JPH0122320B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for demetallizing hydrocarbon oil by contacting the hydrocarbon oil with a catalyst in the presence of hydrogen at elevated temperature and pressure. High-boiling hydrocarbon oils, such as residual oils obtained from the distillation of crude oil at atmospheric or reduced pressure, as well as certain heavy crude oils, especially those from South America, contain significant amounts of high molecular weight, non-distillable compounds; These include, for example, asphaltenes and metal compounds, especially vanadium and nickel compounds. The use of these high-boiling hydrocarbon oils as feeds for catalytic processes, such as cracking, hydrocracking and hydrodeflowing,
Metals such as vanadium and nickel are deposited on the catalyst particles. The increase in vanadium and nickel concentration in the active position of the catalyst results in rapid deactivation of the catalyst. In order to increase the lifetime of the catalyst, it has already been proposed to remove metals from the feed before contacting the feed with a metal-sensitive catalyst. This may be accomplished by contacting the feed with a suitable demetalization catalyst in the presence of hydrogen at elevated temperature and pressure. For this purpose, various catalysts consisting of porous materials of one or more metals with hydrogenation activity have already been proposed. Total vanadium and nickel content with the help of a catalyst with a surface area of at most 100 m ² /g
Research in this application on the hydrodemetallization of hydrocarbon oils above 350 ppmw has shown that a good catalyst for this purpose must meet several requirements regarding porosity and particle size. These requirements depend somewhat on the hydrogen partial pressure at which the hydrodemetallization is carried out. Catalysts within the scope of this patent application that are suitable for the hydrodemetalization of hydrocarbon oils with a total vanadium and nickel content of 350 ppmw or more are such that the demetalization activity of the catalyst is at a sufficiently high level when half of the catalyst life has elapsed. and has a sufficiently high metal uptake capacity. Total vanadium and nickel content with the help of a catalyst with a surface area of at most 100 m ² /g
It has been found that for catalytic hydrodemetalization of hydrocarbon oils of 350 ppmw and above, the requirements regarding porosity and particle size that a good catalyst should meet are as follows. The catalyst should have a total pore volume (V _T ) of at least 0.2 ml/g and a specific average particle diameter (d) of at least 0.4 mm and at most 5 mm. In addition, the catalyst has the following requirements: [In the formula, P _H2 is the hydrogen partial pressure used (P ^* is
nm, d in mm, V _T in ml/g, P _H2 in bars)], the average pore diameter (P ^* ), V _T and d
should have. The above values of d and P ^* were defined as follows based on their measurement methods. The method for measuring d differs depending on the shape of the catalyst particles. In the case of catalyst particles having such a shape that the diameter distribution of the catalyst particles can be determined by sieve analysis,
d is measured as follows. A complete sieve analysis of a representative catalyst sample was performed using a set of standard sieves as described in ASTM Standards, Division 30 (ASTM-E11-61), pages 96-101 (1969). After aging, read d from a graph in which the weight percentage, based on the total weight of the catalyst sample, for each successive sieve section is plotted cumulatively as a function of the linear average diameter of the particles in that sieve section.
That is, d is the particle diameter corresponding to 50% of the total weight. This method can be used to determine the d of spherical and granular materials and similarly shaped materials such as extrudates and pellets with length to diameter ratios in the range 0.9 to 1.1. For extrudates, pellets, and similar cylindrical materials whose length-to-diameter ratio is less than 0.9 or greater than 1.1, and whose particle diameter distribution cannot be determined by sieve analysis, the measurement of d is as follows. It is done as follows. Complete length distribution analysis (if length to diameter ratio is less than 0.9) or complete diameter distribution analysis (if length to diameter ratio is less than 1.1)
For each successive length and diameter segment, the weight percentage based on the total weight of the catalyst sample is cumulatively plotted as a function of the linear average size of that segment. Read d from the graph. That is, d is a value corresponding to 50% of the total weight. After measuring the complete pore diameter distribution of the catalyst sample,
Read P ^* from the following graph. That is, 0~
For pore diameters in the range of 100 nm, 10 of the pore volume
Each successive pore volume increment less than or equal to 10%, where this increment is the increment observed in the pore when the pore is divided into equal diameter intervals smaller than or equal to 2 nm. P ^* is read from a graph in which the quotient of the increment in pore volume and the corresponding pore diameter spacing for each of the following equations is plotted cumulatively as a function of the line average pore diameter for the associated pore diameter spacing. That is, P ^* is the pore diameter corresponding to 50% of the total quotient. The complete pore diameter distribution of the catalyst (the pore diameter distribution is
The extent to which pores with the relevant diameter contribute to the total pore volume is determined. ) is measured using the mercury immersion method (industrial and
Engineering Chemistry, Analytical Edition 17 , 787 (1945)
EV in a combined nitrogen adsorption/desorption method (as described by HLRitter and LCDrake in Analytical Chemistry 32 , 532 (1960))
(as described by Ballou and OKDoolen) is very suitable. In this case, the pore diameter distribution of the catalyst in the pore diameter range below 7.5 nm is the Journal of Catalysis
JCP Broekhoff and JHdo in 10, 377 (1968)
Calculated from the nitrogen desorption isotherm according to the method described by Boer (assuming a cylindrical pore),
The pore diameter distribution of the catalyst in the pore diameter range of 7.5 nm and above is calculated by the formula: Pore diameter (nm) = 15000/absolute mercury pressure (bar). The nitrogen pore volume and total pore volume described in this patent application are measured as follows.
The nitrogen pore volume of the catalyst is measured by the nitrogen adsorption/desorption method described above. The total pore volume of the catalyst is the nitrogen pore volume present in pores with diameters up to and including 7.5 nm (measured using the nitrogen adsorption/desorption method described above).
and the mercury pore volume present in pores with a diameter of 7.5 nm or more (measured by the mercury infiltration method described above)
is the sum of The surface area mentioned in this patent application is
Measured according to the BET method. The present invention therefore relates to a process for demetallizing hydrocarbon oils by contacting them with a catalyst in the presence of hydrogen at elevated temperature and pressure, the hydrocarbon oil being treated having a total vanadium and nickel content. The amount is 350 ppmw or more, and the catalyst used satisfies the above requirements. The catalyst used in the process of the invention consists essentially of alumina, silica or silica-alumina.
Very suitable catalysts are alumina or silica particles prepared by spray-drying alumina or silica gel and then shaping the spray-dried fine particles into larger particles, for example by extrusion, and the well-known oil droplets. This is spherical alumina or silica obtained by the method. The latter method consists of forming an alumina or silica hydrosol, mixing the hydrosol with a gelling agent, and dispersing this mixture as droplets in an oil that can be maintained at elevated temperatures; the droplets solidify into spherical shapes. The particles remain in the oil until they form hydrogel particles, which are then separated, washed, dried, and calcined.
A very suitable silica-alumina catalyst is a cogel of aluminum hydroxide gel on silica hydrogel. The catalysts of the invention may be particularly shaped by extrusion or pelletization. In addition to these shaping methods, the particularly well-known agglomeration method is a very attractive shaping method for the catalysts or catalyst supports of the invention. According to this method, catalyst particles having a diameter of at most 0.1 mm are agglomerated in a granulating liquid to form particles having a diameter of at least 1.0 mm. The catalyst used in the process of the present invention may be any catalyst that satisfies the conditions specified by the present invention, such as Kalichemie, Kaiser, Ketjen, etc.
Rhone-Poulenc and American Cyanamid
Includes commercially available products from Cyanamid. When using the method of the invention for the demetallization of hydrocarbon oils selected from the group consisting of crude oil and topped crude oil and having a total content of vanadium and nickel of 1000 ppmw or more, the following requirements: 1 V _T is 0.6 ml /g, 2 d is at least 1.5 and at most 3 mm,
And 3 formulas: After substituting d, V _T and P _H2 into , we find that P ^* must be greater than some value Q in nm; for the present invention P ^* should have a value greater than Q + 10 nm. A catalyst that satisfies the following is preferred. The demetalization activity of the catalyst of the invention is increased by the addition of hydrogen sulfide. Therefore, the process of the invention is preferably carried out with the addition of hydrogen sulfide. Further research on the effect of adding hydrogen sulfide when using the catalyst of the present invention for the demetalization of heavy hydrocarbon oils revealed that the effect of hydrogen sulfide largely depends on the hydrogen partial pressure and total pressure used. I understood. If we take the view that the use of hydrogen sulfide in demetallization is economically attractive, especially when it results in an increase in demetallization activity of more than 50% at a given total pressure, we can further reduce the amount of hydrogen sulfide to commercial P _H2S It can be seen that this requirement can be met if /P _H2 is selected to be at least 4/P _T +200/(P _T ) ² and at most 2P _T -60/P _T +60. Within the range defined by the formula, the demetalization activity of the catalyst reaches a maximum value at a certain P _H2S (P ^* _H2S ). The value of P ^* _H2S varies for different catalysts and can be determined from several preliminary tests. Application of P _H2S above or below P ^* _H2S but within a defined range still increases the demetalization activity by more than 50%, but this increase is smaller than the highest value that can be reached. During the demetalization operation, P ^* _H2S or other P _H2S may be adjusted by continuously feeding a sufficient amount of hydrogen sulfide externally to the oil being demetallized. However, from an economic point of view, it is more attractive to use the hydrogen sulfide released in the demetalization operation and/or the desulphurization operation carried out after the demetallization operation to the highest possible extent. From this idea, the following three demetalization methods of the present invention in the presence of additional hydrogen sulfide
Two attractive concrete examples were derived. 1 Application of gas recirculation in demetalization operations, leaving as much hydrogen sulfide as possible in the recycle gas until the desired P _H2S is reached. A quantity of hydrogen sulfide is then continuously removed from the recycle gas to maintain the desired hydrogen sulfide concentration. 2. Especially when high P _H2S is required, it takes a considerable amount of time for the hydrogen sulfide concentration in the recycle gas to reach the desired value. This difficulty can be overcome by supplying hydrogen sulfide externally at the beginning of the operation and gradually reducing the supply of hydrogen sulfide as the operation progresses. This additional amount of hydrogen sulfide comes from, for example, hydrodesulfurization operations. 3. Instead of or in combination with gas recirculation to the demetalization reactor, off-gas from a desulfurization reactor installed after the demetalization reactor is used as feed gas to the demetalization reactor. The operating mechanism of the combined demetallization/desulfurization process in the presence of hydrogen, based on the principles described below, is illustrated in the accompanying drawings and is further described hereinafter. The plant consists of a demetallization device 1, a first gas-liquid separation device 2, a hydrodesulfurization device 3, a second gas-liquid separation device 4 and a hydrogen sulfide removal device 5 in order. The metal and sulfur-containing hydrocarbon residue 6 is demetallized together with two hydrogen and hydrogen-sulfide-containing gas streams 7 and 8 and, if necessary, an external hydrogen sulfide stream 9. The product 10 obtained in this way is separated into a metal-poor liquid stream 11 and a hydrogen- and hydrogen-sulfide-containing gas stream 7, the latter being recycled to the demetallization unit. The liquid stream 11 includes a hydrogen-containing gas stream 12 and an external hydrogen stream 13.
Hydrodesulfurization is also carried out. The product 14 thus obtained is a low metal and low sulfur liquid stream 15
and hydrogen and hydrogen-sulfide-containing gas stream 16
and the latter is divided into two parts 8 and 17 of the same composition. Portion 8 is recycled to the demetalization unit and portion 17 is recycled to the demetallization unit, and portion 17 is recycled to the gas stream 12 after removal of the hydrogen sulfide.
recycled to the desulfurization equipment. The process of the present invention involves passing a hydrocarbon oil upwardly in the presence of hydrogen at elevated temperature and pressure into one or more vertically arranged reactors containing a fixed or moving bed of associated catalyst particles. Preferably this is done by passing downwardly or radially. The invention may be carried out, for example, by passing hydrocarbon oil with hydrogen in an upward direction through a vertically arranged catalyst bed, and the liquid and gas velocities used are such as to spread the catalyst bed. operation). A very attractive embodiment of the invention is
Hydrocarbon oil is passed through a vertically arranged catalyst bed where, during the operation, fresh catalyst is introduced periodically at the top of the catalyst bed and used catalyst is removed at the bottom of the catalyst bed (bunker flow method). Operation of). Another very attractive embodiment of the invention is the use of several reactors, each containing a fixed catalyst bed,
These reactors are used alternately for the associated operations; while an operation is being carried out in one or more of these reactors, the catalyst in the other bed is replenished (operation in fixed catalyst oscillation mode). If necessary, the operation can also be carried out by suspending the catalyst in the hydrocarbon oil to be treated (operation in the slurry phase). The method of the present invention is performed at a temperature of 350 to 450°C and a hydrogen partial pressure of 25 to 450°C.
Preferably, it is carried out at 200 bar and a space velocity of 0.1 to 10 Kg·Kg ⁻¹ ·h ⁻¹ . Particularly preferred are the following conditions: temperature 375-425°C, hydrogen partial pressure 50-150.
Bar, space velocity 0.5-5Kg・Kg ^-1・h ^-1 . Hydrodemetallization of metal-containing hydrocarbon oils is of particular importance if the oil is subsequently subjected to catalytic cracking, hydrocracking or hydrodesulfurization. As a result of hydrogenation demetallization, the deactivation of the catalysts used in these operations is suppressed to a considerable extent. Hydrocracking and hydrodesulfurization of hydrocarbon oils involves contacting the oil with a suitable catalyst, which may be present in a fixed bed, a moving bed or in the form of a suspension of catalyst particles, under elevated temperature and pressure and in the presence of hydrogen. I can turn it over and go.
An attractive combination of demetallization and hydrocracking or hydrodesulfurization according to the invention is that the demetallization is carried out in a fixed bed vibratory or bunker flow operation, while the hydrocracking or hydrodesulfurization is carried out in a conventional fixed bed operation. It is something. Examples of hydrocarbon oils having a total vanadium and nickel content of 350 ppmw or more that are suitable for the demetallization of the present invention are crude oil and resid oils obtained by distillation of crude oils such as topped crude oils, long resid oils, and short resid oils. . The invention will be illustrated by the following examples. Example: The total vanadium and nickel content obtained after topping and dehydration of South American crude oil is
A 1250 ppmw hydrocarbon residue was catalytically hydrodemetallized using nine different non-promoted catalysts.
This was followed by a temperature of 410 °C, a hydrogen partial pressure (measured at the inlet of the reactor) of 150 bar, and a space velocity of 1 catalyst per hour.
The oil was passed with hydrogen in a downward direction through a cylindrical vertically arranged fixed catalyst bed at a gas rate of 2.1 Kg of fresh feed per Kg and a gas rate of 1000 Nl _H2 per Kg of fresh feed. The liquid reaction product was divided into two parts of the same composition in a volume ratio of 22:1. A smaller portion was removed from the system and a larger portion was recycled to the reactor inlet. The results of the demetalization experiments are collected in Table A along with the properties of the catalysts used. The nitrogen adsorption/desorption and mercury intrusion methods described above were used to measure P ^* and total pore volume. The catalyst for Experiment 3 was commercially available Kali
Chemie) Ni/V-containing silica-based catalyst (surface area
262m ² /g, average pore diameter 9.5nm, product name Siliperl R600, lot number KC286/1)
was subjected to an acid leaching treatment (to remove undesired metal components from the catalyst) and then heated at 175°C and
Produced by hydrothermal treatment in H ₂ O at a pressure of 8.8 bar. [Table] Catalyst performance is evaluated based on V _nax and K _1.5 . V _nax is the highest amount of vanadium in weight percent based on fresh catalyst that catalyst particles can absorb in their pores, and K 1.5 is the maximum amount of vanadium in weight percent based on fresh catalyst that catalyst particles can absorb into their pores, and K _1.5 is the Kg・Kg ^-1・h ^-1・(ppmwV) ^-1 after conversion)
The catalytic activity is expressed as ^/2 . K _1.5 is calculated using the formula: K _1.5 = (space velocity in Kg Kg ^-1 H ^-1 ) x ppmwV in feed - ppmwV in product / (ppmwV in product) ^{1 1/2} . V _nax is greater than 30% by weight, K _1.5 is 0.08Kg・
If the criterion of greater than Kg ^-1 h ^-1 (ppmwV) ^-1/2 is met, the performance of the catalyst is evaluated as good under the conditions used for this demetalization. V _nax is greater than 40% by weight, K _1.5 is 0.08Kg・
If the criterion of greater than Kg ^-1 h ^-1 (ppmwV) ^-1/2 is met, the performance of the catalyst is evaluated as excellent under the conditions used for this demetalization. Experiments 1 to 6 satisfying the above conditions regarding V _nax and K _1.5 are demetalization experiments according to the invention. In these experiments using catalysts of the formula, these catalysts have a surface area (100 m ² /g), a _V
5 mm). In experiments 3 to 6, P ^* (>Q+
10nm), V _T (>0.6ml/g) and d (1.5-3mm)
A catalyst was used that also met the additional requirements regarding. These are in accordance with the present invention and were evaluated as excellent catalysts. Runs 7-9 which do not meet the above requirements regarding V _nax and K _1.5 are demetallization experiments outside the scope of the present invention. In experiments 7-9, the conditions were:
A catalyst that did not satisfy the formula was used. Furthermore, in Experiment 7, the catalyst used was d > 5 mm, and in Experiment 9, V _T < 0.2 ml/
g of catalyst was used. Example Experiment 4 of Example was repeated several times at different hydrogen sulfide partial pressures. In these experiments hydrogen sulfide was added externally. A constant total pressure of 150 bar (measured at the reactor inlet) was used in all experiments. The results of these experiments are collected in Table B. [Table] In experiments 11 to 13, P H2S /P H2 satisfying the relationship: 4/P _T +200/(P _T ) ² P _H2S /P _H2 2P _T −60/P _{T +60} was used, and 50% _or more desorption was achieved. reached an increase in metal activity. In Experiment 10, P _H2S /P _H2 that did not satisfy the above relationship was used, and the demetalization activity increased by less than 50%. EXAMPLE A Middle Eastern shoot residue having a total vanadium and nickel content of 410 ppmw and a sulfur content of ^4.1 wt. diameter and average particle diameter of 2.4 mm ₎ under standard conditions (temperature 410 °C, hydrogen partial pressure 150 bar, space velocity 2.1 fresh feed per kg of catalyst per hour).
Kg and gas rate per Kg of new feed
The activity of the catalyst (expressed as K _1.5 ) was 0.09 when treated for 200 hours in 1000 Nl H ₂ . The metal absorption capacity of the catalyst was 70% by weight. Example When a South American shoot residue with a total vanadium and nickel content of 763 ppmw and a sulfur content of 5.4 wt. is treated over the same catalyst at the same standard conditions described in the example, K _1.5 A value of 0.09 for was already reached after 170 hours. The metal absorption capacity for this type of feed was 60% by weight.

[Brief explanation of drawings]

The drawing is a flow sheet of an embodiment of the method of the invention. 1... Demetallization device, 2... First gas-liquid separation device, 3... Hydrodesulfurization device, 4... Second gas-liquid separation device, 5... Hydrogen sulfide removal device.

Claims (1)

[Claims] 1. The total content of vanadium and nickel is
Hydrocarbon oil of 350 ppmw or more is heated under increased temperature and pressure in the presence of hydrogen to meet the following requirements: 1 [In the formula, P ^* is the average pore diameter (nm), d is the specific average particle diameter (mm), and V _T is the total pore volume (ml/
g) and P _H2 is the hydrogen partial pressure (bar)], 2 the surface area is at most 100 m ² /g, 3 V _T is greater than 0.2 ml/g, 4 d is at least 0.4 and at most 5 mm A method for demetallizing hydrocarbon oil, characterized by contacting the hydrocarbon oil with a catalyst that satisfies the following and substantially consists of silica, alumina, or silica-alumina. 2. The method according to claim 1, which is carried out by bunker flow operation or fixed bed vibration operation. 3. For the demetallization of hydrocarbon oils selected from the group consisting of crude oil and topped crude oil, with a total vanadium and nickel content of 1000 ppmw or more, the following requirements: 1 V _T from 0.6 ml/g is large, 2 d is at least 1.5 and at most 3 mm, and 3 formula: After substituting d, V _T and P _H2 into , we see that P ^* must be greater than some value Q in nm; in the present invention P ^* should have a value greater than Q + 10 nm, 3. Process according to claim 1, characterized in that a catalyst is used that satisfies the requirements of the invention. 4. The method according to any one of claims 1 to 3, characterized in that the method is carried out by adding hydrogen sulfide. 5 Quotient P _H2S /P _H2 is related: 4/P _T +200/(P _T ) ² P _H2S /P _H2 2P _T -60/P _T +60 [In the formula, P _H2 , P _H2S and P _T are each hydrogen content pressure,
5. The process according to claim 4, characterized in that it is carried out in the presence of an amount of hydrogen sulfide such that the hydrogen sulfide partial pressure and the total pressure (in bars) are satisfied. 6. Process according to claim 4 or 5, characterized in that hydrogen sulfide released during the demetalization operation and/or the desulfurization operation carried out after the demetallization operation is used during the operation. 7 Performing gas recirculation in the demetalization operation,
characterized in that the largest possible amount of hydrogen sulfide remains in the recycle gas until the desired P _H2S is reached, and then a quantity of hydrogen sulfide is continuously withdrawn from the recycle gas to maintain the desired hydrogen sulfide concentration. A method according to claim 6. 8. Process according to claim 7, characterized in that hydrogen sulfide is supplied externally during the initial stages of operation, and the amount of hydrogen sulfide supplied is gradually reduced as the operation progresses. 9 metal and sulfur-containing hydrocarbon residues into two hydrogen and hydrogen-sulfide-containing gas streams (A and B),
Hydrodemetallization is then carried out, if desired, with a hydrogen sulfide stream introduced externally, and the product obtained is divided into a metal-low liquid stream and a hydrogen- and hydrogen-sulfide-containing gas stream, the latter being demetalized as gas stream A. The low metal liquid stream is recycled to the reactor and hydrodesulfurized together with the hydrogen-containing gas stream C and the external hydrogen stream, and the resulting product is combined with the low metal and low sulfur liquid stream containing hydrogen and hydrogen-sulfide. into two gas streams, dividing the latter into two parts of the same composition, one of which is called gas stream B.
Claim 6, characterized in that the hydrogen sulfide is recycled to the demetalization reactor as gas stream C, and the other part is recycled as gas stream C to the desulfurization reactor after removal of the hydrogen sulfide.
The method described in section. 10. A process for catalytic conversion of metal-containing hydrocarbon oils by cracking, hydrocracking or hydrodesulfurization, in which the oil is first demetalized and then catalytically converted,
A method characterized in that the demetallization is carried out according to any one of claims 1 to 9. 11. Any one of claims 1 to 10, characterized in that the process is carried out at a temperature of 350 to 450° ^C , a hydrogen partial pressure of 25 to 200 bar, and a space velocity of 0.1 to 10 Kg·Kg ⁻¹ ·h −1. The method described in. 12. Process according to claim 11, characterized in that it is carried out at a temperature of 375 to 425°C, a hydrogen partial pressure of 50 to 150 bar and a space velocity of 0.5 to 5 Kg·Kg ⁻¹ ·h ⁻¹ .