JPH0237384B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention has a Ramsbottom Carbon Test Value (RTC) lower than 5% and a nickel content of 1.0 ppmw (weight).
ppm) and vanadium content is lower than
A method for producing an oil suitable for use as a feedstock to a catalytic cracking process, the method comprising:
It relates to said production process comprising RCT and/or catalytic hydrogenation of oils with a nickel content and/or vanadium content higher than the above-mentioned limits. In the catalytic cracking of hydrocarbon mixtures, the composition of these mixtures must satisfy certain requirements in order to make the catalytic cracking process economical.
The content of metals, especially that of nickel and vanadium, is at a certain value (1.0 parts per million (ppmw) for nickel and 1.0 parts by weight (ppmw) for vanadium).
(2.5 ppmw), lighter cracking products such as methane are produced in undesirable amounts at the expense of yields of the desired gasoline components. Content of heavy residue components (RCT is a measure of this)
If is too high, carbon deposition on the cracking catalyst will be excessive; RCT generally requires less than 5%. The starting materials in the production of feedstocks for catalytic cracking are usually heavy hydrocarbon oils, such as deasphalted residual oils, and/or high-boiling oils obtained by vacuum flash distillation of mineral oils (so-called flashed distillate). be. This de-asphalted oil and/or flash distilled oil is used in RCT and/or
or if they did not meet the requirements of the feedstock to catalytic cracking in terms of metal content, they were subjected to RCT and hydrotreating to reduce the metal content. In this process, hydrogen pressures of 100 bar and above were used to ensure stable operation during hydrotreating. The necessity of operating at such high hydrogen pressures has proven to be disadvantageous due to the necessity of using expensive high pressure units and the high hydrogen consumption. The present invention provides a process in which, by using certain starting materials and catalysts, hydroprocessing for the production of feedstocks suitable for catalytic cracking processes can be carried out at lower hydrogen pressures and lower hydrogen consumption. do. The present invention therefore provides a process for producing an oil suitable for use as feedstock to a catalytic cracking process, having an RCT of less than 5%, a nickel content of less than 1.0 ppmw, and a vanadium content of less than 2.5 ppmw. , RCT and/or catalytic hydrotreating of oil with a nickel content and/or vanadium content higher than the above limits, in the above production method, hydrotreating a hydrocarbon oil with a pentane asphaltene content lower than 0.2%; If the RCT of the hydrocarbon oil is at least 5%, then the activity in the benzene test described below is at least 0.15.
ml·ml ^-1 ·h ^-1 of nickel- and molybdenum-containing catalysts, and the RCT of the hydrocarbon oil was 5.
%, the activity in the benzene test is
Use of nickel- and vanadium-containing catalysts lower than 0.15 ml·ml ^-1 ·h ^-1 and hydrogenation
The manufacturing method is characterized in that it is carried out at a temperature of 300-450° C. and a hydrogen partial pressure of 10-70 bar. The benzene test, which determines the catalyst activity, is a hydrogenation process carried out in a microreactor with an amount of catalyst from 0.5 to 2.0 g, the weight of which is precisely known and which corresponds to 1.00 ml of compacted catalyst. It's a test. Hydrogen and benzene vapors containing a small amount of H ₂ S are passed through the catalyst under the following conditions: T (temperature) = 400°C; p (pressure) = 46 bar; H ₂ /
C ₆ H ₆ molar ratio = 20. GLC (gas-liquid chromatography) the reaction product
Analyze by. The catalyst activity is expressed as the first-order reaction rate constant for benzene hydrogenation in ml benzene (ml catalyst).
It is expressed as ^-1・h ⁻¹ (ml・ml ⁻¹・h ⁻¹ ). Pentane asphaltene content was revised to use pentane instead of heptane.
Measured by IP143/57. At least 5% hydrocarbon oil to be hydrogenated
, a catalyst with an activity in the benzene test of at least 0.15 ml·ml ⁻¹ ·h ⁻¹ must be used. This activity is 0.25-1.00
It is preferably in the range of ml·ml ⁻¹ ·h ⁻¹ . Activity in benzene test is at least 0.15
An example of a ml·ml ⁻¹ ·h ⁻¹ catalyst is a combination of nickel and molybdenum incorporated on a support. These metals can be incorporated by known methods such as ion exchange, dry mixing, impregnation or precipitation.
These metals can exist as simple metals or in the form of compounds such as oxides and sulfides. Alumina, silica or silica-alumina can be used very advantageously as support. Catalysts having nickel sulphide and molybdenum sulphide on a support alumina are preferred, especially catalysts having 0.5-20 preferably 2-10 pbw of nickel and 3-60 preferably 5-20 pbw of molybdenum per 100 pbw (parts by weight) of alumina. The hydrocarbon oil to be hydrogenated is lower than 5%
RCT, but with a nickel content and/or vanadium content that is too high to be suitable for use as a feedstock to a catalytic cracking process, the activity in the benzene test is less than 0.15 ml·ml ^-1 ·h ^-1 A low catalyst should be used and the activity is preferably between 0.025 and 0.0005 ml·ml ⁻¹ ·h ⁻¹ . Activity in benzene test is 0.15ml・ml ^-1・
An example of a catalyst lower than h ^-1 is a combination of nickel and vanadium incorporated on a support. These metals can be incorporated by known methods such as ion exchange, dry mixing, impregnation or precipitation. These metals can exist as single metals or in the form of compounds such as oxides and sulfides. Alumina, silica or silica-alumina can be used very advantageously as support. Catalysts with nickel sulfide and vanadium sulfide on a silica support are preferred, especially catalysts with 0.1-10 pbw of nickel and 1-20 pbw of vanadium per 100 pbw of silica. Of course, it is also possible to use said catalysts, which are more active in the benzene test (activity >0.15 ml.ml ^{-1.h -1} ), for the hydrogenation of hydrocarbon oils with an RCT lower than 5%. But this is not attractive. This is because using a catalyst with an activity in the benzene test that is higher than necessary results in less hydrogen than when using the preferred catalyst according to the invention, which has an activity in the benzene test lower than 0.15 ml·ml ^-1 ·h ^-1 . This is because consumption will be higher. Preferably, the hydrotreating is carried out at a temperature of 350-400°C and a hydrogen partial pressure of 30-60 bar. 0.1-5, especially 0.3-2 Kg of feedstock per liter of catalyst per hour
A space velocity of is very suitable. Short residue, i.e. approximately
If the purpose is to produce a feedstock for a catalytic cracking process from the mineral oil distillation residue obtained after removing components boiling up to 520°C under reduced pressure, this vacuum residue is first deasphalted to produce pentane and pentane. The asphaltene content must be lower than 0.2%.
This may be accomplished by deasphalting to the desired level with propane, butane or pentane (which may be controlled by the amount of deasphalting agent and/or the deasphalting temperature). The resulting hydrocarbon oil with a pentane asphaltene content below 0.2 can then be catalytically hydrotreated according to the invention. Deasphalting can generally be omitted if a flash distillate is to be converted into a feedstock suitable for a catalytic cracking process. This is because the pentane asphaltene content is generally lower than 0.2.
Which catalyst to use next depends on the RCT of flash distillate oils. Evaporation of the long residue (mineral oil distillation residue obtained after removal at atmospheric pressure of components boiling up to about 350° C.) under reduced pressure yields a flash distillate oil. The remaining vacuum residue is deasphalted to reduce the pentane/asphaltene content to 0.2%.
It can be lower. If the deasphalted oil obtained in this way has an RCT lower than 5%, it can be mixed with a flat distilled oil (if the metal content of the latter is too high) and this mixture can be used to determine the activity in the benzene test. It can be subjected to hydrogenation treatment using a catalyst with a degree lower than 0.15 ml·ml ⁻¹ ·h ⁻¹ . At least 5 RCTs of the above deasphalted oil
%, the oil may be hydrotreated alone with a catalyst having an activity in the benzene test of at least 0.15 ml·ml ⁻¹ ·h ⁻¹ . However, it is also possible to mix this deasphalted oil with components having a lower RCT, especially flash distilled oils. If this mixture has an RCT lower than 5% but the nickel and/or vanadium content is too high,
This can be hydrotreated according to the invention with catalysts whose activity in the benzene test is lower than 0.15 ml·ml ⁻¹ ·h ⁻¹ , which can lead to a considerable reduction in hydrogen consumption. Of course, the pentane and asphaltene content is 0.2%.
The above oils (deasphalted or not) are mixed with an oil having a lower pentane asphaltene content, such as a flat distilled oil, to form a mixture with a _C5 asphaltene content of less than 0.2%, and this mixture can also be subjected to the hydrogenation treatment according to the invention. The oil obtained by the process of the invention with an RCT lower than 5%, a nickel content lower than 0.5 ppmw and a vanadium content lower than 2.5 ppmw:
It can be very advantageously used as feedstock to a catalytic cracking process at temperatures in the range 450-550°C using acidic catalysts such as silica-alumina or molecular sieves. Example Two catalysts: a sulfurized catalyst containing 4.3 pbw of nickel on 100 pbw of alumina and 10.9 pbw of molybdenum and having an activity of 0.61 in the benzene test (catalyst A), and a sulfided catalyst containing 4.3 pbw of nickel on 100 pbw of alumina and 10.9 pbw of molybdenum and having an activity of 0.61 in the benzene test;
A number of experiments were carried out using a sulfided catalyst (Catalyst B) containing 0.5 pbw and 2 pbw of vanadium and an activity in the benzene test of 0.020. These metals were incorporated onto the support by conventional impregnation methods. The starting material used was deasphalted oil (DAO)
and flat distilled oil (FD); asphaltene content, RCT, and nickel and vanadium content are shown in the table. The starting material was subjected to hydrogenation at the temperatures and pressures indicated in the table. In all cases the space velocity is the feedstock per liter of catalyst per hour.
It was 0.5Kg. Experiments 4, 7 and 9 in the table are experiments according to the invention; other experiments are included for comparison. In experiments 1, 2 and 3, the C ₅ asphaltene content was
If the RCT is below 5% at 0.5% (i.e. higher than the value according to the invention), no product is obtained at hydrogen partial pressures below 90 bar, or in other words, hydrogenation at pressures between 10 and 70 bar ( Possible according to the invention) indicates that starting materials with too high a pentane asphaltene content do not give the desired results. Experiment 4 (according to the invention) demonstrates that RCT can successfully hydrotreat 8% of starting material with a catalyst having an activity in the benzene test of at least 0.15 ml·ml ⁻¹ ·h ⁻¹ . In Experiment 5, the activity in the benzene test was 0.15.
It is shown that catalyst B lower than ml·ml ⁻¹ ·h ⁻¹ does not work and that this catalyst cannot reduce the RCT below 5%. Run 6 shows that starting materials with RCT lower than 5% can be hydrotreated with catalyst A, but the hydrogen consumption is considerably higher than when the starting materials are treated with catalyst B according to the invention (run 7). . Runs 8 and 9 (according to the invention) show similar differences in the treatment of flash distillate oils; again, it is preferred to use catalyst B because of the considerably lower hydrogen consumption. 【table】

Claims (1)

[Claims] 1. Use as a feedstock to a catalytic cracking process with a Ramsbottom carbon test value (RTC) lower than 5%, a nickel content lower than 1.0 ppmw (ppm by weight), and a vanadium content lower than 2.5 ppmw. A process for producing oil suitable for use in oils containing RCT and/or catalytic hydrogenation of oils with a nickel content and/or vanadium content higher than the above limits, wherein the pentane-asphaltene content is
hydrotreating hydrocarbon oils lower than 0.2%;
In this case, the RCT of the hydrocarbon oil is at least 5
%, use a nickel- and molybdenum-containing catalyst with an activity in the benzene test of at least 0.15 ml·ml ⁻¹ ·h ⁻¹ and
If the RCT is lower than 5%, use a nickel- and vanadium-containing catalyst whose activity in the benzene test is lower than 0.15 ml·ml ^-1 ·h ^-1 and carry out the hydrogenation at a temperature of 300-450°C and a temperature of 10-70°C. The production method is characterized in that it is carried out at a hydrogen partial pressure of bar. 2 The activity in the benzene test is at least
The catalyst of 0.15ml・ml ^-1・h ^-1 is 0.25－1.00ml・ml ^-1・
The method according to claim 1, characterized in that the method has an activity of h ^-1 . 3. Claims 1 or 2, characterized in that a catalyst having nickel sulfide and molybdenum sulfide on a support alumina is used and has an activity of at least 0.15 ml·ml ^-1 ·h ^-1 in the benzene test.
The method described in section. 4. Process according to claim 3, characterized in that the catalyst contains 2-10 pbw of nickel and 5-20 pbw of molybdenum per 100 pbw (parts by weight) of alumina. 5 Activity in benzene test is 0.15ml・ml
^-1・h The catalyst lower than ^-1 is 0.025―0.0005ml・ml ^-1・
The method according to claim 1, characterized in that the method has an activity of h ^-1 . 6 Activity in benzene test is 0.15ml・ml
6. The method according to claim ¹ , wherein the catalyst having a lower value than -1.h ^-1 consists of a silica support on which nickel and vanadium are deposited. 7 The catalyst is 0.1 nickel per 100 pbw of silica.
7. Process according to claim 6, characterized in that it contains 10 pbw and 1-20 pbw of vanadium. 8. The method according to any one of claims 1 to 7, characterized in that the hydrogenation treatment is carried out at a temperature of 350-400°C. 9. Process according to any one of claims 1 to 8, characterized in that the hydrogenation treatment is carried out at a hydrogen partial pressure of 30-60 bar.