JPS607678B2 - Hydrocarbon conversion method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing one or more atmospheric pressure hydrocarbon oil crab extract from an atmospheric pressure hydrocarbon oil pot residue. In the production of verteous hydrocarbon oil crabmeat oil, in the atmospheric distillation of crude oil, which is carried out on a large scale in oil refineries, kettle residue is obtained as a by-product. Although this kettle residue may be suitable as a base material for the production of lubricating oils, it is now generally used only as a fuel oil, since it generally contains significant amounts of sulfur, metals and asphalt. Considering the increasing demand for atmospheric pressure hydrocarbon distillate oil,
Various processes have been proposed over the years to attempt to convert kettle bottoms to vertical distillate. Examples of such processes are catalytic cracking, pyrolysis, gasification combined with hydrocarbon synthesis, coking and hydrocracking. The use of Kamaiso oil as a feedstock for each of these processes has considerable drawbacks, as it significantly impairs the process on a commercial scale. For example, when these pot residues are catalytically cracked, catalyst consumption is very high and coke and gas are produced in large quantities, so that only a low yield of the desired atmospheric pressure crab product oil can be obtained. There is a significant drawback. Even in the case of producing atmospheric pressure distillate oil by thermally decomposing the pot residue, the decomposition product is stable, so conversion to the target atmospheric distillate oil is low, which is not preferable. Coking of the bottoms produces a significant amount of coke as a product, and the production of this coke comes at the expense of the desired yield of atmospheric crabmeat oil. Gasification of kettle bottoms in combination with hydrocarbon synthesis is rather expensive and, furthermore, in this process very heavy molecules are first broken down into very light molecules, which are then recombined. This is very undesirable because it results in a heavier molecule. Hydrocracking of kettle residue results in rapid deactivation of the catalyst, resulting in increased gas production and hydrogen consumption. Taking into account the above facts and the fact that when crude oil is distilled under atmospheric pressure, approximately half of the crude oil remains as distillation bottoms, it is possible to convert atmospheric hydrocarbon oil bottoms into distillation bottoms in an economically viable manner. It will be clear that there is a pressing need for a process capable of converting atmospheric hydrocarbon oil distillates. In fact, it has become clear that hydrocracking is an excellent process for converting fleasy hydrocarbon oil distillates, such as gas oil, to vertical hydrocarbon oil distillates, such as gasoline. , the present applicant has continued research to find out how to carry out hydrocracking to convert atmospheric hydrocarbon oil bottoms into atmospheric distillate oil. Correct combinations of hydrocracking as the main process (i.e. main step) with catalytic hydrotreating, deasphalting, gasification and pyrolysis or coking as subsidiary processes (i.e. sub-steps) can significantly serve this purpose. It has been found that this method can be suitable. According to the present invention, the following steps are carried out, namely: 'a-- A step of separating atmospheric hydrocarbon oil residue (AR) into vacuum distillate oil (VD) and vacuum residue (VR) by vacuum distillation, 'b 'Process

A step of deasphalting at least a part of the VR obtained in step {a-, which may also contain the distillation residue obtained in [c}, in a deasphalting belt to obtain deasphalted oil and asphalt; {c} At least a part of the stream selected from the VR obtained in the AR before step [a', the VR obtained in Koukae a] and the asphalt obtained in step {b-shape, is mixed with the asphalt obtained in step [f} A step of catalytic hydrotreating with hydrogen and distillation of the hydrotreated product to obtain a still residue, 'd} Step'c
} may also contain the still residue obtained in step {b}
a step of heating at least a part of the asphalt obtained in the heat treatment zone selected from the pyrolysis zone and the coking zone to obtain a liquid heat-treated product, 'e) step'd
} 'f} fractionating the liquid heat-treated product obtained in step 'e' into at least one final distillate product, a heat-treated middle distillate and a heat-treated kettle residue by distillation; AR comprising the above-mentioned steps of gasifying a stream selected from the heat treatment pot residue and coke obtained from the coking zone on the process side in a gasification zone to obtain hydrogen.
In the method for producing atmospheric pressure hydrocarbon oil crab product oil, the main steps include the following steps: (g) step {VD obtained in step a, deasphalted oil obtained in step 'd, a step of hydrogenolyzing at least a portion of the pot residue obtained in step (h) with the hydrogen obtained in step 'f} in a hydrocracking zone to obtain a hydrocracking product; and (h) fractionating the hydrocracked product obtained in step (g) by atmospheric distillation to obtain at least one light crab product final product and bottoms;
There is provided the above method, characterized in that the method includes: The main technical effect of the method of the present invention is that by hydrogenolysis,
The bottoms are essentially converted into gasoline (C5 - 20,000) and medium distillate (200-350 qo). In the method according to the invention, hydrocracking is used as the main process. In the hydrocracking process,
A significant portion of the young feedstock is converted to lighter products. The desired final product is separated from the decomposition products by atmospheric distillation. When one or more types of elevated distillate oils are to be produced as the final product, the bottom residue can be further treated by the following method. 1 Hydrocracking all the bottoms again. 2. The bottoms can be divided into two parts of the same composition, one of which is hydrocracked again and the other removed from the process and used, for example, as a blending component of fuel oil. 3. During the atmospheric distillation of the decomposition products, in addition to one or more types of vertical crab product oil, an atmospheric medium distillate M, which is to be hydrocracked again, is separated. This atmospheric distillation bound residue can be further processed in the following manner. {a} Remove all pot residue from the process. 'b} Split the bottoms into two parts of the same composition, hydrocrack one again and remove the other from the process. (c) Distillate oil is separated from the bottoms by vacuum distillation, and this distillate is again hydrocracked. The bottoms obtained by this vacuum distillation are either removed from the process or separated into two parts of the same composition. split, one is hydrocracked again and the other is removed from the process.In addition to one or more light distillates, an atmospheric medium distillate M, is to be produced as the final product. In this case, the remaining residue can be further treated in the same manner as in 1, 2 and 3'c) above. When the bottoms obtained by distilling the hydrocracked product are further processed, a method is used in which the bottoms are divided into two parts of the same composition, one part is hydrocracked again, and the other part is removed from the process. In this case, the amount of recycled material is preferably 25% by weight or more of the available remaining amount of the pot, and the lower the initial boiling point of the remaining pot, the more preferably this amount is used. The hydrocracking used in the process according to the invention is carried out by contacting the feedstock with a suitable hydrocracking catalyst at high temperature and pressure and in the presence of hydrogen. The hydrocracking is preferably carried out by the hair fall process, and the second stage of hydrocracking mainly reduces the nitrogen and aromatic content of the feedstock to be hydrocracked. This is done after catalytic hydrogenation treatment. Catalysts suitable for use in the one-stage hydrocracking process, like those used in the second stage of the two-stage hydrocracking process, are comprised of one or more metals having hydrogenation activity supported on a carrier. It is a moderately acidic and strongly acidic catalyst. Examples of suitable catalysts for use in the one-step hydrocracking process include nickel and/or
Alternatively, it is a fluorine-containing sulfurization catalyst in which cobalt and further molybdenum and/or tungsten are supported on alumina or amorphous silica alumina as a carrier. Examples of suitable catalysts for use in the second stage of the two-stage hydrocracking process are fluorine-containing sulfurized catalysts comprising nickel and/or cobalt and further molybdenum and/or tungsten supported on an amorphous silica-alumina support; A fluorine-containing or hydrogen-free sulfurization catalyst comprising nickel and/or cobalt and further molybdenum and/or tungsten supported on a crystalline silica-alumina support, and one or more fluorine-free sulfur catalysts. A fluorine-containing or fluorine-free catalyst comprising a noble metal, particularly palladium, supported on a crystalline silica alumina support. Catalysts suitable for use in the first stage of the second stage hydrocracking process include weakly acidic and moderately acidic catalysts comprising one or more metals having hydrogenation activity supported on a support, such as This is a fluorine-containing sulfurization catalyst comprising nickel and/or cobalt and molybdenum and/or tungsten supported on an alumina or malignant crystalline silica-alumina carrier. In the process according to the invention, if the hydrogenolysis is carried out in one step, the following reaction conditions are preferred: temperature 350-4260°C, especially 375-410°C, hydrogen partial pressure 50-30°C, especially 75-15°C. Rule, space velocity 0.25-5k9.1-1. h-1 especially 0.25~
2k9.1-1. h-1 and hydrogen/feedstock ratio 500~
300 sails. k9-1 especially on the 1000-250 side. k9
-1. If, in the process according to the invention, the hydrogenolysis is carried out in two stages, the following reaction conditions are preferred in the first stage: temperature 325-42,500 qo, especially 350-410 qo, hydrogen partial pressure 50-30 lbs, especially 75-150 bar, space velocity 0.1-5k9.1-1. h-1 especially 0.5-1.5
k9.1-1. h-1 and hydrogen/feedstock ratio 500-3
00 sails〆. k9-1. In the second stage, substantially the same conditions as in the one-stage process described above are preferred, except for the temperature, which should preferably be between 300 and 400 q<0>, particularly between 320 and 380<0>C. When hydrocracking is carried out in a two-stage process, it is preferred to use the entire reaction product from the first stage (excluding ammonia, hydrogen sulfide or other volatile components which are separated) as feedstock for the second stage. . In the method according to the present invention, catalytic hydrogenation treatment is applied as a sub-process to normal pressure pot residue, vacuum pot residue, or asphalt. This process converts highly undesirable compounds present in the feedstock for hydrocracking into compounds that are more suitable for hydrocracking. produced and isolated as the final product.
The hydrotreated product is divided into one or more normal pressure bonito distillate oil, normal pressure medium crab distillate oil M2 and an atmospheric residue as final products, and this atmospheric distillation residue is further subjected to vacuum distillation. It can be divided into vacuum distillate oil and vacuum pot residue. When catalytic hydrotreating is carried out on asphalt, the vacuum distillation described above on the atmospheric bottoms of the hydrotreating product can very suitably be replaced by a deasphalting process. The deasphalted oil obtained by deasphalting the residue from the atmospheric reactor is used as a feedstock component for hydrocracking, and asphalt is thermally cracked or coked. When it is intended to produce only one or more types of crab distillate oil as the final product by the method according to the present invention, atmospheric pressure medium distillate M2 is used as a feedstock oil component for hydrocracking. use. However, in addition to one or more types of light distillate oil, when it is intended to produce normal pressure medium quality crab extract oil M2 as the final product, the normal pressure medium quality distillate oil M2 is used as the final product. removed from the process as an object. The catalytic hydrogenation treatment as a secondary process in the method of the present invention is carried out by bringing the feedstock oil into contact with a non-acidic or weakly acidic catalyst at high temperature, high pressure, and in the presence of hydrogen. When carrying out a catalytic hydrogenation treatment, the following reaction conditions are preferred: temperature 380-500°C, especially 0-460 qo total, hydrogen partial pressure 50-30 lbs, especially 75-20 lbs, space velocity 0. .1~5kg. 1-1. h-1 especially 0.1~l
k9.1-1. h-1 and hydrogen/feedstock ratio 200-2
00 dishes Z. K9-1 especially 500-200 sails. k9-1
. The temperature in the case of carrying out the catalytic hydrogenation treatment is preferably at least 10° C., especially at least 2.0° C. higher than the hydrocracking temperature (in this context, when the hydrocracking is carried out in two stages, the temperature is preferably at least 10° C. higher than the hydrocracking temperature). should be understood to be the second stage temperature). Examples of suitable catalysts for catalytic hydrotreating include nickel and/or cobalt and also molybdenum,
Fluorine-containing or fluorine-free alumina, silica, sulfide catalysts comprising tungsten and/or vanadium supported on an alumina support, and nickel and/or cobalt and molybdenum, tungsten and/or vanadium supported on a silica or silica-alumina support. This is a sulfurization catalyst supported on The method according to the present invention further includes deasphalting as a subsidiary process. This deasphalting is preferably carried out at elevated temperatures and pressures and in the presence of an excess of lower hydrocarbons such as propane, butane or pentane as solvent. The method according to the invention further includes pyrolysis or coking as a subsidiary process. In these processes, a significant proportion of the bottom feedstock is converted to crabmeat oil. The product obtained by thermal cracking or coking is distilled, and in addition to the medium distillate M3 as the final product or as a raw material oil for hydrocracking, one or more final products are produced. The vertebral oil can be separated. The kettle residue remaining after processing the coke or pyrolysis products serves as feedstock for gasification. If the pyrolysis is carried out in the process according to the invention, it is preferably carried out at a temperature of 400 to 525 qo, a pressure of 2.5 to 25 bar and a residence time of 1 to 25 minutes. Particular preference is given to carrying out the pyrolysis at a temperature of 425 to 500 qo, a pressure of 5 to 20 bar and a residence time of 5 to 20 minutes. When coking is carried out in the method according to the present invention, it is preferably carried out at a temperature of 400 to 600 qo, a pressure of 1 to 2 dollars, and a residence time of 5 to 5 calm hours. Particular preference is given to coking at a temperature of 425 DEG to 550 DEG C., a pressure of 2.5 to 20 bar and a residence time of 10 to 4 feeding hours. Finally, the method according to the invention includes gasification as a subsidiary process. As raw material for gasification, the kettle residue remaining after processing the coke or the products obtained by pyrolysis is used.
Gasification is performed by incomplete combustion of raw materials with oxygen. Preferably, steam is added to the mixture as a moderator. Incomplete combustion produces crude (crMe), which consists mostly of carbon monoxide and hydrogen and also contains a significant amount of sulfur.
Gas is obtained. The hydrogen content of this crude gas increases if the crude gas is subjected to a water gas conversion reaction. In this reaction, carbon monoxide reacts with steam and is converted into carbon dioxide and hydrogen. The water gas conversion reaction consists of passing the gas to be converted through two or more reactors containing a hot water gas conversion catalyst at a temperature of 325 to 40,030 ℃, and then converting the partially converted gas mixture to a cold water gas at a temperature of 200 to 275 q0. Preferably, it is carried out through a reactor containing a conversion catalyst. Iron-chromium catalysts are very suitable as high temperature water gas conversion catalysts. An effective low temperature water gas conversion catalyst is a copper-zinc catalyst. Considering that contamination of the catalyst by soot is remote, when using conventional reactors, the gas must be freed from soot at least before it is subjected to the catalytic water gas conversion reaction. When using sulfur-sensitive catalysts such as the iron-chromium and copper-zinc catalysts described above, sulfur must also be removed from the gas before it is subjected to the catalytic water gas conversion reaction. Sulfur-insensitive catalysts such as Ni/Mo/AI2Q or Co/84o/A according to Japanese Patent No. 1108382 (Jiko Sho 56-52844)
i203 catalyst or Ni/Mo/AI/ according to the specification of Japanese Patent No. 1108384 (Japanese Patent Publication No. 56-52845)
When using AI203 or Co/Mo/AI/AI203 catalysts, removing sulfur from the crude gas can be omitted. The water gas conversion reaction takes place at a pressure of 10
It is preferred to carry out the reaction at a pressure of 10 to 10 bar, especially 20 to 80 bar. The amount of steam present in the gas mixture carrying out the water gas conversion reaction is between 1 and 5 mol of steam per mole of carbon monoxide.
It is preferable to set it to 0 mol. In order to obtain pure hydrogen after the completion of the water gas conversion reaction, the hydrogen-rich gas must be purified. If soot and sulfur have not been removed prior to the water gas conversion reaction, they must be removed again. Furthermore, the purification of the hydrogen-rich gas consists, inter alia, of removing the carbon dioxide formed and the unconverted carbon monoxide. In the method according to the present invention, hydrogen produced by gasification is
Mainly used for catalytic hydrotreating and hydrocracking. The process is preferably carried out in such a way that the amount of hydrogen produced by gasification is sufficient to at least fully satisfy the hydrogen requirements of catalytic hydrotreating and hydrocracking.
If the amount of hydrogen produced in gasification is greater than that required for catalytic hydrotreating and hydrocracking, the excess amount of hydrogen can be used for purposes outside the scope of the process. If the amount of hydrogen produced by gasification does not meet the hydrogen requirements for catalytic hydrotreating and hydrocracking, the required amount of hydrogen must be newly supplied from outside the process. The amount of hydrogen obtained by gasification is mainly determined by the amount of raw material supplied to the gasification belt. The amount of feedstock can be controlled to some extent by varying the conditions under which the catalytic hydrotreating, deasphalting and pyrolysis or coking are carried out. A further preferred means for controlling the amount of feedstock sent to the gasification zone is as follows: 'a) A portion of the bottom residue of the product obtained from hydrocracking is subjected to pyrolysis, coking, etc. or as a feedstock component for gasification; {b' repeating catalytic hydrogenation on the heavy fraction of a product that has already been catalytically hydrotreated; 'c} instead of treating all of the material, some Catalytic hydrogenation treatment of only suitable substances; [d} Combination of the methods described in 'a-'c-. In the case of 'c), atmospheric distillation residue, vacuum distillation residue obtained by vacuum distilling it, or asphalt obtained by deasphalting vacuum residue, which is useful as a raw material for the process, is used. Only a portion is catalytically hydrotreated and the remainder is mixed with the hydrotreated product. 'c} In each of the three embodiments of the process according to the invention briefly described above, the bottoms obtained by catalytically hydrogenating asphalt and/or the same and distilling the hydrotreated product are: Since it can be converted by pyrolysis or coking, these three embodiments correspond to six process examples. These six process examples will be described in detail below with reference to the accompanying drawings. Process example 1 (see Figure 1) This process includes a catalytic hydrotreating device 1, a first atmospheric distillation device 2, a vacuum distillation device 3, a deasphalting device 4, a pyrolysis device 5,
The process is carried out in a plant consisting of a second atmospheric distillation device 6, a gasification device 7, a catalytic hydrocracking device 8, and a third atmospheric distillation device 9. The atmospheric pressure hydrocarbon oil pot residue 10 is divided into two parts 11 and 12.
11 is catalytically hydrotreated, and the hydrotreated product 13 is divided into C4-crab fraction 14, Ganlin fraction 15, medium distillate fraction 16, and bottom bottom 17 by atmospheric distillation. The bottoms 17 are mixed with 12 from the normal pressure bottoms 10, and the mixture is vacuum distilled to separate into vacuum crab oil 18 and vacuum bottoms 19. The pot residue 19 is deasphalted and separated into deasphalted oil 20 and asphalt 21. The asphalt 21 is thermally decomposed, and the thermal decomposition product 22 is distilled under atmospheric pressure and divided into a C4-crab fraction 23, a Ganlin fraction 24, a medium distillate oil fraction 25, and a pot residue 26. Gasified and the resulting gas is converted into a waste gas 28 consisting of hydrogen 27 and mostly carbon dioxide by a water gas conversion reaction and purification. 30 is supplied for catalytic hydrocracking. The vacuum distillate oil 18 is hydrocracked together with the deasphalted oil 20. The hydrocracked product 31 is distilled under atmospheric pressure to obtain C4-crab fraction 32 and gasoline crab fraction. 33, divide the medium distillate oil into crab fraction 34 and pot residue 35. Divide pot residue 35 into two,
One part 36 is subjected to hydrocracking again, and the other part 37 is used as a raw material component for gasification. Process Example 0 (See Figure 0) This process is carried out in a plant almost identical to that described in Process Example 1, except that the coking device 5 of the previous pyrolysis device 5 is used. . The treatment of the atmospheric pressure hydrocarbon oil pot residue 10 is carried out in substantially the same manner as Process Example 1, from deasphalting the pot residue 19 to dividing the deasphalted oil 20 and asphalt 21' (including the division). The asphalt 21 is converted into crab oil 22 and coke 23 by coking. Crab extract oil 22 is distilled under atmospheric pressure to produce C4
- Divided into fraction 24, gasoline crab fraction 25, medium distillate crab fraction 26 and bottoms 27 removed from the process. Coke 2
3 is gasified and the resulting gas is converted to hydrogen 28 and waste gas 29 consisting mostly of carbon dioxide through a water gas conversion reaction and purification. Hydrogen 28 is divided into two parts, one 30 being supplied for catalytic hydrotreating and the other 31 being supplied for catalytic hydrocracking. The vacuum distillate oil 18 is hydrocracked together with the deasphalted oil 20, but in this case, in addition to hydrogen 31, fresh hydrogen 32 is supplied for hydrocracking. The hydrocracked product 33 is distilled under atmospheric pressure and divided into a C4-crab fraction 34, a gasoline crab fraction 35, a medium crab product fraction 36, and a pot residue 37 to be rehydrocrazed. P. Process example m (see figure m) This process consists of a first vacuum distillation device 1, a catalytic hydrogenation device 2,
First atmospheric distillation device 3, second vacuum distillation device 4, deasphalting device 5
, pyrolysis device calendar 6, second atmospheric distillation device 7, gasification device 8,
The process is carried out in a plant consisting of a catalytic hydrocracking device 9 and a third atmospheric distillation device 10. Atmospheric pressure hydrocarbon oil pot residue 11 is vacuum distilled to vacuum distillate oil 1
2 and vacuum pot residue 13. The vacuum pot residue 13 is divided into two parts 14 and 15. 14 is subjected to catalytic hydrogenation treatment, and the hydrotreated product 16 is distilled at atmospheric pressure and separated into a C4-crab fraction 17, a Ganlin fraction 18, a medium sludge oil crab fraction 19, and two pot residues. The residue 20 is vacuum distilled and separated into a vacuum distillate oil 21 and a vacuum residue 22. The vacuum pot residue 22 is 1 from the vacuum pot residue 13.
5 and the mixture is deasphalted and separated into deasphalted oil 23 and asphalt 24. The asphalt 24 is thermally decomposed, and the thermal decomposition product 25 is distilled under atmospheric pressure and divided into C4-crab fraction 26t Ganlin fraction 27, medium crab extract crab fraction 28, and pot residue 29. The bottoms 29 are gasified and the resulting gas is converted to hydrogen 30 and waste gas 31 consisting mostly of carbon dioxide through a water gas conversion reaction and purification. Hydrogen is divided into three streams, one 32 being supplied for catalytic hydrogenation treatment and the other 33 for catalytic hydrocracking. The vacuum crab oil 12 is hydrocracked together with the deasphalted oil 23. The hydrocracked product 34 is separated into a C4 fraction 35, a Ganlin fraction 36, a medium distillate fraction 37, and a bottom bottom 38 by atmospheric distillation. The bottom 38 is divided into two parts, one part 39 is again hydrocracked and the other part 40 is removed from the process. Process Example W (See Figure W) This process is carried out in a plant almost identical to that described in process example m, except that a coking device 6 is used instead of the pyrolysis device 6 described above. The atmospheric pressure hydrocarbon oil pot residue 11 is treated in substantially the same manner as Process Example M until the mixture of 15 and 22 is deasphalted and divided into deasphalted oil 23 and asphalt 24 (including division). Asphalt 24 is coked and distilled oil 2
5 and coke 26. Distillate 25 is atmospherically distilled into a C4 fraction 27, Ganlin fraction 28, medium distillate fraction 29, and bottoms 30 which are removed from the process.
The coke 26 is gasified and the resulting gas is converted to hydrogen 31 and waste gas 32 consisting mostly of carbon dioxide through a water gas conversion reaction and purification. The hydrogen 31 is divided into two parts, one 33 is supplied for catalytic hydrotreating and the other 34 is supplied for catalytic hydrocracking. The vacuum oils 12 and 21 are hydrocracking together with the deasphalted oil 23. The decomposition product 35 is distilled under atmospheric pressure to obtain C4-crab fraction 36 and gasoline crab fraction 3.
7. It is divided into a medium distillate fraction 38 and a bottom residue 39 to be hydrocracked again. Process Example V (See Figure V) This process consists of a first vacuum distillation device 1, a deasphalting device 2, a catalytic hydrogenation device 3, a first atmospheric distillation device 4, a second vacuum distillation device 5, and a pyrolysis device. 6. Second atmospheric distillation device 7, gasification device 8, catalytic hydrocracking device 9, and third atmospheric distillation device 1
This is done in a plant consisting of 0. The atmospheric pressure hydrocarbon oil pot residue is vacuum distilled to vacuum distillate oil 1.
2 and vacuum pot residue 13. The vacuum pot residue 13 is deasphalted and separated into deasphalted oil 14 and asphalt 15. Asphalt 15 is divided into two parts 16 and 17. 16 was subjected to catalytic hydrogenation treatment, and the hydrogenation product 18 was distilled at atmospheric pressure to obtain C.
4 - Fraction 19, Ganlin fraction 20, Medium distillate fraction 21
and the remainder of the pot is divided into 22 parts. The residue 22 is vacuum distilled and separated into a vacuum distillate oil 23 and a vacuum residue 24. Vacuum pot residue 24 is mixed with asphalt 17 from asphalt 15 and the mixture is pyrolyzed. Pyrolysis product 2
5 is distilled under atmospheric pressure to obtain C4-crab fraction 26 and Ganlin fraction 27.
, medium-quality crab oil is divided into 28 pieces of crab oil and 29 pieces of leftovers from the pot. Remaining pot 29
is gasified and the resulting gas is converted to hydrogen 30 and waste gas 31 consisting mostly of carbon dioxide through a water gas conversion reaction and purification. Hydrogen 30 is divided into two parts, one 32 being fed for catalytic hydrotreating and the other 33 being fed for catalytic hydrocracking. Vacuum crab oil 12 and 23 are deasphalted oil 14
Hydrogenolysis together with The hydrocracked product 34 is distilled under atmospheric pressure and divided into a C4-crab fraction 36, a Ganlin fraction 36, a medium crab product fraction 37, and a bottom 38. The residue 38 is divided into two parts, one part 39 is again hydrocracked, and the other part 40 is recycled. Exclude from Seth. This process is carried out in a plant that is almost the same as that described in Process Example V, except that the second vacuum distillation device 5 does not exist, and the pyrolysis device The caulking device 5 is used instead of the caulking device 6. The atmospheric pressure hydrocarbon oil pot residue 10 is vacuum distilled to obtain 1 vacuum distillate oil.
Divide into 1 and 12 parts left in the vacuum pot. The vacuum pot residue 12 is deasphalted and divided into deasphalted oil 13 and asphalt 14. The asphalt 14 is divided into two parts 15 and 16. 15 was subjected to catalytic hydrogenation treatment, and the hydrogenated product 17 was distilled under atmospheric pressure to produce C4
- Separate into 18 crab parts, 19 gasoline crab parts, 20 medium crab oil parts, and 21 pot residues. Bottoms 21 is mixed with 16 from asphalt 14 and the mixture is coked and converted to distillate 22 and coke 23. Crab extract oil 22 is distilled under atmospheric pressure to obtain C4-fraction 24.
, Ganlin fraction 25, medium distillate fraction 26, and bottoms 27 which are removed from the process. The coke 23 is gasified and the resulting gas is converted to hydrogen 28 and waste gas 29 consisting mostly of carbon dioxide through a water gas conversion reaction and purification. Hydrogen 28 is divided into two parts, one part 30 is supplied for catalytic hydrogenation treatment and the other part 31 is supplied for axial hydrocracking. The vacuum-derived oil 11 is hydrocracked together with the delit oil 13, but in this case, in addition to hydrogen 31, fresh hydrogen 32 is supplied for hydrocracking. Hydrogenolysis product 3
3 is distilled under atmospheric pressure to obtain 34 C4 fractions and 35 gasoline crab fractions.
, a medium distillate fraction 36 and a bottom bottom 37. Remaining pot 37
is split in two, one 38 is hydrocracked again and the other 39 is removed from the process. The present patent application also includes a plant for carrying out the method according to the invention, as shown in the first diagram. The invention is illustrated according to the following examples. The method according to the present invention was carried out on atmospheric distillation residues of crude oil from the Middle East. The Josho distillation still residue had an initial boiling point of 350oo, a sulfur content of 4% by weight, and a C4 asphalt content of 2% by weight. The method was carried out according to Process Example 1 - Town. The following conditions were used in each process. In all process examples,
Sulfide containing 5 parts by weight of cobalt and 1 part by weight of molybdenum to 10 parts by weight of alumina
A Co/Mo/AI203 catalyst was used for the catalytic hydrogenation. In the case of process examples 1 to W, the average temperature is 390qC
, hydrogen partial pressure 100 bar and hydrogen/oil ratio 100 states/
Catalytic hydrogenation treatment was performed with k9. Process examples 1 and 0
'If this is the case, catalytic hydrogenation treatment is performed at a space velocity of 0.7
5 [9.1-1. h-1 and according to process examples m and W, the space velocity is 0.4k9.1-1. h
-1. In accordance with Process Example V and
The catalytic hydrogenation treatment was carried out at an average temperature of 45 psi, a hydrogen partial pressure of 15 ruels, and a space velocity of 0.2 k9.1-1. It was carried out at h-1 and hydrogen/oil ratio of 1500N/k9. In all process examples, deasphalting was carried out using liquid butane as the solvent and a solvent/oil weight ratio of 3.5:1 to 4.5:1. In the case of process examples 1 to m, V and, the deasphalting temperature is set to 12030, and in the case of process example W, the temperature is set to 1.
It was set to 40 qo. In the case of process examples 1, m and V, the pyrolysis was carried out at a pressure of 1 bar, a residence time of 15 minutes and a temperature of 450°C to 47,000°C.
In the case of and, caulking was carried out at a pressure of 3.5 degrees, a temperature of 470 DEG C., and a residence time of 20 to 2 feed hours. In all process examples, gasification was carried out at a temperature of 1300°C, a pressure of 3 ng, and a steam/feedstock weight ratio of
The weight ratio of both raw materials was set to 0.8:1. The water gas shift reaction was carried out over an iron-chromium catalyst at a temperature of 350 °C and a pressure of 30 bar, and at a temperature of 250 °C and a pressure of 3
It was carried out continuously over a copper-zinc catalyst at Ruehl. All pu. In this example, catalytic hydrocracking was carried out in a two-stage process, where all the reaction products from the first stage were used as feedstock for the second stage, and a portion of the cracked products were recycled to the first stage. . In all process examples, 5 parts by weight of nickel and 2 parts by weight of molybdenum per 100 parts by weight of alumina were used for the first stage of catalytic hydrocracking.
Ni/Mo/F sulfide containing parts by weight of and 15 parts by weight of fluorine
/N203 catalyst and for the second stage a Ni/W/F/sulfide containing 3 parts by weight of nickel, 10 parts by weight of tungsten and 5 parts by weight of fluorine per 10 parts by weight of faujasite.
A faujasite catalyst was used. In all process examples, the first stage of catalytic hydrocracking was carried out at an average temperature of 390 °C and a pressure of 12
Lure, hydrogen/oil ratio 2000N. k9-1 and space velocity 0.79.1-. h-1, and the second stage was carried out at an average temperature of 365 °C, a pressure of 120 bar, and a hydrogen/oil ratio of 20.
0 state evening. kg-1 and space velocity 1.9. r1. It was done in h1. Example 1 This example was conducted according to Process Example 1. Starting from 350 parts by weight of 1010 atmospheric distillation residues, the following amounts of each substance were obtained: 1 14
9. parts by weight, 1251 parts by weight, C4-crab part 142.1 parts by weight, C5200oo gasoline part 150.4 parts by weight, 200 parts by weight.
~350oo Medium Distillate Oil Crab 1624 parts by weight, 350q
o + normal pressure pot residue 1744. parts by weight, 350-52000
Vacuum crab extract oil 1850. $ parts by weight, 520oo + vacuum pot residue 1944. Neck weight part, deasphalted oil 2030. Drag weight part, asphalt 2114 parts by weight, C4-crab content 230.1 parts by weight, C5200q0 gasoline crab content 241.1 parts by weight, 200
~350q0 medium quality crab extract oil fraction 251.5 parts by weight, 35 pp0 normal pressure crab extract oil 2611. Parts by weight of round, 272 parts by weight of hydrogen, 290. Loading weight part, 302. parts by weight, C4-crab part 324.4 parts by weight, C520000 gasoline crab part 3353. Parts by weight of 20
0-350qo medium crab oil fraction 3423.4 parts by weight, 3
50oo 10 atmospheric pressure pot residue 356.4 parts by weight, 364.4 parts by weight, and 372. parts by weight. Example 0 This example was conducted according to Process Example nl. Starting from 35,000 parts by weight and 1,010 parts by weight of atmospheric still residue, the following amounts of each substance were obtained: 1 12
7.2 parts by weight, 1272. Part by weight of base, 141.1 parts by weight of C4-distillate, 150 parts by weight of gasoline crab, 200~3
50 qo medium distillate crab content 161.4 parts by weight, 35 qo atmospheric pressure cooker residue 1724. Parts by weight of 350-52 p0 vacuum distillate oil 1847. Mother weight part, 520℃, vacuum pot residue 1949
．． Parts by weight of bamboo, 2032.1 parts by weight of deasphalted oil, 2117 parts by weight of asphalt. parts by weight of distillate, 228.2 parts by weight of distillate, 239.5 parts by weight of coke, 242 parts of C4-crab fraction, 251 parts of C200°C gasoline crab. Beni weight part, 200-3
50°C medium distillate fraction 262.2 parts by weight, 350°C normal pressure pot residue 272. parts by weight of hydrogen, 281. Military weight part, 300.4 weight part, 311. Parts by weight of a, 321.2 parts by weight of hydrogen, 344.5 parts by weight of C4-crab fraction, 3553 parts by weight of C5200. Mother weight part, 20
3624.1 parts by weight of crab in medium quality crab extract oil at 0 to 300°C, and 378.1 parts by weight of 350 qo atmospheric pressure cooker residue. Example m This example was carried out according to Process Example m. Starting from 110 parts by weight of 350 qo and 1 atmospheric still residue, the following amounts of each substance were obtained: 350
~520oo vacuum distillate oil 1244. Wide weight section, 520℃
1356 remaining in the ten-vacuum pot. Parts by weight, 1423. Parts by weight of turtle, 1532.2 parts by weight, C4-crab part 171. Weight part, C520000 gasoline crab part 181. Box weight part, 200
~350oo medium distillate fraction 193. Box weight part, 350
qo 10 normal pressure pot residue 2018.2 parts by weight, 350-5200
0 vacuum distillate oil 218.4 parts by weight, 52 pi 0 vacuum pot residue 2
29. Neck weight part, deasphalted oil 2327.5 parts by weight, asphalt 2414.5 parts by weight, C4-crab fraction 260.2 parts by weight, C5 200°C Ganlin fraction 271. Parts by weight of 200~
350qo medium distillate fraction 281.4 parts by weight, 350°C
2911.9 parts by weight of atmospheric pressure pot residue, 302.9 parts by weight of hydrogen. Round weight parts, 320. Mother weight part: 331.0 parts by weight, C4-distillate: 354.1 parts by weight, C20 pi○ganlin fraction: 3648. Turtle weight part, 200~
3503○Medium quality crab extract crab content 3721.4 parts by weight, 350
℃10 Normal pressure pot residue 3810.5 parts by weight, 393. parts by weight,
and 407.5 parts by weight. Example W This example was conducted according to Process Example W. Starting from 110 parts by weight of 350 pm C + 1 atmospheric still residue, the following noses were obtained for each substance: 35
0-52000 pages air distilled oil 1244. ■Weight part, 520
300 vacuum pot residue] 356. Parts by weight, 1411. Neck weight part, 1544.2 weight part, C4-crab part 170. Neck weight part, C5200oC Ganrin fraction 180.0 parts by weight ~ 200
~35000 Medium quality crab extract crab content 191.5 parts by weight, 350
oo + 9 parts of normal pressure pot residue 2 parts, 350-520 C summer air distilled oil 214. Weight part ~ 520 qo 1 vacuum pot residue 22
44 parts by weight of neck, 2323.5 parts by weight of deasphalted oil, 25.5 parts by weight of asphalt, 2611.0 parts by weight of distillate, 2613 parts by weight of coke, 273.2 parts by weight of C4-crab, C520000 Gasoline crab part: 282. Bamboo weight part: 200
~350qo Medium quality crab extract crab content 293.1 parts by weight, 350
qo 10 atmospheric pressure pot residue 302. Part by weight: Hydrogen 312.5 parts by weight, 330.2 parts by weight, 342 Parts by weight: C4-fraction 364.% by weight, C5200qo gasoline fraction 3750. Broad weight parts, 2
00-35000 Medium Distillate Oil Crab 3820. parts by weight,
and 350oo + normal pressure pot residue 397. Box weight part. Example V This example was conducted according to Process Example V. Starting from 110 parts by weight of 35,000 atmospheric still residues, the following amounts of each substance were obtained: 350
0~520oo vacuum distilled oil 1244. parts by weight, 52
0qo ten vacuum pot remaining 1356. Part by weight of deasphalted oil 1433
．． parts by weight, asphalt 1523.0 parts by weight, 1610. Parts by weight, 1713. Parts by weight, C4-Crab 191. Part by weight, C5200oo Ganlin fraction 200.9 parts by weight, 200
~350oo medium distillate fraction 213. Mother weight part, 350
oo 10 Normal pressure pot residue 224.4 parts by weight, 350-52 and 0 vacuum crab extract oil 232. Box weight part, 520oo + vacuum pot remaining 24
2.1 parts by weight, C4-crab fraction 260.2 parts by weight, Q200qo Ganlin fraction 271. Public weight part, 200~
350qo medium crab oil fraction 281. Tortoise weight part, 350℃
2912.1 parts by weight of atmospheric pressure cooker residue, 302.4 parts by weight of hydrogen, 320.5 parts by weight, 331. $ parts by weight " C4 - 轡 354. Parts by weight, C200qo Ganrin fraction 3652.4 parts by weight, 200
~350pm Medium distillate fraction 3722.8 parts by weight, 35
0:00:00 Remaining pressure pot 386. This example was carried out according to the process example.Starting from 350 oooo and 1000 yen parts by weight of the residue from the atmospheric distillation pot, The following amounts were obtained for the substance; 350-5
20qC vacuum crab oil army 144. Parts by weight, 520oo
1256 remaining in the ten-vacuum pot. Parts by weight of deasphalted oil 1332. Part by weight of Asphalt, 423.1 parts by weight of Asphalt, 511.2 parts by weight of Asphalt, 611.2 parts by weight of C4-distillate, 181.5 parts by weight of C4-distillate, 200 parts by weight of C5, 200°C Ganlin distillate, 91.
35000 medium distillate fraction 204.4 parts by weight, 350q
o + normal pressure pot residue 214. parts by weight, boxed oil 228.5 parts by weight, coke 238. Box parts by weight, C4-Fraction 242. Parts by weight of the box, 200 parts by weight, 251.9 parts by weight of Ganlin distillate, 200~
350°C medium distillate fraction 262. Maru weight department, 350 pm
10 Normal pressure pot residue 272. parts by weight, hydrogen 281.5 parts by weight, 300. Turtle weight part, 310. Base weight department, hydrogen 321. 344.1 parts by weight of C4-distillate, 3550 parts by weight of C5200. Red weight part, 20
0-350oo medium distillate oil crab content 3622.2 parts by weight, 3
50 qo atmospheric pressure pot residue 375 parts by weight, 384.1 parts by weight, and 391.0 parts by weight.

[Brief explanation of drawings]

Figures 1, 0, m, W, V, and 5 show process diagrams according to the present invention. In FIG. 1 and FIG. 5...Pyrolysis device (first
(Figure) or coking device (Figure 0), 6... Second atmospheric distillation device, 7... Gasification device, 8...
- Catalytic hydrocracking device, 9...Third atmospheric distillation device. In Fig. M and Fig. W, 1...first vacuum distillation apparatus, 2...catalytic hydrogenation apparatus, 3...
...First atmospheric distillation device, 4...Second vacuum distillation device, 5...Deasphalting device, 6...Pyrolysis device (Fig. ) or caulking device (Figure W), 7
. . . Second atmospheric distillation device, 8… Gasification device, 9… Catalytic hydrocracking device, 10… Third atmospheric distillation device. In FIG. equipment, 5.
...Second vacuum distillation device, 6...Pyrolysis device,
7... Second atmospheric distillation device, 8... Gasifier, 9... Catalytic hydrocracking device, 10...
...Third atmospheric distillation device. In the figure, 1...
・Vacuum distillation equipment, 2... Deasphalting equipment, 3...
... Catalytic hydrotreating device, 4... First atmospheric distillation device, 5... Coking device, 6...
Second atmospheric distillation device, 7...Gasification device, 8...
...Catalytic hydrocracking device, 9...Third atmospheric distillation device. FIGIFIG. 11FIG OO FIG. Mouth Z FIG・1 [FIG. y is

Claims (1)

[Scope of Claims] 1. The following steps: (a) a step of separating atmospheric hydrocarbon oil bottoms (AR) into vacuum distillate (VD) and vacuum bottoms (VR) by vacuum distillation; b) At least a portion of the VR obtained in step (a), which may also contain distillation residue obtained in step (c),
(c) a step selected from AR before step (a), VR obtained in step (a) and asphalt obtained in step (b) by deasphalting in a deasphalting zone to obtain deasphalted oil and asphalt; (d) catalytically hydrotreating at least a portion of the collected stream with the hydrogen obtained in step (f) and distilling the hydrotreated product to obtain a bottoms; (d) step (c) At least a part of the asphalt obtained in step (b), which may also contain still residue obtained in step (b), is heated in a heat treatment zone selected from a pyrolysis zone and a coking zone to form a liquid heat treatment product. (e) fractionating the liquid heat-treated product obtained in step (d) into at least one light distillate final product, a heat-treated middle distillate and a heat-treated kettle residue by distillation; (f) gasifying a stream selected from the heat-treated kettle residue obtained in step (e) and the coke obtained from the coking zone in step (d) in a gasification zone to obtain hydrogen; In the method for producing atmospheric hydrocarbon oil distillate from AR, the main steps include the following steps: (g) the V obtained in step (a);
D. Hydrocracking the deasphalted oil obtained in step (b) and at least a portion of the bottom residue obtained in step (h) in a hydrocracking zone with hydrogen obtained in step (f). (h) fractionating the hydrocracked product obtained in step (g) by atmospheric distillation to obtain at least one light distillate final product and bottoms; The above method, characterized in that it includes the step of obtaining. 2 obtaining in step (h) at least one light distillate final product, a medium distillate M_1 and a bottom residue, M_
1 in step (g); the residue is subjected to the following treatments, namely (I) removal from the process; (II) dividing it into two parts of the same composition, one of which is subjected to step (g). hydrocracking and removing the other from the process;
and (III) a process of separating by vacuum distillation into the vacuum distillate to be hydrocracked in step (g) and the vacuum pot residue to be subjected to the treatment in (I) or (II). A method according to claim 1, characterized in that it is subjected to selected treatments. 3 obtaining at least one light distillate final product, medium distillate final product M_1 and bottom residue in step (h);
This residue is separated into a vacuum distillate oil and a vacuum residue by vacuum distillation, the vacuum distillate is hydrocracking in step (g), and the vacuum residue is subjected to the following treatment, namely (I). and (II) dividing into two parts of the same composition, subjecting one to a treatment selected from hydrocracking in step (g) and removing the other from the process. A method according to claim 1. 4. Splitting the bottoms obtained in step (h) into two parts of the same composition, one being hydrocracked in step (g) and the other being removed from the process, being recycled to step (g). The method according to any one of claims 1 to 3, characterized in that the amount of the substance is 25% by weight or more of the available pot residue obtained in step (h). . 5
The process (
The method according to any one of claims 1 to 4, characterized in that g) is subjected to hydrogenolysis. 6. Hydrocracking of step (g) is carried out in two hydrocracking zones, i.e. a catalyst selected from weakly acidic and moderately acidic catalysts comprising at least one metal having hydrogenation activity supported on a support. and in the second zone in the presence of a catalyst selected from moderately acidic and strongly acidic catalysts comprising at least one metal having hydrogenation activity supported on a support. 5. A method according to any one of claims 1 to 4, characterized in that: 7. Claim 6, characterized in that the entire reaction product from the first zone is used as feedstock for the second zone.
The method described in section. 8. Claims 1 to 1, characterized in that a part of the pot residue obtained in step (h) is used as a raw oil component for at least one of steps (d) and (f). The method described in any one of Section 7.