JPS637819B2 - - Google Patents

Description

[Detailed description of the invention] The present invention is disclosed in Japanese Patent No. 1294161 (Japanese Patent Publication No. 60-12908).
This is an additional invention to the invention of No.), and the original invention contains nickel, which is used in the hydrogenation demetalization operation of vanadium-containing hydrocarbon oil and is inactivated by losing its activity, and vanadium and/or molybdenum. The present invention relates to a method for regenerating a deactivated catalyst. The hydrodemetallization operation described above generally consists of treating a vanadium-containing hydrocarbon oil with hydrogen in the presence of the catalyst at elevated temperature and pressure.

According to the method of the original invention, the original invention provides a catalyst that is deactivated by use in treating a vanadium-containing hydrocarbon oil with hydrogen at elevated temperature and pressure, the vanadium content of the catalyst being deactivated during said treatment. Vanadium is extracted from the catalyst whose amount has increased by at least 10 parts by weight. According to the method of the original invention, the vanadium content of the catalyst increases by at least the amount increased during the inactivation.
The extraction of vanadium, which is reduced by 40%, is carried out by extracting the deactivated catalyst with an aqueous solution of mineral acid and then separating the vanadium from the vanadium-containing solution thus obtained. If the method
If applied to a deactivated catalyst in the hydrogenation treatment of hydrocarbon oils containing nickel in addition to vanadium, during which treatment the nickel content of the catalyst also increased, nickel is also present. In the process it is removed from the catalyst. Besides extracting vanadium and optionally nickel from deactivated catalysts, the method can also be applied to regenerate deactivated catalysts so that they can be used again for catalytic purposes.

According to the method of the original invention, the acid extraction is preferably carried out in the presence of a reducing agent. It is also more preferred, according to the method of the invention, that before carrying out the acid extraction, the deactivated catalyst is first treated with steam to remove sulfur and then with an oxygen-containing gas to remove carbon. Original invention of treating a small portion of the deactivated catalyst with air at 550° C. for 3 hours when the intended purpose is not only to extract vanadium and optionally nickel from the catalyst, but also to regenerate the catalyst. It should be noted that treating the deactivated catalyst with an oxygen-containing gas in the manner described in the example is not suitable in the case of relatively large amounts of deactivated catalyst because of the large amount of heat generated. be.

If a relatively large amount of deactivated catalyst had to be treated for the purpose of extracting vanadium and optionally nickel from the catalyst and for regenerating the catalyst, the following three-step operation was carried out according to the method of the invention. Until recently, this was considered to be the most attractive implementation. The deactivated catalyst was first treated with a mixture of steam and nitrogen for 1-5 hours at 350-450°C atmospheric pressure, then with a mixture of air and nitrogen for 1-5 days at 350-600°C atmospheric pressure, and finally in the presence of reducing agent
Acid extraction for 0.5-3 hours at 50-150°C. The processing times required in those various stages are, inter alia,
It depends on the amount of sulfur, carbon, and metals present on the deactivated catalyst, as well as on the selected processing conditions, ie, processing temperature, gas flow rate, and composition of the processing gas and extraction liquid. Until now, the long processing time required for the second stage of the three-stage operation was considered to be a significant drawback when using the process of the invention on a commercial scale.

By continuing to study the process as in the original invention, results comparable to those achieved in terms of vanadium and nickel removal and the activity of the regenerated catalyst by carrying out the three-stage process but in a much shorter time. treatment of the deactivated catalyst with a mixture of steam and air with a steam/air ratio greater than 1.0 at a temperature of at least 350° C. and a steam partial pressure of more than 1 bar, followed by the acid extraction in the presence of a reducing agent. I have recently discovered that if you do it first, you can get it. In addition to the fact that using the now discovered process, much shorter processing times are sufficient to achieve comparable results in terms of vanadium and nickel removal and the activity of the regenerated catalyst, the process It has two additional advantages over the three-step operation, in that the number of gases and the number of gases required to treat the deactivated catalyst prior to acid extraction are both reduced by one.

Therefore, the present invention provides a deactivated catalyst containing nickel and vanadium and/or molybdenum which has lost its activity and has been deactivated by being used in the hydrodemetalization operation of vanadium-containing hydrocarbon oil. a) treated with an oxygen-containing gas and/or water vapor at a temperature of at least 350°C, and then (b) at least
A method for regenerating a deactivated catalyst, which comprises treating with an aqueous mineral acid solution at a temperature of 50° C. (referred to as "acid extraction") and isolating the catalyst thus regenerated from the vanadium-containing solution obtained therein. the above
(a) is carried out with a mixture of water vapor and air at a temperature of at least 350°C and a steam/air ratio greater than 1.0 at a water vapor partial pressure of more than 1 bar; and (b) is carried out at a temperature of at least 50°C.
The regeneration method is carried out with an aqueous mineral acid solution in the presence of a reducing agent at a temperature of .

In the process according to the invention, the treatment with the mixture of steam and air should be carried out at a temperature of at least 350°C, but preferably below 600°C, in particular at a temperature of 350 to 425°C. In the treatment of the deactivated catalyst with the mixture of steam and air, the partial pressure of steam is greater than 1 bar but preferably less than 5 bar, especially between 2 and 4 bar.
Should be a crowbar. The water vapor/air mixture used has a water vapor/air ratio greater than 1.0;
However, it should preferably be less than 10 and especially between 4 and 8.

The acid extraction in the presence of a reducing agent, with which the deactivated catalyst is to be treated in the process according to the invention, is preferably carried out at elevated temperature, in particular above 50°C.
The extraction is preferably carried out with an aqueous solution of sulfuric acid saturated with sulfur dioxide.

If the process according to the invention is applied to deactivated catalysts containing nickel in addition to vanadium, it is preferred to extract the deactivated catalyst with water after treatment with a steam/air mixture. This extraction with water, more preferably carried out at elevated temperature, especially above 50° C., results in an aqueous nickel-containing solution from which nickel can be extracted.

The process according to the invention not only aims to extract vanadium and optionally nickel from a deactivated catalyst, but also to extract said catalyst (in fresh, hydrogenated activated form) so that it can be used again for catalytic purposes. This is particularly important if the purpose is also to regenerate metals (containing metals with The present invention therefore not only relates to a method for extracting vanadium and optionally nickel from deactivated catalysts, but also to redirecting this extraction to catalytic purposes, either as such or after addition of supplementary amounts of hydrogenation-active metals. The invention also relates to a method for obtaining a regenerated catalyst that can be used.

The invention will be described in connection with the following examples.

Example: A catalyst containing 0.5 parts by weight of nickel and 2.0 parts by weight of vanadium per 100 parts by weight of silica support was prepared by impregnating the silica support with an aqueous solution of nickel nitrate and vanadyl oxalate and then drying and calcining the composition. . The catalyst (catalyst A) had a total vanadium and nickel content of 62 ppmw, a _C5 -asphaltenes content of 6.4%w, and a sulfur content of 3.9%w.
was used in the sulfide form for the hydrodemetalization of a hydrocarbon oil (oil A) having 1000 ml of oil, which was obtained as a residual oil in the atmospheric distillation of Middle Eastern crude oil. The hydrodemetallization was carried out by transferring the oil together with hydrogen in a downward direction onto a cylindrical vertically arranged fixed catalyst bed at a temperature of 420° C., a total pressure of 150 bar, 5 Kg, l ^-1 , h ^-1 This was carried out by passing at a space velocity of , and a gas flow rate (measured at the outlet of the reactor) of 250 NlH ₂ ·Kg ^-1 . “Vanadium Removal%” (1 ton oil/1 Kg catalyst
The activity of the catalyst, expressed as average vanadium removal over the aging period of 4 tons of oil/Kg of catalyst, was 51. After the catalyst was deactivated in this manner, it was extracted with toluene to remove the remnants in the residual oil, and the catalyst was analyzed after evaporation of the toluene from the catalyst. This deactivated catalyst (catalyst B) contained 9.7 parts by weight of carbon,
20.6 parts by weight of sulfur, 4.1 parts by weight of nickel, and
It contained 24.3 parts by weight of vanadium per 100 parts by weight of silica.

EXAMPLE 5 Kg of catalyst B were treated with a 4:1 steam/nitrogen mixture for 3 hours at 350° C., atmospheric pressure and a gas flow rate of 2 Nl gas mixture (g catalyst) ⁻¹ h ⁻¹ . The catalyst was then heated at 400°C in a 1:19 air/nitrogen mixture.
Atmospheric pressure and gas flow rate 1Nl gas mixture (g catalyst)
^-1 h ^-1 for 50 hours. Finally, the catalyst was extracted with 402N sulfuric acid saturated with sulfur dioxide for 2 hours at 90° C. with stirring. After washing the extraction catalyst with water, it was dried at 120℃ and then dried at 550℃.
It was baked at ℃ for 3 hours. The catalyst thus obtained (catalyst C) was analyzed and found to contain 96% vanadium and 95% vanadium.
It was found that % of nickel was removed from the catalyst by this treatment.

EXAMPLE 5 Kg of catalyst B were treated with a 7:1 steam/air mixture for 25 hours at 400 DEG C., a steam partial pressure of 3.5 bar and a gas flow rate of 0.6 Nl gas mixture (g catalyst) ^-1 h ^-1 . The catalyst was then extracted with 402N sulfuric acid saturated with sulfur dioxide for 2 hours at 90°C with stirring. After washing the extraction catalyst with water,
It was dried at 120°C and calcined at 550°C for 3 hours. The catalyst thus obtained (catalyst D) was analyzed and 96
It was found that % vanadium and 95% nickel were removed from the catalyst by this treatment.

Example 5 Kg of catalyst B were treated with a 5:1 steam/air mixture for 20 hours at 350° C., steam partial pressure 3.0 bar and gas flow rate 0.6 Nl gas mixture (g catalyst) ^-1 h ^-1 . The catalyst was then acid extracted in the same manner as described in the example. The catalyst thus obtained (catalyst E) was analyzed and found to contain 94% vanadium and 92% vanadium.
It was found that % of nickel was removed from the catalyst by this treatment.

EXAMPLE 5 Kg of catalyst B were treated with a 1:2 steam/air mixture for 20 hours at 400 DEG C., a steam partial pressure of 0.6 bar and a gas flow rate of 0.4 Nl gas mixture (g catalyst) ^-1 h ^-1 . The catalyst was then acid extracted in the same manner as described in the example. The catalyst thus obtained (catalyst F) was analyzed and found to contain 95% vanadium and 95% vanadium.
It was found that % of nickel was removed from the catalyst by this treatment.

EXAMPLE 5 Kg of catalyst B were treated with a 2:1 steam/air mixture for 25 hours at 150 DEG C., a steam partial pressure of 1.5 bar and a gas flow rate of 2 Nl gas mixture (g catalyst) ^-1 h ^-1 . The catalyst was then acid extracted in the same manner as described in the example. Analysis of the catalyst thus obtained (Catalyst G) showed that 40% vanadium and 45% nickel were removed from the catalyst by this treatment.

Example: A catalyst containing 0.5 parts by weight of nickel and 2.0 parts by weight of vanadium per 100 parts by weight of silica support,
Catalysts C and F were prepared by impregnating with an aqueous solution of nickel nitrate and vanadyl oxalate and then drying and calcining the composition. Catalysts C′ and F′ thus obtained were used for the hydrodemetallization of oil A in the form of sulfides under the same conditions as for the hydrodemetallization of this oil using catalyst A as described in the example. Using. Catalyst C′ expressed as “percentage vanadium removal” and
The activities of F' were 48 and 10, respectively.

Example In the same way as described in the example, the catalyst
D' and E' were prepared from catalysts D and E and used for the hydrodemetallization of Oil A. The activities of catalysts D' and E' expressed as "percent vanadium removed" were 50 and 49, respectively.

Examples - Examples, and are examples according to the present invention. Other examples were included for comparison.

The example concerns hydrodemetallization of fresh catalyst A to deactivate catalyst B.

The example relates to the three-stage operation described above in which regenerated catalyst C is prepared from deactivated catalyst B and the first two stages are carried out over a total of 53 hours.

The examples and examples relate to an improved process according to the invention for producing regenerated catalysts D and E from deactivated catalyst B.

Comparing Examples, and, it can be seen that the process according to the invention provides the same excellent metal removal as the three-step operation. However, treatment with a steam/air mixture replacing the first and second stages of the three-stage operation takes only 20-25 hours.

The examples and examples relate to the treatment of deactivated catalysts with a mixture of steam and air and subsequent acid extraction to produce "regenerated catalysts" F and G from deactivated catalyst B. During the treatment with the steam/air mixture, the steam partial pressure and the steam/air ratio used were too low in the examples and the temperatures were too low in the examples. This resulted in insufficient metal removal (and resulting low activity) for Catalyst G and, as can be seen from the example, low activity for Catalyst F.

It can be seen from the examples and that the catalysts regenerated according to the invention (catalysts D' and E') exhibit the same high activity as the catalyst regenerated by the three-stage operation (catalyst C').

Additional Relationships The original invention (Patent No. 1294161, invention of Japanese Patent Publication No. 1294161, 1983-12908) is ``Nickel and vanadium and/or which have been used in the hydrogenation demetalization operation of vanadium-containing hydrocarbon oil and have lost their activity and have been inactivated. (a) with an oxygen-containing gas and/or steam at a temperature of at least 350°C; and (b) with an aqueous mineral acid solution at a temperature of at least 50°C. The thus regenerated catalyst is
``A method for regenerating a deactivated catalyst comprising isolating it from the vanadium-containing solution obtained therein'' is all essential to the structure of the invention, and the present invention considers this point to be an essential feature of the invention. 31 of the Patent Act, as the present invention achieves the same purpose as the original invention in terms of regenerating a deactivated catalyst.
It satisfies the requirements stipulated in Article 1.

Claims (1)

[Scope of Claims] 1. A deactivated catalyst containing nickel and vanadium and/or molybdenum that has lost its activity and has been inactivated by being used in the hydrodemetallization operation of vanadium-containing hydrocarbon oil, (a) treated with an oxygen-containing gas and/or water vapor at a temperature of at least 350°C, and then (b) treated with an aqueous mineral acid solution at a temperature of at least 50°C (referred to as "acid extraction"), and thus regenerated. A method for regenerating a deactivated catalyst comprising isolating the catalyst from the vanadium-containing solution obtained therein, comprising at least the treatment of (a) above.
carried out in a mixture of water vapor and air with a water vapor/air ratio greater than 1.0 at a temperature of 350 °C and a water vapor partial pressure greater than 1 bar, and
The regeneration method as described above, characterized in that the treatment (b) is carried out with an aqueous mineral acid solution at a temperature of at least 50° C. in the presence of a reducing agent. 2. Treatment of the deactivated catalyst with a mixture of steam and air at a temperature below 600°C, preferably between 350°C and
The method according to claim 1, characterized in that it is carried out at 425°C. 3. According to claim 1 or 2, the treatment of the deactivated catalyst with a mixture of steam and air is carried out at a steam partial pressure of less than 5 bar, preferably between 2 and 4 bar. the method of. 4. Claims 1 to 3, characterized in that the treatment of the deactivated catalyst with a mixture of steam and air is carried out with a gas mixture in which the steam/air ratio is less than 10, in particular from 4 to 8. The method described in any one of the above. 5 Acid extraction in the presence of a reducing agent preferably at elevated temperature
5. Process according to any one of claims 1 to 4, characterized in that it is carried out at a temperature higher than 50<0>C. 6. Process according to any one of claims 1 to 5, characterized in that the acid extraction in the presence of a reducing agent is carried out with an aqueous solution of sulfuric acid saturated with sulfur dioxide. 7. After treating the deactivated catalyst with a steam/air mixture, the nickel is removed from the deactivated catalyst by extraction with water, preferably at elevated temperatures, in particular at temperatures above 50°C. 1
- the method according to any one of clause 6. 8. Any of claims 1 to 7, characterized in that it is carried out in such a way that a regenerated catalyst is obtained which can be used again for catalytic purposes as is or after addition of a supplementary amount of hydrogenation-active metal. The method described in paragraph (1).