TWI275636B - New hydrocracking process for the production of high quality distillates from heavy gas oils - Google Patents

Abstract

This invention is directed to processes for the conversion of material boiling in the vacuum gas oil boiling range to high quality middle distillates and/or naphtha and lighter products, and more particularly to a multiple stage process using a single hydrogen loop. One embodiment is directed to the use of hot strippers and separators between the first and second stages, while second embodiment is directed to temperature control between hydrocracking and hydrotreating zones. All embodiments employ a single hydrogen loop.

Description

1275636 玖, invention description: ... [Technical Field of the Invention] The present invention relates to a method for converting a material boiling in a vacuum diesel boiling range into a high quality middle distillate and/or naphtha and a lighter product ' More specifically, it relates to a multi-stage approach using a single hydrogen loop. [Prior Art] In the refining of crude oil, a single reaction stage or a multiple reaction stage is used to convert heavy diesel oil into a lighter product by a diesel hydrocracker. In most of the examples, the various reaction stages are operated at similar pressure levels. Separate hydrogen circuits are used where the pressure levels are different. We use multiple reaction stages to achieve the following: • High conversion rate from minimum reactor volume and contact media volume from start to finish • Better product quality φ lower hydrogen consumption However, the use of multiple reaction systems involves more equipment, including Multiple expensive high pressure pumps and compressors. U.S. Patent No. 5,980,729 uses a configuration having multiple reaction zones in a single hydrogen loop. The process uses a thermal stripper downstream of the denitrification/desulfurization zone. The liquid from the hot stripper is pumped to a hydrocracking reactor upstream of the hydrotreating reactor. The recycled oil from the fractionation section is also taken back to the hydrocracking reactor. In conventional hydrotreating, it is desirable to convert hydrogen from a vapor phase to a liquid phase where it will react with a petroleum molecule at the catalyst surface. This is accomplished by circulating a very large amount of hydrogen and oil through a catalyst bed. The oil and hydrogen streams 84200 -6 - 1275636 pass through the catalyst bed and hydrogen is absorbed into the oil film distributed over the catalyst. Since the amount of hydrogen required can be large (1000 to 5000 SCF/bbl of liquid) and the amount of catalyst required can be large, the reactor is very large and can be operated under severe conditions, from hundreds of psi to It is as much as 5000 psi and a temperature of about 400 °F to 90 CTF. U.S. Patent No. 6,224,747 teaches hydrocracking a VGO stream in a hydrocracking reaction zone in an integrated hydroconversion process. The effluent from the hydrocracking reaction zone is combined with a light aromatic feedstock stream and the blended stream is hydrotreated in a hydrotreating reaction zone. The hydrocracked effluent is used as a heating tank for the hydrotreating reaction zone. The integrated reaction system provides a single hydrogen replenishment and recycle system for use in two reaction systems. However, there is no temperature control between the hydrocracking reaction zone and the hydrotreating reaction zone. U.S. Patent No. 3,592,757 (Baral) teaches the use of a heat exchanger for temperature control in two zones, as in the present invention. Baral does not use a single hydrogen loop, as in the present invention. Baral discloses a hydro refiner (similar to a hydrotreater) that operates continuously with a hydrocracker and feeds a fraction product to a hydrogenator. A diesel feed is fed to the hydrorefiner together with both the make and recycle hydrogen. A recycle stream and additional recycle hydrogen are added to the hydrorefiner product stream and the mixture is fed to the hydrocracker. The hydrocracker product stream is cooled and separated into a vapor stream and a liquid stream. The vapor stream is recycled to the hydrorefiner through a recirculating hydrogen compressor. The liquid stream is fractionated into upper, middle and bottom streams. The bottom stream is recycled to the hydrocracker. The intermediate stream is mixed with hydrogen from a supplemental hydrogen compressor and directed to a hydrogenator. The hydrogen recovered from the hydrogenator is compressed in a supplemental hydrogen compressor stage and directed to the hydrorefining unit. U.S. Patent No. 5,114,562 (Haun et al.) teaches a two-stage hydrodesulfurization process (similar to hydrotreating) and a hydrogenation process for distilling hydrocarbons. There is heat exchange between the two stages, but no single hydrogen loop is used. The two separate reaction zones are used continuously, the first zone for hydrodesulfurization and the second zone for hydrogenation. The feed is mixed with recycled hydrocarbons and fed to a desulfurization reactor. Hydrogen sulfide is stripped from the sparse reactor product by a countercurrent hydrogen stream. The liquid product stream from this stripping operation is mixed with the cleaner recycled hydrogen and the mixture is fed to the hydrogenation reaction zone. Hydrogen is recovered from the hydrogenation reactor and recycled to the desulfurization reactor and the hydrogenation reactor as a split. The hydrogen from the stripping operation is passed through a separator, mixed with the recycle hydrogen toward the hydrogenation reactor, compressed, passed through a processing step and recycled to the hydrogenation reactor. Thus, the hydrocarbon feed stream continuously passes through the desulfurization and hydrogenation reactor while providing a lower pressure hydrogen for the desulfurization step and a more south pressure hydrogen for the hydrogenation step. SUMMARY OF THE INVENTION A first embodiment of the present invention is disclosed in the drawings. The method of the first embodiment is configured in many ancient times 兪Μ______________ 〇

Use recycled liquid. It does not make

Pressure operation.

The product I can be adjusted to meet the specifications, and the hydrogen circuit can achieve medium to high conversion. Foot size, remove product loss and save hydrogen 84200 1275636 The reaction is maintained at a level suitable for the specific type of feed characteristics -, = only the most difficult feed is processed - the stage reactor must be at the highest pressure Horizontal operation. The method does not include high temperature, high pressure pumps. The second addition chlorine cracking reactor P! section can be operated in a downstream or countercurrent mode with respect to the reaction gas (which is the main supplementary hydrogen in the present invention). The second aerated cracking reaction stage feeds high purity make-up hydrogen to maximize hydrogen partial pressure. The second stage loading is a very high activity catalyst that can be used for lower pressure hydrocracking. The first particular embodiment of the invention is disclosed in Figures 2 and 3. The stream is initially cracked by nitrogen in a first stage hydrocracking reaction zone in an integrated hydroconversion process. The integrated hydroconversion process has at least one chlorination cracking stage and at least one hydrotreating step 1 from the hydrazine-stage hydrocracking reaction zone, and the effluent is combined with the light aromatic feedstock stream, and The combined stream is subjected to heat exchange between the hydrotreating zone (stage-stage hydrotreating. The chlorination cracking reaction zone in the first stage and the hydrotreating reaction zone in the second stage, and allows the first stage hydrotreating The temperature control of the zone. The temperature of the first stage hydrotreater is lower than that of the first stage hydrocracker. This improves the aromatic saturation of the converted flue gas, and the catalyst of the first stage hydrotreating zone can exist later. The catalyst in the chlorination zone is different. In one embodiment, the effluent from the first stage heating processor is heated in an exchanger and passed to a heat and pressure separator where it is Remove the light pavilion at the top of the tower and transfer it to the - cold Nann separator. In the cold high separator, hydrogen and sulphur chloride gas are removed at the top of the tower' and in the gasoline and diesel range Teng's material is passed to the - divider. Later in - The sulphurized chlorine is removed from the absorber, and the snail, % is recycled for use as an inter-bed quenching, and mixed with vacuum diesel. 84200 -9- 1275636 [ [Knife off-state liquid effluent (which can be included in In the diesel range, the boiling::: material) 5F is passed through the i-reservoir. The bottom of the column is smashed to be subsequently cracked and the product can be hydrotreated in a unit not described. The second embodiment provides some notable advantages. The present invention provides a method for treating two refinery streams using mono-hydrogen replenishment and mono-hydrogen (tetra) hydrogen. Further, the present invention provides an ordinary hydrogen. The feed feeds a method of hydrocracking a refinery stream and hydrotreating a second refining stream. The feed to the blasting reaction zone is not contaminated by the feed to the hydrotreating reaction zone. It is also concerned with hydrotreating one or more dissimilar refinery streams in an integrated hydrogen conversion process while maintaining good catalyst life and high yields of desired products, particularly in the range of oil refining products. Such different refinery streams can From different refinements The method, such as VGO derived from a hydrotreating agent effluent, comprises less catalyst contaminants and/or aromatics, and an FCC circulating oil or straight run diesel comprising a substantial amount of aromatic compound. Figure 1 illustrates the mixing of preheated oil feed stream 1 and hydrogen stream 40, which is preheated recycle and make up hydrogen (reactor feed gas). The feed is pumped to the reactor as soon as it is borrowed. The method of pressure is preheated in the heat exchanger. The mixture of feed and reactor feed gases (now in stream 2) is further heat exchanged (in exchanger 41) and final furnace (42) before entering the first stage. Preheating, flowing down to the fixed bed main reaction (3). The primary or first stage reactor comprises a multiple hydrogen treatment catalyst bed, which may be a bed of hydrotreating or hydrocracking catalyst. -10- 1275636 The cooling hydrogen of the ring gas compressor is used as quenching between beds (4, 5, 6). The effluent 7 of the first stage reactor (which is hydrotreated and partially hydrocracked) contains hydrogen sulfide, ammonia, light gas, naphtha, middle distillate and hydrotreated vacuum diesel . The effluent enters a slightly lower pressure and slightly lower temperature high pressure separator (8) where most of the diesel and lighter materials are separated from the unconverted oil. The hot high pressure separator has a disc shape and a donut shaped plate. The hydrogen rich gas (heated in exchanger 38) is introduced at the bottom via stream 9 for stripping. Stream 11 contains the overhead from a hot high pressure separator. At this time, it is possible to introduce an external feed (10) boiling in the boiling range of the middle distillate, such as light cycle oil (LCO), light coking diesel (LCGO), atmospheric pressure diesel (AGO), light weight reduction Cracking furnace diesel (LVBGO) and so on. Stream 11 is cooled by a process of heat exchange or by a stream prior to entering the high pressure hydrogen stripper-hydrogenation processor (14). The liquid stream 11 flows downward through a bed of packing containing a hydrotreating catalyst while contacting the countercurrent flowing hydrogen from stream 25. The overhead stream 15 contains primarily argon, ammonia and hydrogen sulfide, along with some light gases and naphtha. The stream is cooled by treatment heat exchange (44) before being fed to the No. 1 cold high pressure separator (17), contacted with water (45), and further cooled by air (46). Water injection enables the removal of most of the ammonia from the hydrogen gas as a solution of ammonium disulfide. Hydrogen i hydrogen sulfide and a light hydrocarbon-containing gas are removed at the top of the column into stream 18. Stream 20 is an acid water containing ammonium disulfide. Stream 19 is a hydrocarbon-containing stream comprising naphtha, kerosene, and diesel range products. Stream 18 is passed to an amine absorber (21) wherein the contact amine (47) removes substantially all of the hydrogen sulfide from the hydrogen rich stream. After the hydrogen sulfide is removed, the gas is sent to a recycle gas compressor (23) for compression. The compressed recycle gas (24) splits into streams 25 and 26. Stream 26 is further split into 84200 -11 - 1275636 first stage recycle gas feed (27) and feed stage 1 quench stream 28. The hazardous amine exits the amine absorber as stream 48. The bottoms (stream 12) from the hot high pressure separator can be depressurized and cooled by treatment heat exchange before being fed to the second stage reactor (30), and the hydrocracking reaction is completed in the second stage reactor. The unconverted material in stream 12 is further converted to diesel and lighter products. The second stage reactor is fed with high purity make-up hydrogen (31) from the intermediate stage (49) of the supplemental hydrogen compression. In the preferred mode, <hydrogen flows up the reactor in a countercurrent flow to maximize hydrogen partial pressure. The invention also handles the co-flow introduction of supplemental hydrogen. The necessary conditions for the second stage reactor feed gas, in terms of sufficient gas to oil ratio, can be met by directing all of the supplemental hydrogen required in all stages of the reaction to the second stage of the reaction. However, the present invention defines the introduction of recycled hydrogen from the recycle gas compressor via stream %. The second reaction stage is operated in a clean and ammonia-free and hydrogen sulfide-free environment so that the hydrocracking reaction rate constant is higher. Catalyst deactivation is locally reduced. These factors enable operation at lower hydrogen partial pressures and with reduced catalyst requirements. The lower first stage reaction bed (30) is capable of loading a chlorination catalyst wherein the diesel range material (16) from the hydrogen stripper (14) can be introduced to complete the aromatic saturation and other hydrogen treatment reactions. Alternatively, stream 16 can be directed to the fractionation section if the quality of the diesel is sufficient. At least two hydrogen treatment catalysts (preferably three to four) are present in the reactor 30. The catalyst can be a metal or precious metal hydrogen treatment catalyst. Stream 33 from the top of the reactor contains primarily hydrogen, although there may be one such 84200 -12-1275636 H2S and ammonia. This stream is cooled by a heat exchange (50) before being sent to No. 2 cold high pressure separator (17.5). The overhead vapor of the No. 2 cold high pressure separator is delivered to a supplemental hydrogen compressor (49) to the final compression stage. The liquid effluent from reactor 30 (stream 34, which contains light gas, naphtha, middle distillate, and hydrotreated diesel) is cooled by heat exchange (51) and delivered to No. 2 cold high pressure. Separator (17.5). The bottoms from line 2 cold high pressure separator (line 37) are sent to fractionation. The supplemental hydrogen compressor (49) is a multi-stage machine typically having three to four compression stages. After each compression stage, the gas is cooled and any concentrate is knocked down in a blow barrel (KOD). With respect to the present invention, the gas reaching the second reaction stage is withdrawn after an intermediate stage of compression. The gas stream (31) is passed to a second reaction stage (30) and returned to the final compression stage of the supplemental hydrogen compressor via a No. 2 cold high pressure separator (stream 36). After the final compression stage, the high pressure make-up hydrogen is sent to the first reaction stage (stream 39) and to the hot separator. Referring now to Figure 2, a preferred embodiment of the present invention is disclosed. Various auxiliary equipment (e.g., heat exchangers, condensers, pumps, and compressors) are not included in the drawings, which are not indispensable for the present invention. - In Figure 2, - describes two reactor tanks 5 and 15 flowing downward. Between the two is a heat exchanger 20. Each container contains at least one reaction zone. The first stage reaction (hydrocracking) takes place in vessel 5. The second stage reaction (hydrogenation treatment) takes place in the vessel 15. Each container is described as having three catalyst beds. The first reaction vessel 5 is used to crack the first refinery stream 1. The second reaction vessel 15 is used to remove nitrogen and aromatic molecules from the second refinery stream 17. The appropriate volume ratio of the contact medium in the first reaction vessel 84200 - 13 - 1275636 to the contact volume in the second reaction vessel covers a wide range, depending on the ratio of the first refine stream to the second refine stream. Typical ratios are usually between 20:1 and 1:20. A preferred volume ratio is between 10:1 and 1:10. A better volume ratio is between 5..1 and 1:2. In an integrated process, a first refinery stream 1 is combined with a hydrogen-rich stream 4 to form a first feedstock 12. The stream exiting the furnace 30 (stream 13) is passed to the first reaction vessel 5. The hydrogen rich stream 4 contains more than 50% hydrogen and the remainder is various amounts of light gases, including hydrocarbon gases. The hydrogen rich stream 4 shown in the drawing is a blend of supplemental hydrogen 3 and recycled hydrogen 26. However, for economic reasons, it is generally preferred to use recycled hydrogen 26, but it is not necessary. The first feedstock 1 may be heated in one or more exchangers (e.g., exchanger 10) prior to being directed to the first reaction vessel 5 (where hydrocracking is preferred), in the form of a stream 12, and Or heating in multiple heaters (such as heater 30) (appears in flow 13). Hydrogenation treatment preferably takes place in vessel 15. Hydrogen can also be added via lines 6 and 7 and 9 and 11 as a quench stream (also from hydrogen stream 4) to separately cool the first and second reaction stages. The effluent (stream 14) from the hydrocracking stage is cooled by means of stream 2 in heat exchanger 20. Stream 2 boils in the diesel range and can be a light cycle oil, light diesel oil, atmospheric diesel or a mixture of the three. Stream 2 emerges from exchanger 20 in a stream 16 and combines with stream 14 emerging from exchanger 20 to form a binder 17. The hydrogen of stream 8 is combined with the combined feedstock 17 prior to entering the vessel 15. Stream 17 enters vessel 15 for hydrotreating and escapes in the form of stream 18. The second reaction stage found in vessel 15 comprises at least one catalyst bed (e.g., an argon-added catalyst) maintained at a level sufficient to convert at least a portion of the nitrogen in the second feedstock to 84,200 - 14 to 12,756,36 compounds and at least a portion of the aromatics The state of the compound. Hydrogen stream 4 can be recycled hydrogen from compressor 40. Alternatively, stream 4 can be a fresh stream of hydrogen derived from a source of hydrogen external to the process. Stream 18 (second reaction zone effluent) contains thermal energy that can be recovered by heat exchange (e.g., in heat exchanger 10). The second stage effluent 18 emerges from the exchanger 10 into a stream 19 and passes through a hot high pressure separator 25. The liquid effluent (stream 22) of the hot high pressure separator 25 is passed to fractionation. The overhead gaseous stream (stream 21) from separator 25 is combined with water from stream 23 for cooling. The cooled stream 21 enters the cold high pressure separator 35. The light liquid is passed to a fractionation in stream 27 (which combines stream 22) and the acid water is removed via stream 34. The gaseous overhead stream 24 is passed to an amine absorber 45 to remove hydrogen sulfide gas. The purified hydrogen is then passed via stream 26 to compressor 40 where it is recompressed and passed, as recycled, to one or more reaction vessels and serves as a quench stream for cooling the reaction zone. Such hydrogen uses are well known in the art. An example of a method of hydrogenation is disclosed in U.S. Patent No. 5,082,551, the entire disclosure of which is incorporated herein by reference. The absorber 45 may comprise means for contacting the gaseous component of the reaction effluent 19 with a solution 4 such as 生水_液_液4, so that the removal may be regenerated in the reaction stage and the reaction effluent may be present. 19 pollutants (such as hydrogen sulfide and ammonia). The hydrogen rich stream 24 is preferably recovered from the separation zone at a temperature ranging from 100 °F to 300 °F or from 100 °F to 200 °F. The stream 22 is further separated in the fractionator 50 to produce an overhead gasoline stream 28, a naphtha stream 29, a kerosene fraction 31, a diesel stream 32, and a fractionator bottoms 33. 84200 -15 - 1275636 A preferred distillate product has a boiling point in the range of from 250 T to 700 °F. A gasoline or naphtha fraction having a boiling range in the range of C5-400 °F is also desirable. In Scheme 3, two downwardly flowing reactor vessels 5 and 15 are depicted. The first stage reaction (hydrocracking) takes place in vessel 5. The second stage (hydrogenation treatment) takes place in the vessel 15. Each container contains at least one reaction zone. Each container is described as having three catalyst beds. The first reaction vessel 5 is for cracking the first refining stream 1. The second reaction vessel 15 is used to remove nitrogen and aromatic molecules from the second refinery stream 34. The appropriate volume ratio of the contact medium in the first reaction vessel to the contact volume in the second reaction vessel covers a wide range, depending on the ratio of the first refine stream to the second refine stream. Typical ratios are usually between 20:1 and 1:20. A preferred volume ratio is between 10:1 and 1:10. A better volume ratio is between 5:1 and 1:2. In an integrated process, a first refinery stream 1 is combined with a hydrogen-rich stream 4 to form a first feedstock 12 that is passed to the first reaction vessel 5. The hydrogen rich stream 4 contains more than 50% hydrogen and the remainder is various amounts of light gases, including hydrocarbon gases. The hydrogen rich stream 4 shown in the drawing is a blend of supplemental hydrogen 3 and recycled hydrogen 26. However, for economic reasons, the use of recycled hydrogen is generally preferred, but not necessary. The first feedstock 1 can be heated in one or more heat exchangers or one or more heaters prior to combining with the hydrogen-rich stream 4 to produce stream 12. Stream 12 is then directed to the first stage where the first reaction vessel 5 is positioned (where hydrocracking preferably occurs). The second stage is located in vessel 15, wherein hydrotreating is preferred. The effluent (stream 14) from the first stage is heated in heat exchanger 20. Stream 14 84200 -16-1275636 emerges from exchanger 20 as stream 17 and passes to "hot/hot" high pressure separator 55. Stream 36 emerges from the "hot/hot" high pressure separator 55 and proceeds to fractionator 60. Stream 37 represents the product stream of gasoline and naphtha, stream 38 represents the recirculation back to the inlet of the hydrogenation processor 15, and stream 39 represents the clean bottom material. Stream 34 emerges from a "hot/hot" high pressure separator 55, in combination with stream 2, which boils in the diesel range and may be light cycle oil, light diesel oil, atmospheric diesel or a mixture of the three. The gas stream combines with the hydrogen rich stream 4 prior to entering the vessel 15 for hydrotreating and escaping into stream 18. The second reaction zone is found in vessel 15 to comprise at least one catalyst bed (e.g., a hydrotreating catalyst) maintained in a state sufficient to convert at least a portion of the nitrogen compound and at least a portion of the aromatic hydrocarbons in the second feedstock. . The hydrogen-rich gaseous stream 4 can be recycled hydrogen from the compressor 40. Alternatively, stream 4 can be a fresh stream of hydrogen sourced from a source of hydrogen other than the process. Stream 18 (second stage effluent) contains heat energy that can be recovered by heat exchange (e.g., in heat exchanger 10). The second stage effluent 18 emerges from the exchanger 10 into stream 19 and passes through the hot high pressure separator 25. The liquid effluent (stream 22) of the hot high pressure separator 25 is passed to fractionation. The overhead gas stream (stream 21) from separator 25 is combined with water from stream 23 for cooling. The cooled stream 21 enters a cold high pressure: separator 35. The light liquid is passed to a fractionation in stream 27 (which combines stream 22) and the acid water is removed via stream 41. The gaseous overhead stream 24 is passed to an amine absorber 45 to remove hydrogen sulfide gas. The purified hydrogen is then passed via stream 26 to a compressor 40 where the purified hydrogen is recompressed and passed, as recycled, to one or more reaction vessels and serves as a quench stream to cool the reaction zone. Such hydrogen uses are well known in the art. 84200 -17- 1275636 The absorber 45 may comprise means for contacting the gaseous component of the reaction effluent 19 (stream 24) with a solution (such as an aqueous alkaline solution) so that removal can be regenerated in the reaction zone and there may be a reaction effluent Contaminants in liquid 19 (such as hydrogen sulfide and ammonia). The hydrogen rich stream 24 is preferably recovered from the separation zone at a temperature in the range of 100 °F_3 〇〇 °F or 100 °F - 200 °F. The stream 22 is further separated in the fractionator 50 to produce an overhead gasoline stream 28, a naphtha stream 29, a kerosene fraction 31, a diesel stream 32, and a sub-chamber bottom 33°. A preferred steam product has a boiling point of 250. °F-700 °F temperature range. A gasoline or naphtha fraction having a boiling point in the Cr400T temperature range is also desirable. Feeding Various hydrocarbon feeds can be used in the first embodiment of the invention. Typical materials include any heavy or synthetic oil or processing streams boiling above 392°F (200°C). Such materials include vacuum diesel, heavy atmospheric diesel, delayed coking diesel, debonded cracking furnace diesel, demetalized oil, vacuum residue, atmospheric residue, deasphalted oil, Fischer-Tropsch streams and FCC flow. In the case of the second embodiment, a suitable first refinery feed stream is a VG0 having a boiling range ranging from 500 °F (260 °C), often between 500 °F and _1100 °F (260 °C). -593 ° C) temperature range. A refinery stream (75% by volume of the rerefining stream boiling in the temperature range of 650 °F to 1050 °F) is an example material for the first reaction zone. The first refinery stream may contain nitrogen, often in the form of an organic nitride. The VG0 feed stream of the first reaction zone contains less than about 200 ppm nitrogen and less than 〇25 wt% sulfur, albeit with higher levels of nitrogen and sulfur (including up to 0.5% by weight and higher amounts of nitrogen and up to The feed of 5% by weight and higher sulfur may be 84200 -18- 1275636. In the present method, the treatment of the refinery stream is also preferably a suitable first fine feed; the right contains a μ;

A low asphaltene flow licin, preferably less than 0 ppm asphaltene. 'Example streams · include, deasphalted oil and the like. The first refinery stream (e.g., by hydrotreating) can include a recirculating component. The hydrocracking reaction step removes nitrogen and sulfur from the first refinery feed stream in the first hydrocracking reaction zone and causes a boiling range transition, so the boiling fraction of the liquid portion of the first hydrocracking reaction zone is lower than the first A range of often boiling points of a refined raw material. "Normal," means the boiling point or boiling range based on atmospheric distillation, as determined in a D1160 distillation. Unless otherwise specified, all distillation temperatures listed herein represent normal boiling and normal boiling range temperatures. The method of hydrocracking the reaction zone can be controlled to a non-specific cracking conversion, or to a desired product sulfur content or nitrogen content or both. The conversion process is generally about a reference temperature, such as the lowest sea of hydrocracker feedstock. Point temperature. The degree of conversion is about above the reference temperature; the feed of Verten is converted to the percentage of product boiling below the reference temperature. One hydrocracking - the reaction zone effluent - the liquid - including the normal upper liquid component ( Such as the reaction product of the first refinery stream and the unreacted component) and the normal upper gas phase component (such as gaseous reaction product and unreacted hydrogen). In this method, the hydrocracking reaction zone is maintained at a level sufficient for the first The refining stream boiling range is at least 25% transitioned with a 650 卞 reference thermometer. Therefore, it is above about 650 °F in the first refining stream; at least 25% in the Fraun component. It is also converted to a composition boiling at about 650 °F below 84200 -19 - 1275636 in the first hydrocracking reaction zone. It is also within the scope of the invention to operate at a degree of conversion as high as 100%. Example boiling range shift It is in the range of about 30% to 90% or about 40°/〇 to 80%. The hydrocracking reaction zone effluent reduces the nitrogen and sulfur content in two steps, and at least about 50% nitrogen in the first refining stream. The molecule is converted in the hydrocracking reaction zone. Preferably, the normal liquid product present in the effluent of the hydrocracking reaction zone comprises less than about 1000 ppm sulfur and less than about 200 ppm nitrogen, more preferably less than about 250 ppm sulfur. And about 100 ppm nitrogen. Catalyst In any particular embodiment, each hydrogen treatment zone may comprise only one catalyst or a plurality of catalyst combinations. In a preferred embodiment, hydrocracking occurs in the first zone, Hydrotreating occurs in the second zone. The hydrocracking catalyst typically comprises a cleavage component, a hydrogenation component, and a binder. Such catalysts are well known in the art. The cleavage component can include An amorphous gravel/oxidized phase and/or a stagnation stone, such as a Y-type USY zeolite. Catalysts with high cleavage activity often use REX, REY and USY zeolites. The binder is usually vermiculite or alumina. The hydrogenation component will be a Group VI, Group VII or Group VIII metal or its oxide or Sulfide, preferably one or more of iron, lanthanum, cerium, tungsten, uranium or chain or a sulfide or oxide thereof. If present in the catalyst, these hydrogenation components typically constitute from about 5% to about 40% by weight of the catalyst. Alternatively, a precious metal (especially platinum and/or palladium) may be present as a hydrogenation reaction component alone or in combination with an alkali metal hydrogenation reaction component: iron, complex, molybdenum, tungsten, lead or nickel. If present, the extender metal will typically comprise from about 0.1% to about 2% by weight of the catalyst. Hydrotreating catalysts are often designed to remove sulfur and nitrogen and provide a fragrant fullness of 84,200-20 to 1275636 and degrees. It will typically be a composite of a Group VI metal or a compound thereof and Group VIII or a compound thereof supported on a porous refractory substrate such as alumina. Examples of hydrotreating catalysts are alumina-supported cobalt-ruthenium, nickel sulfide, nickel-tungsten, cobalt-tungsten and nickel-4 mesh. Typically such hydrotreating catalysts are pre-purified. Month media selection is specified by method requirements and product specifications. Specific and s ' When there is a small amount of H2S, a noble catalyst can be used in the second stage. A low acidity catalyst can be used at the bottom of the second stage hydrocracker to avoid excessive cracking of the distillate into gas and naphtha. The reaction conditions of the hydrocracking reaction zone of the condition-hydrocracking stage include a reaction temperature of between about 250 ° C and about 500 ° C (482 ° F - 932 ° F), a pressure of about 3.5 MPa to about 24.2 suspected & (500-3,500 psi), feed rate (oil volume / hourly media volume) from about 0.1 to about 20 hf1. The hydrogen circulation rate is usually in the range of about 350 standard liters of H2/kg oil to 1780 standard liters of H2/kg oil (2,310-11,750 standard cubic feet per barrel). The preferred reaction temperature is from about 340 ° C to about 455 ° C (644 ° F - 851 ° F). Preferably, the total reaction pressure is from about 7.0 MPa to about 20.7 MPa (1,000-3,000 psi). With preferred catalyst systems, it has been found that preferred process conditions include pressures from about 13.8 MPa to about 20.7 MPa (2,000-3000 psi) and gas to oil ratios of about 379-909 standard liters of H2/kg oil (2,500). - 6,000 scf / bbl), LHSV about 0.5-1.5 hf1, at a temperature between 360 ° C and 427 ° C (680 ° F - 800 ° F) under hydrocracking conditions, the gasoline feedstock is contacted with hydrogen. Feed and (charge liquid Ted: the second refinery feed stage of the second refinery process stream generally has a lower boiling point range than the first refinery feed stream. Indeed, the invention is characterized by a comparable second refinery feed stream The portion of 84200-21- 1275636 has a normal boiling point within the middle distillate range and therefore does not require cracking to a lower boiling point. Therefore, at least about 75% by volume of the normal boiling point temperature in the appropriate second refining stream is less than about 1000 ° F. A refinery stream having at least about 75% of the v/v component having a normal boiling point temperature in the range of from 250 °F to 700 °F is an example of a preferred second refinery feed stream. It is particularly suitable for the treatment of middle distillate streams which are not suitable for high quality fuels. For example, the process is suitable for treating a second refinery stream comprising a large amount of nitrogen and/or a large amount of aromatics, including streams containing up to 90% and higher amounts of aromatics. Example of Treatment in the Process The second refinery feed stream comprises vacuum diesel from a crude distillation process, an atmospheric column bottoms or a synthetic cracking material (such as coking diesel, light cycle oil or heavy cycle oil). Including straight firewood The remainder of the oil. After the first refinery feed stream is treated in the hydrocracking stage, the first hydrocracking reaction zone effluent is combined with a second feedstock which passes through the catalyst in the hydrotreating stage together with the hydrogen. Since the hydrocracking effluent is already free of contaminants that will be removed by hydrotreating, the hydrocracker effluent passes through the hydrotreater in large quantities unchanged and remains in the effluent from the hydrotreater. The unreacted or incomplete reaction feed is effectively isolated from the hydrotreater to avoid contamination of the catalyst contained therein. However, the presence of hydrocracker effluent plays an important and unexpected economic benefit in the integrated process. When leaving the hydrocracker, the effluent carries its equivalent thermal energy. This energy can be used to heat the second reactor feed stream in the heat exchanger before the second feed stream enters the hydrotreater. The integrated system adds a colder second feed stream than otherwise needed, and saves furnace capacity and heating costs. 84200 -22- 1275636 When the second feedstock passes through the hydrotreater, due to the second zone The heat is reversed, so the temperature is easy to increase again. The hydrocracker in the second raw material acts as a heating tank, which regulates the temperature rise throughout the hydrotreater, and remains in the liquid in the hydrotreater. The thermal energy in the reaction product can still be used to exchange with other streams requiring heating. Typically, the outlet of the hydrotreater will return to the outlet temperature of the hydrocracker. In this case, the present invention will increase the burden first. The hydrocracker feed temperature provides the advantage of heat transfer transfer for more efficient heat transfer. The effluent from the helium cracker also drives unreacted hydrogen for use in the first stage hydrotreater without any heating or enthalpy The necessary conditions are taken to increase the pressure. The process stage hydrotreater maintains a condition sufficient to remove at least a portion of the nitrogen compound and at least the portion of the aromatic compound from the second refinery stream, except that exothermic heating is generated from the reaction zone. In addition to the possible temperature gradients, the hydrotreater will operate at temperatures below the hydrocracking temperature, by adding a cooler stream to one or more reaction zones. The feed rate of the reactant stream through the reaction zone will be in the range of 20 hr liquid helium hours. The feed rate through the hydrotreater will increase relative to the feed rate through the hydrotreater, by the amount of the second refinery feed stream, and will also be in the range of 〇1 to 2〇 liquid per hour space velocity. These process conditions selected for the first reaction zone can be considered to be more stringent than those normally selected for hydrotreating. Hydrotreating conditions typically used in hydrotreaters at any rate will include a reaction temperature of between about 250. 〇 to about 500. (Between (482卞-932卞), the pressure is about 3.5 MPa to about 24.2 MPa (500-3,500 psi), and the feed rate (oil volume / -23 - 84200 1275636 touch media product • hour) is about 0.1 to about 20 hf1. The hydrogen circulation rate is usually from about 350 standard liters H2/kg oil to 1780 standard liters H2/kg oil (2,310-11,750 standard cubic feet/barrel). The preferred reaction temperature is about 340 °C. Between about 455 ° C (644T-851 ° F). Preferably, the total reaction pressure is between about 7.0 MPa and about 20.7 MPa (1,000-3,000 psi). Using a better catalyst system, it is found Preferably, the method comprises contacting a gasoline feedstock with hydrogen in the presence of a stratified catalyst system under hydrocracking conditions comprising: a pressure of about 16.0 MPa (2,300 psi) and a gas to oil ratio of about 379-909. Standard liters of H2/kg oil (2,500 scf/bbl to approximately 6,000 scf/bbl), LHSV between approximately 0.5-1.5 hr-1, and temperature between 36 (TC to 427 °C (680 °F-800 °F) Within the scope of this, at least about 50% of the aromatics are removed from the second refinery stream in the hydrotreater. We anticipate that the second refinement will also be removed in the process. The flow is as much as 30-70% of nitrogen. However, the cracking conversion in the hydrotreater is usually not high, typically less than 20%. We can determine the aromatic and nitrogen content of the refinery stream. Standard Methods. These include ASTM D5291 for the determination of the nitrogen content of a stream containing more than about 1500 ppm of nitrogen. ASTM D5762 can be used to determine the nitrogen content of a stream containing less than about 1500 ppm of nitrogen. ASTM D2007 can be used to determine refined sulfur. Aromatic content. Products The specific embodiment of the invention is particularly useful for producing a middle distillate fraction boiling in the range of about 250-700 °F (121-371 °C). A middle distillate fraction definition It has an approximate boiling range of about 250 to 700 ° F. At least 75% by volume (preferably 85% by volume) of the components in the middle distillate have a normal boiling point above 250 ° F. At least about 75% by volume in the middle distillate. The (normally 85% by volume) component has a normal boiling point of 84,200 - 24, and 12,756,536, which is less than 700 Torr. "Middle distillate, a range of ketones; kerosene burning heart; "Diesel 亀

37Π:) The hydrocarbons in the range of the beach. Tables other than 250 to W, / fly oil or naphtha can also be produced in the present invention, 赍, 赍 赍 a n 士 万 万. Gasoline or Shiyue® oil hangs under less than 4 〇〇Τ (2〇4. > ^ ^ boil in the yoke. Distillation of various products recovered by any special refining, & original $ & % ^ E Teng target circumference will change with such factors', oil source, regional refining market and product price. Heavy hydrotreating diesel oil (the scope of another ^° 本 of the invention _ Teng. The house is often running) Examples and results:

84200 -25- 1275636 Usually the rise of hexadecane is 20 to 45, and the improvement of kerosene smoke point is 7_27mm. [Simple description of the diagram] The diagram illustrates the multiple reaction stages using a single hydrogen treatment loop. Figure 1 depicts the use of a one-stage thermal stripper and an interstage thermal separator. Figure 2 illustrates a series of hydrogenation crackers and hydrotreaters in a single hydrogen loop separated by a heat exchanger. Lightweight and heavy materials are separated from one another. Hydrogen and hydrogen sulfide may be removed from the light product. The hydrogen is compressed and recycled. The product is delivered to a fractionator. Figure 3 illustrates a hydrocracking step followed by separation and fractionation. The material removed at the top of the column is combined with a light aromatic stream and hydrotreated. Hydrogen is separated from the hydrotreated effluent and recycled. The product is sent to a fractionator. [Character representation of the symbol] Preheating oil feed stream First refining stream 2 Stream 3 Main reactor 3 Replenishing hydrogen 4 Hydrogen-rich gas stream 4, 5, 6 Bed quenching 5, 15 Downflow reactor vessel 6 Straight line 7 Straight-line liquid separator 84200 1275636 8 Flow 9 Flow 9 Straight line 10 Introducing external feed boiling in the boiling range of the middle distillate 10 Heat exchanger 11 Flow 11 Straight line 12 Flow 13 Flow 14 Hydrogen stripper 14 Entering hydrogen Stripper - Hydrogenation Processor 14 Flow 15 Top Flow 15 Hydrogenation Processor 16 Diesel Range Material, Stream 16 Flow 17 No. 1 Cold High Pressure Separator 17.5 No. 2 Cold High Pressure Separator 17 Second Refined Stream 17 Combined Feed, stream 17 stream 18 stream 19 stream 19 stream, reaction effluent 20 stream 84200 -27- heat exchanger amine absorber stream recirculating gas compressor flowing through compressed gas stream top stream hot high pressure separator Flow recirculating hydrogen first stage recycle gas feed stream top gas stream naphtha flow lower second stage reactor bed reactor heater feed high purity supplemental hydrogen kerosene stream diesel stream -28-1262736 33 Stream-33 fractionator Bottom 34 Stream 34 Distillation Stream 35 Flow 35 Cold High Pressure Separator 36 Flow 36 Flow 37 Flow 38 Exchange 38 Flow 39 Flow 40 Mouse Flow 40 Compressor 41 Exchanger 41 Flow 42 Final Furnace 44 Treatment Heat Exchange Cooling 45 Contact with water 45 Amine absorber 46 Further by air cooling 47 Contact with amine 48 Stream 49 Replenishing hydrogen compressor 84200 -29- 1275636 50 50 51 55 60 Handling heat exchange fractionator for heat exchange "hot/hot" high pressure separator Fractionator 84200 -30-

Claims (1)

1275636 Pickup, Patent Application Range: 1. A method of hydrotreating a hydrocarbon feedstock using a multiple reaction zone in a single reaction loop comprising the steps of: (a) delivering a hydrocarbonaceous feedstock to one or more a first hydrotreating zone comprising a hydrotreating catalyst bed maintained in a hydrotreated state wherein the feedstock is contacted with a catalyst and hydrogen; (b) directing the effluent of step (a) Delivered to a hot high pressure separator wherein the effluent is contacted with a hot hydrogen-rich stripping gas to produce a vapor stream comprising 'hydrogen, a hydrocarbon-containing compound boiling below the boiling range of the hydrocarbon-containing feedstock, vulcanized Hydrogen, ammonia and a bottoms stream comprising a hydrocarbon-containing compound boiling in the same range as the hydrocarbon-containing feedstock and a hydrocarbon-containing compound partially boiling in the boiling range of the diesel; (c) cooling the vapor stream from step (b) And partially concentrated and delivered to a thermal hydrogen stripper comprising at least one hydrotreating catalyst bed, wherein the vapor sulfur is in countercurrent contact with hydrogen while the liquid stream of step (b) is delivered to a second stage reactor (d) delivering the overhead vapor stream from the hot hydrogen stripper in step (c) to a first cold high pressure separator after cooling and contacting with water, wherein hydrogen, hydrogen sulfide and light hydrocarbon-containing gas are The top of the tower is removed and a stream comprising naphtha and intermediate remainder is delivered to the branch, thus removing most of the ammonia and some hydrogen sulfide (as in the acid water stream leaving the cold high pressure separator) (e) delivering a liquid stream from the hot hydrogen stripper in step (c) to a hydrotreating catalyst bed in a second reactor stage, wherein the liquid is under hydrotreating conditions 84200 1275636' Contacting the catalyst in the presence of rhodium, (f) delivering the overhead from the cold high pressure separator in step (4) to an amine absorber wherein the hydrogen sulfide is removed and recycled before the hydrogen is compressed To the in-loop hydrotreating vessel; to the second reaction stage, one of the hydrocracking catalyst bed contacts (g) causes the separator bottom of step (b) to deliver the bottoms in the presence of hydrogen and at least one strip stream And the liquid effluent (8) causes the vapor stream of step (g) to cool Delivered to a second cold high pressure separation - wherein the sum and the king are to include a hydrogen and a light flue gas vapor stream; (1) the step (g) 4 liquid effluent is cooled and then delivered to the cold high pressure of step (6) a separator for separating hydrogen from the liquid effluent and the light furnace gas: the same as the vapor stream of steps (8) and (i) is further cooled and separated and concentrated = after being delivered to the supplemental hydrogen compressor; the reactor circuit (k) The compressed hydrogen from the supplemental hydrogen compressor is delivered to the primary reverse; and (1) the liquid effluent from steps (8) and (i) is delivered to the fractionation system. 2. The procedure according to the method of claim 1 of the patent application section bis, 、, 、 ▲ 卞琢 以 以 逆 逆 逆 逆 逆 逆 逆 逆 逆 逆 逆 逆 逆 逆 逆 逆 逆 逆 逆 逆 逆 。 。 。 。 。 。 。 。 。 。 。 。 。 Dan/Children 3. According to the method of claim 1, wherein the feed is selected from the group consisting of direct-air diesel, heavy-duty atmospheric diesel, delayed coking wood, true w, viscous cracking, diesel, demetallized oil, FCC lightweight Circulating oil, vacuum residue, tera muscle, , %, denier, deasphalted oil, Fischer-Tropsch streams and FCC streams. 4. According to the method of claim 1 of the patent application, in which the name + brewing v is 0) occurs in white < 84200 I275636 The sixteen burning value is improved between 20 and 45. 5:=Materials (4) The core of the range of items, wherein the improvement of the smoke from the oil in step (4) is between 7 and 27. 6. According to the old method of the patent scope, wherein the addition of stage i and stage 2 = treatment of the catalyst comprises both a pyrolysis component and a hydrogenation component. 7. An integrated hydroconversion process having at least two stages, each stage having at least one reaction zone, the process comprising: (4) combining a first-refining stream with a hydrogen-rich stream to form a first feedstock; (8) Delivering the first feedstock to the first stage reaction zone, the zone being maintained at a temperature sufficient to complete the conversion of the boiling range to form a first reaction zone effluent comprising the normally upper liquid phase component and the normally upper gas phase component; (c) delivering the first reaction zone effluent of step (9) to a heat exchanger or exchanger train wherein the effluent is exchanged with a second refinery stream; (4) the first reaction zone effluent of step (b) and the step (c) the second refining stream combines to form a second feedstock; (4) the second feedstock of step (d) is delivered to the second stage reaction zone, the zone being maintained at a level sufficient to convert at least a portion of the second refinery The condition of the aromatic smoke in the stream 'to form a second reaction zone effluent; (f) separating the second reaction zone effluent of step (e) into a liquid stream comprising the product and a second hydrogen-rich stream: (g) at least the second hydrogen-rich stream of step 1 Circulating to the reaction zone of the first stage; and (8) delivering a liquid stream comprising the product of step (7) to a branching column, wherein the product stream comprises a gas or naphtha stream removed at the top of the column, one or more intermediates 84200 1275636 The logistics and a bottom stream suitable for further processing. 8. According to the method of claim 7, wherein the reaction zone of step 1 is maintained under hydrocracking reaction conditions, including a reaction temperature of about 34 (TC to about 4551 (644卞-851卞). Between the reaction pressures in the range of about 3.5-24.2 MPa (500-3,500 fields per square inch), the feed rate (oil volume / touch media volume • hour) is about 0.1 to about 10 hr·1, and the hydrogen circulation rate is between Approximately 35 〇 standard liters of IV kg of oil to 1780 liters of liters / kg of oil (2,31 〇 11 11,750 standard cubic metre per barrel). 9. According to the method of claim 7 of the scope of the patent, step 1 ( The reaction zone of e) is maintained under hydrotreating reaction conditions, including a reaction temperature ranging from about 25 Torr to about 50 (TC (482T-932T), and a reaction pressure of about 3.51 ping to 242 碌 (500-3). , 50 (^ 〇 range, feed rate (oil volume / contact media. hours) about 0.1 to about 20 hr · 1, argon circulation rate between about 35 〇 standard liters / kg of oil to 1780 standard liters / kg Between oils (per barrel ^ (1) 丨 咒 标准 standard cube 呎). 1 〇 · - kind of integrated hydroconversion method with at least two stages, each stage The section has at least one reaction zone, the method comprising: (a) combining a first refinery stream with a hydrogen-rich stream to form a first feedstock; (b) delivering the first feedstock to the first stage reaction zone, The fauna is maintained at a condition sufficient to be converted into a stagnation range to form a first reaction zone effluent comprising a normal upper liquid phase component and a normal upper gas phase component; (c) the first step (b) A reaction zone effluent is delivered to a heat exchanger or exchanger train wherein the effluent is exchanged with other refinery streams; (d) the effluent from step (c) is delivered to a hot high pressure separator wherein the stream 84200 1275636 The liquid separation is a liquid stream delivered to the branch and a gas stream combined with a second refining stream comprising light cycle oil, light diesel oil, atmospheric diesel or a mixture of the three; (e) the step ( d) the combined gas stream is delivered to the second stage reaction zone, the zone being maintained at a condition sufficient to convert at least a portion of the aromatic hydrocarbons present in the second refinery stream to form a second reaction zone effluent; (f) Step (e) of the second reaction zone effluent a liquid stream comprising a product and a second rich hydrogen stream; (g) recycling at least a portion of the second hydrogen-rich stream of step (f) to the reaction zone of the first stage; and (h) including the steps (f) The liquid of the product is delivered to the fractionation column, wherein the product stream comprises a gas or naphtha stream removed at the top of the column, one or more intermediate vessels and a bottoms stream suitable for further processing.