JPH0122319B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a process for demetallizing hydrocarbons (removing metals) by contacting hydrocarbon oil with a catalyst in the presence of hydrogen at a temperature and pressure higher than normal temperature and pressure. JP-A-49-44004 discloses that hydrogenation is promoted by one or more metals having hydrogenation activity and under the following conditions: (1) P/d>3.5-0.02V - where P is is the particular average pore diameter in nm, d is the particular average particle diameter in mm, and V is the particular average particle diameter in mm.
(2) total pore volume is greater than 0.40 ml/g; (3) V is less than 50%; and (4) specific surface area. is greater than 100 m ² /g, and if this catalyst has P and d such that the quotient P/d is 10−0.15 V or less, the following conditions are further satisfied: (a) A catalyst is described that also satisfies the following requirements: (b) the specific surface area is greater than 150 m ² /g; and (c) the P content is greater than 5 nm. According to the above-mentioned publications, these catalysts are suitable for hydrodemetallization (hydro-demetallization) of metal-containing hydrocarbon oils.
very suitable for use in demetallization). As shown in the examples of the above publication,
The catalyst is of such importance that it is essential that it is assisted by one or more metals with hydrogenation activity (the combined content of vanadium and nickel is
(Compare experiment 40, which used an "unassisted catalyst" to demetalize 245 ppmw oil). Further studies on the use of catalysts for the hydrodemetallization of hydrocarbons which satisfy the above-mentioned conditions with respect to porosity and particle size have shown that they are not assisted by one or more metals with hydrogenation activity. Similar catalysts have been found to be very suitable for this purpose, although unassisted, when the hydrocarbon oil has a combined vanadium and nickel content of more than 650 ppmw. Catalysts that satisfy the above-mentioned conditions with respect to porosity and particle size, but are not promoted with one or more metals having hydrogenation activity, are referred to in this patent application as ``unfacilitated'' for the sake of simplicity. It's called a catalyst. Accordingly, the present invention provides the above-mentioned method comprising contacting a hydrocarbon oil with a combined content of vanadium and nickel higher than 650 ppmw with an "unfacilitated catalyst" in the presence of hydrogen at a temperature and pressure above normal temperature and pressure. This invention relates to a method (process) for demetallizing hydrocarbon oil. 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 in ASTM Standards Division 30 (ASTME 11-61), pp. 96-101 (1969).
For each successive sieve section, the weight percentage relative to the total weight of the catalyst sample is cumulatively plotted as a function of the linear mean diameter of the particles in that sieve section. Read d from the graph shown. That is, d is 50 of the total weight
% particle diameter. 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 0.9-1.1. 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 measured by sieve analysis, the measurement of d is as follows. It is done as follows. After a complete length distribution analysis (when the length-to-diameter ratio is less than 0.9) or a complete diameter distribution analysis (when the length-to-diameter ratio is greater than 1.1) is performed on a representative catalyst sample, each successive length d is read from a graph in which the weight percentage based on the total weight of the catalyst sample is cumulatively plotted for each size and diameter category as a function of the line average size of that category. 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
For each successive pore volume increment less than or equal to 10%, where this increment is the increment found in the pores when the pores are divided into equal diameter intervals less than or equal to 2 nm. P is read from a graph in which the quotient of each increment in pore volume and the corresponding pore diameter interval is cumulatively plotted as a function of the line mean pore diameter versus the associated pore diameter interval. In other words, P is 100nm
The pore diameter corresponds to 50% of the total quotient. The complete pore diameter distribution of the catalyst can be determined by the nitrogen adsorption/desorption method [E.V. Ballou and O.K. Doolen, Analytical Chemistry, No. 32] Vol. 532 (1960)] using the mercury infiltration method [H.L. Ritter and L.C. Drake, Industrial and Engineering Chemistry (Ind. [Eng. In this case, the pore diameter distribution of the catalyst in the range of pore diameters below 7.5 nm is preferably determined by J.C.P. Broekhoff and G.H. Debord (J.H. de Boer), Journal of Catalysis, Vol. 10, p. 377 (1968)
The pore diameter distribution for catalysts in the pore diameter range greater than 7.5 nm is preferably calculated from the nitrogen desorption isotherm (assuming cylindrical pores) according to the method described in 2011 (2013). Pore diameter (in nm) = 15000 /calculated using absolute mercury pressure in bar. Nitrogen pore volume and total pore volume as described herein are defined as follows. The nitrogen pore volume of the catalyst is the pore volume measured using the nitrogen adsorption/desorption method described above. The total pore volume of the catalyst is
Nitrogen pore volume found in pores with diameters below 7.5 nm (measured using the nitrogen adsorption/desorption method described above)
and the mercury pore volume found in pores with diameters greater than 7.5 nm (measured using the mercury infiltration method described above).
It is the sum of The surface areas described herein were measured by the BET method. Alumina, silica and silica-alumina are used as catalysts in the process according to the invention.
As the catalyst of the present invention, the carrier described in JP-A-49-44004 can be used. 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, as well as the well-known oil drop method. These are spherical alumina or silica particles obtained by. The latter method consists of producing an alumina or silica hydrosol, mixing this hydrosol with a gelling agent, and dissolving the mixture as droplets in an oil that may be kept at a temperature above ambient temperature. Become. The droplets remain in the oil until they solidify to produce spherical hydrogel particles, which are then separated, washed, dried, and fired. A highly preferred alumina catalyst is a co-gel of aluminum hydroxide gel on silica hydrogel. The catalyst according to the invention may be extruded or pelletized, among others. In addition to these forming techniques, the particularly well-known nodule formation (nodule formation)
is also a very attractive shaping technique for the catalysts of this invention. According to this method, catalyst particles with a diameter of up to 0.1 mm are agglomerated by the granulation liquid to produce particles with a diameter of at least 1.0 mm. The catalyst used in the process of the present invention may be one that satisfies the conditions specified by the present invention, such as Kalichemie, Kaiser, Ketjen, etc.
Rho^ne-Poulenc and American Cyanamid
Includes commercially available products from Cyanamid. The demetalization activity of the "unpromoted catalyst" according to the present patent application and the "promoted catalyst" according to JP-A-49-44004 can be increased by adding hydrogen sulfide. Therefore, demetallization of heavy hydrocarbons using these catalysts is preferably carried out with the addition of hydrogen sulfide. As a result of further research on the effect of addition of hydrogen sulfide when using the "unpromoted catalyst" of the present invention and the "promoted catalyst" according to JP-A-49-44004,
It has been found that the effectiveness of hydrogen sulfide is greatly influenced by the hydrogen partial pressure and total pressure used. For the use of hydrogen sulfide in demetalization to be considered economically beneficial, the demetalization activity must be reduced to 50% at a constant total pressure.
To increase the amount of hydrogen sulfide for both unpromoted and promoted catalysts,
It is necessary to choose such that the quotient P _H2S /P _H2 is at least equal to 4/P _T +200/(P _T ) ² and at most equal to 2P _T −60/P _T +60. In addition, P _H2 , P _H2S and P _T are hydrogen partial pressure, hydrogen sulfide partial pressure and total pressure expressed in bars, respectively. Within the limits determined by the above equation, the demetalization activity of the catalyst reaches a maximum value at a certain P _H2S (P ^* _H2S ). P ^*
The value of _H2S varies depending on the catalyst and can be determined by several experimental experiments.
Using P _H2S within the above-mentioned limits but higher or lower than P ^* _H2S will increase the demetalization activity by more than 50%, but this increase is less than the highest value that can be reached. Naturally, during the demetallization process,
P ^* _H2S and other P _H2S are controlled by continuously feeding the oil to be demetallized with a sufficient amount of hydrogen sulfide from an external source. However, from an economic point of view, the demetalization process and/or
Alternatively, it is more advantageous to utilize as much hydrogen sulfide as possible, which is liberated in the desulfurization process that follows the demetallization process. As a result of this consideration, the following three preferred embodiments result from the demetalization process of the present invention in the presence of additional hydrogen sulfide. 1 Employing gas recirculation in the demetalization process and leaving as much hydrogen sulfide as possible in the recycle gas until the desired P _H2S is reached. Thereafter, a certain amount of hydrogen sulfide is continuously removed from the recycle gas to maintain the desired hydrogen sulfide concentration. 2 If particularly high P _H2S is desired, it takes a considerable amount of time for the hydrogen sulfide concentration in the recycle gas to reach the desired value. This problem can be overcome by supplying hydrogen sulfide externally during the initial stages of the process and gradually reducing the supply of hydrogen sulfide as the process progresses. This new amount of hydrogen sulfide may be derived from a hydrodesulfurization process, for example. 3. Instead of recycling the gas in the demetalization reactor or combination thereof, the exhaust gas from the desulphurization reactor placed after the demetallization reactor is used as the feed gas to the demetallization reactor. A process proposal for a combined demetallization/desulphurization process is based on the above-mentioned principles and is illustrated in the accompanying drawings and further explained hereinafter. The plant consists of successive unit groups of a hydrodemetallization unit 1, a first gas-liquid separation unit 2, a hydrodesulphurization unit 3, a second gas-liquid separation unit 4 and a unit 5 for hydrogen sulfide removal. Consisting of The residual hydrocarbon oil 6 containing metals and sulfur is subjected to hydrodesorption together with two hydrogen and hydrogen sulfide containing streams 7 and 8 and a hydrogen sulfide stream 9 from an external source if desired. Served on metal. Product 1 so obtained
0 is separated into a low metal liquid stream 11 and a hydrogen-hydrogen sulfide containing gas stream 7, the latter being recycled to the demetallization unit. Liquid stream 11 is subjected to hydrodesulfurization together with a hydrogen-containing gas stream 12 and a hydrogen gas stream 13 from an external source. The product 14 so obtained
is separated into a low metal, low sulfur liquid stream 15 and a hydrogen-hydrogen sulfide containing gas stream 16, the latter being divided into two parts 8 and 17 of the same composition. Portion 8 is recycled to the demetallization unit and portion 17 is recycled to the desulfurization unit as air stream 12 after the hydrogen sulfide has been removed. The method (process) according to the present invention comprises one or more catalyst particles containing a fixed bed or a fluidized bed of the catalyst particles in an upward, downward or radial direction in the presence of hydrogen at a temperature and pressure higher than normal temperature and pressure. This is preferably carried out by flowing the oil through a further vertically arranged reactor. The process may be carried out, for example, by flowing a hydrocarbon oil together with hydrogen upwardly through a vertically arranged catalyst bed, using liquid and gas velocities that cause expansion of the catalyst bed. (ebulated bed operation). A highly preferred embodiment of the process is one in which the hydrocarbons are passed through a vertically arranged catalyst bed while fresh catalyst is periodically fed from the top of the catalyst bed while spent catalyst is withdrawn from the bottom thereof. Yes (processed by bunker flow operation). Another highly desirable embodiment of the process is to provide several reactors, each containing a fixed bed of catalyst, and use these reactors alternately in the process; one of them
The catalyst in the other layer is replenished during one or more runs (fixed bed swing operation). If desired, the process may be carried out by suspending the catalyst in the hydrocarbon oil to be treated (processing by slurry phase operation). The catalyst of the invention is preferably used in the form of particles having a diameter of 0.5 to 4.0 mm, especially 0.6 to 3.0 mm. The method (process) according to the present invention has 350 to 450
Temperature in °C, hydrogen partial pressure in 25-200 bar and 0.1-10
Preferably, it is carried out at a space velocity of Kg·Kg ⁻¹ ·h ⁻¹ . Particularly preferred are the following conditions.
Namely, a temperature of 375-425°C, a hydrogen partial pressure of 50-150 bar and a space velocity of 0.5-5 Kg·Kg ⁻¹ ·h ⁻¹ . Hydrodemetallization of metal-containing hydrocarbon oils is of particular importance when the oil is subsequently subjected to catalytic cracking, hydrocracking, or hydrodesulfurization. As a result of hydrodemetallization, deactivation of the catalysts used in these processes is significantly reduced. Hydrocracking and hydrodesulfurization of hydrocarbon oils involves the treatment of the oil in the presence of hydrogen at temperatures and pressures above normal temperature and pressure, in the form of a fixed bed, a fluidized bed, or a suspension of catalyst particles. This is carried out by contacting with a suitable catalyst which may be used.
The preferred combination of demetalization and hydrocracking or hydrodesulphurization according to the invention is that the demetallization is carried out in a fixed bed swing operation or a bunker flow operation, while the hydrocracking or hydrodesulfurization is carried out in a conventional fixed bed operation. This is done in Examples of hydrocarbon oils with a total content of vanadium and nickel higher than 650 ppmw that are suitable for demetallization according to the invention are crude oil and kettle residues obtained by distillation of crude oil, such as topped crude oil, atmospheric distillation residues. and vacuum distillation residual oil. The present invention will be specifically explained in the following examples. Example 1 The total content of vanadium and nickel is
1250 ppmw of residual hydrocarbon oil (this oil was obtained by topping* and dewaxing of South American crude oil - *topping is the removal of the most volatile parts) was extracted from six different types of stimulants. Hydrodemetalization was carried out by a catalytic reaction using a non-containing catalyst. For this purpose, the oil is pumped together with hydrogen in a downward direction through a cylindrical vertically arranged fixed catalyst.
A temperature of 410 °C, a hydrogen partial pressure of 150 bar (measured at the inlet of the reactor), a space velocity of 2.1 [Kg of fresh feedstock/Kg of catalyst/hour], and a space velocity of 1000 [ _H2
A gas rate of Nl/Kg of fresh feedstock was flowed. The liquid reaction product was divided into two parts of the same composition in a volume ratio of 22:1. The smaller portion was removed from the system and the larger portion was returned to the reactor inlet. The results of the demetalization experiments are summarized in Table A along with the properties of the catalysts used. The catalyst for experiment 1 was a commercially available Kali Chemie Ni/V-containing silica-based catalyst (surface area 262 m ² /g, average pore diameter
9.5 nm, Siliperl R600, lot number KC286/1) and by removing the metal components present on this silica-based catalyst by a process known as acid leaching. The catalyst of Experiment 4 was obtained by subjecting the silica catalyst listed in Experiment 1 of Table A to a mild hydrothermal treatment (at 125 DEG C. and 2.3 bar steam pressure).

[Table] Catalyst performance is evaluated based on V _nax and K _1.5 . V _nax is the maximum amount of vanadium in % w on the fresh catalyst (the catalyst particles can be adsorbed in the pores), and K _1.5 is the catalyst lifetime (in terms of the amount of vanadium adsorbed)
Kg・Kg ^-1・h ^-1・(ppmwV) after half of
It is the activity of the catalyst expressed as −1/2. K _1.5 is calculated by the formula: K _1.5 = (space velocity in Kg·Kg ^-1 ·h ^-1 ) × ppmwV of feedstock – ppmwV of product / (p of product
pmwV) ^{1 1/2} . V _nax is higher than 30%w and K _1.5 is 0.08Kg・Kg
If the criterion of greater than ^-1 h ^-1 (ppmwV) -1/2 is satisfied, the performance of the catalyst is evaluated as good under the conditions adopted for this demetalization. Experiments 1 and 2 in which the above conditions regarding V _nax and K _1.5 were satisfied are demetallization experiments according to the present invention. In experiment 1, 10−0.15V＞P/d＞3.5−0.02V
A catalyst with a total pore volume (>0.40 ml/g), V (<50%), nitrogen pore volume (>
0.6ml/g), surface area (>150m ² /g) and P (>
5 nm). In experiment 2, we used a catalyst with P/d>10−0.15V, which has a total pore volume (>0.40
ml/g), V (<50%) and surface area (>100m ² /g)
Further conditions of the invention are also satisfied with respect to. Experiments 3 to 6 are demetallization experiments outside the scope of the present invention, in which the conditions described above regarding V _nax and K _1.5 were not met. In experiment 3, 10−0.15V＞P/d＞
A 3.5-0.02V catalyst was used whose nitrogen pore volume was less than 0.60ml/g. In experiment 4, 10−
A catalyst with 0.15V>P/d>3.5−0.02V was used, but
Its surface area is less than 150 m ² /g. Experiment 5 used a catalyst with P/d>10-0.15V, whose total pore volume was less than 0.40ml/g. In experiment 6, a catalyst with P/d<3.5-0.02V was used. Example 2 Experiment 1 of Example 1 was repeated several times, each time applying a different hydrogen sulfide partial pressure. In these experiments, hydrogen sulfide was added from an external source. A constant total pressure of 150 bar (measured at the inlet of the reactor) was adopted in all experiments. The results of these experiments are summarized in Table B.

[Table] In experiments 8 _to 10, when P H2S /P H2 was used that satisfied the relational expression: 4/P _T +200/(P _T ) ² P _H2S /P _H2 2P _T -60/P _{T +60} , 50 % increase in demetalization activity was obtained. Experiment 7
In this case, P _H2S /P _H2 , which does not satisfy the above-mentioned relational expression, was used, but an increase rate of demetalization activity lower than 50% was obtained. Example 3 South American vacuum distillation residue having a combined vanadium and nickel content of 763 ppmw and a sulfur content of 5.4% by weight was treated with the catalyst described in Experiment 1 of Example 1 (262 m ² /g surface area, 10 nm under standard conditions (temperature of 410 °C, hydrogen partial pressure of 150 bar, 2.1 [Kg _of fresh feedstock/Kg of catalyst/h
The activity of the catalyst (expressed in K _1.5 ) when treated for 150 hours at a space velocity of 1 hour] and a gas velocity of 1000 [Nl of _H2 /Kg of fresh feedstock]
is 0.10 (i.e. at least 0.08, which is one of the factors to be satisfied for the catalyst according to the invention)
). The metal adsorption capacity of the catalyst was 40% by weight.

[Brief explanation of drawings]

The accompanying drawing is a process diagram for a combined demetalization/desulfurization process. 1, 2, 3, 4, 5...Unit, 6...Hydrocarbon oil, 13...Hydrogen stream, 14...Product, 1
5...Low metal, low sulfur liquid stream.

Claims (1)

[Claims] 1 Hydrocarbon oil is heated at a temperature higher than room temperature and under pressure of hydrogen under the following conditions: (1) P/d>3.5-0.02V - where P is expressed in nm. is the particular average pore diameter in mm, d is the particular average particle diameter in mm, and V is the particular average particle diameter in mm.
is the percentage of the total pore volume of pores with a diameter greater than 100 nm, (2) the total pore volume is greater than 0.40 ml/g, (3) V is less than 50%, and (4) the specific surface area is be larger than 100m ² /g; however, in the case of a catalyst with P and d such that the quotient P/d is not larger than 10-0.15V, the following conditions must be met: Contact with a catalyst that also satisfies the following: (a) nitrogen pore volume is greater than 0.60 ml/g, (b) specific surface area is greater than 150 m ² /g, and (c) P is greater than 5 nm. In the demetalization method of hydrocarbon oil, the total content of vanadium and nickel is
Said method, characterized in that a hydrocarbon oil higher than 650 ppmw is contacted with an unassisted silica, alumina or silica-alumina catalyst. 2. Process according to claim 1, characterized in that a catalyst with d of from 0.5 to 4.0 mm is used, preferably from 0.6 to 3.0 mm. 3. The method according to claim 1 or 2, characterized in that it is carried out in a bunker flow operation or a fixed bed swing operation. 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 The quotient P _H2S /P _H2 has the following relationship: 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 5. A process according to claim 4, characterized in that it is carried out in the presence of hydrogen sulfide in an amount such that the hydrogen partial pressure, hydrogen sulfide partial pressure and total pressure in bars are satisfied. 6. The method according to claim 4 or 5, characterized in that hydrogen sulfide liberated in a demetallization process and/or a desulfurization process carried out after the demetallization process is used. 7 In this demetalization process, gas recirculation is employed to leave as much hydrogen sulfide as possible in the recycle gas until the desired P _H2S is reached, and then a certain amount of hydrogen sulfide is removed from the recycle gas. 7. The method according to claim 6, wherein the hydrogen sulfide concentration is maintained at a desired concentration by continuous removal. 8. During the initial stages of the process, hydrogen sulfide from an external source is fed to the process;
8. A method according to claim 7, characterized in that the amount of hydrogen sulfide supplied is gradually reduced as the process progresses. 9. Residual hydrocarbon oil containing metals and sulfur,
Two hydrogen-hydrogen sulfide-containing streams (A and B) and optionally a hydrogen sulfide stream from an external source are subjected to hydrodemetallation and the resulting product is combined with a low metal liquid stream. separating into a hydrogen-hydrogen sulfide-containing gas stream, circulating the latter as gas stream A to the demetalization reactor, and subjecting the low-metal liquid stream to hydrodesulfurization together with hydrogen-containing gas stream C and a hydrogen gas stream from an external source; The resulting product is separated into a low-metal, low-sulfur liquid stream and a hydrogen-hydrogen sulfide-containing gas stream, the latter being divided into two parts of the same composition and one of these parts being recycled as gas stream B to the demetalization reactor. 7. The method according to claim 6, wherein the remaining one is recycled to the desulfurization reactor as gas stream C after removing hydrogen sulfide. 10 In a process for catalytic conversion of metal-containing hydrocarbon oil by cracking, hydrocracking or hydrodesulfurization, the oil is first demetallized and then converted by catalytic reaction, but the demetallization is not claimed. A method characterized in that it is carried out according to any one of the ranges 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 0.1/10 Kg·Kg −1 ·} h −1. The method described in paragraph 1. 12. A process according to claim 11, characterized in that it is carried out at a temperature of 375 DEG to 425 DEG C., a hydrogen partial pressure of 50 to 150 bar and a space velocity of 0.5 to 5 Kg.Kg ^{-1.h -1} .