• 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:
    The invention relates to a process to improve the stability of a catalyst to be used for lowering the cloud or turbidity point and the filterability limit temperature of gas-oils. The catalyst is formed of a composite system constituting 5 to 90% of a hydrodesulfuration type catalyst A and 95 to 10% of a hydroconversion type catalyst B, these two catalysts being either mixed or superposed, in which case catalyst A forms the top of the catalytic bed.
    公开号:SU1181522A3
    申请号:SU813279154
    申请日:1981-05-07
    公开日:1985-09-23
    发明作者:Бускэ Жак；Гэган Клод；Вотье Даниель
    申请人:Элф Франс (Фирма)；
    IPC主号:
    专利说明:

    1118 The invention relates to a catalytic system for hydrotreating petroleum fractions containing heavy H-paraffins, and to a method for hydroprocessing petroleum fractions using this catalytic system. The purpose of the invention is to increase the stability of the system, as well as to increase the flowability of petroleum fractions. The loads used are petroleum diesel fractions. The characteristics of these diesel fuels are given in Table 1, I. Table1 Indicators Diesel 1 I 2
    0.875
    0.850
    1.84
    1.4314 4
    20
    ASTM overclocking
    Content, wt,%, com catalyst
    ponents
    SiOg
    Co Ni
    Moe
    4 116040
    -4 114060
    4 112575
    - -4 111090
    4 О 112575 These conditions provide very low (24 bar) hydrogen pressure for this type of reaction, which favors coke formation deactivation reactions on the catalyst. The hydroconversion catalysts used in example 1 are of type B, they are prepared by dry impregnation of oxide. Alumina - with different content of alumina, ammonium molybdate and nickel or cobalt nitrate. The catalysts thus obtained are calcined at 500 ° C and precipitated in the reactor. The content of components in type B catalysts is given in Table 2. Table I
    Notes e.PTF is the filterability temperature; TP - cloud point, Example 1. Handle diesel fuel. 1 in the following operating conditions: total pressure 30 bar; the molar ratio hydrogen to hydrocarbon is 4; volumetric speed 1; The temperature between 390 and. The activity of the catalysts is estimated by indicating the degree of desulfurization (GOS), obtained in such a way as to obtain the corresponding decrease in the limiting filterability temperature (DPTF) and cloud point (l TP). The decrease is measured in degrees as the difference between the corresponding values of the initial charge and the output liquid. The results are shown in Table 3, depending on the duration of the experiment and the reaction temperature. Lp maintains the operating characteristics of the catalyst constant and regulates the temperature depending on time. Therefore, it is necessary to express the deactivation rate with respect to PTF and GP:
    410
    10,425
    20,435
    40,415
    80 420
    90 440
    120 415
    120 430
    160 435
    190 410
    . 40 420
    50
    420
    70 410
    ten
    . 410
    20,420
    40
    As can be seen from the table. 3 the use of catalysts: a metal of the U1 group and a metal of the USH group on oxide cream and aluminum oxide, improves the flow properties of diesel fuels, but it is necessary to increase the reaction temperature over time in order to preserve the constant activity of catalysts, at the same time, the activity of: hydrodesulphurisation decreases, Example 2. The used hydrogen desulfurization catalyst was 90% 1S + 10% A 10.
    415
    425
    thirty
    425
    60
    Table3
    0.83
    4 5 5 6 6 5 6 6 6 5
    5 6 6 6 7 6 7 7 7 6
    0.6
    0.30
    0.33
    0.3
    It is a catalyst used for hydrodesulfurization of diesel TOSTILC, consisting of 2.2 wt.% Co and 12 wt.% Mo on non-acid alumina, i.e. containing from 0.5 to 2.0 wt.% silicon dioxide.
    The catalytic layer consists of 10% hydrodesulphurisation catalyst A with a content of 0.5 wt.% SiOj, located in the upper part of the reactor, and 90% catalyst B (see).
    k a l and c a 4
    0.2
    85
    86
    84
    415
    B + 10% A 10 30 60 415 415 435
    SG + 10% A 190 435 230 445
    250 50 70 410
    4B + 10% A 415 420
    120 10 20 40 10 410
    5B + 10% A 410 410 410 410
    20 60 410 PRI me R 3, Association of catalysts A and B in optimal proportions, which can immediately extend the life of the desulfurization (desulfurizing) function, as well as hydroconversion, can be explained by a considerably smaller coke formation on catalyst B. This can be confirmed by the oxidative regeneration of catalysts B; alone or in a complex A + B system, under the same working conditions, with the same load and the same time. Regeneration is traditional and consists in using an air + nitrogen mixture, when the proportion of oxygen in the mixture varies from 3 to 20%. The regeneration start temperature is between 300 and the final temperature is between 450
    Continuation of table.4.
    five
    6 6
    6
    6
    7
    0.16
    6
    7
    7
    eight
    6
    7
    0.15
    five
    five
    6
    7
    five
    eight
    five
    four
    four
    3
    five
    four
    one
    2
    one
    one
    ABOUT
    2 and 550 ° C. During this operation, it is ensured that at no time does the temperature in the bed exceed 550 ° C. It has been found that in the case of a single catalyst. At the time of combustion more and the maximum observed temperature is equal. In the case of the A + B mixture, the time required for complete burning of the coke decreases and the maximum observed temperature decreases by. in tab. 5 shows the results of comparative regeneration. Table 5 After regeneration, it was found that the catalytic system contains the same amount of residual carbon. PRI me R A. A catalytic .5 layer is formed by a variable amount Example 5. The catalytic systems, including a 90% 5V hydroconversion catalyst and hydrodesulfurization catalysts of the following composition,%, are subjected to testing.
    A - CO 2.2. Mo 12 (Al20, CO, 5%
    SiO.2.)
    Table
    And, - WITH 2.2 Mo 12 (AljO with 1.255
    SiOy) A.- CO 2.2 Mo 12 (AljOs with 2.0 / 5
    SiOj)
    The test results are summarized.
    tab. 7, "
    Table 7 is for catalyst A, dispersed (in the upper part of the reactor and supplemented to 100 by the amount of catalyst B (see tab. 6).
    10 20 4.0 10 20 40
    90% 5B + 10% A
    90% 5B + 10% A,
    Continuation of table 7,
    95 94 94 95 94 94
    0.07
    4 3 3 4 3 3
    5 4 4 5 4 4
    0.13
    权利要求:
    Claims (2)
    [1]
    1. Catalytic system for hydroprocessing of petroleum fractions containing heavy n-paraffins, including a hydroconversion catalyst containing 4 masD of nickel or cobalt and 11 May.% Molybdenum on aluminosilicate carrier containing 10-60 wt.% Silicon dioxide and 4090 may,% of oxide aluminum, characterized in that, in order to increase stability, it additionally includes a hydrodesulphurisation catalyst containing 2.2 May. 2! cobalt and 12 may. £ molybdenum on alumina containing 0.52.0 wt.% Silica, in the following ratio of catalyst, wt.%:
    Hydroconversion catalyst, 50-90
    10-50 hydrodesulfurization catalyst
    [2]
    2. · Method for hydrotreating oil fractions containing heavy I-paraffins by treating oil fractions at 390–450 ° C with a volumetric flow rate of 1 • χΓ * at pressures of 30 bar and a molar ratio of hydrogen and hydrocarbon equal to 4 in the presence of a catalytic system comprising a hydroconversion catalyst containing 4 masD of nickel or cobalt, 11 wt.% molybdenum on an aluminosilicate carrier containing 10-60 wt.% silicon dioxide:
    'and 40-90 May. 7 aluminum oxide, characterized in that, in order to increase the fluidity of petroleum fractions, hydrotreatment is carried out in the presence of a catalytic system, further comprising a hydrodesulfurization catalyst containing 2.2 wt.% Cobalt and 12 wt.% Molybdenum on alumina containing 0, 5-2.0 wt.% & Silicon dioxide, with the following ratio of catalysts, May. %:
    hydroconversion catalyst 50-90
    The catalyst is hydro-.
    desulfurization 10-50
    however, both catalysts are used as separate layers, the hydrodesulfurization catalyst is located above the hydroconversion catalyst.
    one
    1 181522.
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    同族专利:
    公开号 | 公开日
    JPH0372676B2|1991-11-19|
    FR2482126A1|1981-11-13|
    IT1142018B|1986-10-08|
    GB2075358A|1981-11-18|
    JPS573887A|1982-01-09|
    IT8121575D0|1981-05-08|
    SE8102812L|1981-11-09|
    US4409130A|1983-10-11|
    GB2075358B|1984-09-05|
    DE3118352A1|1982-06-24|
    SE449756B|1987-05-18|
    FR2482126B1|1985-05-24|
    CA1160975A|1984-01-24|
    US4363719A|1982-12-14|
    NL8102241A|1981-12-01|
    BE888716A|1981-08-28|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    RU2444406C2|2008-12-18|2012-03-10|Ифп|Hydrodemetallation and hydrodesulphurisation catalysts and use in method for binding in one composition|US3431194A|1966-10-14|1969-03-04|Exxon Research Engineering Co|Process for lowering the pour point of a middle distillate|
    FR2017966A1|1968-08-14|1970-05-29|Chevron Res|Preparation of a catalyst for the hydrocracking of - hydrocarbons|
    US3684691A|1969-12-29|1972-08-15|William F Arey Jr|Dewaxing process wherein relatively small pore size crystalline aluminosilicate zeolites are used to chemically convert n-paraffins in hydrocarbon oils|
    US3804747A|1969-12-29|1974-04-16|Exxon Research Engineering Co|Hydrocarbon conversion with catalyst mixture of x and y zeolites|
    US3730878A|1971-03-04|1973-05-01|Universal Oil Prod Co|Hydrocarbon conversion catalyst|
    US4028223A|1974-11-08|1977-06-07|Uop Inc.|Guard beds in hydrocarbon conversion with an acidic multimetallic catalytic composite|
    US4054508A|1975-02-21|1977-10-18|Mobil Oil Corporation|Demetalation and desulfurization of residual oil utilizing hydrogen and trickle beds of catalysts in three zones|
    JPS5814257B2|1975-04-18|1983-03-18|Mitsubishi Petrochemical Co|
    US4057488A|1976-11-02|1977-11-08|Gulf Research & Development Company|Catalytic pour point reduction of petroleum hydrocarbon stocks|
    US4210521A|1977-05-04|1980-07-01|Mobil Oil Corporation|Catalytic upgrading of refractory hydrocarbon stocks|
    EP0018777B1|1979-05-02|1983-10-05|Mobil Oil Corporation|Catalytic upgrading of refractory hydrocarbon stocks|
    US4139493A|1977-08-03|1979-02-13|Union Oil Company Of California|Silica-promoted hydrofining catalyst and process|
    NL7713122A|1977-11-29|1979-05-31|Shell Int Research|PROCESS FOR THE PREPARATION OF HYDROCARBONS.|
    US4238316A|1978-07-06|1980-12-09|Atlantic Richfield Company|Two-stage catalytic process to produce lubricating oils|
    US4212771A|1978-08-08|1980-07-15|Exxon Research & Engineering Co.|Method of preparing an alumina catalyst support and catalyst comprising the support|US4773987A|1986-06-13|1988-09-27|Mobil Oil Corporation|Shape-selective conversion of organic feedstock using clathrate group tectosilicates|
    US4867862A|1987-04-20|1989-09-19|Chevron Research Company|Process for hydrodehazing hydrocracked lube oil base stocks|
    EP0367021B1|1988-10-19|1993-12-29|Research Association For Petroleum Alternatives Development|Process for hydrogenation of heavy oil|
    US5071805A|1989-05-10|1991-12-10|Chevron Research And Technology Company|Catalyst system for hydrotreating hydrocarbons|
    US4990243A|1989-05-10|1991-02-05|Chevron Research And Technology Company|Process for hydrodenitrogenating hydrocarbon oils|
    JP2567291B2|1990-03-28|1996-12-25|株式会社コスモ総合研究所|Hydroprocessing method for hydrocarbon oil|
    US5565086A|1994-11-01|1996-10-15|Exxon Research And Engineering Company|Catalyst combination for improved wax isomerization|
    US5865985A|1997-02-14|1999-02-02|Akzo Nobel Nv|Process for the production of diesel|
    EP0870817A1|1997-04-11|1998-10-14|Akzo Nobel N.V.|Process for effecting deep HDS of hydrocarbon feedstocks|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    FR8010307A|FR2482126B1|1980-05-08|1980-05-08|
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