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    1526927 Recovering vanadium from hydroconversion catalysts SHELL INTERNATIONALE RESEARCH MAATSCHAPPIJ BV 13 Oct 1975 [15 Oct 1974] 44604/74 Heading B1E [Also in Divisions Cl and C5] Vanadium and optionally nickel, is recovered from a catalyst which has become deactivated in a process in which a vanadiumcontaining hydrocarbon oil has been treated with hydrogen and the vanadium content of the catalyst has increased by at least 10 pbw per 100 pbw of catalyst carrier, the recovery of vanadium being achieved by extracting the deactivated catalyst with an aqueous solution of a mineral acid so as to reduce the vanadium content by at least 40% of the vanadium deposited during the catalytic treatment, the vanadium and possibly nickel are then isolated from the solution obtained. Mineral acid solutions exemplified are sulphuric: sulphurous and nitric acids. The catalysts may be any used conventionally in the treating of hydrocarbon oils with hydrogen, for example metal(s) with hydrogenating activity as a carrier, i.e. Ni, Co, Mo, W, V an alumina, silica on silica-alumina, or catalysts such as alumina or silica alone. These deactivated catalysts can be regenerated by removing as much of the Ni and V as is possible (if the catalyst required is to be free of these components) or by removing only enough of the Ni and V to obtain a catalyst containing desired quantities thereof. The regenerated catalyst can be used directly as such or after the addition of further amount of metals with hydrogenating activity.
    公开号:SU741780A3
    申请号:SU752182547
    申请日:1975-10-13
    公开日:1980-06-15
    发明作者:Хендрик Ван Донген Роберт；Воутер Коувенховен Герман
    申请人:Шелл Интернэшнл Рисерч Маатсхаппий Б.В. (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to methods for the regeneration of vanadium nickel-containing catalysts for the hydrodemetallization of crude oil. A known method for extracting vanadium from spent petroleum refining catalysts consists in treating the catalyst with hydrogen sulfide at 300-500 ° C and a pressure of 50 atm, then chlorine at 300-500 ° C and a pressure of 50 atm 1. The disadvantage of this method is the use of elevated temperatures and pressures gases that lead to catalyst deactivation. The closest to the invention is the method of regeneration of vanadium-nickel-containing catalyst for hydrometalization of crude oil containing vanadium and nickel impurities by removing from the treated catalyst deposited on it in the process of hydrodemetallization of vanadium and nickel by treatment with sulfuric acid followed by washing, drying and casting 2 The disadvantage of this method is the relatively low percentage of metal recovery from spent: g of catalyst. So this way you can extract only 45% vanschi, settled on the granules of the catalyst, which reduces the initial activity of the catalyst. In order to improve the degree of regeneration, before regeneration, the catalyst is pre-treated with water vapor at 200–550 ° C and treated with sulfuric acid at 50–200 ° C. As a result, the recovery rate of vanadium is increased by almost 2 times and is 84%. Example 1. A catcher, consisting of 0.5 parts by weight, is prepared. Nickel and 2.0 weight.h. Vanadium per 100 weight parts. silicon carrier as a result of impregnation of the silicon carrier with water: a nickel nitrate solution; and oxa ata vanadium, followed by drying and calcining the composition. The catalyst (catalyst A) is obtained in sulphide form for hydrodemetallization of hydrocarbon oil (oil A) having a total content of vanadium and nickel on the order of 62 tons, a Cg content of asphaltene 6.4 wt.% And a sulfur content of 3.9 wt.%, And this the oil is obtained as a residue from atmospheric distillation of Mid-West crude oil. Hydrodemetallization is carried out by passing the oil together with hydrogen through a cylindrical-vertically positioned fixed catalyst bed at a temperature of 420 ° C; a total pressure of 150 bar, a space velocity of 5 KGl per hour and a gas velocity (measured at the exit of the reactor) 250 IL Hj.-. The catalyst activity is 51 (vanadium removed,% to the average amount of vanadium removed at the rate of 1-4 ton / kg of catalyst). After the catalyst has been deactivated in this process, it is extracted with toluene to remove traces of residual oil and, after evaporation of the toluene, the catalyst is analyzed. Deactivated catalyst (catalyst B) contains 9.7 carbon, 20.6 sulfur, 4.1 nickel, and 24.3 parts by weight. Vanadium per 100 weight parts. flint Example 2. 50 g of the catalyst is subjected to extrusion for 2 hours with, under stirring, with 1.8 l of 2N sulfuric acid. After washing the extracted catalyst with 2 l of water, it is dried at and calcined for 3 hours at. As a result of the treatment, 45% of vanadium and 46% of nickel are removed from the catalyst. Example 3. The catalyst is treated in the same manner as in Example 2, instead of 1.8 g of 2N sulfuric acid, 1.8 l of water is used, which is saturated with dioxide of sulfur. Analysis shows that 48% of vanadium and 55% of nickel are recovered from the catalyst. Example 4. Catalyst B is treated as in Example 2, but sulfuric acid is precipitated with sulfur dioxide. Anaipiz shows that as a result of this treatment, 78% of vanadium and 81% of nickel are removed from the catalyst. Example 5. Catcher B is processed in the same way as in Example 2, but instead of 1.8 l of 2N sulfuric acid, 0.2 l of 2N sulfuric acid is used, which is saturated with sulfur dioxide. The analysis shows that as a result of this treatment, 8% of vanadium and 60% of nickel are removed from the catachiser. PRI m e. R b. Catalyst B is treated in the same manner as Example 4, but for 3 hours with steam treatment (steam pressure of 0.8 bar and nitrogen of 0.2 bar) before extraction with sulfuric acid. The analysis shows that as a result of this treatment, 7.9% nickel and 84% vanadium are obtained from the catalyst. Example 7. Catalyst B is treated as indicated in example 6 nd while the heater is heated with a current of air for 3 hours, between the steam treatment and the extraction with sulfuric acid. The analysis indicates that as a result of this treatment, 98% of nickel and 93% of vanadium are removed from the catalyst. Example 8. The catalyst is treated as described in example 2, but the catalyst is heated in a stream of air for 3 hours with sulfuric acid before extraction. Angshis indicates that as a result of this treatment, 97% of nickel and 81% of vanadium are removed from the catalyst. Example 9. The catalyst is treated as described in example 3, but the catalyst is heated in a stream of air for 3 hours at the time of extraction with water saturated with sulfur dioxide. Analysis indicates that 89% of vanadium and 94% of nickel are removed from the catalyst as a result of this treatment. Example 10. Catcher B is treated as indicated in Example 4, but the catalyst is heated in a stream of air for 3 hours at 550 ° C before extraction with sulfuric acid and sulfur dioxide. Analysis of the catalyst thus obtained (catalyst C) shows. that as a result of this treatment, 96% of vanadium and 95% of nickel are extracted from it. Example 11. Catalyst containing 0.5 weight.h. nickel and 2.0 weight, h, vanadium per 100 weight.h. silica carrier, prepared by impregnating catalyst C with an aqueous solution of vanadyl nickel oxalate nitrate, followed by drying and calcining the composition. The resulting catalyst (catalyst D) is used in a sulfide form to hydrodemetallize oil A under the same conditions as catalyst A in example 1. The activity of this catalyst, expressed as% vanadium removed, is 43. Example 12. Catalyst B is treated, as indicated in example 5, but in this case the catalyst is heated in a stream of air for 3 hours with sulfuric acid saturated with sulfuric acid before extraction. The analysis shows that by this treatment, 89% of vanadium and 89% of nickel are removed from the catalyst. Example 13. Catalyst B is treated as indicated in Example 12, but in this case, it is not washed with water after extraction with sulfuric acid and sulfur dioxide. The catalyst thus obtained (catalyst B), which contains iO, 8 parts by weight nickel and 4.9 weight.h. van; di per 100 weight.h. silicon carrier, is used in the sulfide form 1
    , the same conditions as in example 1. The catalyst activity, equal to% vanadium removed, is 41
    Example 14. Catalyst B is treated as indicated in Example J10, however, in this case, the catalyst is extracted for 2 hours at 909s, with stirring from 1.8 l of water in the interval between heating in air and extraction with sulfuric acid saturated with sulfur dioxide. The analysis shows that as a result of extraction with water, 74% of nickel and 2% of vanadium are removed from the catalyst, while as a result of extraction with sulfuric acid saturated with sulfur dioxide, 92% of vanadium and 23% of nickel are extracted additionally from the catalyst.
    Example 15. Catalyst B is treated as described in Example 9, however in this case the water is saturated with sulfur dioxide and the catalyst is extracted with a pressure of sulfur dioxide 3 bar. The analysis shows that as a result of this treatment, 90% of the vanadium and 91% of nickel are removed from the catalyst.
    Example 16. Catalyst B is treated as described in Example 12, however, in this case, the saturation of sulfuric acid with sulfur dioxide and the extraction of the catalyst is carried out under a pressure of sulfur dioxide 2 bar. The analysis shows that by this treatment, 91% of vanadium and 89% of nickel are removed from the catalyst.
    Example 17. The procedure is similar to Example 1, however, in this case, instead of extracting the deactivated catalyst with toluene, the catalyst is treated with steam for 1 hour at; 150 ° C and a vapor pressure of 1.5 bar to remove traces of residual oil. The deactivated catalyst (catalyst F) is treated as in Example 12. The analysis shows that as a result of this treatment, 85% of vanadium and 87% of nickel are removed from the catalyst.
    Example 18. Catalyst B is treated as indicated in Example 11, however, in this case, instead of 1.8 l of 2N sulfuric acid, 1.8 l of a 10% aqueous solution of nitric acid is used. The analysis shows that as a result of this treatment, 97% of vanadium and 96% of nickel are removed from the catalyst.
    Example 19. The catalyst containing 1 weight.h. nickel and 4 weight parts molybdenum per 100 weight.h. aluminum, prepared by impregnating the aluminum carrier with an aqueous solution of nickel nitrate and ammonium olibdate, followed by drying and calcining the composition. The resulting catalyst (catalyst G) is used in sulphide form for
    hydrodemetallization of oil A under the same conditions as in Example 1. The catalyst activity, expressed in% vanadium removed, is 52. The deactivated catalyst is extracted with toluene to remove traces of residual oil and after evaporation of toluene from the catalyst it contains 35.5 carbon, 45.0 sulfur, 9.6 nickel, 81 vanadium and 4.0 wt.h. molybdenum per 100 weight.h. aluminum (catalyst H).
    Example 20. Catalyst. It is treated as indicated in Example 9. Catalyst O is obtained. Analysis shows that as a result of this treatment, 64% of vanadium, 21% of nickel and 23% of molybdenum are removed from the catalyst.
    Example 21. A catalyst;}, consisting of silicon oxide, is used for hydrodemetallization of crude hydrocarbon fuel, the vanadium content of which is 1190, nickel 107 million and sulfur, 5.53 wt.%. Hydrodemetalization-Osuk ec is emitted by passing fuel along with hydrogen from top to bottom through a cylindrical vertically fixed catalyst bed located tipK temperature 410С, total pressure 160 bar, spatial velocity Tfi 2.0 kg-kg and at a feed rate of hydrogen to a fresh batch equal to 1000 l / kg The liquid effluent recirculates in the ratio of 24 kg of recycled liquid per 1 kg of the injected substance. The activity of catalyst 3, which is expressed as the rate constant of first order vanadium extraction, is in kg. kg, hour (K) ice falls; K at 20 pbw per 100 pbw of silica deposited on the catalyst is given as a measure of vanadium recovery activity. The experiment with catalyst 3 is interrupted at a time when about 32 pbw of vanadium precipitated onto 100 pbw of silicon oxide, after which the spent catalyst is regenerated by treating it with steam at 350 ° C and a pressure of 3 bar for 5 hours, after which four extractions are carried out, each with 1 hour, 1.2 M at, washed with water and dried in air at. The activity of the regenerated catalyst (catalyst K) is determined as described above. The K catalyst K slowly falls and after 88 pbw of vanadium has settled, the experiment is interrupted and the spent catalyst K is regenerated. The catalyst L thus obtained is again used in hydrodemetallization. After precipitation of 32 pbw of vanadium per 100 pbw of silicon oxide, the experiment is interrupted, and at this point no decrease in Q is noted.
    Example 22. 5 kg of catalyst B are treated with steam for 5 hours at a pressure of 6 bar and a rate of 2.6 kg of steam (kg of catalyst), for an hour. Then katgshizator extracted for 2 hours at 90 ° C with stirring 40 l of 2N sulfuric acid. After extraction, the catalyst is washed with water and dried at 120 ° C. In the case of the angshise, the catalyst thus obtained (catalyst M) recovers 93% of vanadium and 57% of nickel.
    Catalyst N, containing nickel, 2.0 pbw of nickel, 2.0 pbw of vanadium per 100 pbw of silicon oxide substrate, is obtained by impregnating the catalyst with M aq {A4) vanadium oxalate solution, after which the resulting composition is dried. Catalyst N is used to control the oil A in the same manner as in Example 1. The catalyst activity, expressed as% of vanadium extracted, is 49.
    权利要求:
    Claims (2)
    [1]
    1. Authors certificate of the USSR 0 263569, cl. In 01 3 11/02, published
    1969.
    [2]
    2. Japanese Patent 22806, cl. 152, published. 1970 (prototype).
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    同族专利:
    公开号 | 公开日
    SE410474B|1979-10-15|
    AR224854A1|1982-01-29|
    GB1526927A|1978-10-04|
    FR2288154B1|1980-07-25|
    NL186587C|1991-01-02|
    ZA756443B|1976-09-29|
    JPS5164412A|1976-06-03|
    NO143521B|1980-11-24|
    NL7511993A|1976-04-21|
    JPS6012908B2|1985-04-04|
    AU498495B2|1979-03-15|
    DE2545787A1|1976-04-29|
    CA1071413A|1980-02-12|
    NL186587B|1990-08-01|
    FR2288154A1|1976-05-14|
    SE7511450L|1976-04-20|
    DE2545787C2|1989-08-03|
    IT1043322B|1980-02-20|
    AU8566975A|1977-04-21|
    NO143521C|1981-03-04|
    NO753452L|1976-04-21|
    MX3049E|1980-03-04|
    BE834257A|1976-04-07|
    引用文献:
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    US3791989A|1971-03-12|1974-02-12|Chevron Res|Catalyst rejuvenation with oxalic acid|
    JPS4923447A|1972-06-27|1974-03-01|NL7703181A|1977-03-24|1978-09-26|Shell Int Research|IMPROVED METHOD FOR RECOVERING VANADIUM FROM DEACTIVATED CATALYSTS.|
    NL7703180A|1977-03-24|1978-09-26|Shell Int Research|IMPROVED METHOD FOR RECOVERING VANADIUM FROM DEACTIVATED CATALYSTS.|
    US4272401A|1978-09-01|1981-06-09|Exxon Research & Engineering Co.|Regeneration of spent hydrodesulfurization catalyst with heteropoly acids|
    CA1163810A|1980-02-20|1984-03-20|Petrus J.W.M. Van Den Bosch|Process for the removal of vanadium-containing acidfrom an acid-extracted deactivated demetallizationcatalyst|
    US4595666A|1981-11-02|1986-06-17|Hri, Inc.|Catalyst rejuvenation process for removal of metal contaminants|
    US4454240A|1981-11-02|1984-06-12|Hri, Inc.|Catalyst regeneration process including metal contaminants removal|
    DE3460144D1|1983-04-01|1986-06-26|Monsanto Co|Recovery of vanadium and copper from adipic acid production|
    DD239348A5|1985-07-19|1986-09-24|Institut Metallurgii I Obogaschenia Akademmii Nauk Kazakhskoi Ssr,Su|PROCESS FOR PROCESSING VANADIN-CONTAINING ALTAT CATALYSTS|
    CA1293380C|1985-12-11|1991-12-24|Just Jan Christiaan Jansz|Vanadium recovery process|
    GB8610442D0|1986-04-29|1986-06-04|Shell Int Research|Regeneration of spent alumina-based catalysts|
    FR2614613B1|1987-04-29|1989-06-09|Rhone Poulenc Chimie|VANADIUM RECOVERY PROCESS|
    US5254513A|1991-05-20|1993-10-19|Texaco, Inc.|Method for the reactivation of spent alumina-supported hydrotreating catalysts|
    US5230791A|1991-07-03|1993-07-27|Texaco Inc.|Process for the reactivation of spent alumina-supported hydrotreating catalysts|
    DE4216798A1|1992-05-21|1993-11-25|Metallgesellschaft Ag|Process for processing residues containing vanadium|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    GB44604/74A|GB1526927A|1974-10-15|1974-10-15|Process for recovering vanadium from deactivated catalyst|
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