• 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 process for the removal of vanadium-containing aqueous solution of an acid from a deactivated demetallization catalyst, in particular a silica based one used for hydrodemetallization of a residual oil, from which catalyst vanadium deposited thereon has been extracted with the aid of an aqueous solution of said acid, in which process the catalyst is washed with water or an aqueous solution of an acid, in particular sulphuric acid, until the vanadium-containing solution is substantially removed, which washing procedure is carried out in a fluidized bed in case the washing liquid has a pH greater than two.
    公开号:SU1169521A3
    申请号:SU813286601
    申请日:1981-02-18
    公开日:1985-07-23
    发明作者:Йоханнес Вальтерус Мария Ван Ден Босх Петрус；Мебур Боб
    申请人:Шелл Интернэшнл "Рисеч Маатсхаппий Б.В." (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to a method for removing an aqueous vanadium-containing acid solution from a catalyst that has lost its activity to extract a metal, and that the vanadium deposited on this catalyst is extracted with an aqueous solution of said acid. The purpose of the invention is to prevent the catalyst particles from sticking together by using demineralized water or an aqueous solution of sulfuric acid as the washing liquid and carrying out the washing under certain conditions. Example 1 (comparative). The catalyst containing 0.5 wt. nickel dioxide and 2.0 parts by weight Vanadium per 100 weight parts. silica as a carrier, is prepared by impregnating silicon dioxide - the nose of the bodies with an aqueous solution of nickel nitrate and vanadium oxalate, followed by drying and calcining the composition. The catalyst is used in the sulfide form to remove the metal in the presence of hydrogen from a hydrocarbon oil that has an effective content of vanadium and nickel of 6/2 ppm, a C-asphaltenes content of 6.4 wt.% And sulfur of 3.9 wt. Such an oil was obtained as a residue, by atmospheric distillation with medium-eastern oil. The removal of metal in the presence of hydrogen is carried out by passing the oil along with hydrogen along the direction from top to bottom through a vertically positioned cylindrical stationary packed catalyst bed at 420 ° C, total pressure, 150 bar, 5 km-l volumetric velocity and gas velocity (measured at reactor) 230. After the catalyst has lost its activity during this process, the catalyst is removed, stored in heavy gas oil and analyzed. The catalyst, deactivated by oil (catalyst A), contains, wt%: carbon 9.7j sulfur 20.6} nickel 4.1 and vanadium 24.3 per 100 weight.h. silicon dioxide. Oil was removed from 500 g of catalyst A for 14 hours at 35 ° F, a pressure of 3.3 bar and a gas flow rate of 0.5 nl of nitrogen / g of catalyst / h. Then the catalyst was treated with steam for 7 hours at a pressure of 2.8 bar and feed rate of 1.25 nl para- / g cat- a lysator / h. After cooling under nitrogen, the catalyst is extracted for 7 hours at 0.6 L of a 2 N solution of sulfuric acid / kg of catalyst / h. Then the catalyst is rinsed in a fixed bed for 7 hours at 70 ° C with 0.6 l of demineralized water (catalyst / h). After this treatment, it is observed that the removal of the catalyst from the tank in which the extraction is performed is very difficult due to the formation of solid clots in the catalyst mass. According to the analysis, as a result of this treatment, 70% of vanadium and 30% of nickel are removed from the composition of the catalyst. EXAMPLE 2 Catalyst A is treated analogously to Example 1 with the difference that, after extraction with a 2 N solution of sulfuric acid, the catalyst npbfff — is housed for 7 hours at 70 ° C with 0.6 l of demineralized water (pH, f 7 / kg of catalyst / h ), and the catalyst is kept in suspension by circulating 50 liters of demineralized water (pH 7 / kg catalyst / h). After this treatment, the entire mass of the catalyst has free flow. According to the analysis of the catalyst. 90% vanadium and 40% nickel are extracted. EXAMPLE 3 Catalyst A on-j is prepared as in Example 1 with the difference that after extraction with 2 N sulfuric acid solution, the catalyst is washed in a fixed bed for 7 hours at 0.6 liter of 2 N sulfuric acid solution (pH 7 / kg of catalyst / h), then washed for 7 hours at 70 ° C with 0.6 l of demineralized water (pH 7 of catalyst / h). After this treatment, the entire mass of the catalyst has free flow. According to the analysis, 92% of vanadium and 47% of nickel were extracted from the catalyst. PRI me R 4 (comparative). Catalyst A is treated analogously to Example 1 with the difference that after extraction with 2 N aqueous sulfuric acid, the catalyst is washed in a fixed bed for 7 hours at 70 ° C with 0.6 l of approximately 0.001 N aqueous 3
    sulfuric acid solution (catalyst / h) and then washed for 7 h with 0.6 l of demineralized water (catalyst / h). After the treatment, it was found that it was very difficult to remove the catalyst from the extraction vessel. agglomerated.
    Example 5. Catalyst A is treated as in Example 1 with the only difference that after extraction with 2 N sulfuric acid solution, the catalyst is flashed for 7 hours at 0.6 l 0.00001 N sulfuric acid (catalyst / h), while maintaining the catalyst in a fluidized state due to the circulation of 50 liters of 0.00001 N sulfuric acid (kg / catalyst / h). After
    21. 4
    By such treatment, the catalytic mass is capable of free flow.
    According to analysis, 93% of vanadium and 41% of nickel were removed from the catalyst.
    EXAMPLE 6 Catalyst A is treated as in Example 1 with the only difference that, after extraction with 2 N sulfuric acid, the catalyst is fixed in a fixed bed state for 7 hours at 0.6 l 0.02 N sulfuric acid. acids, 7 / kg of catalyst / h and then flush for 7 hours at 70 ° C with 0.6 l of demineralized water (kg / catalyst / h). After such treatment, the entire catalytic mass is capable of free flow.
    According to the analysis, 91% of vanadium and 45% of nickel were removed from the catalyst.
    权利要求:
    Claims (3)
    [1]
    1. METHOD FOR REMOVING VANADIUM-CONTAINING AQUEOUS 'ACID SOLUTION FROM THE DEACTIVATED DEMETALLIZATION CATALYST by extracting vanadium that has precipitated on it during hydrodemetallization with sulfuric acid and subsequent washing with a liquid, which is used to prevent the particles from rinsing with the purpose of rinsing with liquid demineralized water or 0.00001-0.2 N aqueous solution of sulfuric acid, and when the pH value of the washing liquid is 3-7, washing is carried out until water will not pass through the catalyst to maintain the catalyst particles in a liquid in suspension, using a sulfuric acid wash is carried out in a fixed bed of catalyst followed by removal of acid by washing with water.
    [2]
    2. The method according to claim 1, characterized in that apply 2 N aqueous solution of sulfuric acid.
    [3]
    3. The method of pop. G, characterized in that the washing of the catalyst with water or an aqueous solution of acid is carried out at 70 ° C.
    "SUm 1169521
    1 1169521
    类似技术:
    公开号 | 公开日 | 专利标题
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    同族专利:
    公开号 | 公开日
    JPS56134519A|1981-10-21|
    AR227414A1|1982-10-29|
    EP0034853A1|1981-09-02|
    JPH0323215B2|1991-03-28|
    NO154335C|1986-09-03|
    AU6740481A|1981-08-27|
    MX157081A|1988-10-27|
    CA1163810A|1984-03-20|
    ZA811068B|1982-03-31|
    AU550601B2|1986-03-27|
    DE3164491D1|1984-08-09|
    SG67984G|1985-03-15|
    EP0034853B1|1984-07-04|
    NO154335B|1986-05-26|
    NO810545L|1981-08-21|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    GB767122A|1954-03-08|1957-01-30|British Petroleum Co|Improvements relating to the removal of vanadium and/or sodium from petroleum hydrocarbons|
    NL175732C|1972-07-07|Shell Int Research|PROCEDURE FOR THE CATALYTIC DEMETALLIZATION OF RESIDUAL HYDROCARBON OILS AND THE FURTHER CATALYTIC CONVERSION OF THE OIL OBTAINED THEREIN.|
    GB1526927A|1974-10-15|1978-10-04|Shell Int Research|Process for recovering vanadium from deactivated catalyst|
    NL187026C|1976-07-08|1991-05-01|Shell Int Research|METHOD FOR THE METALIZATION OF HYDROCARBON OILS.|
    NL7703181A|1977-03-24|1978-09-26|Shell Int Research|IMPROVED METHOD FOR RECOVERING VANADIUM FROM DEACTIVATED CATALYSTS.|
    US4089806A|1977-04-01|1978-05-16|Union Oil Company Of California|Method for rejuvenating hydroprocessing catalysts|US4454240A|1981-11-02|1984-06-12|Hri, Inc.|Catalyst regeneration process including metal contaminants removal|
    US4818373A|1984-10-19|1989-04-04|Engelhard Corporation|Process for upgrading tar and bitumen|
    US4863884A|1987-04-09|1989-09-05|Hri, Inc.|Method for rejuvenating used catalysts|
    DE19628212B4|1996-07-12|2008-06-05|Enbw Energy Solutions Gmbh|Process for purifying and / or regenerating completely or partially deactivated catalysts for denitrification of flue gases|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    GB8005758|1980-02-20|
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