocarbon processing
    US4292170A|1981-09-29|Removal of quinoline insolubles from coal derived fractions
    US3326796A|1967-06-20|Production of electrode grade petroleum coke
    GB1601644A|1981-11-04|Treatment of pyrolysis fuel oil
    US5092982A|1992-03-03|Manufacture of isotropic coke
    US4211633A|1980-07-08|Separation of asphaltic materials from heptane soluble components in liquified solid hydrocarbonaceous extracts
    US4405439A|1983-09-20|Removal of quinoline insolubles from coal derived fractions
    US3707461A|1972-12-26|Hydrocracking process using a coal-derived ash
    US4151066A|1979-04-24|Coal liquefaction process
    US3338818A|1967-08-29|Process for converting asphaltenecontaining hydrocarbon feeds
    US2118940A|1938-05-31|Destructive hydrogenation of distillable carbonaceous material
    EP0285261A1|1988-10-05|Premium coking process
    US4188235A|1980-02-12|Electrode binder composition
    同族专利:
    公开号 | 公开日
    FR2216340B1|1976-11-26|
    DE2404925A1|1974-08-08|
    IT1009615B|1976-12-20|
    JPS49103901A|1974-10-02|
    GB1441675A|1976-07-07|
    US3896023A|1975-07-22|
    DE2404925B2|1978-09-28|
    FR2216340A1|1974-08-30|
    DE2404925C3|1979-05-23|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    RU2455337C2|2010-09-09|2012-07-10|Общество с ограниченной ответственностью "Информ-технология" |Method of obtaining petroleum additive in coal coking charge|US2775549A|1954-01-25|1956-12-25|Great Lakes Carbon Corp|Production of coke from petroleum hydrocarbons|
    US2922755A|1957-10-14|1960-01-26|Jr Roy C Hackley|Manufacture of graphitizable petroleum coke|
    FR1314633A|1962-01-19|1963-01-11|Continental Oil Co|Coke production process|
    US3547804A|1967-09-06|1970-12-15|Showa Denko Kk|Process for producing high grade petroleum coke|
    US3617481A|1969-12-11|1971-11-02|Exxon Research Engineering Co|Combination deasphalting-coking-hydrotreating process|US4490244A|1982-09-29|1984-12-25|Great Lakes Carbon Corporation|Production of premium grade petroleum coke|
    US4720338A|1986-11-03|1988-01-19|Conoco Inc.|Premium coking process|
    US4832823A|1987-04-21|1989-05-23|Amoco Corporation|Coking process with decant oil addition to reduce coke yield|
    US20020179493A1|1999-08-20|2002-12-05|Environmental & Energy Enterprises, Llc|Production and use of a premium fuel grade petroleum coke|
    US6168709B1|1998-08-20|2001-01-02|Roger G. Etter|Production and use of a premium fuel grade petroleum coke|
    US8372264B2|2006-11-17|2013-02-12|Roger G. Etter|System and method for introducing an additive into a coking process to improve quality and yields of coker products|
    US9011672B2|2006-11-17|2015-04-21|Roger G. Etter|System and method of introducing an additive with a unique catalyst to a coking process|
    US8206574B2|2006-11-17|2012-06-26|Etter Roger G|Addition of a reactor process to a coking process|
    CN103710042B|2006-11-17|2017-03-01|罗杰·G·埃特|Selective cracking and the coking of component is not needed in coking cycle material and diesel oil|
    US8361310B2|2006-11-17|2013-01-29|Etter Roger G|System and method of introducing an additive with a unique catalyst to a coking process|
    CN104031669B|2013-03-07|2016-08-10|神华集团有限责任公司|A kind of electrode pitch and preparation method thereof|
    CN109135789B|2018-08-16|2021-09-28|中钢集团鞍山热能研究院有限公司|Method for preparing needle coke from medium-low temperature coal tar|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    JP48013369A|JPS49103901A|1973-02-03|1973-02-03|
    [返回顶部]