• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
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  • 引用文献
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  • 优先权
    • 专利摘要:
    Process for the manufacture of kerosene and/or gas oil(s) wherein a hydrocarbon feedstock is catalytically treated in the presence of hydrogen at elevated temperature and pressure and wherein the material obtained is subjected to a distillation treatment, in which process a hydrocarbon feedstock is used containing flashed distillate produced via a catalytic residue conversion process.
    公开号:SU1681735A3
    申请号:SU874203972
    申请日:1987-12-09
    公开日:1991-09-30
    发明作者:Иоханнес Антониус Ван Хелден Хенрикус；Фабрициус Нильс；Матеус Мария Деккерс Ваутерус
    申请人:Шелл Интернэшнл Рисерч Маатсхаппий Б.В. (Фирма)；
    IPC主号:
    专利说明:

    g-
    23
    The invention relates to a method for producing kerosene and / or gas oils and can be used in the refining and petrochemical industries.
    The aim of the invention is to simplify the process technology.
    The drawing shows the scheme of the method.
    Crude oil is fed through line 1 in an atmospheric distillation unit 2, in which gaseous products are obtained, discharged through line 3, a kerosene fraction discharged through -4 line, a gas oil fraction discharged through line 5, and an atmospheric residue, which through line 6 directs in a vacuum distillation unit 7, where an additional gas oil fraction, discharged via line 8, is distilled in the vapor phase of a single equilibrium distillation, boiling away at 320-660 ° C, which is sent to hydrocracking unit 10 for hydrocracking unit 10, and a vacuum balance k, discharged through line 11. A vacuum residue is combined with the distillation residue recirculated through line 12 and fed through line 13 to a catalytic hydroconversion unit 14 of the residue. If necessary, part of the vacuum residue (before or after mixing with recirculation) can be removed from the system (not shown). The product of plant 14 is directed through line 15 to distillation unit 16, thereby obtaining a gas oil fraction discharged through line 17, distillation in the vapor phase of a single equilibrium distillation discharged through line 18, the remainder of the distillation being discharged through line 19, part of which line 20 can be removed from the process.
    The distillate in the vapor phase, discharged through line 15, is combined with the distillate discharged through line 9 and directed to hydrocracking. The hydrocracking product is sent to a distillation unit 21, where kerosene is withdrawn from line 22 and gas oil is withdrawn from line 23.
    The residue from the distillation is withdrawn through line 24.
    Distillate in the vapor phase of a single equilibrium distillation under vacuum of an oil residue discharged through line 9, and distillate in the vapor phase of a single equilibrium distillation under vacuum of a catalytic hydroconversion oil residue discharged through line 18 can be subjected to catalytic hydrocracking separately followed by separate by distillation to the desired products.
    The process of catalytic hydroconversion residue is carried out at 300 to 500 ° C
    in particular 350-450 ° C, a pressure of 50-300 bar, in particular 75-200 bar, a space velocity of 0.02-10 kg / kg-h, in particular 0.1-2 kg / kg h, and the ratio hydrogen / feedstock
    100-5000 l / kg, in particular 500-2000 l / kg.
    Catalysts containing at least one metal selected from the group formed by nickel and cobalt and at least one are used.
    a metal selected from the group formed by molybdenum and tungsten on a carrier, preferably containing a significant amount of alumina, for example, 40% by weight.
    Asphaltene-containing hydrocarbon residues having a nickel and vanadium content of more than 50 parts of the primary waste are demetallized. This treatment is carried out in the presence of hydrogen using a catalyst containing a significant amount of silica, for example at least 80% by weight. If necessary, the demetallization catalyst may contain one or more metals or metal compounds having hydrogenating activity, such as nickel and / or vanadium. Since catalytic demetallization and hydroconversion can be carried out under the same conditions,
    Two processes can be carried out in a single reactor containing one or more layers of demetallization catalyst over one or more layers of hydroconversion catalyst.
    Catalytic hydrocracking is carried out at 250-500 ° C, pressures up to 300 bar and a space velocity of 0.1-10 kg of feedstock per liter of catalyst per hour. It is possible to use the ratio of gas / source
    raw materials 100-5000 l / kg. It is preferable to carry out hydrocracking at 300-450 ° C, a pressure of 25-200 bar, a space velocity of 0.2-5 kg / l of catalyst per hour, a gas / feedstock ratio of 250-2000.
    In this case, both amorphous catalysts and zeolite-based catalysts are used.
    As zeolites, in particular, synthetic zeolite Y and its modifications, such as various forms of superstable zeolite Y, are used. Preference is given to using catalysts based on modified zeolite Y, where zeolite has a significant amount of pores,
    having a diameter of at least 8 nm. Zeolite catalysts may also contain other active ingredients, such as aluminosilicates, as well as binding materials, such as alumina.
    The catalysts used contain at least one hydrogenation component from a metal of group VI and / or at least one hydrogenation component from a metal of group V1H. Preferably, the catalytic composition comprises one or more components of nickel or cobalt and one or more components of molybdenum and / or tungsten, or one or more components of platinum or palladium. The amount of hydrogenation components in the catalytic composition is 0.05-10 wt.% Components from a metal of group VIII and 2-40 wt.%, Components from a metal of group VI, calculated as the ratio of metal to 100 parts by weight of the total catalyst. The hydrogenation components in the catalyst compositions may be in oxide and / or sulphide form. If a combination of at least a component of a metal of group VI and group VIII is present in the form of oxides (mixed), then it is subjected to preliminary sulphurization.
    The invention is illustrated by the examples below.
    Example 1. The method is carried out according to the scheme shown in the drawing.
    The atmospheric residue of Middle Eastern origin (100 parts by weight) along line 6 is sent to a vacuum distillation unit 7, where 40.5 parts by weight are obtained. distillate in the vapor phase of a single equilibrium distillation under vacuum (hereinafter referred to as distillate in the vapor phase) and 59.5 wt.h. vacuum residue. The latter, via lines 11 and 13, are directed to a catalytic hydroconversion unit 14 for the residue. Catalytic conversion of the residue is carried out at 435 ° C and. a hydrogen partial pressure of 150 bar in the presence of a molybdenum or alumina conversion catalyst. The conversion is carried out at a volume rate of 0.30 kg / kg l using 2.4 parts by weight. hydrogen.
    The product of catalytic hydroconversion residue is directed through line 15 to a distillation unit 16, including atmospheric and vacuum distillations. You get 3.5 wt.h. hydrogen sulfide and ammonia, 5.3 wt.h. products boiling below the boiling range of l-igroin (called ligroin), 5.5 wt.h. ligroin, 12.3 wt.h. kerosene, 16.7 wt.h. gas oil (discharged through line 17), b wt.h, vacuum residue (discharged via line 19) and 12.6 wt.h, distillate in the vapor phase of a single equilibrium distillation, which under vacuum (hereinafter referred to as distillate in the vapor phase) in the hydrocracking unit
    lines 18. Distillate has the following characteristics: density (15/4) 0.93, content, wt.%: hydrogen 11.9, sulfur 0.6, nitrogen 0.21, Conradson coke residue 0.5; average boiling point is 445 ° C.
    The distillates in the vapor phase are subjected to catalytic hydrocracking in unit 10, using nickel / tungsten on alumina as catalyst. The hydrocracker is conducted at 405 ° C, a hydrogen partial pressure of 130 bar and a space velocity of 0.84 kg / kgh using 0.4 wt.h. hydrogen. The resulting product is subjected to atmospheric distillation at the unit 21 with
    5 to obtain 0.1 wt.h. hydrogen sulfide and ammonia, 0.6 wt.h. ligroin, 2.7 wt.h. ligroin and 5.1 wt.h. kerosene (discharged through line 22) and 4.5 wt.h. gas oil (discharged through line 23).
    0 When using 100 wt.h. of atmospheric residue of Middle Eastern origin directly as a feedstock of catalytic hydroconversion residue (14) during the process
    5 under conditions similar to those described above, 3.2 wt.h. hydrogen, get to 26.7 wt.h. distillate in the vapor phase, from which, after catalytic cracking (consumption of water 0,7 wt.h.) receive 0.2 wt.h. hydrogen sulfide to ammonia, 1.2 wt.h. ligroin, 5.7 wt.h. lmgroine 10.8 wt.h. kerosene and 9.4 wt.h. gas oil
    Example 2. The method is carried out by
    Example 5: Atmospheric residue of Middle Eastern origin (100 parts by weight) is sent via line 6 to a vacuum distillation unit 7, where 40.5 parts by weight are obtained. distillate in the vapor phase and 59.5 wt.h. vacuum
    0 balance. The latter is treated under the conditions of example 1 (hydrogen consumption 2.4 parts by weight) and 12.6 parts by weight are obtained. distillate in vapor phase. The latter is mixed with the distillate in the vapor phase, starting from line 9, and subjected to catalytic hydrocracking at unit 10. The mixed distillate has the following characteristics: density (15/4) 0.93; content wt.%: hydrogen 12.2, sulfur 2.4,
    0 nitrogen 0.09, coke residue Conradson / S, 5; average boiling point is 445 ° C.
    The mixed distillate is subjected to catalytic hydrocracking as described in Example 1. The consumption of hydrogen is 1.5 parts by weight.
    5 The resulting product was sent to atmospheric distillation and 1.4 parts by weight of hydrogen sulfide and ammonia, 2.6 parts by weight were obtained. ligroine (), 11.1 ma.ch. ligroin, 21.1 wt.h. kerosene (discharged through line 22) and 18.4 May, h. gazry l (diverted through line 23).
    Example 3. The method is carried out as in example 2 using recirculation of the distillation residue through line 12. Atmospheric residue of Middle Eastern origin (100 parts by weight) is sent through line 6 to the unit 7 for vacuum distillation, where 40.5 parts by weight are obtained . distillate in the vapor phase and 59.5 wt.h. a vacuum residue, which is directed along lines 11 and 13 to a unit 14 for catalytic hydroconversion of the residue (hydrogen consumption 2.3 parts by weight).
    The product of catalytic hydroconversion residue is directed to a distillation unit 16, which includes atmospheric and vacuum distillations. At the same time get 3.4 wt.h. hydrogen sulfide and ammonia, 3.9 wt.h. ligroin, 5.0 wt.h. ligroin, 11.8 wt.h. kerosene, 16.3 msec. gas oil (discharged through line 17), 18 wt.h. vacuum residue, part of which in the amount of 12 wt.h. recycle in line 12 to a unit 14 for catalytic hydroconversion residue 14, and 15.4 wt.h. vapor distillate that is sent to catalytic hydrocracking.
    Mixed distillates in the vapor phase have the following characteristics: density (15/4) 0.93; content, wt.%: hydrogen 12.1, sulfur 2.3, nitrogen 0.09, Konradson coke residue 0.5; boiling point 445 ° C.
    Mixed distillates are subjected to catalytic hydrocracking under conditions of freezing 1. Hydrogen consumption is 1.7 wt.h. The resulting product is sent to an atmospheric distillation unit 21 and 1.4 parts by weight are obtained. hydrogen sulfide and ammonia, 2.8 wt.h. ligroin, 11.7 wt.h. ligroin, 22.3 wt.h. kerosene (discharged through line 22) and 19.4 wt.h, gas oil (discharged through line 23).
    Example 4. The method is carried out as described in Example 3. Atmospheric residue of Middle Eastern origin (100 parts by weight) is sent via line 6 to a vacuum distillation unit 7, where 40.5 parts by weight are obtained. distillate in the vapor phase, discharged through line 9, and 59.5 wt.h. a vacuum residue, which is directed along lines 11 and 13 to a catalytic hydroconversion unit 14 of the residue. The consumption of hydrogen is 2.3 wt.h.
    The product of catalytic hydroconversion residue is directed to a distillation unit 16, which includes atmospheric and vacuum distillations. This gives 3.4 wt.h. hydrogen sulfide and ammonia, 3.9 wt.h. ligroin, 5.0 wt.h. ligroin, 11.8 wt.h. kerosene, 16.3 wt.h. gas oil (Discharge through line 17), 28 wt.h. vacuum residue, part of which in quantity
    12 parts by weight recycle along line 12 to a unit 14 for catalytic hydroconversion of the residue, and 15.4 wt.h. The distillate is in the vapor phase discharged through line 18, which is sent to catalytic hydrocracking.
    A distillate sent to catalytic hydrocracking has the following properties: density (15/4) 0.93; content wt.%: hydrogen 11.9, sulfur 0.7, nitrogen 0.23; Coke residue Conradson 0.5 weight.h .; average boiling point is 445 ° C. Distillate in the vapor phase, sent for catalytic hydrotreatment through line 9. It has the following properties: density (15/4) 0.926; content, wt.%: hydrogen 12.5, sulfur 2.69, nitrogen 0.05; Konradson coke residue 0.5 wt.%; average boiling point is 445 ° C.
    The distillate in the vapor phase, discharged through line 9, and the distillate in the vapor phase, discharged through line 18, is subjected to catalytic hydrocracking separately.
    The latter is subjected to catalytic hydrocracking under the conditions of Example 1. The consumption of hydrogen in this case is 0.5 wt.h. During subsequent distillation, 0.2 parts by weight is obtained. hydrogen sulfide and ammonia, 0.8 wt.h. ligroin, 3.3 wt.h. ligroin, 6.2 wt.h. kerosene and 5.4 wt.h. gas oil
    The first distillate is subjected to catalytic hydrocracking under the same conditions, but at a hydrogen consumption of 1.1 parts by weight. During the subsequent distillation of the obtained product, 1.3 wt.h. hydrogen sulfide, and ammonia, 2.0 wt.h. ligroin, 8.4 wt.h ligroin, 15.9 wt.h. kerosene and 14.0 wt.h. gas oil
    Thus, the method according to the invention allows to simplify the process technology by eliminating the cooling stage and reheating the streams subjected to hydrotreatment, as well as the possibility of conducting the hydrotreating stages in close temperature conditions.
    权利要求:
    Claims (1)
    [1]
    Claim 1. Method for producing kerosene and / or gas oil by catalytic hydrocracking in the presence of hydrogen at elevated temperature and pressure of the distillate separated from the product of catalytic hydroconversion of the oil residue, followed by distillation of the obtained product to the desired products and the residual fraction, that, in order to simplify the process, the dis
    til t. in the vapor phase of a single equal-spring distillation under vacuum oil
    spring distillation under vacuum of the product of the atmospheric residue,
    catalytic hydroconversion of petroleum2. The method according to claim 1, wherein
    residue with a boiling range of the fact that the residual fraction of recycled
    320-600 ° C or the specified distillate and dis-5 are fed to the catalytic hydrocrackingtilla stage in the vapor phase once equal to the feedstock.
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    同族专利:
    公开号 | 公开日
    AU8200187A|1988-06-16|
    US4994171A|1991-02-19|
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    EP0271148A1|1988-06-15|
    DK643287A|1988-06-11|
    KR880007694A|1988-08-29|
    JPS63165485A|1988-07-08|
    CN87107356A|1988-06-22|
    ZA879013B|1988-05-27|
    NO173610B|1993-09-27|
    DE3787710T2|1994-04-28|
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    NO875135D0|1987-12-09|
    CA1298223C|1992-03-31|
    KR960014922B1|1996-10-21|
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    CN1020627C|1993-05-12|
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    EP0271148B1|1993-10-06|
    AU604798B2|1991-01-03|
    DE3787710D1|1993-11-11|
    AT95555T|1993-10-15|
    FI875415A0|1987-12-09|
    AR247914A1|1995-04-28|
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    IN170269B|1992-03-07|
    BR8706678A|1988-07-19|
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    引用文献:
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    US4213847A|1979-05-16|1980-07-22|Mobil Oil Corporation|Catalytic dewaxing of lubes in reactor fractionator|
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    CN100372875C|2006-04-13|2008-03-05|上海交通大学|High molecular benzophenone photoinitiator and its prepn process|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    GB868629477A|GB8629477D0|1986-12-10|1986-12-10|Manufacture of kerosene/gas oils|
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