CN1476475A

CN1476475A - Hydrocracking process

Info

Publication number: CN1476475A
Application number: CNA018171141A
Authority: CN
Inventors: T・N・卡尔尼斯; T·N·卡尔尼斯; 盖茨; D·B·盖茨
Original assignee: Universal Oil Products Co
Current assignee: Honeywell UOP LLC; Universal Oil Products Co
Priority date: 2000-09-26
Filing date: 2001-09-24
Publication date: 2004-02-18
Also published as: AU2001293035A1; WO2002026917A1; MXPA03002517A; EP1326948A1; CA2423946A1

Abstract

A catalytic hydrocracking process wherein a hydrocarbonaceous feedstock and a liquid recycle stream is contacted with hydrogen in a hydrocracking reaction zone at elevated temperature and pressure to obtain conversion to lower boiling hydrocarbons. The process utilizes a hydrogenation zone located in the lower end of a hot, high pressure stripper to hydrogenate downwardly flowing liquid hydrocarbons in contact with upwardly flowing hydrogen.

Description

Method for hydrogen cracking

Background of invention

The technical field that the present invention relates to is the hydrocracking of hydrocarbon raw material.Usually, refinery is produced required product by hydrocracking derived from the hydrocarbon feed of crude oil for example turbine fuel, diesel-fuel and other is called the product and the low boiling hydrocarbon class I liquid I of middle runnings, for example petroleum naphtha and gasoline.The raw material that is most commonly used to carry out hydrocracking is gas oil and the heavy gas oil that obtains by distillation from crude oil.Heavy gas oil commonly used comprises that most of boiling point is higher than 371 ℃, normally at least 50 weight % boiling points are higher than 371 ℃ hydrocarbon composition.The boiling spread of vacuum gas oil commonly used is 315 ℃ to 565 ℃.

Hydrocracking generally contacts with suitable hydrocracking catalyst in the presence of hydrogen under the temperature and pressure that raises in hydrocracking reaction container or reaction zone by the gas oil that will handle or other raw material and realizes, thereby generates the product that contains the required hydrocarbon product distribution of refinery.The yield that operational condition in the hydrocracking reactor and hydrocracking catalyst influence isocrackate.

Although various process flow sheets, operational condition and catalyzer have been used for business activity, always need to have the novel hydrogenation cracking method of more low-cost and higher liquid product yield.It has been generally acknowledged that, under by the lower condition of the per pass conversion of hydrocracking zone, can improve product selectivity (60% to 90% transformation efficiency of raw feed).Yet, before thought, all be negligible in any service advantages that are lower than under the 60% per pass conversion condition, or only regard as and reduced rate of profit.Per pass conversion is low more expensive usually, yet the present invention has improved the economic benefit of the low process of per pass conversion significantly and shown beyond thought advantage.

Prior art

US-A-5,720,872 disclose the method for utilizing the two or more hydrotreatment stage hydrotreatment liquid starting material that carries out in the reaction vessel that separates, and each step of reaction wherein all is equipped with the bed of hydrotreating catalyst.The product liquid that is derived from first step of reaction is delivered to the low pressure stripping stage and stripping goes out hydrogen sulfide, ammonia and other dissolved gases.Then, to be delivered to the next downstream reaction stage through steam stripped product stream, the product stripping that also will be derived from this step of reaction simultaneously goes out dissolved gases and is delivered to the next downstream reaction stage, until last step of reaction, the product liquid stripping in final reaction stage is gone out dissolved gases and collect, or transmit, with further processing treatment.It is opposite with liquid flow direction in the step of reaction to handle the gas flow direction.Each stripping stage all is the stage separately, but all stages are included in the identical stripping container.

International open WO 97/38066 (PCT/US 97/04270) discloses reverse fractionated method in the hydrotreating reactor system.

Summary of the invention

The present invention has higher liquid product yield, particularly higher turbine fuel and the catalytic hydrocracking method of diesel yield.The hydrocarbon that flows downward that the hydrogenation zone that utilization of the present invention is positioned at the high pressure hot separator lower end comes hydrogenation to contact with mobile hydrogen upwards.Because the hydrocarbon that flows downward of process hydrogenation zone stripping goes out hydrogen sulfide and ammonia, so hydrogenation is carried out under the condition that is called the low-sulfur environment, described low-sulfur environment is very beneficial for removing the sulphur of relative low levels from hydrocarbon.In addition, the mobile hydrogen hydrogen sulfide of stripping generation effectively that makes progress, thus produce the further hydro carbons that reduces of the sulphur content that can remove from the bottom of high pressure hot separator at last.The usefulness dissolved hydrogen that is generated saturated and the low-down hydrocarbon material flow of sulphur concentration can use the catalyzer of hydrocracking zone, this catalyzer to have good performance characteristic and very responsive to the existence of organic and inorganic sulfur.Therefore, method of the present invention can be used previous disabled high-performance catalyst for hydrocracking.

In one embodiment, the present invention relates to the method for hydrocracking hydro carbons raw material, this method comprises: (a) hydro carbons is imported logistics and hydrogen and be delivered to the hydrocracking zone that contains hydrocracking catalyst to generate the hydrocracking effluent; (b) at least a in input logistics of a kind of hydrocarbon raw material and hydro carbons or the hydrocracking effluent mixed mutually; (c) will be in first disengaging zone from the liquid of effluent separation to produce first logistics and to flow downward of hydrocracking zone, described first logistics comprises hydrogen and boiling point is lower than the hydrocarbon that hydro carbons is imported the boiling range of logistics, and the described liquid that flows downward comprises the hydrocarbon compound of boiling point in the boiling range of hydro carbons input logistics; (d) in first disengaging zone liquid that flows downward is contacted with the mobile hydrogen stream that makes progress to produce first liquid stream with hydrotreating catalyst simultaneously, described first liquid stream comprises the hydrocarbon compound of boiling point in the boiling range of hydro carbons input logistics; (e) at least a portion first liquid stream recirculation is got back to hydrocracking zone so that at least a portion hydro carbons input logistics to be provided; (f) contain recovering liquid hydrocarbon product stream first logistics of hydrocarbon of boiling range that hydrogen and boiling point be lower than hydro carbons input logistics from least a portion is described.

The accompanying drawing summary

Fig. 1 is the process flow diagram of method for hydrogen cracking of the present invention.

Fig. 2 is the another kind of process flow diagram of method for hydrogen cracking of the present invention.

Detailed Description Of The Invention

Have now found that above-mentioned method for hydrogen cracking can obtain higher liquid product yield and lower Production cost. The present invention provides more effectively, more for the good hydrocracking catalyst of wide region more Purposes for economy.

Method of the present invention be particularly useful for hydrocracking contain hydrocarbon and/or other organic hydrocarbon ils with Generation contains hydrocarbon and/or other the organic product that mean boiling point is lower, mean molecule quantity is lower. Can Comprise all mineral oil and artificial oil with the hydrocarbon feed that carries out hydrocracking by method of the present invention (for example, shale oil, tar sand product etc.) and cut thereof. Illustrative hydrocarbon feed comprises and contains boiling point Those raw materials that are higher than 288 ℃ composition, for example AGO (atmospheric gas oil), vacuum gas oil (VGO), deasphalting, The residual oil of hydrocracking decompression residuum and reduced crude, hydrotreatment or slight, coking distillate, Straightrun virgin, solvent-deasphalted oils, pyrolysis-derived oils, higher boiling artificial oil, recycle oil and catalysis The cracker distillate. Preferred hydrocracking raw material is gas oil or contains at least 50 % by weight, warp Often be other hydrocarbon-fraction of the component of at least 75 % by weight boiling points end point of distillation that is higher than required product, heavy In the situation of matter gasoline, the described end point of distillation is generally 193 ℃ to 215 ℃. A kind of most preferred gas The oil raw material will contain the hydrocarbon composition that boiling point is higher than 288 ℃, when charging contains at least 25 volume % boiling points be Can obtain best result during 315 ℃ to 538 ℃ composition.

Wherein the boiling point of at least 90% composition is in 149 ℃ to 426 ℃ petroleum distillate is also included within.This petroleum distillate can be handled to generate light benzine cut (for example boiling range is 10 ℃ to 85 ℃) and heavy gasoline cut (for example boiling range is 85 ℃ to 204 ℃).The present invention is particularly suitable for and will comprises the yield maximization of the product liquid of middle runnings product.

In one embodiment, under the hydrotreatment reaction conditions, at first the raw material selected is incorporated into denitrogenation and desulfurization reaction zone with the effluent of hot hydrocracking zone.Preferred denitrogenation and desulphurization reaction conditioned disjunction hydrotreatment reaction conditions comprise that temperature is 204 ℃ to 482 ℃, and pressure is 3.55MPa to 17.3MPa, and the liquid hourly space velocity of the hydrocarbon raw material of raw feed is 0.1hr ^-1To 10hr ^-1, use the combination of hydrotreating catalyst or hydrotreating catalyst.

Term used herein " hydrotreatment " is meant in the presence of suitable catalyzer the method for using hydrogen-containing treat gas, described catalyzer mainly to remove heteroatoms for example the hydrogenation of sulphur and nitrogen and some aromatics activity is arranged.The suitable hydrotreating catalyst of available of the present invention be any known conventional hydrotreating catalyst and comprise those be stated from the high carrier substance of surface-area, the preferred aluminum oxide by at least a group VIII metal, preferred iron, cobalt and nickel, the more preferably catalyzer formed of cobalt and/or nickel and at least a VI family metal, preferred molybdenum and tungsten.Other suitable hydrotreating catalyst comprises zeolite catalyst and noble metal catalyst, and wherein precious metal is selected from palladium and platinum.The hydrotreating catalyst that uses more than one in identical reaction vessel also within the scope of the invention.The group VIII metal exists with the amount of 2 to 20 weight %, preferred 4 to 12 weight % usually.VI family metal exists with the amount of 1 to 25 weight %, preferred 2 to 25 weight % usually.Hydrotreatment temperature commonly used is 204 ℃ to 482 ℃, and pressure is 3.55MPa to 17.3MPa, preferred 3.55MPa to 13.9MPa.

In another embodiment of the invention, the effluent that generates is incorporated into hydrocracking zone from the denitrogenation and the desulfurization zone of selected raw material.Hydrocracking zone can contain one or more beds of identical or different catalyzer.In one embodiment, when preferred product is middle runnings, preferred hydrocracking catalyst utilization and one or more group VIIIs or group vib metal hydrogenation composition blended amorphous component or a small amount of zeolite component.In another embodiment, when in the boiling range of preferred product at gasoline, the catalyzer that hydrocracking zone contains is generally comprised within any crystalloid zeolite as cracking component of little deposit flow control VIII family metal hydrogenation composition on it.Other hydrogenation component can be selected from and zeolite component bonded group vib.The zeolite as cracking component is called molecular sieve sometimes in this area and for example sodium, magnesium, calcium, rare earth metal etc. are formed by silicon-dioxide, aluminum oxide and one or more tradable positively charged ions usually.Their feature is that also the uniform relatively crystal pores in aperture is 4 to 14 dusts (10 ^-10Rice).The preferred molar ratio that uses silica/alumina is higher relatively and be 3 to 12 zeolite.Naturally occurring suitable zeolite comprises for example mordenite, stilbite, heulandite, ferrierite, dachiardite, chabazite, erionite and faujusite.The synthetic zeolite that is suitable for comprises for example B, X, Y and L crystal formation, for example synthetic faujusite and mordenite.Preferred zeolite is that the crystal aperture is a 8-12 dust (10 ^-10Rice) those zeolites, wherein the molar ratio of silica/alumina is 4 to 6.The main example of preferred zeolite is the synthetic Y molecular sieve.

Naturally occurring zeolite normally exists with the form of sodium, the form or the blended form of alkaline-earth metal.Synthetic zeolite almost always at first makes with the form of sodium.Under any circumstance, for being used as the cracking component, preferably the great majority of original zeolite or all monovalent metal and polyvalent metal and/or ammonium salt are carried out ion-exchange, heat then to decompose and zeolite bonded ammonium ion, stay hydrogen ion in its position and/or in fact further removed water and the exchange position of decationizingization.The Hydrogen of this character or " decationizingization " Y zeolite more specifically are recorded in US-A-3, in 130,006.

Blended polyvalent metal h-type zeolite can by at first with ammonium salt carry out ion-exchange, then with polyvalent metal salt partly carry out back exchange, then the calcining make.In some cases, for example under the situation of synthesizing flokite, h-type zeolite can be by directly making alkali metal zeolites with acid treatment.Preferred cracking component be have 10% at least, those compositions of preferred at least 20% metal cation deficient, according to initial ion-exchange capacity meter.The stable zeolite type of particularly suitable is that wherein at least 20% ion-exchange capacity is by zeolite that hydrogen ion compensated.

In preferred hydrocracking catalyst of the present invention, can be those metals of group VIII as the reactive metal of hydrogenation component, just, iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium and platinum.Except these metals, other helps catalyst component also can combine with it, and it comprises the metal of group vib, for example molybdenum and tungsten.The amount of hydrogenation metal can change in wide region in the catalyzer.In broad terms, can use any amount between 0.05 to the 30 weight %.Under the situation of precious metal, preferred usually 0.05 to the 2 weight % that uses.The preferred method of introducing hydrogenation metal is that the aqueous solution of zeolite based material with the suitable compound of required metal is contacted, and wherein metal exists with cationic form.After the hydrogenation metal that brings Selection In, then with the catalyst fines filtration, the drying that generate, if desired, with granulations such as the lubricant that adds, binding agents.Then, in air temperature for example 371-648 ℃ down calcining with deactivated catalyst and decompose ammonium ion.In addition, can be at first with the zeolite component granulation, add hydrogenation component then and activate by calcining.Aforementioned catalyzer can use with undiluted form, or with relative less catalyzer, thinner or the binding agent of powder-type zeolite catalyst with other activity for example cogelled, the activated clay etc. of aluminum oxide, silica gel, silica-alumina mix and granulation jointly with the ratio of 5 to 90 weight %.Can use these thinners itself, or their hydrogenation metal metals of group vib and/or group VIII for example that can contain a small amount of adding.

Also can utilize the hydrocracking catalyst of other metal promoted in the method for the invention, comprise for example aluminophosphate molecular sieve, crystalloid silicochromium hydrochlorate and other crystalloid silicate.Crystalloid silicochromium hydrochlorate is recorded in US-A-4 more fully, in 363,718.

Hydrocarbon raw material or hydro carbons input logistics are through also preferably carrying out under hydrocracking condition in the presence of the hydrogen with the hydrocracking that contacts of hydrocracking catalyst.Described hydrocracking condition comprises that temperature is 232 ℃ to 468 ℃, and pressure is 3.55MPa to 20.8MPa, and liquid hourly space velocity (LHSV) is 0.1 to 30hr ^-1, hydrogen circulation rates is 337 standard m ³/ m ³To 4200 standard m ³/ m ³According to the present invention, term " changes into low-boiling products " and is meant the transformation efficiency of at least 10 volume % that newly advance raw material basically.

The heat exchange (without cooling) had a mind to is not carried out in the transmission that the effluent that generates carries out from denitrogenation and desulfurization reaction zone or hydrocracking zone, and is introduced into the thermal high stripping zone that maintains substantially the same pressure with denitrogenation and desulfurization reaction zone or hydrocracking reaction district.With the air-flow adverse current stripping that is rich in hydrogen, contain boiling point less than the first gas hydrocarbon material flow of 371 ℃ hydrocarbon compound, hydrogen sulfide and ammonia with contain the hydrocarbon liquids that flow downward of boiling point at this stripping zone greater than 371 ℃ hydrocarbon compound thereby generate.Stripping zone preferably maintains 232 ℃ to 468 ℃.The effluent in denitrogenation and desulfurization reaction zone or hydrocracking reaction district does not cool off before stripping basically, and occurs over just the process from reaction zone to stripping zone the temperature that causes because of inevitable thermosteresis and reduce.Any cooling of effluent before stripping in preferred denitrogenation and desulfurization reaction zone or hydrocracking reaction district is less than 38 ℃.The pressure of stripping zone is maintained the pressure substantially the same with denitrogenation and desulfurization reaction zone or hydrocracking reaction district be meant any pressure reduction, thereby make that flowing out logistics flows to stripping zone from reaction zone all owing to needed pressure drop.Pressure drop should be less than 0.800MPa.

To contain boiling point contacts with the hydrotreating catalyst of hydrogenation zone and the upwards mobile hydrogen stream of thermal high stripping tower lower end simultaneously greater than the hydrocarbon material flow that flows downward of 371 ℃ hydrocarbon compound.Hydrotreating catalyst can be selected from any known catalyzer, and the example of described catalyzer is recorded in above.Preferably including temperature in the operational condition of this hydrogenation zone is 204 ℃ to 482 ℃, and pressure is 3.55MPa to 17.3MPa, and liquid hourly space velocity is 0.1hr ^-1To 10hr ^-1Upwards mobile hydrogen can be by the hydrogen make air-flow, be rich in the circulating current of hydrogen or its and make up and supply.The mobile hydrogen that preferably makes progress in hydrogenation zone contains the sulphur less than 50wppm.The hydrocarbon liquids that flows downward is through after the hydrogenation zone, removes saturated and preferably contain and contain the liquid hydrocarbon logistics of boiling point greater than 371 ℃ hydrocarbon compound less than 100wppm sulphur with hydrogen from the thermal high stripping tower.

The air-flow that is rich in hydrogen preferably is supplied to stripping zone with the amount greater than 1 weight % hydrocarbon raw material.In one embodiment, the air-flow that is rich in hydrogen that is used as the stripping medium in the stripping zone is at first introduced the backflow heat transfer zone that is positioned at the stripping zone upper end reflux to produce, the air-flow that is rich in hydrogen of the heating that will generate is incorporated into the lower end of stripping zone to carry out the stripping function then.Be rich in the air-flow of hydrogen or introducing below hydrogenation zone, perhaps introduce from the position of the top and bottom of hydrogenation zone.Because the quantity of stripping gas is preferably greater than the required amounts of hydrogen of hydrogenation zone, so in one embodiment preferably at least two positions of thermal high stripping tower or highly introduce the gas that this is rich in hydrogen.Utilizing under the hydrotreating catalyst situation of high-performance, low pressure drop, in another embodiment, preferably below hydrogenation zone, introducing the gas that great majority (if not whole words) are rich in hydrogen.

That at least a portion is reclaimed from stripping zone and contain the first liquid hydrocarbon logistics that boiling point is higher than 371 ℃ hydrocarbon compound and be introduced directly into hydrocracking zone with the hydrogen of adding.In preferred embodiments, the per pass conversion of hydrocracking zone is 15% to 45%.More preferably per pass conversion is 20% to 40%.

Preferably the boiling point that contains that is generated is incorporated into aftertreatment hydroconversion reaction zone with hydrogenation at least a portion aromatics from stripping zone with whole gas phase forms less than the first gas hydrocarbon material flow of 371 ℃ hydrocarbon compound, hydrogen sulfide and ammonia, thereby improves the quality of middle runnings, particularly aviation spirit.The aftertreatment hydroconversion reaction zone can flow to flow downward, to make progress or the operator scheme of radial flow is carried out, and can utilize any known hydrogenation catalyst.To preferably be cooled to from the effluent of aftertreatment hydroconversion reaction zone 4 ℃ to 60 ℃ and at least in part condensation to produce the second liquid hydrocarbon logistics.Described second liquid stream is reclaimed also fractionation to generate required hydrocarbon product stream.Simultaneously, also generate second air-flow that is rich in hydrogen, described second air-flow that is rich in hydrogen is separated, thereby interpolation hydrogen and at least a portion of providing at least a portion to be incorporated into hydrocracking zone as indicated above are incorporated into the air-flow that first of stripping zone is rich in hydrogen.The new hydrogen that replenishes can any suitable, introduce the position easily, but preferably introduce stripping zone, and more preferably introducing stripping zone below hydrogenation zone.Before second air-flow that is rich in hydrogen is introduced hydrocracking zone, preferably by known ordinary method will be at least most, for example at least 90 weight % hydrogen sulfide are removed and are reclaimed.In preferred embodiments, the air-flow that is rich in hydrogen that is incorporated into hydrocracking zone contains the hydrogen sulfide less than 50wppm.

Description of drawings

Referring now to Fig. 1, the feed stream that will comprise vacuum gas oil and heavy coker gas oil be incorporated in the technological process by circuit 1 and with mix mutually from hydrocracking zone 31, the effluent hereinafter described that transmits by circuit 32.The mixture that generates is sent to hydrotreatment district 3 by circuit 2.The effluent that is generated is transmitted and is incorporated into stripping zone 5 from hydrotreatment district 3 by circuit 4.Contain on the steam flow of hydrocarbon and hydrogen and contact through stripping zone 5 and with interchanger 25, by circuit 7 from stripping zone 5 discharges wherein at least a portion and be incorporated into aftertreatment hydrotreatment district 8.The hydrocarbon liquids that flows downward enters and process hydrotreatment district 40.The liquid hydrocarbon logistics is incorporated into hydrocracking zone 31 from stripping zone 5 by circuit 6 discharges and by circuit 6 and circuit 30.Interchanger 10 is discharged and be incorporated into to a kind of gaseous effluent stream from aftertreatment hydrotreatment district 8 by circuit 9.The cooling effluent that is generated is transmitted and is incorporated into gas-liquid separator 12 from interchanger 10 by circuit 11.Sour gas recovery zone 18 is discharged and be incorporated into to the air-flow that is rich in hydrogen that will contain the sour gas compound from gas-liquid separator 12 by circuit 17.Lean solvent is incorporated into sour gas recovery zone 18 by circuit 35 and contacts with the dissolving sour gas with the air-flow that is rich in hydrogen.The dense solvent that will contain sour gas is removed and is reclaimed by circuit 36 from sour gas recovery zone 18.The hydrogen rich gas air-flow that the concentration of acid gas-containing is reduced is discharged by circuit 19 from sour gas recovery zone 18 and is mixed mutually with the new hydrogen of introducing by circuit 20 that replenishes.The mixture that generates is transmitted and is incorporated into compressor 22 by circuit 21.The air communication that the compressibility that generates is rich in hydrogen is crossed circuit 23 transmission and at least a portion is got back to hydrocracking zone 31 by circuit 29 and circuit 30 recirculation.The air communication that another part is rich in hydrogen is crossed circuit 24 transmission and is incorporated into interchanger 25.Interchanger 27 is discharged and be incorporated into to the hydrogen rich gas air-flow of the heating that generates from interchanger 25 by circuit 26.The air-flow that is rich in hydrogen of the heating that generates is discharged and transmitted by circuit 28 from interchanger 27, and the position below hydrotreatment district 40 is incorporated into stripping zone 5 then.Aqueous stream introduced by circuit 33 and contact, be introduced into gas-liquid separator 12 according to hereinafter description subsequently with flow stream in the circuit 9.The aqueous stream that will contain water-soluble salt is discharged and is reclaimed by circuit 34 from gas-liquid separator 12.The liquid stream that will contain hydrocarbon compound is discharged, is reduced pressure and be incorporated into disengaging zone 14 by circuit 13 from gas-liquid separator 12.The air-flow that will contain hydrogen and carburet hydrogen commonly used 14 is discharged by circuit 15 from the disengaging zone.The liquid stream that will contain hydrocarbon 14 is discharged and is reclaimed by circuit 16 from the disengaging zone.

Referring now to Fig. 2, the feed stream that will contain vacuum gas oil and heavy coker gas oil is incorporated in the technological process and with the recirculation stream of passing through circuit 56 transmission hereinafter described by circuit 51 and mixes mutually.The mixture that generates is transmitted by circuit 56 and contacts with the hydrogen rich gas air-flow of supplying by circuit 129, the mixture that generates is incorporated into hydrotreatment district 131 by circuit 130.This hydrotreatment district also changes or the hydrocracking feed stream indistinctively, but heteroatomic compound is transformed ammonification and hydrogen sulfide.The effluent that is generated is transmitted and is incorporated into hydrocracking zone 53 from hydrotreatment district 131 by circuit 52.The effluent that is generated is transmitted and is incorporated into stripping zone 58 from hydrocracking zone 53 by circuit 54.The air-flow that contains hydrocarbon and hydrogen upwards passes through stripping zone 58 and contacts filler 57, and the contact heat-exchanging device 125 then, and at least a portion wherein is incorporated into aftertreatment hydrotreatment district 132.The hydrocarbon liquids that flows downward enters and process hydrotreatment district 55.The liquid hydrocarbon logistics is incorporated into hydrotreatment district 131 from stripping zone 58 by circuit 56 discharges and by circuit 56 and circuit 130.Disengaging zone 114 is discharged and be incorporated into to the logistics of another part liquid hydrocarbon from stripping zone 58 by circuit 56 and circuit 137.Interchanger 110 is discharged and be incorporated into to gaseous effluent stream from aftertreatment hydrotreatment district 132 by circuit 59.The cooling effluent that is generated is transmitted and is incorporated into gas-liquid separator 112 from interchanger 110 by circuit 111.Sour gas recovery zone 118 is discharged and be introduced into to the air-flow that is rich in hydrogen that will contain the sour gas compound from gas-liquid separator 112 by circuit 117.Lean solvent is incorporated into sour gas recovery zone 118 by circuit 135 and contacts with the dissolving sour gas with the air-flow that is rich in hydrogen.The dense solvent that will contain sour gas 118 is discharged and is reclaimed by circuit 136 from the sour gas recovery zone.The hydrogen rich gas air-flow that contained acidic gas concentration is reduced mixes mutually from sour gas recovery zone 118 by circuit 119 discharges and with the new hydrogen of introducing by circuit 120 that replenishes.The mixture that generates is transmitted and is incorporated into compressor 122 by circuit 121.The air communication that the compressibility that generates is rich in hydrogen is crossed circuit 123 transmission and at least a portion is got back to hydrotreatment district 131 by circuit 129 and circuit 130 recirculation.The air communication that another part is rich in hydrogen is crossed circuit 124 transmission and is incorporated into interchanger 125.The hydrogen rich gas air-flow of the heating that generates is discharged by circuit 126 and the position of at least a portion from filler 57 below is incorporated into stripping zone 58 by circuit 128 from interchanger 125, another part at least is incorporated into stripping zone 58 by circuit 127 transmission and the position below hydrotreatment district 55.Aqueous stream introduced by circuit 133 and contact, subsequently according to the gas-liquid separator 112 that is introduced into mentioned above with flow stream in the circuit 59.The aqueous stream that will contain water-soluble salt is discharged and is reclaimed by circuit 134 from gas-liquid separator 112.The liquid stream that will contain hydrocarbon compound is discharged, is reduced pressure and be incorporated into disengaging zone 114 by circuit 113 from gas-liquid separator 112.The air-flow that will contain hydrogen and carburet hydrogen commonly used 114 is discharged by circuit 115 from the disengaging zone.The liquid stream that will contain hydrocarbon 114 is discharged and is reclaimed by circuit 116 from the disengaging zone.

Embodiment 1

A part of hydrocracker raw material that will have feature shown in the table 1 carries out hydrocracking with the described product of generation table 3 under the operational condition shown in the table 2 in the single-stage hydrocracker of routine.Use catalyzer of the same type as the reference scheme, in that identical hydrocracker raw material carries out hydrocracking with the described product of generation table 3 in hydrocracker of the present invention with another part under the operational condition shown in the table 2.Raw feed calculated yield when beginning according to test conditions.

Table 1-hydrocracker feedstock analysis

80/20 blended straight run vacuum gas oil-coker gas oil proportion, 15 ℃ of 0.928 distillation, volume % IBP, ℃ 351 10 379 30 408 50 436 70 471 90 518 FBP, 565 sulphur, weight % 3.01 nitrogen, PPM 1256 bromine numbers 7.5 heptane insolubles, weight %＜0.05 carbon residue, weight % 0.36 nickel and vanadium, PPM 0.4

The pressure of the operational condition high-pressure separator of the low per pass conversion reactor of the general introduction flow process reference scheme raising yield of table 2-operational condition, Mpa 16 11.8 liquid hourly space velocity hydrotreatment districts 2.18 1.13 hydrocracking zones, 0.93 3.0 total amount, 0.65 0.82 parallel feeding ratio ^*1.5 ^{* *}3.0H ₂/ raw feed, m ³/ m ³1,955 1955 per pass conversion ^*, % 60 30 total conversion rates, % ^*The maximum Δ T of number 30 reactors of 100 100 quenching of gases points, ℃ HT/HC 30,/18 36/30 ^*Change into 382 ℃ of final boiling point cuts and light ends ^*The liquid of recirculation at first arrives HT, then to HC ^{* *}The liquid of recirculation at first arrives HC, then to HT

Table 3-product yield

The present invention of reference scheme

Wt.% Vol.% Wt.% Vol.%NH ₃0.15 0.15H ₂S 3.20 3.20C ₁-C ₄3.68 2.97 light naphtha (C ₅-C ₆) 6.32 8.76 5.08 7.04 heavy naphtha (C ₇-127 ℃) total middle runnings 78.88 90.13 83.45 95.01C of 10.38 12.87 7.68 9.52 kerosene (127 ℃-288 ℃), 50.16 58.15 48.34 55.92 diesel oil (288 ℃-382 ℃) 28.72 31.98 35.11 39.09 ₅₊Total amount 95.58 111.76 96.21 111.57C ₄₊Total amount 98.20 116.01 98.32 115.00 chemistry H ₂Consumption m ₃/ m ³2.61 284 2.53 276

Can find out significantly that from top tabulation the present invention can operate, and the use internal volume is little by 30%, the hydrocracking reactor of catalyst inventory few 20% under 11.8MPa or the pressure than reference scheme about little 1/4th.Because the complicated operation degree in hydrocracking reactor zone reduces in the present invention, so per pass conversion reduces to 30% from 60%.The variation of these property enumerated that the present invention uses provides method for hydrogen cracking more cheaply and has increased the total recovery of middle runnings product.The present invention has also reduced 8m ³/ m ³The chemical hydrogen gas consumption and reduced by 50% fuel gas hydrogen loss.

The specification sheets of front, drawings and Examples have clearly illustrated the advantage that method of the present invention is included and have used the resulting interests of this method.

Claims

1, a kind of method of hydrocracking hydro carbons raw material, this method comprises:

(a) hydro carbons is imported logistics and hydrogen and be delivered to the hydrocracking zone that contains hydrocracking catalyst to generate the hydrocracking effluent;

(b) at least a in input logistics of hydrocarbon raw material and hydro carbons or the hydrocracking effluent mixed mutually;

(c) will in first disengaging zone, separate liquid from the effluent of hydrocracking zone to produce first logistics and to flow downward, described first logistics comprises hydrogen and boiling point is lower than the hydrocarbon that hydro carbons is imported the boiling range of logistics, and the described liquid that flows downward comprises the hydrocarbon compound of boiling point in the boiling spread of hydro carbons input logistics;

(d) in first disengaging zone liquid that flows downward is contacted to produce first liquid stream with the hydrotreating catalyst and the mobile hydrogen stream that makes progress simultaneously, described first liquid stream comprises the hydrocarbon compound of boiling point in the boiling spread of hydro carbons input logistics;

(e) at least a portion first liquid stream recirculation is got back to hydrocracking zone so that at least a portion hydro carbons input logistics to be provided;

(f) from least a portion first logistics recovering liquid hydrocarbon product stream, described first logistics contains hydrogen and boiling point is lower than the hydrocarbon that hydro carbons is imported the boiling range of logistics.

2, the described method of claim 1, wherein before separate first disengaging zone, will be delivered to denitrogenation and the desulfurization reaction zone that contains catalyzer, the effluent of denitrogenation and desulfurization reaction zone will be separated liquid to generate first logistics and to flow downward from the effluent and the hydrocarbon raw material of hydrocracking zone.

3, claim 1 and 2 described methods, wherein the effluent of denitrogenation and desulfurization reaction zone or the effluent of hydrocracking directly are delivered to first disengaging zone, described first disengaging zone comprises the thermal high stripping tower of the hydrogen rich gas stripping gas that utilizes heating, generate first logistics thus, described first logistics comprises the hydrocarbon compound that hydrogen and boiling point are lower than the boiling range of hydrocarbon raw material, and generate the liquid that flows downward, the described liquid that flows downward comprises the hydrocarbon compound of boiling point in the scope of hydrocarbon raw material.

4, the described method of claim 3 wherein will be delivered to denitrogenation and desulfurization reaction zone from the effluent of hydrocracking zone, and the liquid that at least a portion is flowed downward is transported to hydrocracking zone as hydro carbons input logistics.

5, the described method of claim 3 wherein will comprise first logistics of hydrocarbon compound that hydrogen and boiling point be lower than the boiling range of hydrocarbon raw material and be delivered to the aromatics saturation region that contains hydrogenation catalyst.

6, the described method of claim 1-5, wherein the boiling point of hydrocarbon raw material is 315 ℃ to 538 ℃.

7, the described method of claim 3-6, wherein the service temperature of thermal high stripping tower is lower than the temperature out of denitrogenation and desulfurization reaction zone, and its temperature head is less than 38 ℃, and working pressure is than the low 689kPa at least of top hole pressure of denitrogenation and desulfurization reaction zone.

8, the described method of claim 1-7, wherein hydrocracking zone is to operate under 15 to 45 the condition at per pass conversion.