EP3497185A1 - Verfahren und vorrichtung zur entfernung von schweren mehrkernigen aromaten in einem hydrokrackverfahren - Google Patents
Verfahren und vorrichtung zur entfernung von schweren mehrkernigen aromaten in einem hydrokrackverfahrenInfo
- Publication number
- EP3497185A1 EP3497185A1 EP17840008.1A EP17840008A EP3497185A1 EP 3497185 A1 EP3497185 A1 EP 3497185A1 EP 17840008 A EP17840008 A EP 17840008A EP 3497185 A1 EP3497185 A1 EP 3497185A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- stream
- hydrocracking
- line
- bottoms
- fractionator
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
- C10G67/06—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including a sorption process as the refining step in the absence of hydrogen
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/205—Metal content
Definitions
- the technical field generally relates to processes and apparatuses for
- hydrocracking of hydrocarbon streams More particularly, the technical field relates to an improved process and apparatus for removing heavy polynuclear aromatics from a hydrocracking process.
- Hydroprocessing can include processes which convert hydrocarbons in the presence of hydroprocessing catalyst and hydrogen to more valuable products.
- Hydrocracking is a hydroprocessing process in which hydrocarbons crack in the presence of hydrogen and hydrocracking catalyst to lower molecular weight hydrocarbons.
- a hydrocracking unit may contain one or more fixed beds of the same or different catalyst.
- Hydrotreating is a process in which hydrogen is contacted with
- hydrocarbon in the presence of hydrotreating catalysts which are primarily active for the removal of heteroatoms, such as sulfur, nitrogen and metals from the hydrocarbon feedstock.
- hydrotreating hydrocarbons with double and triple bonds may be saturated.
- Aromatics may also be saturated.
- HPNA polynuclear aromatic
- HPNA compounds in the recycle oil may deposit on the catalyst as coke, which may degrade catalyst performance and result in shorter catalyst cycle length.
- HPNA can deposit on equipment in the cooler sections of the process. Production of undesired HPNA compounds can be more pronounced for hydrocracking units processing heavier feeds. Thus, it would be desirable to remove the HPNA compounds from the unconverted oil so as to minimize the catalyst deactivation.
- Various embodiments contemplated herein relate to processes and apparatuses for removing HPNA's from a hydrocracking process.
- the exemplary embodiments taught herein provide an improved process and apparatus for removing HPNA from a two-stage or a single- stage hydrocracking process.
- a process for of removing HPNA compounds from a hydrocracked stream comprising passing at least a portion of the hydrocracked stream to a fractionation column to provide a plurality of fractionator product streams and a fractionator bottoms stream comprising unconverted hydrocarbons.
- a first stream and a second stream are taken from the fractionator bottoms stream.
- the first stream is passed through a HPNA adsorption zone to obtain a treated bottoms stream having a reduced concentration of HPNA compounds.
- the second stream is bypassed around the HPNA adsorption zone. Finally, the treated bottoms stream and the bypassed second stream are hydrocracked.
- a process for upgrading a hydrocarbon stream comprising passing the hydrocarbon feedstream to a first hydrocracking reactor, the first hydrocracking reactor containing at least one bed of a first hydrocracking catalyst, wherein the hydrocarbon feedstream is contacted with the first hydrocracking catalyst under first hydrocracking conditions in the presence of hydrogen to produce a first hydrocracked effluent stream.
- At least a portion of the first hydrocracked effluent stream is passed to a fractionation column to provide a plurality of fractionator product streams and a fractionator bottoms stream comprising unconverted hydrocarbons.
- the fractionator bottoms stream is split to provide a first stream and a second stream.
- the first stream is passed through a HPNA adsorption zone to obtain a treated bottoms stream having a reduced concentration of HPNA compounds.
- the second stream is bypassed around the HPNA adsorption zone.
- the treated bottoms stream and the bypassed second stream are passed to a second hydrocracking reactor, the second hydrocracking reactor containing at least one bed of a second hydrocracking catalyst, wherein the treated bottoms stream and the bypassed second stream are contacted with a second hydrocracking catalyst under second hydrocracking conditions in the presence of hydrogen to provide a second hydrocracked effluent stream.
- an apparatus for removing HPNA compounds from a hydrocracked stream comprising a fractionation column in communication with a hydrocracked effluent line to provide a plurality of fractionator product streams and a fractionator bottoms stream in a fractionator bottoms line.
- a first fractionator bottoms line is fiuidly connected to the fractionator bottoms line.
- a second fractionator bottoms line is fiuidly connected to the fractionator bottoms line.
- HPNA adsorption zone is in downstream communication with the first fractionator bottoms line to provide a treated bottoms stream in a treated bottoms line having a reduced
- a hydrocracking reactor in communication with the treated bottoms line and the second fractionator bottoms line, the second fractionator bottoms line bypassing the HPNA adsorption zone.
- FIG. 1 is a schematic drawing of a two-stage hydrocracking unit.
- FIG. 2 is a schematic drawing of a single-stage hydrocracking unit.
- downstream communication means that at least a portion of material flowing to the subject in downstream communication may operatively flow from the object with which it communicates.
- upstream communication means that at least a portion of the material flowing from the subject in upstream communication may operatively flow to the object with which it communicates.
- direct communication means that flow from the upstream component enters the downstream component without undergoing a compositional change due to physical fractionation or chemical conversion.
- each column includes a condenser on an overhead of the column to condense and reflux a portion of an overhead stream back to the top of the column and a reboiler at a bottom of the column to vaporize and send a portion of a bottoms stream back to the bottom of the column.
- Absorber and scrubbing columns do not include a condenser on an overhead of the column to condense and reflux a portion of an overhead stream back to the top of the column and a reboiler at a bottom of the column to vaporize and send a portion of a bottoms stream back to the bottom of the column. Feeds to the columns may be preheated.
- the overhead pressure is the pressure of the overhead vapor at the vapor outlet of the column.
- the bottom temperature is the liquid bottom outlet temperature.
- Overhead lines and bottoms lines refer to the net lines from the column downstream of any reflux or reboil to the column unless otherwise indicated.
- Stripping columns omit a reboiler at a bottom of the column and instead provide heating requirements and separation impetus from a fluidized inert vaporous media such as steam.
- TBP Truste Boiling Point
- ASTM D-2892 for the production of a liquefied gas, distillate fractions, and residuum of standardized quality on which analytical data can be obtained, and the determination of yields of the above fractions by both mass and volume from which a graph of temperature versus mass % distilled is produced using fifteen theoretical plates in a column with a 5: 1 reflux ratio.
- T5 or T95 means the temperature at which 5 volume percent or 95 volume percent, as the case may be, respectively, of the sample boils using ASTM D-86.
- diesel boiling range means hydrocarbons boiling in the range of between 132°C (270°F) and the diesel cut point between 343°C (650°F) and 399°C (750°F) using the TBP distillation method.
- separatator means a vessel which has an inlet and at least an overhead vapor outlet and a bottoms liquid outlet and may also have an aqueous stream outlet from a boot.
- a flash drum is a type of separator which may be in downstream
- zone can refer to an area including one or more equipment items and/or one or more sub-zones.
- Equipment items can include one or more reactors or reactor vessels, heaters, exchangers, pipes, pumps, compressors, controllers and columns. Additionally, an equipment item, such as a reactor, dryer, or vessel, can further include one or more zones or sub-zones.
- HPNA typically refer to compounds with six or more aromatic rings and often refer to compounds with eleven or more aromatic rings and typically produced in a hydrocracking reaction zone.
- the apparatus and process 10 for hydrocracking a hydrocarbon stream comprise a first stage hydrocracking unit 12, a fractionation section 14 and a second stage hydrocracking unit 150.
- a hydrocarbonaceous stream in hydrocarbon line 18 and a first stage hydrogen stream in a first stage hydrogen line 22 are fed to the first stage hydrocracking unit 12.
- the first stage hydrocracking unit may include a hydrotreating reactor 30 and a first
- the second stage hydrocracking unit 150 may include a second hydrocracking reactor 170.
- hydrocarbonaceous feed stocks include hydrocarbon streams having initial boiling points (IBP) above 288°C (550°F), such as atmospheric gas oils, vacuum gas oil (VGO) having T5 and T95 between 315°C (600°F) and 600°C (1100°F), deasphalted oil, coker distillates, straight run distillates, pyrolysis-derived oils, high boiling synthetic oils, cycle oils, clarified slurry oils, deasphalted oil, shale oil, hydrocracked feeds, catalytic cracker distillates, atmospheric residue having an IBP at or above 343°C (650°F) and vacuum residue having an IBP above 510°C (950°F).
- IBP initial boiling points
- VGO vacuum gas oil
- T5 and T95 between 315°C (600°F) and 600°C (1100°F
- deasphalted oil coker distillates, straight run distillates, pyrolysis-derived oils, high boiling synthetic oils, cycle oils, clarified slurry oils, deasphalted
- a hydrotreating hydrogen stream in a hydrotreating hydrogen line 24 may be split off from the first stage hydrogen line 22.
- the first hydrotreating hydrogen stream may join the hydrocarbonaceous stream in feed line 18 to provide a first hydrocarbon feed stream in a first hydrocarbon feed line 26.
- the first hydrocarbon feed stream in the first hydrocarbon feed line 26 may be heated by heat exchange with a first hydrocracked effluent stream in line 48 and in a fired heater.
- the heated first hydrocarbon feed stream in line 28 may be fed to a hydrotreating reactor 30.
- Hydrotreating is a process wherein hydrogen is contacted with hydrocarbon in the presence of hydrotreating catalysts which are primarily active for the removal of heteroatoms, such as sulfur, nitrogen and metals from the hydrocarbon feedstock.
- hydrocarbons with double and triple bonds may be saturated.
- Aromatics may also be saturated.
- Some hydrotreating processes are specifically designed to saturate aromatics.
- the hydrotreating reactor 30 may comprise a guard bed of hydrotreating catalyst followed by one or more beds of higher quality hydrotreating catalyst.
- the guard bed filters particulates and picks up contaminants in the hydrocarbon feed stream such as metals like nickel, vanadium, silicon and arsenic which deactivate the catalyst.
- the guard bed may comprise material similar to the hydrotreating catalyst.
- Supplemental hydrogen in a first hydrotreating supplemental hydrogen line 31 may be added at an interstage location between catalyst beds in the hydrotreating reactor 30.
- Suitable hydrotreating catalysts for use in the hydrotreating reactor are any known conventional hydrotreating catalysts and include those which are comprised of at least one Group VIII metal, preferably iron, cobalt and nickel, more preferably cobalt and/or nickel and at least one Group VI metal, preferably molybdenum and tungsten, on a high surface area support material, preferably alumina.
- Other suitable hydrotreating catalysts include zeolitic catalysts. In the high sulfur and nitrogen environment of the hydrotreating reactor 30, noble metal catalysts would be discouraged. More than one type of hydrotreating catalyst may be used in the hydrotreating reactor 30.
- the Group VIII metal is typically present in an amount ranging from 2 to 20 wt%, preferably from 4 to 12 wt%.
- the Group VI metal will typically be present in an amount ranging from 1 to 25 wt%, preferably from 2 to 25 wt%.
- Preferred reaction conditions in the hydrotreating reactor 30 include a temperature from 290°C (550°F) to 455°C (850°F), suitably 316°C (600°F) to 427°C (800°F) and preferably 343 °C (650°F) to 399°C (750°F), a pressure from 2.1 MPa (gauge) (300 psig), preferably 4.1 MPa (gauge) (600 psig) to 20.6 MPa (gauge) (3000 psig), suitably 12.4 MPa (gauge) (1800 psig), preferably 6.9 MPa (gauge) (1000 psig), a liquid hourly space velocity of the fresh hydrocarbonaceous feedstock from 0.1 hr -1 , suitably 0.5 hr"', to 10 hr -1 , preferably from 1.5 to 8.5 hr -1 , and a hydrogen rate of 168 Nm 3 /m 3 (1,000 scf/bbl), to 1,011 Nm
- the first hydrocarbon feed stream in the first hydrocarbon feed line 28 is hydrotreated over the hydrotreating catalyst in the hydrotreating reactor 30 to provide a hydrotreated hydrocarbon feed stream that exits the hydrotreating reactor 30 in a
- hydrotreating effluent line 32 which can be taken as a first hydrocracking feed stream.
- the hydrogen gas laden with ammonia and hydrogen sulfide may be removed from the first hydrocracking feed stream in a separator, but the first hydrocracking feed stream is typically fed directly to the hydrocracking reactor 40 without separation.
- the first hydrocracking feed stream may be mixed with a first hydrocracking hydrogen stream in a first hydrocracking hydrogen line 33 from the first stage hydrogen line 22 and is fed through a first inlet 32i to the first hydrocracking reactor 40 to be hydrocracked.
- Hydrocracking is to a process in which hydrocarbons crack in the presence of hydrogen to lower molecular weight hydrocarbons.
- the first hydrocracking reactor 40 may be a fixed bed reactor that comprises one or more vessels, single or multiple catalyst beds 42 in each vessel, and various combinations of hydro treating catalyst, hydroisomerization catalyst and/or hydrocracking catalyst in one or more vessels. It is contemplated that the first hydrocracking reactor 40 be operated in a continuous liquid phase in which the volume of the liquid hydrocarbon feed is greater than the volume of the hydrogen gas.
- hydrocracking reactor 40 may also be operated in a conventional continuous gas phase, a moving bed or a fluidized bed hydroprocessing reactor.
- the hydrotreated first hydrocracking feed stream is hydrocracked over a first hydrocracking catalyst in first hydrocracking catalyst beds 42 in the presence of a first hydrocracking hydrogen stream from a first hydrocracking hydrogen line 33 to provide a first hydrocracked effluent stream in line 48.
- Subsequent catalyst beds 42 in the hydrocracking reactor may comprise hydrocracking catalyst over which additional hydrocracking occurs to the hydrocracked stream.
- Hydrogen manifold 44 may deliver supplemental hydrogen streams to one, some or each of the catalyst beds 42.
- the supplemental hydrogen is added to each of the catalyst beds 42 at an interstage location between adjacent beds, so supplemental hydrogen is mixed with hydroprocessed effluent exiting from the upstream catalyst bed 42 before entering the downstream catalyst bed 42.
- the first hydrocracking reactor 40 may provide a total conversion of at least 20 vol% and typically greater than 60 vol% of the first hydrocracking feed stream in the hydrotreating effluent line 32 to products boiling below the diesel cut point.
- the first hydrocracking reactor 40 may operate at partial conversion of more than 30 vol% or full conversion of at least 90 vol% of the feed based on total conversion.
- the first hydrocracking reactor 40 may be operated at mild hydrocracking conditions which will provide 20 to 60 vol%, preferably 20 to 50 vol%, total conversion of the hydrocarbon feed stream to product boiling below the diesel cut point.
- the first hydrocracking reactor 40 comprises a plurality of catalyst beds 42.
- the first catalyst bed in the hydrocracking reactor 40 may include a hydrotreating catalyst for the purpose of saturating, demetallizing, desulfurizing or denitrogenating the first hydrocarbon feed stream before it is hydrocracked with the first hydrocracking catalyst in subsequent vessels or catalyst beds 42 in the first hydrocracking reactor 40. Otherwise, the first or an upstream bed in the first hydrocracking reactor 40.
- the first hydrocracking catalyst may utilize amorphous silica-alumina bases or low-level zeolite bases combined with one or more Group VIII or Group VIB metal hydrogenating components if mild hydrocracking is desired to produce a balance of middle distillate and gasoline.
- a catalyst which comprises, in general, any crystalline zeolite cracking base upon which is deposited a Group VIII metal
- Additional hydrogenating components may be selected from Group VIB for incorporation with the zeolite base.
- the zeolite cracking bases are sometimes referred to in the art as molecular sieves and are usually composed of silica, alumina and one or more exchangeable cations such as sodium, magnesium, calcium, rare earth metals, etc. They are further characterized by crystal pores of relatively uniform diameter between 4 and 14 Angstroms (10 -10 meters). It is preferred to employ zeolites having a relatively high silica/alumina mole ratio between 3 and 12. Suitable zeolites found in nature include, for example, mordenite, stilbite, heulandite, ferrierite, dachiardite, chabazite, erionite and faujasite.
- Suitable synthetic zeolites include, for example, the B, X, Y and L crystal types, e.g., synthetic faujasite and mordenite.
- the preferred zeolites are those having crystal pore diameters between 8 and 12 Angstroms (10 -10 meters), wherein the silica/alumina mole ratio is 4 to 6.
- One example of a zeolite falling in the preferred group is synthetic Y molecular sieve.
- the natural occurring zeolites are normally found in a sodium form, an alkaline earth metal form, or mixed forms.
- the synthetic zeolites are nearly always prepared first in the sodium form.
- Hydrogen or "decationized" Y zeolites of this nature are more particularly described in US 3,100,006.
- Mixed polyvalent metal-hydrogen zeolites may be prepared by ion-exchanging first with an ammonium salt, then partially back exchanging with a polyvalent metal salt and then calcining.
- the hydrogen forms can be prepared by direct acid treatment of the alkali metal zeolites.
- the preferred cracking bases are those which are at least 10 wt%, and preferably at least 20 wt%, metal- cation-deficient, based on the initial ion-exchange capacity.
- a desirable and stable class of zeolites is one wherein at least 20 wt% of the ion exchange capacity is satisfied by hydrogen ions.
- the active metals employed in the preferred first hydrocracking catalysts of the present invention as hydrogenation components are those of Group VIII, i.e., iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium and platinum.
- other promoters may also be employed in conjunction therewith, including the metals of Group VIB, e.g., molybdenum and tungsten.
- the amount of hydrogenating metal in the catalyst can vary within wide ranges. Broadly speaking, any amount between 0.05 wt% and 30 wt% may be used. In the case of the noble metals, it is normally preferred to use 0.05 to 2 wt% noble metal.
- the method for incorporating the hydrogenation metal is to contact the base material with an aqueous solution of a suitable compound of the desired metal wherein the metal is present in a cationic form. Following addition of the selected hydrogenation metal or metals, the resulting catalyst powder is then filtered, dried, pelleted with added lubricants, binders or the like if desired, and calcined in air at temperatures of, e.g., 371°C (700°F) to 648°C (1200°F) in order to activate the catalyst and decompose ammonium ions.
- the base component may first be pelleted, followed by the addition of the hydrogenation component and activation by calcining.
- the foregoing catalysts may be employed in undiluted form, or the powdered catalyst may be mixed and copelleted with other relatively less active catalysts, diluents or binders such as alumina, silica gel, silica-alumina cogels, activated clays and the like in proportions ranging between 5 and 90 wt%. These diluents may be employed as such or they may contain a minor proportion of an added hydrogenating metal such as a Group VIB and/or Group VIII metal. Additional metal promoted hydrocracking catalysts may also be utilized in the process of the present invention which comprises, for example, aluminophosphate molecular sieves, crystalline chromosilicates and other crystalline silicates. Crystalline chromosilicates are more fully described in US 4,363,718.
- the hydrocracking conditions may include a temperature from 290°C (550°F) to 468°C (875°F), preferably 343°C (650°F) to 445°C (833°F). a pressure from 4.8 MPa (gauge) (700 psig) to 20.7 MPa (gauge) (3000 psig). a liquid hourly space velocity (LHSV) from 0.4 to less than 2.5 hr -1 and a hydrogen rate of 421 Nm 3 /m 3 (2.500 scf/bbl) to 2,527 Nm 3 /m 3 oil (15,000 scf/bbl).
- LHSV liquid hourly space velocity
- conditions may include a temperature from 315°C (600°F) to 441°C (825°F), a pressure from 5.5 MPa (gauge) (800 psig) to 13.8 MPa (gauge) (2000 psig) or more typically 6.9 MPa (gauge) (1000 psig) to 1 1.0 MPa (gauge) (1600 psig), a liquid hourly space velocity (LHSV) from 0.5 to 2 hr -1 and preferably 0.7 to 1.5 hr -1 and a hydrogen rate of 421 Nm 3 /m 3 oil (2,500 scf/bbl) to 1,685 Nm 3 /m 3 oil (10,000 scf/bbl).
- LHSV liquid hourly space velocity
- the first hydrocracked effluent stream may exit the first hydrocracking reactor 40 in line 48 and be separated in the fractionation section 14 in downstream communication with the first hydrocracking reactor 40.
- the fractionation section 14 comprises one or more separators and fractionation columns in downstream communication with the hydrocracking reactor 40.
- the first hydrocracked effluent stream in the first hydrocracked effluent line 48 may in an aspect be heat exchanged with the hydrocarbon feed stream in line 26 to be cooled and be mixed with a second hydrocracked effluent stream in a second hydrocracked effluent line 46.
- the combined hydrocracked effluent line 49 may deliver a combined stream to a hot separator 50.
- the hot separator separates the first hydrocracked effluent stream and the second hydrocracked effluent stream to provide a hydrocarbonaceous, hot gaseous stream in a hot overhead line 52 and a hydrocarbonaceous, hot liquid stream in a hot bottoms line 54.
- the hot separator 50 may be in downstream communication with the first hydrocracking reactor 40.
- the hot separator 50 operates at 177°C (350°F) to 371°C (700°F) and preferably operates at 232°C (450°F) to 315°C (600°F).
- the hot separator 50 may be operated at a slightly lower pressure than the first hydrocracking reactor 40 accounting for pressure drop through intervening equipment.
- the hot separator 50 may be operated at pressures between 3.4 MPa (gauge) (493 psig) and 20.4 MPa (gauge) (2959 psig).
- the hydrocarbonaceous, hot gaseous separated stream in the hot overhead line 52 may have a temperature of the operating temperature of the hot separator SO.
- the hot gaseous stream in the hot overhead line 52 may be cooled before entering a cold separator 56.
- ammonia and hydrogen sulfide are formed.
- ammonia and hydrogen sulfide will combine to form ammonium bisulfide and ammonia
- chlorine will combine to form ammonium chloride.
- Each compound has a characteristic sublimation temperature that may allow the compound to coat equipment, particularly heat exchange equipment, impairing its performance.
- a suitable amount of wash water may be introduced into the hot overhead line 52 upstream of a cooler at a point in the hot overhead line where the temperature is above the characteristic sublimation temperature of either compound.
- the hot gaseous stream may be separated in the cold separator 56 to provide a cold gaseous stream comprising a hydrogen-rich gas stream in a cold overhead line 58 and a cold liquid stream in a cold bottoms line 60.
- the cold separator 56 serves to separate hydrogen rich gas from hydrocarbon liquid in the first hydrocracked effluent stream and the second hydrocracked effluent stream for recycle to the first stage hydrocracking unit 12 and the second stage hydrocracking unit 150 in the cold overhead line 58.
- the cold separator 56 therefore, is in downstream communication with the hot overhead line 52 of the hot separator 50 and the first hydrocracking reactor 40.
- the cold separator 56 may be operated at 100°F (38°C) to 150°F (66°C).
- the cold separator 56 may be operated at pressures between 3 MPa (gauge) (435 psig) and 20 MPa (gauge) (2,901 psig).
- the cold separator 56 may also have a boot for collecting an aqueous phase.
- the cold liquid stream in the cold bottoms line 60 may have a temperature of the operating temperature of the cold separator 56.
- the cold gaseous stream in the cold overhead line 58 is rich in hydrogen.
- hydrogen can be recovered from the cold gaseous stream.
- the cold gaseous stream in the cold overhead line 58 may be passed through a frayed or packed recycle scrubbing column 62 where it is scrubbed by means of a scrubbing extraction liquid such as an aqueous solution fed by line 64 to remove acid gases including hydrogen sulfide and carbon dioxide by extracting them into the aqueous solution.
- aqueous solutions include lean amines such as alkanolamines DEA, MEA, and MDEA. Other amines can be used in place of or in addition to the preferred amines.
- the lean amine contacts the cold gaseous stream and absorbs acid gas contaminants such as hydrogen sulfide and carbon dioxide.
- the resultant "sweetened" cold gaseous stream is taken out from an overhead outlet of the recycle scrubber column 62 in a recycle scrubber overhead line 68, and a rich amine is taken out from the bottoms at a bottom outlet of the recycle scrubber column in a recycle scrubber bottoms line 66.
- the spent scrubbing liquid from the bottoms may be regenerated and recycled back to the recycle scrubbing column 62 in line 64.
- the scrubbed hydrogen-rich stream emerges from the scrubber via the recycle scrubber overhead line 68 and may be compressed in a recycle compressor 70.
- the scrubbed hydrogen-rich stream in the scrubber overhead line 68 may be supplemented with make-up hydrogen stream in the make-up line 20 upstream or
- the compressed hydrogen stream supplies hydrogen to the first stage hydrogen stream in the first stage hydrogen line 22 and a second stage hydrogen stream in a second stage hydrogen line 166.
- the recycle scrubbing column 62 may be operated with a gas inlet temperature between 38°C (100°F) and 66°C (150°F) and an overhead pressure of 3 MPa (gauge) (435 psig) to 20 MPa (gauge) (2900 psig).
- the hydrocarbonaceous hot liquid stream in the hot bottoms line 54 may be fractionated.
- the hot liquid stream in the hot bottoms line 54 may be let down in pressure and flashed in a hot flash drum 80 to provide a flash hot gaseous stream of light ends in a flash hot overhead line 82 and a flash hot liquid stream in a flash hot bottoms line 84.
- the hot flash drum 80 may be in direct, downstream communication with the hot bottoms line 54 and in downstream communication with the first hydrocracking reactor 40.
- light gases such as hydrogen sulfide may be stripped from the flash hot liquid stream in the flash hot bottoms line 84.
- a stripping column 100 may be in downstream communication with the hot flash drum 80 and the hot flash bottoms line 84.
- the hot flash drum 80 may be operated at the same temperature as the hot separator 50 but at a lower pressure of between 1.4 MPa (gauge) (200 psig) and 6.9 MPa (gauge) (1000 psig). suitably no more than 3.8 MPa (gauge) (550 psig).
- the flash hot liquid stream in the flash hot bottoms line 84 may be further fractionated in the fractionation section 14.
- the flash hot liquid stream in the flash hot bottoms line 84 may have a temperature of the operating temperature of the hot flash drum 80.
- the cold liquid stream in the cold bottoms line 60 may be directly fractionated.
- the cold liquid stream may be let down in pressure and flashed in a cold flash drum 86 to separate the cold liquid stream in the cold bottoms line 60.
- the cold flash drum 86 may be in direct downstream communication with the cold bottoms line 60 of the cold separator 56 and in downstream communication with the first
- the flash hot gaseous stream in the flash hot overhead line 82 may be fractionated in the fractionation section 14.
- the flash hot gaseous stream may be cooled and also separated in the cold flash drum 86.
- the cold flash drum 86 may separate the cold liquid stream in line 60 and/or the flash hot gaseous stream in the flash hot overhead line 82 to provide a flash cold gaseous stream in a flash cold overhead line 88 and a flash cold liquid stream in a cold flash bottoms line 90.
- light gases such as hydrogen sulfide may be stripped from the flash cold liquid stream in the flash cold bottoms line 90. Accordingly, the stripping column 100 may be in downstream communication with the cold flash drum 86 and the cold flash bottoms line 90.
- the cold flash drum 86 may be in downstream communication with the cold bottoms line 60 of the cold separator 56, the hot flash overhead line 82 of the hot flash drum 80 and the first hydrocracking reactor 40.
- the flash cold liquid stream in the cold bottoms line 60 and the flash hot gaseous stream in the hot flash overhead line 82 may enter into the cold flash drum 86 either together or separately.
- the hot flash overhead line 82 joins the cold bottoms line 60 and feeds the flash hot gaseous stream and the cold liquid stream together to the cold flash drum 86 in a cold flash feed line 92.
- the cold flash drum 86 may be operated at the same temperature as the cold separator 56 but typically at a lower pressure of between 1.4 MPa (gauge) (200 psig) and 6.9 MPa (gauge) (1000 psig) and preferably between 3.0 MPa (gauge) (435 psig) and 3.8 MPa (gauge) (550 psig).
- a flashed aqueous stream may be removed from a boot in the cold flash drum 86.
- the flash cold liquid stream in the flash cold bottoms line 90 may have the same temperature as the operating temperature of the cold flash drum 86.
- the flash cold gaseous stream in the flash cold overhead line 88 contains substantial hydrogen that may be recovered.
- the fractionation section 14 may further include the stripping column 100 and a fractionation column 130.
- the fractionation section 14 may include a HPNA adsorption zone 200.
- the stripping column 100 may be in downstream communication with a bottoms line in the fractionation section 14 for stripping volatiles from a first hydrocracked effluent stream and a second hydrocracked effluent stream.
- the stripping column 100 may be in downstream communication with the hot bottoms line 54, the flash hot bottoms line 84, the cold bottoms line 60 and/or the cold flash bottoms line 90.
- the stripping column 100 may be a vessel that contains a cold stripping column 102 and a hot stripping column 104 with a wall that isolates each of the stripping columns 102, 104 from the other.
- the cold stripping column 102 may be in downstream communication with the first hydrocracking reactor 40, the second hydrocracking reactor 170, the cold bottoms line 60 and, in an aspect, the flash cold bottoms line 90 for stripping the cold liquid stream.
- the hot stripping column 104 may be in downstream communication with the first hydrocracking reactor 40, the second hydrocracking reactor 170, and the hot bottoms line 54 and, in an aspect, the flash hot bottoms line 84 for stripping a hot liquid stream which is hotter than the cold liquid stream.
- the hot liquid stream may be hotter than the cold liquid stream, by at least 25°C and preferably at least 50°C.
- the flash cold liquid stream comprising the first hydrocracked effluent stream and the second hydrocracked effluent stream in the flash cold bottoms line 90 may be heated and fed to the cold stripping column 102 at an inlet which may be in a top half of the column.
- the flash cold liquid stream which comprises the first hydrocracked effluent stream and the second hydrocracked effluent stream may be stripped of gases in the cold stripping column 102 with a cold stripping media which is an inert gas such as steam from a cold stripping media line 106 to provide a cold stripper gaseous stream of naphtha, hydrogen, hydrogen sulfide, steam and other gases in a cold stripper overhead line 108 and a liquid cold stripped stream in a cold stripper bottoms line 110.
- the cold stripper gaseous stream in the cold stripper overhead line 108 may be condensed and separated in a receiver 112.
- a stripper net overhead line 114 from the receiver 112 carries a net stripper gaseous stream for further recovery of LPG and hydrogen in a light material recovery unit.
- Unstabilized liquid naphtha from the bottoms of the receiver 112 may be split between a reflux portion refluxed to the top of the cold stripping column 102 and a liquid stripper overhead stream which may be transported in a condensed stripper overhead line 1 16 to further recovery or processing.
- a sour water stream may be collected from a boot of the overhead receiver 112.
- the cold stripping column 102 may be operated with a bottoms temperature between 149°C (300°F) and 288°C (550°F), preferably no more than 260°C (500°F), and an overhead pressure of 0.35 MPa (gauge) (50 psig), preferably no less than 0.70 MPa (gauge) (100 psig), to no more than 2.0 MPa (gauge) (290 psig).
- the temperature in the overhead receiver 112 ranges from 38°C (100°F) to 66°C (150°F) and the pressure is essentially the same as in the overhead of the cold stripping column 102.
- the cold stripped stream in the cold stripper bottoms line 110 may comprise predominantly naphtha and kerosene boiling materials.
- the cold stripped stream in line 110 may be heated and fed to the fractionation column 130.
- the fractionation column 130 may be in downstream communication with the first hydrocracking reactor 40 and the second hydrocracking reactor 170, the cold stripper bottoms line 110 of the cold stripping column 102 and the stripping column 100.
- the fractionation column 130 may comprise more than one fractionation column.
- the fractionation column 130 may be in downstream communication with one, some or all of the hot separator 50, the cold separator 56, the hot flash drum 80 and the cold flash drum 86.
- the flash hot liquid stream comprising a hydrocracked stream in the hot flash bottoms line 84 may be fed to the hot stripping column 104 near a top thereof.
- the flash hot liquid stream may be stripped in the hot stripping column 104 of gases with a hot stripping media which is an inert gas such as steam from a line 120 to provide a hot stripper overhead stream of naphtha, hydrogen, hydrogen sulfide, steam and other gases in a hot stripper overhead line 118 and a liquid hot stripped stream in a hot stripper bottoms line 122.
- the hot stripper overhead line 118 may be condensed and a portion refluxed to the hot stripping column 104.
- the hot stripper overhead stream in the hot stripper overhead line 118 from the overhead of the hot stripping column 104 may be fed into the cold stripping column 102 directly in an aspect without first condensing or refluxing.
- the inlet for the cold flash bottoms line 90 carrying the flash cold liquid stream may be at a higher elevation than the inlet for the hot stripper overhead line 1 18.
- the hot stripping column 104 may be operated with a bottoms temperature between 160°C (320°F) and 360°C (680°F) and an overhead pressure of 0.35 MPa (gauge) (50 psig), preferably 0.70 MPa (gauge) (100 psig), to 2.0 MPa (gauge) (292 psig).
- At least a portion of the hot stripped stream comprising a hydrocracked stream in the hot stripped bottoms line 122 may be heated and fed to the fractionation column 130.
- the fractionation column 130 may be in downstream communication with the hot stripped bottoms line 122 of the hot stripping column 104.
- the hot stripped stream in line 122 may be at a hotter temperature than the cold stripped stream in line 110.
- the hot stripped stream in the hot stripped bottoms line 122 may be heated and fed to a prefractionation separator 124 for separation into a vaporized hot stripped stream in a prefractionation overhead line 126 and a liquid hot stripped stream in a prefractionation bottoms line 128.
- the vaporous hot stripped stream may be fed to the fractionation column 130 in the prefractionation overhead line 128.
- the liquid hot stripped stream may be heated in a fractionation furnace and fed to the fractionation column 130 in the prefractionation bottoms line 128 at an elevation below the elevation at which the
- prefractionation overhead line 126 feeds the vaporized hot stripped stream to the fractionation column 130.
- the fractionation column 130 may be in downstream communication with the cold stripping column 102 and the hot stripping column 104 and may comprise more than one fractionation column for separating stripped hydrocracked streams into product streams.
- the fractionation column 130 may fractionate hydrocracked streams, the cold stripped stream, the vaporous hot stripped stream and the liquid hot stripped stream, with an inert stripping media stream such as steam from line 132 to provide plurality of fractionator product streams and a fractionator bottoms stream comprising unconverted hydrocarbons.
- the product streams from the fractionation column 130 may include a net fractionated overhead stream comprising naphtha in a net overhead line 134, an optional heavy naphtha stream in line 136 from a side cut outlet, a kerosene stream carried in line 138 from a side cut outlet and a diesel stream in line 140 from a side cut outlet.
- the fractionator bottoms stream comprising unconverted hydrocarbons boiling above the diesel cut point may be taken in a fractionator bottoms line 142 from a bottom of the fractionation column 130. At least a portion of the fractionator bottoms stream may be recycled for further hydrocracking, which in the instant embodiment of FIG. 1 as discussed, occurs in the second hydrocracking reactor 170.
- the fractionator bottoms stream being recycled may range from 10 to 100 wt% of a fresh feed rate, preferably between 30 and 70 wt% of the fresh feed rate.
- a first stream in a first fractionator bottoms line 202 may be taken from the fractionator bottoms stream in the fractionator bottoms line 142.
- a second stream in a second fractionator bottoms line 204 may be taken from the fractionator bottoms stream in the fractionator bottoms line 142. Accordingly, the fractionator bottoms stream may be split to provide the first stream in line 202 and the second stream in line 204. Therefore, in accordance with various embodiments, the first fractionator bottoms line 202 and the second fractionator bottoms line 204 may be fluidly connected to the fractionator bottoms line 142.
- a third stream may be taken in a bottoms purge line 205 from the fractionator bottoms line 142 and may be rejected as a bleed stream. The first stream, the second stream and the third stream may be taken as aliquot portions of the fractionator bottoms stream.
- the first stream in line 202 may be passed through the HPNA adsorption zone 200 to obtain a treated bottoms stream in line 206 having a reduced concentration of HPNA compounds. Accordingly, the HPNA adsorption zone 200 may be in downstream
- the first stream may be contacted with a suitable adsorbent, which may selectively retain the HPNA compounds.
- suitable adsorbents may include one or more of a molecular sieve, a silica gel, an activated carbon, an activated alumina, a silica-alumina gel, and a clay.
- the HPNA adsorption zone 200 may comprise an activated carbon.
- the adsorbent may be installed in the adsorption zone 200 in any suitable manner, such as a fixed bed arrangement. The adsorbent may be installed in one or more vessels and either in series or parallel flow.
- the HPNA adsorption zone 200 may be operated in a swing bed or in a lead-lag configuration.
- the HPNA adsorption zone 200 can be maintained at a pressure from 170 kPa (25 psig) to 4,300 kPa (624 psig), a
- the flow of the first stream through the HPNA adsorption zone 200 may be conducted in an upflow, downflow or radial flow manner with the hydrocarbons in the liquid phase.
- the first stream in line 202 passing through the HPNA adsorption zone 200 may be between 2 to 10% of the fresh feed rate.
- the second stream in line 204 may be passed around the HPNA adsorption zone 200.
- the second stream and the second fractionator bottoms line 204 bypasses and may be out of communication with the HPNA adsorption zone 200.
- the treated bottoms stream in line 206 and the bypassed second stream in line 204 may be subsequently hydrocracked.
- the process may include hydrocracking the treated bottoms stream and the bypassed second stream.
- the treated bottoms stream and the bypassed second stream may be combined in a line 208 and passed to the second hydrocracking reactor 170 present in the second stage hydrocracking unit ISO.
- the treated bottoms stream and the bypassed second stream may combine as a feed stream to the second stage hydrocracking unit 150.
- the treated bottoms stream and the bypassed second stream may pass through a hydrotreating reactor (not shown) prior to being passed to the second hydrocracking reactor 170.
- Heat may be removed from the fractionation column 130 by cooling at least a portion of the product streams and sending a portion of each cooled stream back to the fractionation column. These product streams may also be stripped to remove light materials to meet product purity requirements.
- a fractionated overhead stream in an overhead line 148 may be condensed and separated in a receiver 1 SO with a portion of the condensed liquid being refluxed back to the fractionation column 130.
- the net fractionated overhead stream in line 134 may be further processed or recovered as naphtha product.
- the fractionation column 130 may be operated with a bottoms temperature between 260°C (500°F), and 385°C (725°F), preferably at no more than 350°C (650°F), and at an overhead pressure between 7 kPa
- a portion of the unconverted oil stream in the atmospheric bottoms line 142 may be reboiled and returned to the fractionation column 130 instead of adding an inert stripping media stream such as steam in line 132 to heat to the fractionation column 130.
- the combined stream in line 208 may be mixed with a second hydrotreating hydrogen stream in a second hydrocracking hydrogen line 152 to provide second
- hydrocracker feed stream in a second hydrocracker feed line 154 may be heated by heat exchange with a second hydrocracked effluent stream in line 46 and in a fired heater before being passed to the second hydrocracking reactor 170.
- the second hydrocracker feed stream is fed through a first inlet 162i to the second hydrocracking reactor 170 to be hydrocracked.
- the second hydrocracking reactor 170 may be a fixed bed reactor that comprises one or more vessels, single or multiple catalyst beds 172 in each vessel, and various combinations of hydrotreating catalyst, hydroisomerization catalyst and/or hydrocracking catalyst in one or more vessels. It is contemplated that the second hydrocracking reactor 170 be operated in a continuous liquid phase in which the volume of the liquid hydrocarbon feed is greater than the volume of the hydrogen gas. The second hydrocracking reactor 170 may also be operated in a conventional continuous gas phase, a moving bed or a fluidized bed hydroprocessing reactor.
- the second hydrocracker feed stream in the second hydrocracker feed line 134 is hydrocracked over the second hydrocracking catalyst in the second hydrocracking catalyst beds 172 in the presence of hydrogen to provide a second hydrocracked effluent stream.
- Subsequent catalyst beds 172 in the hydrocracking reactor may comprise hydrocracking catalyst over which additional hydrocracking occurs.
- Hydrogen manifold 176 may deliver supplemental hydrogen streams to one, some or each of the catalyst beds 172.
- the supplemental hydrogen is added to each of the downstream catalyst beds 172 at an interstage location between adjacent beds, so supplemental hydrogen is mixed with hydrocracked effluent exiting from the upstream catalyst bed 172 before entering the downstream catalyst bed 172.
- the second hydrocracking reactor 170 may provide a total conversion of at least 1 vol% and typically greater than 40 vol% of the second hydrocracking feed stream in the second hydrotreating effluent line 162 to products boiling below the diesel cut point.
- the second hydrocracking reactor 170 may complete the conversion partially achieved in the first hydrocracking reactor 40.
- the second hydrocracking reactor 170 may operate at partial conversion of more than 30 vol% or full conversion of at least 90 vol% of the first hydrocracking feed stream in the first hydrocracking feed line 32 based on total conversion.
- the second hydrocracking reactor 170 may be operated at mild hydrocracking conditions which will provide 1 to 60 vol%, preferably 20 to 50 vol%, total conversion of the hydrocarbon feed stream to product boiling below the diesel cut point.
- the second hydrocracking reactor 170 comprises a plurality of catalyst beds 172.
- the first catalyst bed in the hydrocracking reactor 170 may include a hydrotreating catalyst for the purpose of saturating aromatic rings in the second hydrocracker feed stream in the second hydrocracker feed line 154 before it is hydrocracked with the second hydrocracking catalyst in subsequent vessels or catalyst beds 172 in the second hydrocracking reactor 170.
- the second hydrocracking catalyst may be the same as or different than the first hydrocracking catalyst or may have some of the same as and some different than the first hydrocracking catalyst in the first hydrocracking reactor 40.
- the second hydrocracking catalyst may utilize amorphous silica-alumina bases or low-level zeolite bases combined with one or more Group VIII or Group VIB metal hydrogenating components. Additional hydrogenating components may be selected from Group VIB for incorporation with the zeolite base.
- the hydrocracking conditions in the second hydrocracking reactor 170 may be the same as or different than in the first hydrocracking reactor 40.
- Conditions in the second hydrocracking reactor may include a temperature from 290°C
- the second hydrocracked effluent stream may exit the second hydrocracking reactor 170 in the second hydrocracked effluent line 46, be heat exchanged with the second hydrocracker feed stream in the second hydrocracker feed line 154 and combined with the first hydrocracked effluent stream in first hydrocracked effluent line 48.
- the first hydrocracked effluent stream and the second hydrocracked effluent stream combined in combined hydrocracked effluent line 49 are separated and fractionated in the fractionation section 14 in downstream communication with the second hydrocracking reactor 170 as previously described.
- FIG. 2 shows an embodiment of the apparatus and process 10' that illustrates a single hydrocracking unit. Elements in FIG. 2 with the same configuration as in FIG. 1 will have the same reference numeral as in FIG. 1. Elements in FIG. 2 which have a different configuration as the corresponding element in FIG. 1 will have the same reference numeral but designated with a prime symbol ('). The configuration and operation of the embodiment of FIG. 2 is essentially the same as in FIG. 1 with the following exceptions.
- the process and apparatus 10' does not comprise a second stage hydrocracking unit 150. Accordingly, the treated bottoms stream in line 206 and the bypassed second stream in line 204 may be combined in a line 208' and passed back to the hydrocracking reactor 40. In an aspect, the treated bottoms stream and the bypassed second stream may combine in a combined stream to the hydrocracking unit 12'. In accordance with an exemplary embodiment as shown in FIG.2, the combined stream in line 208' may be mixed with the hydrocarbon line 18' to provide the hydrocarbon feed stream in the hydrocarbon feed line 26' which is subsequently processed as described in FIG.1. In an aspect, the combined stream in line 208' may bypass the hydrotreating reactor 30 and is provided to the hydrotreating effluent line 32 and passed to the hydrocracking reactor 40 for further processing a described in FIG.l.
- the present process and apparatus allows the operator to tailor the operation for the actual HPNA removal requirements as operating severity and feed changes. If the unit is processing a feed high in HPNA precursors, the operator has the option to increase the flow to the HPNA adsorption zone by reducing the bypass. Likewise, during periods of feeds low in HPNA precursors, the flow to the chambers could be reduced by increasing the bypass. Further, as the flow to the HPNA adsorption zone is reduced, this results in smaller activated carbon chamber and reduced frequency of activated carbon replacement.
- a first embodiment of the invention is a process of removing HPNA compounds from a hydrocracked stream, the process comprising passing at least a portion of the hydrocracked stream to a fractionation column to provide a plurality of fractionator product streams and a fractionator bottoms stream comprising unconverted hydrocarbons; taking a first stream from the fractionator bottoms stream; taking a second stream from the
- fractionator bottoms stream passing the first stream through a HPNA adsorption zone to obtain a treated bottoms stream having a reduced concentration of HPNA compounds;
- An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph further comprising hydrocracking a hydrocarbon feedstream in a first
- hydrocracking reactor wherein the hydrocarbon feedstream is contacted with a first hydrocracking catalyst under first hydrocracking conditions in the presence of hydrogen to provide the hydrocracked stream.
- An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph, wherein the step of hydrocracking the treated bottoms stream and the bypassed second stream occurs in the first hydrocracking reactor.
- An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph, wherein the step of hydrocracking the treated bottoms stream and the bypassed second stream occurs in a second hydrocracking reactor.
- An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph, wherein the HPNA adsorption zone comprises an activated carbon.
- An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph further comprising hydrotreating the hydrocarbon feedstream in a
- hydrotreating reactor prior to hydrocracking the hydrocarbon feedstream in the first hydrocracking reactor.
- An embodiment of the invention is one, any or all of prior
- An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph further comprising passing the hydrocracked stream through one or more vapor- liquid separators to provide a recycle hydrogen gas stream and at least one liquid process stream; and passing the at least one liquid process stream to the fractionation column to provide the plurality of fractionator product streams and the fractionator bottoms stream.
- An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph further comprising taking a third stream from the fractionator bottoms stream and rejecting the third stream as a bleed stream.
- a second embodiment of the invention is a process for upgrading a hydrocarbon stream, the process comprising passing the hydrocarbon feedstream to a first hydrocracking reactor, the first hydrocracking reactor containing at least one bed of a first hydrocracking catalyst, wherein the hydrocarbon feedstream is contacted with the first hydrocracking catalyst under first hydrocracking conditions in the presence of hydrogen to produce a first hydrocracked effluent stream; passing at least a portion of the first hydrocracked effluent stream to a fractionation column to provide a plurality of fractionator product streams and a fractionator bottoms stream comprising unconverted hydrocarbons; splitting the fractionator bottoms stream to provide a first stream and a second stream; passing the first stream through a HPNA adsorption zone to obtain a treated bottoms stream having a reduced concentration of HPNA compounds; bypassing the second stream around the HPNA adsorption zone; and passing the treated bottoms stream and the bypassed second stream to a second
- hydrocracking reactor the second hydrocracking reactor containing at least one bed of a second hydrocracking catalyst, wherein the treated bottoms stream and the bypassed second stream are contacted with a second hydrocracking catalyst under second hydrocracking conditions in the presence of hydrogen to provide a second hydrocracked effluent stream.
- An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph, wherein the HPNA adsorption zone comprises an activated carbon.
- An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph further comprising hydrotreating the hydrocarbon feedstream in a hydrotreating reactor prior to hydrocracking the hydrocarbon feedstream in the first hydrocracking reactor.
- embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph, wherein the treated bottoms stream and the bypassed second stream are passed through the hydrotreating reactor prior to being passed to the second hydrocracked reactor.
- An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph further comprising passing the first hydrocracked effluent stream through one or more vapor-liquid separators to provide a recycle hydrogen gas stream and at least one liquid process stream; passing the at least one liquid process stream to the fractionation column to provide the plurality of fractionator product streams and the fractionator bottoms stream.
- embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph further comprising obtaining a third stream from the fractionator bottoms stream, the third stream being rejected as a bleed stream.
- a third embodiment of the invention is an apparatus for removing HPNA compounds from a hydrocracked stream, the apparatus comprising a fractionation column in communication with a hydrocracked effluent line to provide a plurality of fractionator product streams and a fractionator bottoms stream in a fractionator bottoms line; a first fractionator bottoms line fluidly connected to the fractionator bottoms line; a second fractionator bottoms line fluidly connected to the fractionator bottoms line; a HPNA adsorption zone in downstream communication with the first fractionator bottoms line to provide a treated bottoms stream in a treated bottoms line having a reduced concentration of HPNA compounds; and a hydrocracking reactor in communication with the treated bottoms line and the second fractionator bottoms line, the second fractionator bottoms line bypassing the HPNA adsorption zone.
- An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the third embodiment in this paragraph, wherein the HPNA adsorption zone comprises an activated carbon.
- An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the third embodiment in this paragraph further comprising a first hydrocracking reactor to provide a hydrocracked stream in the hydrocracked effluent line.
- An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the third embodiment in this paragraph, wherein the hydrocracking reactor is the first hydrocracking reactor.
- An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the third embodiment in this paragraph, wherein the hydrocracking reactor is a second hydrocracking reactor, the second hydrocracking reactor in downstream communication with the first hydrocracking reactor.
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US201662373189P | 2016-08-10 | 2016-08-10 | |
PCT/US2017/044292 WO2018031252A1 (en) | 2016-08-10 | 2017-07-28 | Process and apparatus for removal of heavy polynuclear aromatics in a hydrocracking process |
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EP3497185A1 true EP3497185A1 (de) | 2019-06-19 |
EP3497185A4 EP3497185A4 (de) | 2020-03-18 |
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EP17840008.1A Withdrawn EP3497185A4 (de) | 2016-08-10 | 2017-07-28 | Verfahren und vorrichtung zur entfernung von schweren mehrkernigen aromaten in einem hydrokrackverfahren |
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US (1) | US20180044599A1 (de) |
EP (1) | EP3497185A4 (de) |
CN (1) | CN109715763A (de) |
WO (1) | WO2018031252A1 (de) |
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US11692146B1 (en) * | 2022-01-03 | 2023-07-04 | Saudi Arabian Oil Company | Systems and processes for upgrading crude oil through hydrocracking and solvent assisted on-line solid adsorption of asphaltenes |
US11542442B1 (en) | 2022-04-05 | 2023-01-03 | Saudi Arabian Oil Company | Hydrocracking process and system including separation of heavy poly nuclear aromatics from recycle with heteropoly acids |
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US5190633A (en) * | 1992-03-19 | 1993-03-02 | Chevron Research And Technology Company | Hydrocracking process with polynuclear aromatic dimer foulant adsorption |
US5464526A (en) * | 1994-05-27 | 1995-11-07 | Uop | Hydrocracking process in which the buildup of polynuclear aromatics is controlled |
US6217746B1 (en) * | 1999-08-16 | 2001-04-17 | Uop Llc | Two stage hydrocracking process |
FR2883004B1 (fr) * | 2005-03-09 | 2007-04-20 | Inst Francais Du Petrole | Procede d'hydrocraquage avec recyclage comprenant l'adsorption de composes polyaromatiques de la fraction recyclee sur un adsorbant a base de silice-allumine a teneur controlee en macropores |
US8877040B2 (en) * | 2012-08-20 | 2014-11-04 | Uop Llc | Hydrotreating process and apparatus relating thereto |
-
2017
- 2017-06-01 US US15/611,613 patent/US20180044599A1/en not_active Abandoned
- 2017-07-28 EP EP17840008.1A patent/EP3497185A4/de not_active Withdrawn
- 2017-07-28 CN CN201780057425.8A patent/CN109715763A/zh active Pending
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CN109715763A (zh) | 2019-05-03 |
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