CN1032355A - The control of Ppolynuclear aromatic by product in the hydrogenolysis - Google Patents
The control of Ppolynuclear aromatic by product in the hydrogenolysis Download PDFInfo
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- CN1032355A CN1032355A CN 87106790 CN87106790A CN1032355A CN 1032355 A CN1032355 A CN 1032355A CN 87106790 CN87106790 CN 87106790 CN 87106790 A CN87106790 A CN 87106790A CN 1032355 A CN1032355 A CN 1032355A
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Abstract
The method that control Ppolynuclear aromatic by product generates in a kind of hydrogenolysis comprises that (a) adds topped oil in the vacuum fractionation section; (b) the vacuum gas oil distillate that generates in (a) is changed into low-boiling products in the hydrocracking section; (c), and be separated into lower boiling and high boiling fraction with the hydro carbons partial condensation that generates in (b); (d) will contain at least a portion adding vacuum fractionation section of the PNA compound cut that generates in unconverted hydro carbons and the above-mentioned steps, thereby in side line waxy stone cut, reclaim most of polycyclc aromatic compound.This quantity that just effectively deleterious PNA compound is entered the hydrocracking section is reduced to minimum level.
Description
Technical field involved in the present invention is to have hydro carbons (hydrocarbonaceous) the raw material hydrocracking of generation Ppolynuclear aromatic (PNA) compound tendency, and does not make the excessive fouling of production equipment.More particularly, the present invention relates to a kind of catalytic cracking method, this method comprises: (a) add reduced oil in the vacuum fractionation section, to generate a kind of vacuum gas oil distillate and a kind of side line waxy stone cut, contain the material that can generate the PNA compound in the hydrocracking section in this gas oil fraction; (b) the vacuum gas oil distillate is contacted at the hydrogen of hydrocracking Duan Zhongyu adding and the hydrocracking catalyst of metal promoters, the temperature and pressure during contact is higher, is enough to obtain the low-boiling products of suitable high conversion; (c) make the hydro carbons effluent partial condensation of hydrocracking section, and it is separated into a kind of low boiling point hydrocarbon product cut and another kind contains the unconverted hydro carbons of boiling point more than 650 (343 ℃) and the cut of trace PNA compound; (d) in the vacuum distilling section, add the cut that a part contains unconverted hydro carbons and PNA compound at least, thereby in side line waxy stone cut, reclaim a large portion PNA compound.This harmful PNA compound that just will enter the hydrocracking section is effectively minimized.
United States Patent (USP) 4,447,315(draw nurse (Lamb) etc.) in a kind of hydrocarbon raw material hydrogenolysis that generates the polycyclc aromatic compound tendency that has is disclosed, this method comprises: hydrocarbon raw material is contacted with crystal zeolite hydrocracking catalyst; The unconverted hydro carbons oil that contains polycyclc aromatic compound that at least a portion is obtained contacts with a kind of sorbent material, and this sorbent material optionally adsorbs polycyclc aromatic compound; Wherein the lowered unconverted hydro carbons oil of polycyclc aromatic compound concentration is sent into the hydrocracking section, circulates.
United States Patent (USP) 3,619, a kind of method that prevents the hydroeracking unit fouling is disclosed in the 407(Hendricks (Hendricks), this method comprises: the effluent of hydrocracking section is partly cooled off, make wherein sub-fraction normal liquid hydro carbons condensation, thereby generate the partial condensation liquid of rich polycyclc aromatic compound, and this partial condensation liquid is discharged a part.As prior art, United States Patent (USP) 3,619,407 confirm, turning oil (the heavy part of hydrocracking section effluent) or its a large portion are carried out air distillation or vacuum distilling,, also can solve above-mentioned scale problems to separate the heavy tower bottom distillate that contains polycyclc aromatic compound.
The present invention is a kind of method for hydrogen cracking, this method can make used catalyzer of hydrocracking process and equipment drop to bottom line by the fouling that polycyclc aromatic compound causes, if this polycyclc aromatic compound does not add control, to be deposited in equipment, the hole on particularly cooling apparatus surface, and blocking catalyst.Above-mentioned purpose is to realize like this, to reclaim by the hydrocracking section, the unconverted hydro carbons that contains the trace polycyclc aromatic compound carries out vacuum fractionation, thereby in side line waxy stone cut, reclaim a large portion polycyclc aromatic compound, therefore when the hydro carbons with these recovery is recycled in the above-mentioned hydrocracking section, can effectively the polycyclc aromatic compound amount that enters this section be dropped to minimum level.
One embodiment of the present of invention relate to a kind of catalytic hydrocracking method, this method comprises: (a) add a kind of reduced oil in the vacuum fractionation section, has the compound that in the hydrocracking section, generates the polycyclc aromatic compound tendency to produce a kind of vacuum gas oil distillate and a kind of side line waxy stone cut, to comprise in this gas oil fraction; (b) this vacuum gas oil distillate is contacted at hydrogen and the catalytic catalyzer of a kind of metal promoted that hydrocracking Duan Zhongyu adds, the temperature and pressure during contact is higher, is enough to obtain the low-boiling products of suitable high conversion; (c) with the hydro carbons effluent of hydrocracking section partly condensation get off, and it is separated into a kind of low boiling point hydrocarbon product cut and a kind of unconverted hydro carbons of boiling point more than 650 (343 ℃) and cut of trace polycyclc aromatic compound of containing; (d) will contain at least a portion adding vacuum fractionation section of the cut of unconverted hydro carbons and polycyclc aromatic compound, thereby in side line waxy stone cut, reclaim a large portion polycyclc aromatic compound.This harmful polycyclc aromatic compound amount that just will enter the hydrocracking section effectively drops to minimum level.
Another embodiment of the present invention relates to a kind of method for hydrogen cracking, this method comprises: (a) add a kind of reduced oil in the vacuum fractionation section, to produce a kind of vacuum gas oil distillate, a kind of side line waxy stone cut and a kind of vacuum tower Residual oil, this gas oil fraction contains the compound that can generate polycyclc aromatic compound; (b) with vacuum tower Residual oil solvent deasphalting, to produce a kind of deasphalted oil cut that is suitable for hydrocracking; (c) with vacuum gas oil distillate and deasphalted oil cut, the hydrogen and the catalytic catalyzer of a kind of metal promoted that add at hydrocracking Duan Zhongyu contact, and the temperature and pressure during contact is higher, is enough to obtain the low-boiling products of suitable high conversion; (d) be separated into a kind of low boiling point hydrocarbon product cut and a kind of unconverted hydro carbons of boiling point more than 650 (343 ℃) and cut of trace polycyclc aromatic compound of containing with the partly condensation of hydro carbons effluent of hydrocracking section, and with it; (e) at least a portion that will contain unconverted hydro carbons and polycyclc aromatic compound cut adds the vacuum distilling section, thereby reclaim a large portion polycyclc aromatic compound in side line waxy stone cut, this harmful polycyclc aromatic compound amount that just will enter the hydrocracking section effectively drops to minimum level.
Other embodiment of the present invention comprise further details, and for example type of feed, catalyzer, distillation preferably and separation process and operational condition preferably are comprising temperature and pressure.All these will be disclosed in the discussion about all respects of the present invention below.
Accompanying drawing is the simplification production scheme of embodiment preferably of the present invention.Above-mentioned accompanying drawing just as the present invention is schematically illustrated, is not construed as limiting it.
Have been found that in above-mentioned method for hydrogen cracking, the recycle to extinction of unconverted oil can ad infinitum keep, and can not run into fouling and the sedimentation problem of pointing out above.
At United States Patent (USP) 3,619, ground such as 407(Hendricks) point out in, the partial condensation liquid of the rich polycyclc aromatic compound of reactor effluent is discharged sub-fraction, fouling or sedimentation problem can be reduced to minimum level or thoroughly eliminate.But this liquid effluent contains unconverted raw material, thereby after this liquid is discharged, promptly loses a part of potential circulation fluid, and loses the chance that reclaims valuable low boiling point hydrocarbon subsequently, and they originally can obtain from liquid effluent.
As mentioned above, original technology points out that by fractionation, polycyclc aromatic compound can be removed in the unconverted hydro carbons effluent by the hydrocracking section effectively, contains the heavy tower bottom distillate of polycyclc aromatic compound with generation.But this method of removing polycyclc aromatic compound has been got rid of and has been used the heavy tower bottom distillate to come the required possibility of adding raw material of production hydrocracking section.
United States Patent (USP) 4,447,315(draws ground such as nurse) propose, before unconverted hydro carbons loops back the hydrocracking reaction section, from no conversion hydrocarbon class effluent, remove polycyclc aromatic compound, but do not propose or advise method of the present invention.
According to the present invention, have been found that, at least a portion of the unconverted hydro carbons effluent of hydrocracking reaction section is joined when being used for the vacuum fractionation section of production initial vacuum gas oil feedstocks, be recovered in the side line waxy stone cut of in by the vacuum fractionation section, discharging unanticipated to, the polycyclc aromatic compound that quantity is surprising.This side line waxy stone cut is sideing stream of vacuum tower preferably among the embodiment at one of the present invention, but extract out more than the point at the vacuum tower Residual oil below the extraction point of heavy vacuum gas oil the position of taking-up.By convention, this waxy stone cut preferably contains 90% hydro carbons and the content that distillates o'clock more than 1050 (565 ℃) and is approximately higher than 0.5%(weight) bituminous matter.Because this discovery, little waxy stone cut (cheap hydrocarbon fraction) of quantity can be by separating in the hydroeracking unit with polycyclc aromatic compound comparatively speaking for this, so can prevent easily that any subsequently PNA compound from entering the hydrocracking reaction section and in this conversion zone fouling.And after most of polycyclc aromatic compound was removed by the vacuum fractionation section with the waxy stone cut, the residual oil fraction of this fractionation section promptly becomes and is more suitable for upgrading was the deasphalted oil cut, and the deasphalted oil cut is suitable for adding in the hydrocracking reaction section.
In some cases, when scale forming matter content is not high, only the unconverted hydrocracking section of part oils effluent need be added the fractionation section, in the waxy stone cut, reclaim a large portion polycyclc aromatic compound, can keep the content of polycyclc aromatic compound to be lower than and facilitate precipitation and the required level of fouling on heat exchanger surface.Here used " trace polycyclc aromatic compound " speech, best illustration be for being less than about 10/1000000ths, and content 000(PPM) is lower than approximately 5, and 000PPM is better.
According to method of the present invention, hydrocarbon raw material to be processed is advisable with reduced oil.Usually reduced oil prepares by whole crude is carried out fractionation, generates a kind of separation column residual oil fraction through fractionation, and its boiling point is approximately higher than 650 °F (343 ℃).
According to method of the present invention, a kind of reduced oil is added the fractionation section, produce a kind of vacuum gas oil distillate and a kind of waxy stone cut, this gas oil fraction comprises the compound that has in hydrocracking section generation polycyclc aromatic compound tendency.This vacuum gas oil distillate can comprise a kind of light vacuum gas oil cut and a kind of heavy vacuum gas oil cut, and the two is produced in the vacuum fractionation section respectively, is mixed subsequently, to make the raw material of hydrocracking reaction section.At one preferably among the embodiment of the present invention, this waxy stone cut is that a kind of vacuum fractionation tower sides stream, a certain position taking-up below vacuum gas oil is extracted point out as previously mentioned.
The vacuum gas oil distillate that makes in the above-mentioned vacuum fractionation section is added the hydrocracking section.This hydrocracking section preferably contains catalyzer, and this catalyzer generally can comprise any crystal zeolitic cracking catalyst carrier, is loaded with the hydrogenation catalyst component of sub-fraction VIII family metal above.The hydrogenation cocatalyst component can be by choosing with the metal that Zeolite support is used in the VI B family.This zeolitic cracking catalyst carrier is called molecular sieve sometimes in technology, usually by silicon-dioxide, aluminum oxide and one or more tradable positively charged ion, as compositions such as sodium, hydrogen, magnesium, calcium, uncommon earth metalss.They further are characterized as: the diameter of intercrystal pore is quite even, about 4 and 14 dusts (10
-10Rice) between.Preferably use the zeolite of silica/alumina mole ratio higher relatively (between 3 and 12), this mol ratio is better between 4 and 8.Naturally occurring suitable zeolite comprises: mordenite, stilbite, heulandite, magnesium sodium mazzite, dachiardite, chabazite, erionite and faujusite.The synthetic zeolite that is suitable for comprises B, X, Y and L crystal formation, for example synthetic faujasites and mordenite.Preferably zeolite be those crystal pore diameters between the 8-12 dust, wherein silica/alumina mole ratio is about 4 to 6 zeolite.The best example that belongs to the zeolite in this better scope is exactly synthetic Y zeolite.
Naturally occurring zeolite exists with sodium type, alkaline-earth metal type or mixed type usually.Synthetic zeolite almost always is prepared as the sodium type earlier.Under any circumstance, when as cracking catalyst carrier, preferably original whole or most of monovalence metals in the zeolite are carried out ion-exchange with polyvalent metal and/or ammonium salt, heat subsequently, to decompose with the associating ammonium ion of zeolite, with remaining hydrogen ion and/or exchange spot on their position, these points are actual by further dehydration is sloughed positively charged ion.This Hydrogen or " sloughing cationic " y-type zeolite at United States Patent (USP) 3,130, are illustrated in 006 especially.
Blended polyvalent metal-h-type zeolite can be prepared as follows: at first carry out ion-exchange with ammonium salt, carry out the exchange of part gegenion, calcining then with a kind of polyvalent metal salt subsequently.In some cases, when for example using synthesizing flokite, h-type zeolite can directly be prepared with acid treatment by alkali metal zeolites.Cracking catalyst carrier is that those lack 10% left and right sides metallic cation at least preferably, and preferably 20%(is as the criterion with the initial ion exchange capacity at least).Suitable especially and a stable class zeolite are to have at least the loading capacity about 20% saturated by hydrogen ion.
In the used better catalyst of the present invention, belong to VIII family as the reactive metal of hydrogenation component, i.e. iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium and platinum.Except that these metals, also other promotors and they can be united use, comprising VI B family metal, for example molybdenum and tungsten.Hydrogenation metal consumption in the catalyzer can change in very wide scope.In a broad sense, about 0.05% and 30%(weight) between any amount all can use.When using precious metal, generally preferably use about 0.05%) to about 2%(weight.Mixing hydrogenation with the better method of metal is, the aqueous solution of Zeolite support material with a kind of suitable compound of required metal is contacted, and this metal exists with cationic form in this solution.One or more hydrogenation that bring Selection In with metal after, the catalyst fines that generates is filtered, dry, with lubricant, binding agent or other required auxiliary agent granulations of adding, under the temperature of 700 °-1200 (371 °-648 ℃), in air, calcine then, make catalyst activation, and ammonium ion is decomposed.Perhaps,, add the hydrogenation catalyst component subsequently again, calcine then and make it activation at first with the zeolite component granulation.Preceding a kind of catalyzer can non-dilute form use, perhaps with the zeolite powder catalyzer with 5 to 90%(weight) ratio relatively hang down a little catalyzer, thinner or binding agents with other activity,, activated clay cogelled as aluminum oxide, silica gel, silica-alumina or the like mixes mutually, and common granulation.These thinners can as above use, and they also can contain a spot of hydrogenation metal, as VI B and/or VIII family metal.
In the method for the invention, also can adopt the catalytic hydrocracking catalyst of auxiliary metal promoted, for example, they comprise: aluminium phosphate molecular sieve, crystal silicic acid chromium and other crystalline silicate.Crystal silicic acid chromium is at United States Patent (USP) 4,363,718(clo thatch (Klote)) in introduce more fully.
Hydrocarbon raw material and hydrocracking under hydrocracking catalyst contacts, be in the presence of hydrogen, and be preferably under the following hydrocracking condition and carry out: temperature by about 450 °F (232 ℃) to about 850 (454 ℃), pressure by about 500 pounds/inch
2Gauge pressure (3448 kPas of gauge pressures) is to about 3000 pounds/inch
2Gauge pressure (20685 kPas of gauge pressures), liquid hour space flow speed (LHSV) were by about 0.2 to about 20 hours
-1, the about 2000 mark feet of hydrogen cycle rate
3/ bucket (355 mark rice
3/ rice
3) to about 10,000 mark feet
3/ bucket (1778 mark rice
3/ rice
3).
As mentioned above, when hydrocarbon raw material through after the hydrocracking, the product cut that a kind of boiling point preferably is lower than 650 (343 ℃) is separated and is recovered; The hydrocarbon fraction that also has a kind of boiling point preferably to be higher than about 650 (343 ℃) is separated and reclaims as recycle fraction.Above-mentioned separation and recovery are preferably in the fractionation section that matches with the hydrocracking section to be carried out.At least a portion of above-mentioned recycle fraction is added the above-mentioned fractionation section that is used to produce the vacuum gas oil fresh feed.The selection of its amount generally should be able to guarantee to prevent the PNA compound precipitation on the heat exchanger surface of hydroeracking unit, and preferably send whole circulating fluids back to vacuum column basically.
Because we find, by removing the waxy stone cut by the fractionation section, can reach the effect of separating and reclaiming polycyclc aromatic compound unexpectedly, thereby becoming the even more ideal cut of production deasphalted oil by the Residual oil that the fractionation section is told, this deasphalted oil is the suitable component of hydrocracking reaction section raw material.Preferably, generate and reclaim a kind of waxy stone cut, contain the polycyclc aromatic compound of the adding fractionation section more than 50%.At least a portion Residual oil that the vacuum fractionation section is told adds in the solvent deasphalting device preferably among the embodiment at one of the present invention, and to produce a kind of deasphalted oil and a kind of asphaltic liquid stream, this deasphalted oil adds in the hydrocracking reaction section subsequently.
This solvent deasphalting technology is that the people that are familiar with the hydrocarbon processing process know and imitate T vermachen office and bite uncommon fragrance shackles aphid In and suck and timidly waste extensive order fragrance refining and pound extensive toe In and tick and look which old woman's hair worn in a bun or coil leg steathily. calamity ticket is dared extensive deasphalted oil and the bitum hydrocarbon fraction of a kind of richness, and the latter is commonly referred to pitch.According to the present invention, be preferably in residual oil fraction and the hydrocarbon selective solvent counter current contact of solvent deasphalting section with the fractionation section, the selection of its diasphaltene condition should be able to generate a kind of lean solvent asphaltic liquid stream and a kind of rich solvent diasphaltene hydrocarbon fraction.The rich solvent diasphaltene hydrocarbon fraction that generates is carried out fractionation, to separate and the recovery selective solvent.If desired, this solvent fractionation capable of circulation.Then, not solvent-laden diasphaltene hydrocarbon fraction is added the hydrocracking section.
The more satisfactory operational condition of solvent deasphalting section is: in the scope of about 600 (315 ℃), pressure is by about 100 pounds/inch at about 50 °F (10 ℃) for temperature
2Gauge pressure (689 kPas of gauge pressures) is to about 10000 pounds/inch
2Gauge pressure (6895 kPas of gauge pressures), the volumetric ratio of solvent/raw material was by about 2: 1 to about 10: 1.Preferably select suitable temperature and pressure condition, carry out to keep diasphaltene to operate in liquid phase.Recently, the solvent deasphalting section can be operated under solvent is in condition under the supercritical state.
The suitable solvent comprises light hydrocarbons such as ethane, propane, butane, Trimethylmethane, pentane, iso-pentane, neopentane, hexane, isohexane, heptane, its monoolefine counterpart and composition thereof.
In the accompanying drawings, come diagram method of the present invention with a schema of simplifying.In this schema, pump, instrument, interchanger and recovery of heat pipeline, compressor and similar equipment, owing to be not main concerning understanding included technology, so leave out.The various devices that adopt, it is common to be the people that are familiar with this technical field.By this figure as seen, crude oil feeding enters this course of processing via pipeline 12, enter crude oil atmospheric distillation tower 13 then, produce a kind of gasoline fraction (discharging), a kind of kerosene(oil)fraction (discharging), a kind of diesel oil distillate (discharging) and a kind of topped oil cut (discharging) by pipeline 1 by pipeline 16 by pipeline 15 by pipeline 14.This topped oil is introduced into vacuum tower 2 via pipeline 1.Hydro carbons recycle fraction (will there be explanation its adquisitiones back) enters vacuum tower 2 via pipeline 10.The vacuum gas oil distillate is discharged via pipeline 3 by vacuum tower 2, and enters hydrocracking section 8 by pipeline 3 and 7.The hydro carbons waxy stone cut that contains polycyclc aromatic compound is discharged by vacuum tower 2 through pipeline 11.The vacuum tower Residual oil is discharged through pipeline 4 by vacuum tower 2, enters solvent deasphalting device 5 then.The deasphalted oil cut is discharged through pipeline 7 by solvent deasphalting device 5, enters hydrocracking section 8 then.Heavy bitumen liquid stream is discharged through pipeline 6 by solvent deasphalting device 5.The hydrocarbon product cut is discharged through pipeline 9 by hydrocracking section 8.Unconverted hydro carbons recycle fraction is discharged through pipeline 10 by hydrocracking section 8, enters vacuum tower 2 then, as previously mentioned.
The example of enumerating below can further specify hydrocracking catalyst of the present invention.This example can not that is to say that its purpose is explanation rather than restriction as for the whole broad scope of the present invention incorrect restriction of (as specified in the appended claim).
Embodiment
(flow is 100 kilograms/hour with a kind of topped oil, its character is listed in the table 1) and a kind of circulating fluid (explanation is seen below, flow is 24.5 kilograms/hour) add vacuum tower, generate 42.0 kilograms/hour of 77.0 kilograms/hour of vacuum gas oils, 5.5 kilograms/hour of waxy stones and vacuum tower Residual oils.
The character of table 1 topped oil
Proportion 0.9633
Cut, the %(volume)
Initial boiling point, °F (℃) 637 (336)
10 772 （411）
20 830 （443）
30 869 （465）
40 921 （494）
50 970 （521）
60 1054 （568）
Final boiling point reclaims 66% 1107 (597)
Sulphur, %(weight) 2.5
Nitrogen, %(weight) 0.15
The proportion of the vacuum gas oil distillate that generates is 0.9100, boiling range be 518 °F (270 ℃) to 1049 °F (565 ℃), (flow is 1300 to mark meter with the deasphalted oil (flow is 17.5 kilograms/hour) introduced and hydrogen with the back with it
3/ rice
3Raw material) mixes, add the hydrocracking section.The vacuum tower residual oil fraction carries out solvent deasphalting, and to produce aforesaid deasphalted oil cut, its output is 17.5 kilograms/hour.The raw material that contains gas oil, deasphalted oil and hydrogen contacts at the catalyzer of hydrocracking section with two fixed beds.The catalyzer of first fixed bed comprises a kind of silicon-dioxide one alumina supporter of nickeliferous and tungsten, and the hourly space velocity of liquid is about 0.4 during operation, and the average catalyst temperature is about 734 °F (390 ℃).Second fixed bed catalyst comprises a kind of alumina silica y-type zeolite carrier that contains nickel and tungsten, and the hourly space velocity of liquid is about 1 during operation, and the medial temperature of catalyzer is about 660 °F (349 ℃).Two kinds of catalyst beds are all at about 2400 pounds/inch
2The pressure of gauge pressure (16548 kPas of gauge pressures) is operation down.The effluent of catalyst bed is cooled to about 120 °F (49 ℃), by a high-pressure separator, is maintained at about 2000 pounds/inch in this separator then
2Gauge pressure (13790 kPas of gauge pressures).Hydrogen-rich gas stream is discharged by high-pressure separator, enters the hydrocracking catalyst section with freshly prepd hydrogen, circulates.The liquid hydrocarbon that is come out by high-pressure separator adds separation column, and the normal liquid hydrocarbon that boiling point is lower than about 650 (343 ℃) in this tower is separated, and extracts out as product, and its flow is 68.8 kilograms/hour.Boiling point is higher than the hydro carbons of about 650 (343 ℃), contains 115/1000000ths weight (WPPM) polycyclc aromatic compound of having an appointment, and, and enters vacuum tower and circulates by extracting out in the separation column with 24.5 kilograms/hour flows.
About various hydrocarbon fractions, the characteristic of each cut and the result of study of selecting of polycyclc aromatic compound respective concentration, list in the table 2.
The concentration of table 2 polycyclc aromatic compound
The concentration of hydrocarbon fraction PNA (PPM)
Topped oil charging 0
Vacuum gas oil 12
Vacuum tower Residual oil 3
Return the circulating fluid 115 of vacuum tower
The waxy stone 190 of vacuum tower
This studies show that, but the topped oil charging does not contain the polycyclc aromatic compound of detection limit, contains 115ppm and entered by the hydrocracking section in the recycle fraction of vacuum tower.Obviously, the hydrocracking section can form polycyclc aromatic compound, knows, and is if the circulation of this compound by unconverted vacuum gas oil enters the hydrocracking section, then unfavorable to the operation of hydrocracking section.
According to United States Patent (USP) 3,619,407(Hendricks etc.) viewpoint is carried out partial condensation by the part of the normal liquid hydrocarbon that will be come out by the hydrocracking catalyst section, the polycyclc aromatic compound that generates can be isolated at least a portion.The partial condensation liquid of the rich polycyclc aromatic compound that generates contains unconverted hydro carbons, and it can not be used to produce valuable product cut.Therefore, the loss of the valuable product of potential is the shortcoming of this original technology.Another original Technology is pointed out, distills by making at least a portion turning oil, separates the heavy still bottoms that contains polycyclc aromatic compound, can solve scale problems.
As mentioned above, have been found that, in fact have only the sub-fraction polycyclc aromatic compound in the heavy still bottoms cut of separation column, to reclaim, and wondrous and unexpectedly, most of polycyclc aromatic compound is to reclaim in side stream (being commonly referred to the waxy stone cut) of separation column.Asphaltenes hydro carbons (hydrocarbonace-ous) cut that this waxy stone cut is a kind of heavy.Therefore, polycyclc aromatic compound is discharged with the waxy stone cut,, also its amount of throwing aside can be minimized, generate valuable hydrocarbon products cut thereby gas oil is transformed at hydrocracking Duan Zhongneng even can not avoid throwing aside gas oil fully.And, according to the present invention, by throwing aside the polycyclc aromatic compound that the waxy stone cut removes, than by throwing aside many that the distillation tower Residual oil removes.According to one embodiment of present invention, owing to found that the separation column Residual oil only contains the polycyclc aromatic compound of trace, so this Raffinate stream can carry out diasphaltene, to make the deasphalted oil cut, this cut can add the hydrocracking section then, to improve the overall yield of valuable hydrocarbon product to greatest extent.
Above description, drawings and Examples have clearly illustrated that advantage that method of the present invention had and the benefit that adopts the inventive method to bring.
Claims (7)
1, a kind of catalytic hydrocracking method, this method comprises:
(a) topped oil is added the vacuum fractionation section, generate a kind of vacuum gas oil distillate, a kind of side line waxy stone cut and a kind of vacuum tower Residual oil, this gas oil fraction contains the compound that can generate deleterious polycyclc aromatic compound in the hydrocracking section;
(b) above-mentioned vacuum gas oil distillate is contacted at hydrogen and the catalytic catalyzer of a kind of metal promoted that hydrocracking Duan Zhongyu adds, temperature and pressure during contact is higher, be enough to obtain the low-boiling products of suitable high conversion, and generate the polycyclc aromatic compound of trace;
(c) the hydro carbons effluent with above-mentioned hydrocracking section carries out partial condensation, and it is separated into a kind of low boiling point hydrocarbon product cut and a kind of boiling point that contains is higher than the unconverted hydro carbons of about 650 (343 ℃) and the cut of polycyclc aromatic compound.
(d) above-mentioned at least a portion that contains the cut of unconverted hydro carbons and polycyclc aromatic compound is added in the above-mentioned vacuum fractionation section, thereby in above-mentioned side line waxy stone cut, reclaim the major part in the above-mentioned polycyclc aromatic compound.This quantity that just effectively above-mentioned deleterious polycyclc aromatic compound is entered above-mentioned hydrocracking section is reduced to minimum level.
2, the described method of claim 1, the pressure of wherein said hydrocracking section remains on by about 500 pounds/inch
2Gauge pressure (3448 kPas of gauge pressures) is to about 3000 pounds/inch
2Gauge pressure (20685 kPas of gauge pressures), temperature remains on by about 450 °F (232 ℃) to about 850 °F (454 ℃).
3, the described method of claim 1, the catalytic hydrocracking catalyst of wherein said metal promoted comprises synthetic faujasites, nickel and tungsten.
4, the described method of claim 1, wherein said side line waxy stone cut contain the about more than 50% of the polycyclc aromatic compound that adds above-mentioned fractionation section.
5, the described method of claim 1, wherein said vacuum fractionation tower Residual oil carries out solvent deasphalting, and to generate the deasphalted oil cut, this cut adds hydrocracking step (b) subsequently.
6, the described method of claim 5, the operational condition of wherein said solvent deasphalting comprises: temperature by about 50 °F (10 ℃) to about 600 °F (315 ℃); Pressure is by about 100 pounds/inch
2Gauge pressure (689 kPas of gauge pressures) is to about 1000 pounds/inch
2Gauge pressure (6895 kPas of gauge pressures); Solvent to the volumetric ratio of raw material by about 2: 1 to about 10: 1.
7, the described method of claim 5, the solvent that wherein said solvent deasphalting process uses is selected from following one group of compound: ethane, propane, butane, Trimethylmethane, pentane, iso-pentane, neopentane, hexane, isohexane, heptane, their monoolefine counterpart and composition thereof.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 87106790 CN1017719B (en) | 1986-01-23 | 1987-10-05 | Control of polynuclear aromatic by-products in hydrocracking process |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/821,721 US4698146A (en) | 1986-01-23 | 1986-01-23 | Hydrocracking and recovering polynuclear aromatic compounds in slop wax stream |
| CN 87106790 CN1017719B (en) | 1986-01-23 | 1987-10-05 | Control of polynuclear aromatic by-products in hydrocracking process |
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| Publication Number | Publication Date |
|---|---|
| CN1032355A true CN1032355A (en) | 1989-04-12 |
| CN1017719B CN1017719B (en) | 1992-08-05 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 87106790 Expired CN1017719B (en) | 1986-01-23 | 1987-10-05 | Control of polynuclear aromatic by-products in hydrocracking process |
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| CN (1) | CN1017719B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103421541A (en) * | 2012-05-15 | 2013-12-04 | 中国石油天然气股份有限公司 | Hydrocracking process method |
| CN107075392A (en) * | 2014-10-22 | 2017-08-18 | 国际壳牌研究有限公司 | Integrate to reduce the process for hydrocracking of hydrocarbonaceous of weight Ppolynuclear aromatic accumulation with vacuum distillation and solvent dewaxing |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1342774A1 (en) * | 2002-03-06 | 2003-09-10 | ExxonMobil Chemical Patents Inc. | A process for the production of hydrocarbon fluids |
-
1987
- 1987-10-05 CN CN 87106790 patent/CN1017719B/en not_active Expired
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103421541A (en) * | 2012-05-15 | 2013-12-04 | 中国石油天然气股份有限公司 | Hydrocracking process method |
| CN107075392A (en) * | 2014-10-22 | 2017-08-18 | 国际壳牌研究有限公司 | Integrate to reduce the process for hydrocracking of hydrocarbonaceous of weight Ppolynuclear aromatic accumulation with vacuum distillation and solvent dewaxing |
| CN107075392B (en) * | 2014-10-22 | 2020-03-17 | 国际壳牌研究有限公司 | Hydrocracking process integrated with vacuum distillation and solvent deasphalting to reduce build-up of multiple polycyclic aromatics |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1017719B (en) | 1992-08-05 |
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