• 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 hydrocarbon feedstock derived from crude oil or other sources is subjected continuously to thermal cracking under pressure and in the presence of hydrogen in order to convert the feedstock to products of lower molecular weight containing high proportions of olefinic components. In a first processing step, a catalytic hydrogenating pretreatment is performed at a temperature within the range of 300 DEG C. to 600 DEG C. and under a pressure within the range of 12 to 85 bars. In a second step, a thermal cracking treatment is performed under a pressure within the range of 10 to 70 bars with residence times of less than 0.5 second and at a temperature within the range of 625 DEG C. to 1,000 DEG C., the quantity of hydrogen employed being such that the molar concentration in the effluents is at least equal to 20%.
    公开号:SU850011A3
    申请号:SU782634495
    申请日:1978-07-05
    公开日:1981-07-23
    发明作者:Шавекилян Эдгар；Бруар Рене
    申请人:Сека С.А. (Фирма)；
    IPC主号:
    专利说明:

    (54) METHOD OF OBTAINING OLEFINS
    This invention relates to methods for producing olefins by the pyrolysis of hydrocarbon feedstock in the presence of hydrogen. A known method for producing olefins by hydropyrolysis of hydrocarbon feedstock at a temperature of 600-1000 ° C 1 is closest to the proposed method. This is a method for the production of olphins by hydropyrolysis of a hydrocarbon feedstock at a temperature of 625-1000 ° C and a pressure of 10-70 atm in the presence of H, in an amount that ensures its content in the products of the process is 20-80 mol% 2. A disadvantage of the known methods is the relatively low yield of the target products. The purpose of the invention is to increase the yield of olefins. This goal is achieved by the fact that according to the method of producing olefins by hydropyrolysis of hydrocarbon feeds at a pressure of 10-70 atm and a temperature of 625-1000 ° C in the presence of hydrogen in an amount that provides its content in gyropyrolysis products equal to 20-80 mol.%, The feedstock It is preliminarily subjected to catalytic hydroprocessing at a temperature of 3OO-BOO C and a pressure of 12-85 atm in a catalytic reactor located in the heating-steaming zone of the hydropyrolysis reactor, in which the temperature is equal to the catalytic temperature th hydroprocessing. The following advantages result from the combination of a pre-hydra / 5track + hydropyrolysis: under severe conditions of cracking reduces coking, hence reducing the conditions of cracking and, consequently, increasing the yield of the useful product, in case of using raw materials with high sulfur content it is possible to desulfurize before hydropyrolysis, from which follows improvement of the characteristics of the cracking products obtained, namely in terms of heavy products. The desired effect of pretreatment can be obtained by using methods such as hydroprocessing known in the petroleum and chemical industries, which is carried out under hydrogen pressure and in the presence of specific catalysts, the main role of which is in the destruction of sulfur-containing compounds (and possible nitrogen- and oxygen-containing raw materials. In practice, such treatment is always accompanied by more or less destructive hydrogenation, the value of which, if desired, can be increased by using catalysts of a pronounced hydrogenating or hydrocracking nature.
    Cobalt and / or molybdenum based catalysts are used, but they may contain or be based on other metals, for example, nickel, chromium tungsten, iron, etc. The balance between the desulfurization activity and the hydrogenating activity or hydrocracking activity depends not only on the base metals, but also on the substrate (alumina, silicoalumin, zeolite).
    The catalysts may contain cobalt and molybdenum, and are particularly recommended in the case of heavy sulfur containing feedstock and when desulfurization is of great importance.
    This combination is an advantage of the present invention.
    With respect to the scheme containing the hydroprocessing of the raw material regardless of hydropyrolysis, this combination avoids preheating the hydroprocessing reagents, condensation and separation of the effluents, as well as the watercycle that is inherent in this operation, and with it the use of pressure cleaning agents. This results in significant cost savings and energy consumption.
    The pretreatment reactor is placed in the preheating-steaming loop in the hydropyrolysis reactor at the point where the temperature reaches the level required for the specified hydrogenation treatment. This temperature, depending not only on the catalyst, but also on the reduced conditions and the desulfurization ratio, can be in the range of 300-600 ° C, preferably 350500 ° C. At the exit of the pretreatment reactor, products that are always under pressure and contain hydrogen in excess are reintroduced into the preheating circuit, evaporated to power the hydropyrolysis reactor. Due to the exothermicity of the hydrogenation-desulfurization reactions, their temperature is several tens of degrees above the temperature at the entrance to the pretreatment reactor.
    The residence time in the hydropyrolysis reactor is less than C, .5 s, and sometimes 0.1 s. A reduction in transit time affects a decrease in the degree of conversion, but this unfavorable factor is retired, if necessary, by an increase in temperature.
    The temperature may vary within very large limits depending on the purpose of the operation and the duration of the reaction, with a useful temperature range at the outlet of the reactor being from 625 to 1000 ° C.
    The pressure at the outlet of the reactor is maintained at 10-70 atm, preferably 10-45 atm.
    As for hydrogen, it must be applied in such quantities that its molar concentration in reactor effluents is 2080 mol% each. The increased content is beneficial in terms of overall conversion and as an anti-tar product - coke generators, but at the same time they increase the tendency for the hydrogenation of intermediate olefinic products, as well as the volume of gas circulated and the costs of hydrogen separation and recycling of hydrogen.
    When applying the proposed invention, it is not necessary to use only pure hydrogen. As for the hydropyrolysis itself, the hydrogenation gas may contain other components to the extent that they are inert with respect to the hydrocarbons and the hydrogen itself under the given reaction conditions or at least. if they do not cause unwanted side reactions. These can be hydrocarbons. (CH, SdH, CjHa, etc.), carbon oxides. (CO and COj), nitrogen, water vapor, minor amounts of hydrogen sulfide, etc. Some of the listed compounds. can be used for a specific purpose, for example, Light hydrocracking hydrocarbons, steam, and other possible diluents.
    If necessary, some reagents (e.g. ethane, steam or other recycled fractions) or import diluents such as water vapor can also be introduced after the pre-hydrotreatment reactor, if their passage over the catalyst should be avoided.
    Typically, under the conditions of temperature and pressure of the hydrogenating pretreatment, the reaction mixture has a condensed phase and it is recommended that a downward flow be introduced to ensure proper flow of this phase through the catalyst.
    Example i A gas oil from distillation in vacuum (BrO) with the following characteristics is used as a feedstock:
    Specific gravity at 0.904
    Hydrogen content,% 12.48
    Sulfur content,% 1.95
    Distillation intervals at 760 mm Hg:
    2 33 ° C
    ID
    10% 335 ° C
    20% 361 ° С
    50% 416 ° C
    80% 4470С
    90%
    502 ° C
    CD
    2% balance
    As it follows from this, very heavy raw materials are used, which are considered particularly unfavorable for the production of light olefins.
    The table lists the process conditions and the results obtained at 840 s without and with pretreatment, as well as the results obtained at 870 ° C with pretreatment.
    Cobalt / molybdenum containing 3% CoO and 15% MoO is used as a catalyst for pretreatment. The desulfurization coefficient under these non-limiting conditions is about 80%.
    It is established that the amount of C, which is 29.8% without preliminary preparation
    Average temperature
    The pressure at the outlet of the reactor
    The ratio of ND / VGO, MN / H
    U 1 Consumption M VGO / M catalyst / h
    Hydropyrolysis
    Reactor inlet temperature
    Temperature at the reactor outlet pressure at the reactor outlet, atm
    Residence time between 600 ° C and out
    Dilution H, 0 / VGO, wt.%
    The total weight,% kg
    CH ;,
    SoNl
    C2,
    C ,, Nd
    Cracked gasoline i
    The residue is 200 ° C
    Hjs
    Sulfur residue in liquid fractions
    K consumption (minus hydrogen
    cracking result
    CjH and C.jHg)
    Simultaneous treatment goes to 31.4% with pretreatment at a temperature at the outlet of the hydropyrolysis reactor of 40 s and reaches 34.8% at a temperature of 870 ° C
    It should be noted that if VGO does not undergo preliminary hydrotreatment, the operation of hydropyrolysis is complicated at temperatures above 840-850 0 due to an increased tendency to coking, then it decreases when performing this treatment.
    In addition, during pretreatment, the amount of heavy residue (fraction above 200 s) decreases, which decreases at a reactor outlet temperature of 840 ° C to 22.119, 9% and even to 19.2% at.
    430 30
    1,380 1,05
    600 870 20 0.060
    269
    权利要求:
    Claims (2)
    [1]
    202 85 The invention of the method of producing olefins by hydropyrolysis of hydrocarbon feedstock at a pressure of 10-70 atm and a temperature of 625-1000 ° C in the presence of hydrogen in an amount that provides its content in the products of hydropyrolysis equal to 20-80 mol.%, And that, in order to increase the yield of target products, the feedstock is preliminarily subjected to catalytic hydrotreatment at 18 300-600 C and pressure of 1285 atm in a catalytic reactor located in the heating-steaming zone of the hydropyrolysis reactor, in which the rate rature equal to the temperature of the catalytic hydrotreatment of information sources, the received note in the examination 1. Japanese Patent 43522, cl. 16 B 121, published, 1972.
    [2]
    2. The patent of France 2164450, cl. From 10 G 13/00, published 1975 (prototype) ..
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    同族专利:
    公开号 | 公开日
    BR7804299A|1979-04-03|
    SE7807520L|1979-01-06|
    US4216077A|1980-08-05|
    FR2396794A1|1979-02-02|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US2052148A|1933-12-27|1936-08-25|Ernest A Ocon|Process for the conversion of heavy hydrocarbon oils into lower boiling point hydrocarbon products|
    US3720729A|1970-11-02|1973-03-13|Lummus Co|Pyrolysis of hydrotreated feedstocks|
    GB1361671A|1971-01-06|1974-07-30|Bp Chem Int Ltd|Process for the production of gaseous olefins from petroleumdistillate feedstocks|
    US3730875A|1971-02-16|1973-05-01|Universal Oil Prod Co|Combination process for black oil conversion|
    DD113022A1|1974-09-04|1975-05-12|DE2941851C2|1979-10-16|1990-05-03|Linde Ag, 6200 Wiesbaden, De|
    FR2508898B1|1981-07-03|1986-11-14|Inst Francais Du Petrole|PROCESS FOR CONVERTING RICH CUTS INTO POLYAROMATIC HYDROCARBONS IN METHANE, ETHANE AND POSSIBLY BENZENE|
    FR2516932B1|1981-11-24|1985-07-19|Inst Francais Du Petrole|PROCESS FOR CONVERTING HEAVY OILS OR OIL RESIDUES INTO GASEOUS AND DISTILLABLE HYDROCARBONS|
    US4446004A|1982-12-23|1984-05-01|Mobil Oil Corporation|Process for upgrading vacuum resids to premium liquid products|
    US4592827A|1983-01-28|1986-06-03|Intevep, S.A.|Hydroconversion of heavy crudes with high metal and asphaltene content in the presence of soluble metallic compounds and water|
    GB2142930B|1983-03-19|1987-07-01|Asahi Chemical Ind|A process for cracking a heavy hydrocarbon|
    JPH0452316B2|1983-12-07|1992-08-21|Asahi Chemical Ind|
    US4661238A|1985-09-05|1987-04-28|Uop Inc.|Combination process for the conversion of a distillate hydrocarbon to maximize middle distillate production|
    DE3914057A1|1989-04-28|1990-10-31|Ruhrkohle Ag|STRIPING OF RESIDUES|
    ES2645919T3|2009-02-11|2017-12-11|Natural Energy Systems Inc.|Process for the conversion of organic material into combustible gas rich in methane|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    FR7720637A|FR2396794A1|1977-07-05|1977-07-05|HYDROGEN PRESSURE CRACKING PROCESS FOR OLEFIN PRODUCTION|
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