CN1729275A - Process for the conversion of heavy feedstocks such as heavy crude oils and distillation residues - Google Patents
Process for the conversion of heavy feedstocks such as heavy crude oils and distillation residues Download PDFInfo
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- CN1729275A CN1729275A CN 200380106962 CN200380106962A CN1729275A CN 1729275 A CN1729275 A CN 1729275A CN 200380106962 CN200380106962 CN 200380106962 CN 200380106962 A CN200380106962 A CN 200380106962A CN 1729275 A CN1729275 A CN 1729275A
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Abstract
The present invention provides a process for the conversion of heavy feedstocks selected from heavy crude oils, distillation residues, heavy oils coming from catalytic treatment, thermal tars, oil sand bitumens, various kinds of coals and other high-boiling feedstocks of a hydrocarbon origin known as black oils, by the combined use of the following three process units: hydroconversion with catalysts in slurry phase (HT), distilla tion or flash (D), deasphalting (SDA), comprising the follow ing steps: mixing at least part of the heavy feedstock and/or at least most of the stream containing asphaltenes obtained in the deasphalting unit with a suitable hydrogenation catalyst and sending the mixture obtained to a hydrotreatment reactor (HT) into which hydrogen or a mixture of hydrogen and H2S is charged; sending the stream containing the hydrotreatment reaction product and the catalyst in dispersed phase to one or more distillation or flash steps (D) whereby the different frac tions coming from the hydrotreatment reaction are separated; recycling at least part of the distillation residue (tar) or liquid leaving the flash unit, containing the catalyst in dispersed phase, rich in metal sulfides produced by demetallation of the feedstock and possibly coke, to the deasphalting zone (SDA) in the presence of solvents, optionally also fed with at least a fraction of the heavy feedstock, obtaining two streams, one consisting of deasphalted oil (DAO) and the other containing asphaltenes, characterized in that the stream containing the hydrotreatment reaction product and the catalyst in dispersed phase, before being sent to one or more distillation or flash steps, is subjected to a high pressure separation pre-step in order to obtain a light fraction and a heavy fraction, the heavy fraction alone being sent to said distillation step(s) (D).
Description
The present invention relates to a kind of method that heavy feed stock is transformed, in the described heavy feed stock heavy crude is arranged, oil sands bitumen, distillation residue and various coal, adopting the mixture flow that suitably connects and form with fresh feed and converted product is three main technique unit of charging: transform the heavy feed stock unit with the disperse phase catalyst hydrogenation, distillation unit and diasphaltene unit, one will be from the flushing materials flow processing unit of deasphalting unit, in order to reduce its amount, the catalyst recirculation that the further upgrading of raw material is become oil product and at least a portion is reclaimed arrives hydrotreating reactor.
Basically can realize heavy crude, oil sands bitumen and petroleum residual oil are converted into the purpose of liquid product by two kinds of methods: a kind of method only adopts heating hand district, and the opposing party's rule will be through passing through hydrotreating step.
Present research mainly concentrates on hydrotreatment because heat treating method by product particularly coke (with respect to raw material, the quantity that obtains is greater than 30% (weight)) dispose and there are some problems converted product aspect of poor quality.
Hydroprocessing process is in the presence of hydrogen and suitable catalyzer raw material to be handled.
Hydroconversion process in the market is with fixed-bed reactor or ebullated bed reactor and is carried on the catalyzer that the transition metal (Mo, W, Ni, Co etc.) on the silica (or equivalent material) constitutes by one or more usually.
Fixed-bed process is having sizable problem aspect the special heavy feed stock of handling high heteroatoms, metal and asphalt content, because these impurity can make rapid catalyst deactivation.
Developed and the multiple ebullated bed technology that is used to handle these raw materials of industrialization, their performance is interesting, but very complicated and expense is high.
Can be with the hydroprocessing technique of disperse phase form catalyzer operation and to solve the shortcoming of using fixed bed or ebullated bed technology to run into an attractive terms of settlement is provided.In fact, the advantage that slurry process can be big with feed flexibility combines with conversion and upgrading aspect high-performance, from the viewpoint of technology, makes them simpler in principle.
The granules of catalyst form very little with median size and that can effectively be scattered in medium that is characterized as of slurry process exists, so hydrogenation process is simpler and play a greater role in all positions of reactor.Significantly reduced the coke growing amount, the product of upgrading raw material are higher mutually.
The powder that catalyzer is can size enough little or the form of oil soluble precursor are introduced.In one situation of back,, in its reaction process or suitably, form activity of such catalysts form (being generally metallic sulfide) on the spot after the pre-treatment by compound used therefor is carried out the pyrolysated method.
The metal cut of disperse phase catalyzer is generally one or more transition metal (preferred Mo, W, Ni, Co or Ru).Molybdenum and tungsten than nickel, cobalt or ruthenium in addition than vanadium and iron have more satisfactory performance (N.Panariti et al., Appl.Catal. A:Gen.2000,
204, 203).
Though the use of disperse phase catalyzer has solved the listed most of problem of above-mentioned technology, but still there are some shortcomings relevant with the products obtained therefrom quality with the life-span of catalyst themselves.
In fact, from the viewpoint and environmental influence two aspects of economy, the working conditions of these catalyzer (type of precursor, concentration etc.) is epochmaking.
Catalyzer can use in " one way " process layout by lower concentration (hundreds of ppm), but in this case, to reaction product upgrading usually not enough (November 1995,35 for A.Delbianco et al., Chemtech).When mode was operated, the quality that obtains product was much better with high active catalyst (for example molybdenum) and high concentration catalyst (thousands of ppm metal), but must catalyzer to be circulated.
Leave reactor catalyzer can with traditional method for example decant, centrifugation or filtration method separate with hydrotreatment products obtained therefrom (preferably the base product from reactor downstream obtains) and reclaim (US-3240718, US-4762812).The described catalyzer of a part just loops back hydrogenation process without further processing.But the catalyzer that adopts known hydroprocessing process to reclaim decreases than the activity of live catalyst usually, must have suitable regeneration step to recover catalytic activity and makes the described catalyst recirculation of at least a portion to hydrotreating reactor.And from the viewpoint of technology, these method expenses that reclaim catalyzer are high and extremely complicated.
Above-mentioned all hydroconversion process can reach or high or low level of conversion will depend on raw material and used technology type, can be but the unconverted residual oil (being called tar here) that under any circumstance, is produced under the stability limit condition is according to circumstances different from 15% to 85% of initial feed.This product is used for producing oil fuel, pitch or is used as the raw material of gasification.
In order to improve total level of conversion of residuum (cracking) process, the various flow processs of a large amount of tar circulation step in the cracking unit that makes have more or less been proposed to comprise.Adopting catalyzer to be scattered in the hydroconversion process of slurry phase, the circulation of tar is reclaimed catalyzer, for this reason, same applicant has described in IT-95A001095 and has not a kind ofly produced under the condition of residual oil (sludgeless oil oil refining apparatus) simultaneously obtaining high-quality product, makes the catalyzer of recovery just be recycled to the method for hydrotreating reactor without other regeneration step.
This method may further comprise the steps:
Heavy crude or distillation residue are mixed with the hydrogenation catalyst that is fit to, and the gained mixture sent into hydrogen or hydrogen and H are housed
2The hydrotreating reactor of S mixture;
The distillation zone is sent in the materials flow that will comprise hydrotreatment reaction product and disperse phase state catalyzer, isolates volatile cut (petroleum naphtha or gas oil);
Therefore the high boiling fraction that distilation steps obtains is sent into the diasphaltene step, produce two bursts of materials flows, one comprises deasphalted oil (DAO), and another strand comprises bituminous matter, disperse phase state catalyzer and presumable coke and be rich in metal from initial feed;
At least 60% of bituminous matter, disperse phase state catalyzer and the presumable coke materials flow that comprise of being rich in metal preferably at least 80% is recycled to the hydrotreatment district.
As described in the patent application IT-MI2001A-001438, again find thereafter, with regard to above-mentioned these methods, when the hydrocarbon mixture with heavy crude or oil sands bitumen upgrading one-tenth complexity further is converted into the raw material of distillate process to be used as, can use different process layouts.
The described heavy feed stock method for transformation of patent application It-MI2001A-001438 is used in combination following three technique units: catalyzer is in hydrocracking unit (HT), flash distillation or distillation unit (D), diasphaltene unit (SDA) of slurry phase, it is characterized in that, three unit are to begin operation with the mixture flow that fresh feed and cycle stock are formed, and adopt following steps:
At least a portion heavy feed stock is sent into the diasphaltene district (SDA) that has solvent, make two bursts of materials flows, one comprises deasphalted oil (DAO), and another thigh then comprises bituminous matter;
The bituminous matter materials flow is mixed with the remainder heavy feed stock of not sending into the diasphaltene district and suitable hydrogenation catalyst, and the gained mixture delivered to charge into hydrogen or hydrogen and H
2The hydrotreating reactor of S mixture (HT);
One or more distillation or flash distillation step (D) are sent in the materials flow that will contain hydrotreatment reaction product and disperse phase state catalyzer, thereby isolate volatile cut, and the gas, petroleum naphtha and the gas oil that generate in the hydrotreatment reaction are wherein arranged;
At least 60% preferably at least 80% more preferably at least 95% be recycled to the diasphaltene district with what leave the distillation residue (tar) that comprise disperse phase state catalyzer, rich metallic sulfide that raw material demetalization step is generated and presumable coke and various carbonaceous residues of flash evaporation unit or liquid.
Usually need wash the bituminous matter materials flow of leaving diasphaltene district (SDA), in hydrotreating reactor, can not accumulate too much, and under the situation of catalyst deactivation, shift out a part of catalyzer and substitute with live catalyst so that guarantee these elements.But when catalyzer can keep it active for a long time, normally do not need to do like this, but must will wash for above-mentioned reasons the time, though obviously some catalyzer far away complete deactivation also must abandon.In addition, though compare with other hydroprocessing techniques, the quantity (with respect to the 0.5-4% of raw material) of flushing materials flow is extremely limited, and they still exist sizable utilization or handling problems.
When the heavy ends of the complicated hydrocarbon mixture that this process must be produced (distillation Tata at the bottom of) when carrying out the catalytic cracking unit raw material of hydrocracking (HC) and fluid catalystic cracking (FCC) simultaneously, described application particularly suitable.
Catalytic hydrogenation unit (HT) and being used in combination of extraction process (SDA) can make the diasphaltene well cuts produced (metal, sulphur, nitrogen, contain the carbonaceous residue) content low, thereby can handle in catalytic cracking process easilier.
But what will consider is that the petroleum naphtha of hydrotreatment unit direct production and gas oil still contain many impurity (sulphur, nitrogen on the other hand ...), under any circumstance all must handle again, so that make the finished product.
Have now found that, can patent application IT-MI2001A-001438 and the described two kinds of methods of patent application IT-95A001095 (all introducing present patent application as a reference) be further improved by the method for inserting an additional flushing materials flow solid fraction aftertreatment hydrogenation section.
This solid fraction hydrogenation section purpose is aftertreatment is carried out in the flushing materials flow, so that significantly reduce its quantity, makes the still activated catalyst recirculation of at least a portion return hydrotreating reactor.
The objective of the invention is to be selected from the method that heavy crude, distillation residue, the heavy oil from the catalytic treatment process, thermal tar, oil sands bitumen, various coal and some other heavy feed stock that is derived from the hydro carbons high boiling point raw material that is called dirty oil transform, present method has been used in combination following three technique units: adopt hydrocracking (HT) unit, distillation or flash distillation (D) unit, diasphaltene (SDA) unit of slurry phase state catalyzer, may further comprise the steps:
● the materials flow of at least a portion heavy feed stock and/or most of at least asphaltenes that obtains in the diasphaltene unit is mixed with suitable hydrogenation catalyst, and the mixture that obtains delivered to charge into hydrogen or hydrogen and H
2The hydrotreating reactor of S mixture (HT);
● one or more distillation or flash distillation step (D) are sent in the materials flow that will contain hydrotreatment reaction product and disperse phase state catalyzer, thereby will separate from the different fractions of hydrotreatment reaction;
● contain disperse phase state catalyzer with what at least a portion was left flash evaporation unit, the distillation residue (tar) of rich metallic sulfide that raw material demetalization process generates and possibility coke or liquid circulation are to the diasphaltene district (SDA) that has solvent, optional also have at least a portion heavy feed stock as charging, obtain two bursts of materials flows, one comprises deasphalted oil (DAO) and another thigh comprises bituminous matter, described method is characterised in that, a part to be called the treatment zone that suitable solvent is sent in the asphaltenes materials flow of washing materials flow from diasphaltene section (SDA), so that product is separated into solid fraction and liquid distillate, from liquid distillate, shift out described solvent subsequently.
Flushing effluent (preferably accounting for the 0.5-10% (volume) of fresh feed) processing section is made up of solvent (toluene or gas oil or other are rich in the materials flow of aromatic fraction) de-oiling step and liquid distillate and solid fraction separating step.
The described liquid distillate of at least a portion can be sent into:
" fuel oil sump ", former state is sent into or is isolated behind the solvent and/or after adding suitable diluted liquid and sends into;
And/or former state is sent into hydrotreating reactor (HT).
Under some particular cases, solvent can be identical with diluted liquid.
But solid fraction treated as such, or more favourable way is it to be sent to transition metal or transition-metal catalyst institute containing metal (for example molybdenum) are carried out the selective recovery processing (with respect to other metals that exist in the raw material residual oil, nickel and vanadium) loop back hydrotreating reactor (HT) so that can choose the materials flow that will be rich in transition metal (molybdenum) wantonly.
Compare with traditional method, this comprehensive treatment method has following advantage:
The quantity of flushing part significantly reduces;
Most of elution fraction can become oil fuel by the method upgrading of isolating metal and coke;
Owing to have at least a part to be recycled from the selective recovery treatment step molybdenum that comes together, thus in the first hydrotreating step raw material with the quantity minimizing of live catalyst.
The de-oiling step is to handle the flushing materials flow, its representative is minimized from the asphaltenes fractions of the heavy feed stock first hydrotreater diasphaltene section (SDA), and solvent for use is wanted to bring the organic compound of maximum possible into liquid phase and with metallic sulfide, coke with contain carbonaceous residue (be insoluble to toluene or similarly product) than infusible and stay solid phase.
The cut of considering metalline might spontaneous combustion under drying conditions very, and therefore reasonably way is to operate in the inert atmosphere that contains the least possible oxygen and moisture.
In this de-oiling step, preferably use all kinds of SOLVENTS; What wherein can mention is for example toluene and/or dimethylbenzene concoction of aromatic solvent, the gas oil that the hydrocarbon raw material that obtains in this device is for example produced, or in the refinery available hydrocarbon raw material for example from the unitary light cycle of FCC or from the unitary hot gas oil of visbreaking/thermally splitting.
Can promote operating rate by improving temperature and reaction times within the specific limits, but because economic cause, it is unsuitable that over-drastic improves.
Service temperature depends on the pressure condition of solvent for use and employing; But the temperature range of recommendation is 80-150 ℃; Reaction times can be 0.1-12 hour, did not wait in preferred 0.5-4 hour.
The volume ratio of solvent/flushing materials flow also is the important parameter of considering, can be at 1-10 (volume/volume), preferred 1-5, more preferably change between 1.5-3.5.
In case the clouding stage of closing finishes between solvent and flushing materials flow, just effluent sent into liquid phase and solid phase segregation section keeping under the agitation condition.
This step working method can be one of industrial practice working method commonly used, for example decant, centrifugation or filtration method.
Then liquid phase is delivered to solvent stripping and recovery zone, solvent cycle is backwashed and is washed materials flow first treatment step (de-oiling).It is preferably that remaining heavy ends is used for refinery because in fact this materials flow containing metal and sulphur content are not lower.If for example handle operation with gas oil, then a part of described gas oil can be stayed in the heavy product, makes it meet the specification requirement of fuel oil sump.
Perhaps liquid phase is recycled to hydrogenator.
Solid part can in statu quo be disposed, or handles selective recovery will loop back the catalyzer (molybdenum) of hydrotreating reactor in addition.
In fact, found by with metal-free heavy feed stock such as a part from the unitary deasphalted oil of the own diasphaltene of device (DAO) add above-mentioned solid mutually in and described system mixed with acidified water (carrying out acidifying with mineral acid usually), nearly all molybdenum is remained in the organic phase, and other metal of most of amount move into water.Two-phase can be easy to separate, and preferably organic phase is recycled to hydrotreating reactor thereafter.
Solid is scattered in the capacity organic phase mutually the deasphalted oil of same process (for example from), to wherein adding acidified water.
The ratio of water and organic phase can be 0.3-3 and does not wait; The pH value of water can be 0.5-4, preferred 1-3 does not wait.
Except flushing materials flow aftertreatment section, also can there be one again to C from the high pressure segregation section that is positioned at the still-process upstream
2-500 ℃ of cuts, preferred C
5-350 ℃ of cuts carry out the section of the second processing hydrogenation.
In this case, the materials flow that contains hydrotreatment reaction product and disperse phase state catalyzer wanted advanced horizontal high voltage to separate pre-treatment step before being sent to one or more distillation or flash distillation step, obtain light ends and heavy ends, separately heavy ends is delivered to described distilation steps (D).
The light ends that the high pressure separating step obtains can be delivered to the hydrotreatment section, generates to contain C
1-C
4Gas and H
2The lighter fraction of S and contain the petroleum naphtha of hydrotreatment and gas oil than last running.
The optional C that inserts
2-500 ℃ of cuts, preferred C
5-350 ℃ of cut second aftertreatment hydrogenation sections have been developed and have been obtained this cut simultaneously and near the possibility of the hydrogen of hydrotreating reactor elevated pressures, can obtain following benefit:
It can be met the fuel of the harshest sulphur content specification requirement (＜10-50ppm sulphur) by the oils raw material production capacity in next life that is rich in sulfur-bearing, and is improving to some extent aspect other characteristics of diesel engine gas oil such as density, polycyclic aromatic hydrocarbon content and the cetane value;
There is not stability problem in the distillate of producing.
The reaction effluent of hydrotreating reactor (HT) is carried out pre-separation in that to carry out hydrofinishing process on the fixed bed be the separator operated under by one or more high pressure and high temperature.The heavy that takes out from the bottom is partly delivered to main distillation unit, and the part that take out at the top is C
2-500 ℃ of cuts, preferred C
5-350 ℃ of cuts are delivered to second treatment zone that has high pressure hydrogen, wherein reactor is fixed-bed reactor, typical desulfurization/dearomatization catalyst is housed, so that obtain the product of low sulfur content very and low nitrogen content, low overall consistency, concerning the gas oil fraction of being concerned about, cetane value increases simultaneously.
The hydrotreatment section is made up of one or more tandem reactor usually; Available then distillation method makes the petroleum naphtha and the diesel engine gas oil that meets fuel specification of complete desulfurization with the further fractionation of this system's product.
Described fixed bed hydrogenation desulfurized step uses typical gas oil hydrogenating desulfurization fixed bed catalyst usually, this catalyzer or also may to be that reactor that catalyst mixture or is assembled with various different properties catalyzer obtains light ends by following effect refining considerably: the hydrogenation degree that significantly reduces sulphur and nitrogen content, raising raw material, thereby reduce the density of gas oil fraction and improve cetane value, reduce the generation of coke simultaneously.
Catalyzer contains the pars amorpha based on aluminum oxide, silicon oxide, silica-alumina and various inorganic oxide mixtures usually, and the hydrogenating desulfurization cut deposits on it with hydrogenation reagent and (ins all sorts of ways).The nickel and/or cobalt on being deposited on the amorphous material carrier, be the used typical catalyst of this generic operation based on the catalyzer of molybdenum or tungsten.
The aftertreatment hydrogenation reaction is lower than slightly in absolute pressure under the pressure of first hydrotreating step carries out, and is generally 7-14 MPa, preferred 9-12 MPa; The hydrogenating desulfurization temperature is 250-500 ℃, preferred 280-420 ℃; Temperature depends on required desulfurization level usually.In the time will controlling the products obtained therefrom quality, air speed is another important parameter: it can be 0.1-5 hour-1, preferred 0.2-2 hour-1.
Mix with raw material send into materials flow amounts of hydrogen at 100-5000Nm
3/ m
3, preferred 300-1000Nm
3/ m
3Between.
Can handle all kinds of heavy feed stocks: they are optional to be derived from the hydro carbons high boiling point raw material that this specialty often is called dirty oil from heavy crude oil, oil sands bitumen, all kinds of coal, distillation residue, bottom product, thermal tar (for example from visbreaking or similar heat treatment process) from the heavy cycle oil of for example catalytic cracking treating processes of mink cell focus of catalytic treatment process, hydrocracking treating processes and other.
With regard to processing condition commonly used, can be with reference to defined terms in patent application IT-MI2001A-001438 and IT-95A001095.
IT-95A001095 is described according to patent application, all heavy feed stocks can be mixed with the hydrogenation catalyst that is fit to, send into hydrotreating reactor (HT) then, but will be with at least 60%, preferred at least 80% asphaltenes and also contain disperse phase state catalyzer and may coke and the materials flow of being rich in from the initial feed metal be recycled to the hydrotreatment district.
IT-MI2001A-001438 is described according to patent application, with a part of heavy feed stock and most of at least asphaltenes and also contain disperse phase state catalyzer and materials flow that may coke mixes with suitable hydrogenation catalyst, and send into hydrotreating reactor, and the heavy feed stock of remainder is sent into the diasphaltene section.
Described in patent application IT-MI2001A-001438, the materials flow (being made of described bituminous matter substantially) of most of at least asphaltenes is mixed with the hydrogenation catalyst that is fit to, and send into hydrotreating reactor, and all heavy feed stocks are sent into the diasphaltene section.
When diasphaltene section (SDA) is returned in the distillation residue (tar) that only a part is left flash evaporation unit or liquid circulation, with the described distillation of at least a portion residual content or flash distillation residual oil is optional send into hydrotreating reactor from the asphaltenes materials flow of diasphaltene section (SDA) with at least a portion.
Used catalyzer is selected from the precursor (metal derivative of metal ring alkyl salt, phosphoric acid, metal carbonyl etc.) that can decompose on the spot or is selected from based on one or more transition metal premolding compound of Ni, Co, Ru, W and Mo for example, because of latter's catalytic activity height, so be preferred.
In metal or the many metal concentrations that exists in the hydroconversion reactions device, the catalyst concn scope is 300-20000ppm, preferred 1000-10000ppm.
Hydrotreating step preferably 370-480 ℃, more preferably 380-440 ℃ and 3-30 MPa, more preferably carry out under the 10-20 MPa.
Hydrogen is sent into reactor, can be downwards and upwards flow two kinds of modes and preferred above stream mode operation.Described gas can be sent into the different sections of reactor.
Distilation steps is preferably in the 0.0001-0.5 MPa, more preferably carry out under the reduced pressure of 0.001-0.3 MPa scope.
Hydrotreating step can be made up of one or more reactor of operating in the afore mentioned rules condition and range.The part distillate of producing in first reactor can be recycled to the reactor of back.
By solvent, hydro carbons or non-hydrocarbons (C for example
3-C
6Alkane or isoparaffin) the extraction diasphaltene step of carrying out normally carries out under 40-200 ℃ of range temperature and 0.1-7 MPa scope pressure.Also can be made of one or more section with identical or different solvent operation, solvent recovery step can divide a step or multistep to carry out under subcritical or super critical condition, makes deasphalted oil (DAO) and residual oil can further carry out fractionation like this.
The materials flow that contains deasphalted oil (DAO) can be chosen wantonly and mix with distillate with former state as synthetic crude, or as the raw material of fluid catalystic cracking or hydrocracked, treated process.
Preferably the characteristic of based on crude (metal content, sulphur and nitrogen content, contain the carbonaceous residue) changes the feeding manner of whole process by following measure: with heavy oil residue or send into the diasphaltene unit or send into the hydrotreatment unit, perhaps send into two unit simultaneously, adjust:
Send into the heavy oil residue (fresh feed) of hydrotreatment section and will send to ratio between the deasphalting heavy oil residue, described ratio is preferably 0.01-100, more preferably 0.1-10 even more preferably 1-5;
Send into the fresh feed of diasphaltene section and the recycle ratio between tar, described ratio is preferably at 0.01-100, more preferably change between 0.1-10;
Send into the fresh feed and the bitum recycle ratio of hydrotreatment section, described ratio can according to above-mentioned these than variation change;
Send into the tar and the bitum recycle ratio of hydrotreatment section, described ratio can change according to the change of aforementioned ratio.
This handiness is particularly useful to full-scale development diasphaltene unit (reduce and disperse nitrogen and remove aromatic hydrocarbons) and the complementary characteristic of hydrogenation unit (the high decreasing ratio of metal and sulphur).
The stability of the type of based on crude, the materials flow of studying and the quality of products obtained therefrom (also relevant with the concrete treatment step in downstream), fresh feed is sent into the mark of diasphaltene section and hydrotreatment section and can be adjusted by best mode.
When the complicated hydrocarbon mixture heavy ends (base product product) of process institute output is raw material as the catalytic cracking unit of carrying out hydrocracking (HC) and fluid catalytic cracking (FCC) simultaneously, described application particularly suitable.
The keying action of catalytic hydrogenation unit (HT) and extraction process (SDA) can make the deasphalted oil of being produced have low impurity (metal, sulphur, nitrogen, contain the carbonaceous residue) content, thereby easilier handles in catalytic cracking process.
Hereinafter provide an embodiment preferred of the present invention, but never should think restriction the scope of the invention itself by accompanying drawing 1.
Heavy feed stock (1) or its at least a portion (1a) are sent into diasphaltene unit (SDA), operate by the solvent extraction means.
Make two bursts of materials flows from diasphaltene unit (SDA): one is the materials flow (2) that contains deasphalted oil (DAO), and another is the materials flow (3) of asphaltenes.
Will except that the asphaltenes materials flow of flushing materials flow (4) with remedy with flushing materials flow (4) loss aequum add live catalyst (5), do not send into the diasphaltene section a part of heavy feed stock (1b), do not send into a part of tar (24) of diasphaltene section (SDA) and choose wantonly from the materials flow (15) of washing thing processing section (further specifying hereinafter) and mix, formation materials flow (6) is delivered to and is charged into hydrogen (or hydrogen and H
2The S mixture) hydrotreating reactor of (7) (HT).Reactor is left in the materials flow (8) that contains hydrogenation products and disperse phase state catalyzer, carries out fractionation earlier in the separator (HPSep) of one or more high top pressure operation.Overhead fraction (9) is sent into fixed bed hydrogenation treatment reactor (HDTC
5-350), generation contains C
1-C
4Gas and H
2The light ends of S (10) and contain hydrotreated naphtha and the C of gas oil
5-350 ℃ of cuts (11).Heavy ends (12) leaves the high-pressure separator bottom, and carries out fractionation in separation column (D), isolates vacuum gas oil (13) from the distillation residue that contains dispersion state catalyzer and coke.This materials flow is called tar (14), and major part (25) it is whole or except that above-mentioned cut (24) is recycled to diasphaltene reactor (SDA).
Flushing materials flow (4) can be sent into hydrotreatment section (de-oiling) with solvent (16), form the mixture (17) that contains liquid distillate and solid fraction.Described mixture is sent into solids treatment section (solids constituent from), therefrom isolate solid effluent (18) and liquid efflunent (19), the latter is delivered to solvent recuperation section (solvent recuperation).Send recovered solvent (16) back to the de-oiling section, and heavy effluent (20) in statu quo or after adding possible diluted liquid (21) is delivered to oil fuel fractionation process (22).
Solid fraction (18) but former state dispose, or as hereinafter with described in the embodiment, choose wantonly it is delivered to other treatment zone (filter cake processing), obtain not containing substantially the cut (23) of molybdenum, send to processing and can loop back the cut that is rich in molybdenum (15) of hydrotreating reactor.
For the present invention is described better, some embodiment hereinafter are provided, but never should be with them as limitation of the scope of the invention.
Carry out following experiment by schema shown in Figure 1.
The diasphaltene step
Raw material: 300 grams are from the vacuum residuum (table 1) of Ural crude oil
Diasphaltene reagent: 2000 milliliters of liquid propane (re-extract three times)
Temperature: 80 ℃
Pressure: 35 crust
Show 1:500 ℃
+The characteristic of Ural vacuum residuum
| API severe | 10.8 |
| Sulphur (% (weight)) | 2.6 |
| Nitrogen (% (weight)) | 0.7 |
| Conradson carbon residue (% (weight)) | 18.9 |
| Ni+V(ppm) | 80+262 |
Hydrotreating step
Reactor: 3000 milliliters, steel, suitable shape also is equipped with magnetic stirrer
Catalyzer: 3000ppm raw material that Mo/ adds, use molybdenum naphthenate as precursor
Temperature: 410 ℃
Pressure: 16 MPa hydrogen pressures
The residence time: 4 hours
The flash distillation step
Implement (T=120 ℃) with a liquid evaporation laboratory equipment
Experimental result
Circulate fully by making experiment for the first time be added catalyzer, carry out 10 continuous diasphaltene experiments, each is tested and all uses by Ural residual oil (fresh feed) with by the C of preceding step
3The raw material that the long residuum that bituminous matter hydrotreatment reaction obtains is formed.For each step, be with a certain amount of by Ural vacuum residuum (fresh feed) and diasphaltene unit gained C
3The raw material that bituminous matter is formed is sent into autoclave, so that the total mass of institute's charging feed (fresh feed+round-robin C
3Bituminous matter) reaches 300 initial values that restrain.
Under these operational conditions, the ratio between fresh feed amount and the circulation products amount is 1: 1.
Hereinafter provide last circulation back and discharge the related data (with respect to the % (weight) of raw material) of materials flow.
Gas: 7%
Petroleum naphtha (C
5-170 ℃): 8%
Atmospheric gas oil (AGO, 170-350 ℃): 17%
Deasphalted oil (VGO+DAO): 68%
The bituminous matter materials flow of reclaiming when experiment finishes contains metal Ni and the sulfide of V and the coke that resid feed total amount about 1% (weight) in relative Ural is measured that generates in whole catalyzer of sending at first, 10 the hydrotreatment reaction process.In described embodiment, do not need to carry out the rinse step of recycle stream.Table 2 is listed the characteristic of products therefrom.
Table 2: the experiment reaction product characteristic of pressing embodiment 1
| Sulphur (% (weight)) | Nitrogen (ppm) | Proportion (grams per milliliter) | RCC (% (weight)) | Ni+V (ppm) | |
| Petroleum naphtha C 5-170℃ | 0.06 | 450 | 0.768 | - | - |
| AGO 170-350℃ | 0.52 | 2100 | 0.870 | - | - |
| VGO+DAO | 1.45 | 2500 | 0.938 | 3 | 1 |
Restrain from 500 ℃ in Ural residual oil 20.7
+The flushing materials flow of conversion system (composition that table 3 is listed) was handled 3 hours down at 100 ℃ with 104 gram toluene (weight ratio of solvent/flushing materials flow is 5).The cut that obtains is filtered.Collect 3.10 gram solids (composition that table 4 is listed) and 17.60 and restrain mink cell focuses (evaporation remove toluene after), listed in its metal content such as the table 5.
Table 3: handle 500 ℃ from Ural residual oil
+The characteristic of flushing materials flow
| Proportion (grams per milliliter) | 1.1 |
| S (% (weight)) | 2.4 |
| Mo (% (weight)) | 0.68 |
| Ni (% (weight)) | 0.12 |
| V (% (weight)) | 0.36 |
| Fe (% (weight)) | 0.07 |
Table 4: 500 ℃ in the O for toluene Ural residual oil of using by oneself
+Solid (filter cake) characteristic of flushing materials flow
| C (% (weight)) | 82.0 |
| H (% (weight)) | 3.9 |
| S (% (weight)) | 4.8 |
| Mo (% (weight)) | 4.1 |
| Ni (% (weight)) | 0.6 |
| V (% (weight)) | 2.2 |
| Fe (% (weight)) | 0.4 |
Table 5: to from 500 ℃ in Ural residual oil
+The flushing materials flow for the treatment of processes handle come together and metal content in the heavy oil
| Mo(ppm) | 10 |
| Ni(ppm) | 26 |
| V(ppm) | 23 |
| Fe(ppm) | 10 |
Adopt embodiment 2 described same steps as, 10.6 gram flushing materials flows (the listed composition of table 3) are handled with 62 milliliters of gas oils (in the Ural residual hydrocracking experimentation that is undertaken by top embodiment 1 described step output and the listed quality of table 2 is arranged), the ratio of gas oil/flushing materials flow is 5, and is to carry out operation in 6 hours under 130 ℃.The cut of output is carried out centrifugation (5000 rev/mins).Collect 1.78 gram solids (the listed composition of table 6) and 8.82 and restrain mink cell focuses (evaporation remove gas oil after).
Table 6: handle 500 ℃ of Urals with gas oil
+The flushing resulting solid of materials flow (filter cake) characteristic
| Mo (% (weight)) | 3.43 |
| Ni (% (weight)) | 0.53 |
| V (% (weight)) | 1.75 |
1.0 gram solid residues (obtain from embodiment 2 described treating processess, form and list in table 4) are handled with the mixture of the deasphalted oil (DAO) of 50 milliliters of acidified waters (pH=2) and 50 milliliters of listed compositions of table 7.
70 ℃ after following 24 hours, decant goes out liquid phase, and the metal in the two-phase is analyzed.
All the molybdenum of amount (＞99%) is stayed organic phase, and finds nickel and vanadium at aqueous phase, and its quantity corresponds respectively to percentage extraction 23.5% and 24.4%.
The organic phase that will contain molybdenum is then sent to the hydrotreatment experiment with fresh Ural residual oil, is undertaken by the step that embodiment 1 describes, and molybdenum keeps its catalytic activity character.
Table 7: from 500 ℃ of Urals
+The DAO characteristic of residual oil treating processes
| Sulphur (% (weight)) | Nitrogen (ppm) | Proportion (grams per milliliter) | RCC (% (weight)) | Ni+V (ppm) | |
| DAO | 1.02 | 2100 | 0.934 | 3 | ＜1 |
Adopt the same steps as of describing with embodiment 4, but be to use gas oil (referring to embodiment 1) (replacing DAO) and the acidified water (pH=2) that produces in the Ural residual hydrocracking process.
All the molybdenum of amount is stayed in the organic phase, and finds nickel and vanadium at aqueous phase, and it is 41.0% and 26.8% that its quantity corresponds respectively to percentage extraction.
According to flow process shown in Figure 1, the product that leaves the high-pressure separator top is sent into fixed-bed reactor, with the reagent materials flow charging that flows downward.Reactor is equipped with a kind of typical commercially available Hydrobon catalyst based on molybdenum and nickel.
Operational condition is as follows:
LHSV:0.5 hour
-1
Hydrogen pressure: 10 MPas
Temperature of reactor: 390 ℃
Table 8 illustrates the quality of fixed-bed reactor charging and makes the quality of product.
Show 8:500 ℃
+Ural residual oil is handled the C that obtains
5The hydrotreatment of-350 ℃ of cuts
| Raw material | Product | |
| Proportion (grams per milliliter) | 0.8669 | 0.8294 |
| Mononuclear aromatics (% (weight)) | 30.1 | 19.5 |
| Double ring arene (% (weight)) | 8.3 | 1.2 |
| Thrcylic aromatic hydrocarbon (% (weight)) | 2.8 | 0.4 |
| Polycyclic aromatic hydrocarbons (% (weight)) | 11.1 | 1.6 |
| Sulphur (ppm) | 5300 | 37 |
| Nitrogen (ppm) | 2280 | 3 |
| Distillation curve | ||
| T 10(℃) | 187 | 145 |
| T 50(℃) | 271 | 244 |
| T 90(℃) | 365 | 335 |
Claims (36)
1. one kind will be selected from the method that heavy crude, distillation residue, the heavy oil from the catalytic treatment process, thermal tar, oil sands bitumen, various coal and some other heavy feed stock that is derived from the hydro carbons high boiling point raw material that is called dirty oil transform, described method is used in combination following three technique units: adopt hydrocracking (HT) unit, distillation or flash distillation (D) unit, diasphaltene (SDA) unit of slurry phase state catalyzer, may further comprise the steps:
● the materials flow of at least a portion heavy feed stock and/or most of at least asphaltenes that obtains in the diasphaltene unit is mixed with suitable hydrogenation catalyst, and the mixture that obtains delivered to charge into hydrogen or hydrogen and H
2The hydrotreating reactor of S mixture (HT);
● one or more distillation or flash distillation step (D) are sent in the materials flow that will contain hydrotreatment reaction product and disperse phase state catalyzer, thereby will separate from the different fractions of hydrotreatment reaction;
● at least a portion is left the distillation residue (tar) that contains rich metallic sulfide that disperse phase state catalyzer, raw material demetalization process generate and possible coke of flash evaporation unit or liquid circulation to the diasphaltene district (SDA) that has solvent, optional also have at least a portion heavy feed stock as charging, obtain two bursts of materials flows, one comprises deasphalted oil (DAO) and another thigh comprises bituminous matter;
Be characterised in that, a part be called the treatment zone that suitable solvent is sent in the asphaltenes materials flow of washing materials flow from diasphaltene section (SDA),, from liquid distillate, remove described solvent subsequently so that product is separated into solid fraction and liquid distillate.
2. by the process of claim 1 wherein that the scope of flushing materials flow amount is the 0.5-10% (volume) of fresh feed.
By the process of claim 1 wherein with at least a portion from flushing materials flow processing section obtain liquid distillate in statu quo or isolate solvent and/or add and be fit to dilution and send into later on the oil fuel cut with liquid.
4. by the process of claim 1 wherein at least a portion is recycled to hydrotreating reactor (HT) from the liquid distillate that washes treatment zone.
5. by the process of claim 1 wherein that the solvent that uses is aromatic solvent or that produce or that refinery provides the certainly gas oil mixture of present method in flushing materials flow processing section.
6. by the method for claim 5, wherein aromatic solvent is the mixture of toluene and/or dimethylbenzene.
7. by the process of claim 1 wherein that the volume ratio of solvent/flushing materials flow is 1-10.
8. by the method for claim 7, wherein the volume ratio of solvent/flushing materials flow is 1-5.
9. by the method for claim 8, wherein the volume ratio of solvent/flushing materials flow is 1.5-3.5.
10. by at least one method among the claim 1-9, wherein all heavy feed stocks to be mixed with the hydrogenation catalyst that is fit to, and send into hydrotreating reactor (HT), and asphaltenes that will at least 60% and also contain disperse phase state catalyzer and possible coke and the materials flow of being rich in from the initial feed metal are recycled to the hydrotreatment district.
11. by the method for claim 10, wherein general at least 80% asphaltenes materials flow is recycled to the hydrotreatment district.
12. by at least one method among the claim 1-9, wherein with a part of heavy feed stock and most of at least asphaltenes and also contain disperse phase state catalyzer and the materials flow of possible coke mixes with the hydrogenation catalyst that is fit to, and send into hydrotreating reactor, and the heavy feed stock of remainder is sent into the diasphaltene section.
13. by at least one method among the claim 1-9, wherein most at least asphaltenes materials flow (being made up of described bituminous matter basically) is mixed with the hydrogenation catalyst that is fit to, and send into hydrotreating reactor, and all heavy feed stocks are sent into the diasphaltene section.
14. by the process of claim 1 wherein that distillation residue (tar) or liquid circulation that a part is left flash evaporation unit go back to diasphaltene district (SDA) and the described distillation or the flash distillation residual oil of at least a portion residual content are sent into hydrotreating reactor.
15., wherein at least a portion distillation or flash distillation residual oil are sent into hydrotreating reactor with at least a portion from the asphaltenes materials flow of diasphaltene section (SDA) by the method for claim 14.
16. by the process of claim 1 wherein that the distillation residue with at least 80% (weight) is recycled to the diasphaltene district.
17. by the method for claim 16, wherein the distillation residue with at least 95% (weight) is recycled to the diasphaltene district.
18. by the process of claim 1 wherein that the residual content distillation residue (tar) that at least a portion is not recycled to the diasphaltene district is recycled to the hydrotreatment section.
19. by the process of claim 1 wherein that distilation steps carries out under the reduced pressure of 0.0001-0.5 MPa scope.
20. by the method for claim 19, wherein distilation steps carries out under the reduced pressure of 0.001-0.3 MPa scope.
21. by the process of claim 1 wherein that hydrotreating step carries out under 370-480 ℃ of range temperature and 3-30 MPa pressure.
22. by the method for claim 21, wherein hydrotreating step carries out under the pressure of the temperature of 380-440 ℃ of scope and 10-20 MPa scope.
23. by the process of claim 1 wherein that the diasphaltene step carries out under the pressure of the temperature of 40-200 ℃ of scope and 0.1-7 MPa.
24. by the process of claim 1 wherein that deasphalting solvent is C
3-C
7Light paraffins.
25. by the process of claim 1 wherein the diasphaltene step under subcritical or super critical condition, divide one or multistep carry out.
26. by the process of claim 1 wherein that the materials flow of being made up of deasphalted oil (DAO) carries out fractionation with traditional distillation method.
27. mix after materials flow that deasphalted oil (DAO) is formed and the condensation of distilation steps separated products by the process of claim 1 wherein.
28. by the process of claim 1 wherein that but hydrogenation catalyst is a kind of decomposition of precursors or premolding compound based on one or more transition metal.
29. by the method for claim 28, wherein transition metal is a molybdenum.
30. by the process of claim 1 wherein that the concentration of catalyzer in the hydroconversion reactions device is 300-20000ppm by the metal concentration that exists.
31. by the method for claim 30, wherein the concentration of catalyzer in the hydroconversion reactions device is 1000-10000ppm.
32. by at least one method among the claim 1-9, the materials flow advanced horizontal high voltage before delivering to one or more distillation or flash distillation step that wherein contains hydrotreatment reaction product and disperse phase state catalyzer separates pre-treatment step, so that obtain light ends and heavy ends, only heavy ends is delivered to described distilation steps (D).
33. by the method for claim 32, wherein the light ends that the high pressure separating step is obtained is sent into the second aftertreatment hydrogenation section, generates to contain C
1-C
4Gas and H
2The lighter fraction of S and contain hydrotreated naphtha and gas oil than last running.
34. by the method for claim 33, wherein aftertreatment hydrogenation reaction is to carry out under the pressure of 7-14 MPa scope.
35. by the method for claim 1 and 28, the solid fraction that wherein will handle product is delivered to the treating processes of the contained transition metal of further selective recovery hydrogenation catalyst.
36., wherein the transition metal that reclaims is recycled to hydrotreating reactor (HT) by the method for claim 35.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| ITMI20022713 ITMI20022713A1 (en) | 2002-12-20 | 2002-12-20 | PROCEDURE FOR THE CONVERSION OF HEAVY CHARGES SUCH AS |
| ITMI2002A002713 | 2002-12-20 | ||
| ITMI2003A000693 | 2003-04-08 |
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| Publication Number | Publication Date |
|---|---|
| CN1729275A true CN1729275A (en) | 2006-02-01 |
| CN100497548C CN100497548C (en) | 2009-06-10 |
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|---|---|---|---|
| CNB2003801090397A Expired - Lifetime CN1331992C (en) | 2002-12-20 | 2003-12-12 | Process for the conversion of heavy feedstocks such as heavy crude oils and distillation residues |
| CNB2003801069625A Expired - Lifetime CN100497548C (en) | 2002-12-20 | 2003-12-12 | Process for the conversion of heavy feedstocks such as heavy crude oils and distillation residues |
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| CN102989495A (en) * | 2011-09-14 | 2013-03-27 | 中国石油化工股份有限公司 | Heavy oil hydrogenation modification catalyst and preparation method thereof, and heavy oil hydrogenation modification method |
| CN103059915A (en) * | 2011-10-21 | 2013-04-24 | 中国石油化工股份有限公司 | Poor-quality heavy oil hydro-upgrading method |
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|---|---|---|---|---|
| US20100122934A1 (en) * | 2008-11-15 | 2010-05-20 | Haizmann Robert S | Integrated Solvent Deasphalting and Slurry Hydrocracking Process |
| ITMI20131137A1 (en) | 2013-07-05 | 2015-01-06 | Eni Spa | PROCEDURE FOR REFINING THE CRUDE |
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| US4454023A (en) * | 1983-03-23 | 1984-06-12 | Alberta Oil Sands Technology & Research Authority | Process for upgrading a heavy viscous hydrocarbon |
| CA1222471A (en) * | 1985-06-28 | 1987-06-02 | H. John Woods | Process for improving the yield of distillables in hydrogen donor diluent cracking |
| US5242578A (en) * | 1989-07-18 | 1993-09-07 | Amoco Corporation | Means for and methods of deasphalting low sulfur and hydrotreated resids |
| IT1275447B (en) * | 1995-05-26 | 1997-08-07 | Snam Progetti | PROCEDURE FOR THE CONVERSION OF HEAVY CRUDE AND DISTILLATION DISTILLATION RESIDUES |
| FR2753982B1 (en) * | 1996-10-02 | 1999-05-28 | Inst Francais Du Petrole | MULTI-STAGE CATALYTIC PROCESS FOR CONVERTING A HEAVY HYDROCARBON FRACTION |
| FR2753984B1 (en) * | 1996-10-02 | 1999-05-28 | Inst Francais Du Petrole | METHOD FOR CONVERTING A HEAVY HYDROCARBON FRACTION INVOLVING HYDRODEMETALLIZATION IN A BUBBLE BED OF CATALYST |
| CN1400997A (en) * | 2000-02-15 | 2003-03-05 | 埃克森美孚研究工程公司 | Heavy feed upgrading based on solvent deasphalting and followed method of slurry hydroprocessing of asphalt from solvent deasphalting |
| CN1152945C (en) * | 2000-10-26 | 2004-06-09 | 中国石油化工股份有限公司 | Process for refining and coverting residual oil |
| ITMI20011438A1 (en) * | 2001-07-06 | 2003-01-06 | Snam Progetti | PROCEDURE FOR THE CONVERSION OF HEAVY CHARGES SUCH AS HEAVY FATS AND DISTILLATION RESIDUES |
-
2002
- 2002-12-20 IT ITMI20022713 patent/ITMI20022713A1/en unknown
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2003
- 2003-12-12 CN CNB2003801090397A patent/CN1331992C/en not_active Expired - Lifetime
- 2003-12-12 CN CNB2003801069625A patent/CN100497548C/en not_active Expired - Lifetime
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Also Published As
| Publication number | Publication date |
|---|---|
| CN1738890A (en) | 2006-02-22 |
| ITMI20022713A1 (en) | 2004-06-21 |
| CN1331992C (en) | 2007-08-15 |
| CN100497548C (en) | 2009-06-10 |
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