CN103102982A - Combined process for conversion of residual oil - Google Patents
Combined process for conversion of residual oil Download PDFInfo
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- CN103102982A CN103102982A CN201110352419XA CN201110352419A CN103102982A CN 103102982 A CN103102982 A CN 103102982A CN 201110352419X A CN201110352419X A CN 201110352419XA CN 201110352419 A CN201110352419 A CN 201110352419A CN 103102982 A CN103102982 A CN 103102982A
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Abstract
The invention discloses a combined process for conversion of residual oil. The combined process comprises the following steps: (1) allowing a residual oil raw material to enter into a solvent deasphalting unit so as to obtain deasphalted oil and de-oiled asphalt; (2) mixing the de-oiled asphalt obtained in step (1) with heavy distillate oil of a catalytic cracking unit and allowing an obtained mixture to enter into a fluidized bed hydrotreatment unit for fluidized bed hydrotreatment; (3) mixing an effluent of fluidized bed hydrotreatment obtained in the step (2) with the deasphalted oil and carrying out fixed bed hydrotreatment, wherein generated oil of an effluent of fixed bed hydrotreatment is used as a raw material for the catalytic cracking unit; and (4) mixing the de-oiled asphalt with a catalytic heavy fraction obtained after dry gas, liquefied gas and catalytic gasoline are separated from an effluent of a catalytic cracking reaction and subjecting an obtained mixture to fluidized bed hydrotreatment. Compared with the prior art, the combined process provided by the invention has the advantages of wide sources of the raw materials, low equipment investment, stable operation, a long operation period and a good synergistic and coordination effect.
Description
Technical field
The present invention relates to the combined technical method that a kind of residual oil transforms, be specially adapted to the higher poor residuum of heavy metal content, this technique is that the technological processs such as solvent deasphalting, ebullated bed and fixed bed, catalytic cracking are organically combined, and residual oil is transformed.
Background technology
Along with the increase of crude oil heaviness, in poor quality degree, and market is to the variation of light oil demand structure, and inferior heavy oil (comprising various heavy oil and residual oil etc.) processing technology has become the research emphasis direction of each major oil companies and oil scientific research institution.The processing treatment of inferior heavy oil will be not still lower boiling product with its cracking, as petroleum naphtha, intermediate oil and pressure reduction gas wet goods, but also will improve their hydrogen-carbon ratio, so the Basic Ways of its processing is to adopt hydrogenation or two kinds of methods of decarburization substantially.Decarbonization process comprises coking, solvent deasphalting, heavy oil fluid catalytic cracking etc.; Hydrogenation comprises hydrocracking, hydrofining etc.Hydrogenation method can hydrocracking residual oil, improves the productive rate of liquid product, and can also remove heteroatoms wherein, and quality product is not bad.Residual hydrogenation has been developed fixed bed, ebullated bed, suspension bed and four kinds of technology types of moving-bed at present.Wherein fixed-bed conversion rate lower (generally lower than 35%), be mainly catalytic cracking unit high quality raw material be provided; Ebullated bed transformation efficiency higher (generally higher than 60%) can obtain a large amount of light-end products, but light-end products need further processing just can obtain qualified product; Suspension bed can obtain higher transformation efficiency (generally higher than 80%), but device stability is relatively poor, still is difficult to realize at present industrial operation; Moving-bed is between fixed bed and ebullated bed, and the problem of existence is that device is complicated, and operation is solid difficult.
Cheap residual oil is converted into high value-added product, is the lifeline of petroleum refining industry.The utilization ratio that improves to greatest extent vacuum residuum is one of target of enterprise's pursuit.Solvent deasphalting is a kind of method of heavy oil upgrading, and the method flow process is simple, and energy consumption is lower, and the deasphalted oil that obtains is good hydrotreated feed.The Residue Hydrotreating Technology liquid yield is high, all has obvious advantage aspect product structure, quality product and environmental protection.
Solvent de-asphalting process is by selecting suitable solvent and processing condition, making bituminous matter in residual oil carry out appropriateness with oil separates, and make metal, sulphur, nitride major part or partial concentration in residual oil in bituminous matter, the foreign matter content decreases such as the bituminous matter in deasphalted oil and heavy metal can be by technique deep processings such as hydrotreatment, hydrocracking, hydrogenation and catalystic crackings.
USP7214308 discloses the technological process of a kind of solvent deasphalting and the effective combination of ebullated bed.This technique principal feature is that heavy vacuum residuum feed is sent in solvent deasphalting unit, adopts C
4Or C
5Solvent obtains deasphalted oil and de-oiled asphalt.These two kinds of raw materials adopt respectively the ebullated bed system to process, and design and operation conditions optimization according to feedstock property.Deasphalted oil ebullated bed reactor operational condition wherein: stagnation pressure 3.45 ~ 20.69MPa, 388 ~ 438 ℃ of temperature of reaction, liquid volume air speed 0.2 ~ 1.5h
-1De-oiled asphalt ebullated bed reactor operational condition: stagnation pressure 10 ~ 20.69MPa, 399 ~ 454 ℃ of temperature of reaction, liquid air speed 0.1 ~ 1.0h
-1Require this technique total conversion rate greater than 65%.The method adopts two cover boiling bed hydrogenation systems, and plant investment is large, complicated operation, and total conversion rate is too high, can cause the local coking of ebullated bed reactor of processing de-oiled asphalt, thereby affect the device smooth operation.
CN200710157792.3 discloses a kind of combination process of processing poor residuum.The method comprises that residual oil raw material enters solvent deasphalting unit, obtain deasphalted oil and de-oiled asphalt, the deasphalted oil of gained enters the boiling bed hydrogenation device and processes, obtaining light ends and hydrogenation tail oil goes catalytic cracking unit to process, and the light ends that obtains thus and slurry oil, at least part of slurry oil and de-oiled asphalt are mixed into the floating bed hydrogenation device and process, obtain light ends and unconverted tail oil, wherein unconverted tail oil loops back solvent deasphalting unit, and light ends and deasphalted oil are mixed into the boiling bed hydrogenation device.The method is not given full play to the ability of ebullated bed and suspension bed processing poor residuum, and the floating bed hydrogenation technology has brought solid difficulty also for the method practical application because stability problem still is difficult to normal industrial application at present.
CN1393525A discloses a kind of solvent deasphalting, fixed bed hydrogenation is processed and the method for the combined processing high-sulfur high-metal residual oil of catalytic cracking.Residual oil obtains deasphalted oil and de-oiled asphalt through solvent extraction, wherein deasphalted oil is sent into fixed bed hydrogenation treatment unit upgrading with optional heavy catalytic cycle oil, hydrogenation tail oil is sent into the catalytic cracking unit cracking, in its product, all or part of heavy cycle oil is circulated to the fixed bed hydrogenation treatment unit, and all or part of catalytic slurry loops back solvent deasphalting unit.There is following problem in this method, contain the catalytic cracking catalyst powder in the one catalytic slurry, easily be carried in deasphalted oil by solvent extraction, after the fixed bed hydrogenation device is sent in deasphalted oil, catalyst fines is easy to be deposited on beds, finds out bed pressure drop and raises and stop up; It two is that the pitch that solvent deasphalting unit removes is not used preferably, and this part component is difficult to become asphaltic products., can only as pitch blending stock or oil fuel, cause the wasting of resources.
Because inferior heavy oil adds man-hour, its volume space velocity is lower, therefore generally needs a plurality of reactors in series to use (series connection is used and referred to that reaction mass is successively by each reactor), and 2 or 2 above parallel series are set simultaneously.Therefore, the inferior heavy oil hydrogenation unit generally comprises a plurality of reactors, for the device of 2,000,000 tons of scales of year amount of finish, usually needs 8 reactors by present device fabrication level.For ebullated bed reactor, each reactor all needs a cover catalyzer to add online heat-extraction system, the investment that this cover catalyzer adds heat-extraction system online very high (accounting for half left and right of boiling bed hydrogenation device gross investment through assessment), complicated operation, the failure rate of appearance is also the highest.
In catalytic cracking process, the energy consumption of fractionation plant accounts for larger ratio, and the energy consumption that how to reduce fractionation plant is also the content that needs emphasis to consider.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of combination process that heavy oil, residual oil raw material are transformed, this technique can effectively be processed inferior raw material, makes residual oil be converted into valuable light ends.
Residual oil of the present invention transforms combined technical method, comprises the steps:
(1) residual oil raw material enters solvent deasphalting unit, obtains deasphalted oil and de-oiled asphalt;
(2) de-oiled asphalt that obtains in step (1) and the heavy distillate of catalytic cracking unit are mixed into the boiling bed hydrogenation treatment unit, under hydrogen and boiling bed hydrogenation treatment catalyst exist, carry out boiling bed hydrogenation and process;
(3) the boiling bed hydrogenation processing reaction effluent that step (2) is obtained mixes with deasphalted oil, then enter the fixed bed hydrogenation treatment unit, process under the catalyzer existence at hydrogen and fixed bed hydrogenation, be fixed bed hydroprocessing and process, the generation oil that fixed bed hydrogenation processing reaction effluent obtains is as the raw material of catalytic cracking unit;
(4) the catalytic cracking reaction effluent is isolated catalytic cracking last running after dry gas, liquefied gas and catalytically cracked gasoline and is mixed with de-oiled asphalt and carry out boiling bed hydrogenation and process.
The inferior heavy oil raw material that relates in step (1) comprises vacuum residuum that crude distillation obtains or the inferior heavy oil in other source, and the metal content in the inferior heavy oil raw material is at least 120 μ g/g, more than being preferably 180 μ g/g, more than most preferably being 220 μ g/g.Solvent deasphalting unit and operational condition are contents well known to those skilled in the art, and solvent is selected from C
3-C
8Alkane, C
3-C
8One or more in alkene, condensate oil or light naphthar, preferred light naphthar.
Inferior heavy oil raw material and solvent can be respectively enter from the upper and lower of solvent deasphalting unit, carry out counter current contact in extraction tower, also can first enter extraction tower by pre-mixing again and separate.In the present invention, the operational condition of solvent deasphalting is generally: temperature is 60～250 ℃, and pressure is 1.0～5.0MPa, and the agent oil volume is 1.0:1～10.0:1 than (solvent and inferior heavy oil volume feed); Preferred temperature is 60～200 ℃, and pressure is 2.5～5.0MPa, and the agent oil volume is than being 4.0:1～8.0:1.Old process is adopted in the solvent deasphalting operation, can be that single hop can be also two sections.
Solvent deasphalting unit is controlled index, and in deasphalted oil (DAO), the content of heptane insolubles is generally less than 1.5wt%, preferably less than 0.5wt%; And the DAO weight yield is generally 20%-85%, and preferred 20%-60% requires in DAO metal content lower than 80 μ g/g, preferably lower than 50 μ g/g simultaneously.
Relate to ebullated bed reactor in step (2) and can adopt conventional ebullated bed reactor of the prior art.An ebullated bed reactor can be set, the ebullated bed reactor that 2 series connection arrange also can be set, series connection arranges and refers to the reaction mass reactor by arranging successively.The boiling bed hydrogenation treatment condition can be concrete definite according to feedstock property and reaction conversion ratio requirement, and be generally: temperature of reaction is 350～430 ℃, best 380～430 ℃; Reaction pressure is 8～25MPa, is preferably 8.0～16MPa; Hydrogen to oil volume ratio 100:1 ~ 1000:1 is preferably 500:1 ~ 1000:1; Liquid volume air speed (LHSV) is 0.3～5.0h
-1, be preferably 0.3-2.0h
-1Boiling bed hydrogenation is processed not take transformation efficiency (lighting) and desulfurization removing nitric as major objective, provide qualified charging to be major objective but process take demetalization as fixed bed hydrogenation, after the boiling bed hydrogenation processing reaction in product liquid metal content require lower than 120 μ g/g, preferably lower than 90 μ g/g, most preferably lower than 60 μ g/g.
Contain a large amount of resin and asphalts in de-oiled asphalt due to the processing of boiling bed hydrogenation treatment unit, and bitum chemical structure is very complicated, is comprised of polymerization aromatic hydrocarbons, alkane chain, naphthenic hydrocarbon, molecular weight is very large, and the mean molecule size is 6～9nm approximately.Also contain the heteroatomss such as sulphur, nitrogen, metal in structure of asphaltene, in crude oil, 80%～90% metal all is enriched in bituminous matter.These impurity all " the dark Tibetan ", need to could imurity-removal under the operational condition of harshness at intramolecule.Bituminous matter is relevant with the aperture of used catalyst in the rate of decomposition of hydrogenation process.The catalyzer aperture is greater than 10nm at least, and bituminous matter might be diffused in the catalyzer duct.Therefore to boiling-bed catalyst, more macropore must be arranged.This boiling bed hydrogenation catalyst specific surface is 80～200m
2/ g, the pore volume of bore dia 30～300nm account for 35%～60%(mercury penetration method of total pore volume), the average pore diameter of catalyzer is more than 20nm, to be preferably 22 ~ 40nm.In catalyzer, by weight, catalyzer contains VI B family metal oxide (as MoO
3) 1.0%～10.0%, be preferably 1.5%～8.5%, contain group VIII metal oxide compound (as NiO or CoO) 0.1%～8.0%, preferably 0.5%～5.0%.Carrier can be aluminum oxide, aluminium oxide-silicon oxide, one or more of aluminium oxide-titanium oxide, and the shape of catalyzer can be bar shaped or spherical, particle diameter is 0.1～0.8mm.
The preferred mixed catalyst that uses two kinds of catalyzer in boiling bed hydrogenation treatment reactor of the present invention, it is the mixed catalyst of catalyst A and catalyst B, described catalyst A and catalyst B mixed volume are than being 1:(0.1～2), be preferably 1:(0.2～0.5), the mixed volume ratio that is catalyst A and catalyst B is 1:0.1 ~ 1:2, is preferably 1:0.2 ~ 1:0.5.Catalyst A is the above-mentioned boiling bed hydrogenation catalyst that contains more macropore.Wherein the character of catalyst B is: catalyst specific surface is 180～300m
2/ g, bore dia accounts for 70% of total pore volume, bore dia at least in the hole of 5～20nm〉the shared pore volume in hole of 20nm is not less than 0.1mL/g, is generally 0.1 ~ 0.3mL/g; By weight, catalyzer contains VI B family metal oxide (as MoO
3) 3.0%～25.0%, be preferably 6.0%～20.0%, contain VIII family metal oxide (as NiO or CoO) 0.3%～8.0%, preferably 0.5%～5.0%.Contain at least a auxiliary agent, be selected from following several element: B, Ca, F, Mg, P, Si, Ti etc., auxiliary agent content is 0.5%～5.0%.In oxide weight, catalyst B hydrogenation active metals (VI B family metal oxide and VIII family metal oxide) is higher 1 ~ 18 percentage point than catalyst A hydrogenation active metals content, and is preferred high 3 ~ 15 percentage points.Catalyst A and catalyst B particle are spherical, and diameter is 0.1～0.8mm, is preferably 0.1～0.6mm; Wearing and tearing≤2.0wt%.The flat footpath of the particle of catalyst A and catalyst B diameter is identical.
The raw material that uses in the fixed bed hydrogenation treating processes that relates in step (3) is the reaction effluent of ebullated bed and the deasphalted oil mixture of step (1), the heavy feed stock that also can add other suitable employing fixed bed to process.Metal content in the liquid phase feeding that fixed bed hydrogenation is processed will be lower than 80 μ g/g, preferably lower than 50 μ g/g, with the long operational cycle of protection.The fixed bed hydrogenation process is used the combination catalyst system of this area routine, generally comprise Hydrodemetalation catalyst, Hydrobon catalyst and hydrodenitrogenation catalyst etc., these catalyzer are all generally take porous refractory inorganic oxides such as aluminum oxide as carrier, the oxide compound of group vib and/or VIII family's metal such as W, Mo, Co, Ni etc. is active ingredient, the catalyzer that optionally adds other various auxiliary agents such as P, Si, the elements such as F, B, for example, residual oil hydrocatalyst heavy by the FZC series that Fushun Petrochemical Research Institute develops.
The fixed bed hydrogenation treatment condition are generally: temperature of reaction is 350～420 ℃, and reaction pressure is 8～25MPa, hydrogen to oil volume ratio 100:1 ~ 1000:1, and liquid volume air speed (LHSV) is 0.2～2.0h
-1According to required hydrotreatment degree and unit scale, a fixed bed hydrogenation reactor can be set, also a plurality of fixed bed hydrogenation reactors can be set.
In the inventive method, catalytic cracking can be adopted this area routine techniques.Catalytic cracking unit can be that more than a cover or overlaps, every covering device should comprise a reactor, a revivifier at least.Catalytic cracking unit arranges separation column, can every cover catalytic cracking unit set respectively, also can share.Catalytic cracking fractionating tower is dry gas, liquefied gas, catalytically cracked gasoline and catalytic cracking last running with the fractionation of catalytic cracking reaction effluent.The present invention's catalytic cracking fractionating tower used is compared with conventional catalytic cracking fractionating tower can simplified design, only fractionate out dry gas, liquefied gas and catalytically cracked gasoline, described catalytic cracking double distilled is divided into initial boiling point the last running of 170-220 ℃, comprises catalytic cracking diesel oil, heavy catalytic cycle oil and slurry oil.Described catalytic cracking last running loops back and first filters out the micro-catalytic cracking catalyst powder that contains before ebullated bed reactor, also can filtration unit or incrustation device be set in the ebullated bed outlet, enters fixed-bed reactor after filtering out solid impurity again.Catalytic cracking unit operates by this area general condition: temperature of reaction is generally 450～600 ℃, preferably 480～550 ℃; Regeneration temperature is 600～800 ℃, is preferably 650～750 ℃, agent oil (catalyzer and stock oil) weight ratio 2:1～30:1, preferably 4:1～10:1; With 0.1～15 second duration of contact of catalyzer, best 0.5～5 second; Pressure 0.1～0.5MPa.The catalytic cracking catalyst that adopts comprises the catalyzer that is generally used for catalytic cracking, as silica-alumina catalyst, silica-magnesia catalyst, acid-treated carclazyte and X-type, Y type, ZSM-5, M type, layer post equimolecular sieve cracking catalyst, molecular sieve cracking catalyst preferably, this is because molecular sieve cracking catalyst active high, green coke is few, gasoline yield is high, and transformation efficiency is high.The reactor of described catalytic cracking unit can be the catalyst cracker of various types, and preferably riser reactor or riser tube add the bed reactor.Technical process is generally: stock oil is from riser reactor bottom injection, contact with the high-temperature regenerated catalyst from revivifier, the oil gas that cracking reaction generates and the catalyst mixture of deposit coke move up along riser reactor, complete the catalytic cracking reaction of whole stock oil.
In the inventive method, can specifically determine the concrete technology condition according to raw material sources character and processing request, the optimization of processing condition and determine it is content well known to those skilled in the art.
The inventive method has following advantage:
1, solvent deasphalting, boiling bed hydrogenation and fixed bed hydrogenation technique and catalytic cracking process are organically combined, the scope of application of the raw material that enlarges, can process heavy more, vacuum residuum feed more inferior etc., particularly can process the higher inferior raw material of metals content impurity, residual oil is transformed.
2, this combination process takes full advantage of solvent de-asphalting process byproduct de-oiled asphalt, has realized utilizing to greatest extent residual oil raw material.
3, in whole combination process, main products is high octane number catalytic cracking gasoline, liquefied petroleum gas (LPG) and a small amount of dry gas, thereby can guarantee maximum ground production gasoline.
4, catalytic cracking last running circulation joins in ebullated bed reactor, can play diluting effect to de-oiled asphalt, and its character is improved, and has reduced boiling bed residual oil hydrogenation reaction difficulty and processing severity; Especially the reduction of material viscosity can improve flow distribution and the mass transfer of raw material in reactive system, reduce to be diffused in the impact in boiling bed residual oil hydrotreatment process, improve the deposition distribution of poisonous metal in catalytic reaction system such as nickel, vanadium, reduce the reaction difficulty, improve the impurity removal degree of depth.
5, ebullated bed reactor generally only arranges one, and its purpose is that fixed bed hydrogenation reactor carries out raw materials pretreatment, needs the operation purpose of higher conversion different from present boiling bed residual oil hydrogen addition technology, combines the comprehensive advantage of fixed bed and ebullated bed.Ebullated bed reactor uses the mixed catalyst of suitable character catalyzer, has improved boiling bed hydrogenation processing reaction effect.
Description of drawings
Fig. 1 is that residual oil of the present invention transforms the combination process schematic flow sheet.
Wherein: 1-residual oil raw material, 2-solvent, 3-static mixer, 4-diasphaltene extraction tower, 5-deasphalted oil, 6-de-oiled asphalt, 7-hydrogen, 8-boiling bed hydrogenation reactor, 9-fixed bed hydrogenation reactor (can connect and arrange or several), 10-fixed-bed reactor reaction effluent, 11-gas-liquid separator, 12-recycle hydrogen, the 13-catalyst cracker, 14-catalytic cracking fractionating tower, 15-liquefied gas, 16-gasoline, 17-heavy distillate 18-strainer.
Embodiment
Below in conjunction with Fig. 1, method provided by the invention is further illustrated.
Residual oil raw material 1 and solvent 2 are pre-mixed, also oil pipeline is sent into static mixer 3 and is mixed respectively, the material that mixes is sent into solvent deasphalting unit 4, the solvent deasphalting operation can be that one-part form can be also two-part, obtain deasphalted oil (DAO) 5 and de-oiled asphalt 6, be mixed into boiling bed hydrogenation reactor 8 with hydrogen 7 after de-oiled asphalt 6 preheatings, carry out hydrogenation reaction under the boiling bed hydrogenation catalyst of the above-mentioned preparation of packing into and processing condition, remove the heteroatomss such as metal, sulphur, making asphaltenes conversion is colloid or small molecules more, reduces product viscosity.Ebullating bed reactor effluent and deasphalted oil and catalytic cracking heavy distillate 17 are mixed into fixed bed hydrogenation reactor 9, carry out hydrogenation reaction under fixed bed grating catalyzer and reaction conditions, obtain reaction effluent 10, further get in gas-liquid separator 11, separate and obtain looping back reactive system as recycle hydrogen 12 after the further depriving hydrogen sulphide of gas phase, separate the liquid phase obtain directly as the catalytic cracking unit raw material, liquid phase also can enter fractionating system and fractionate out hydrogenated residue and enter catalytic cracking unit.Catalytic cracking unit comprises catalyst cracker 13 and catalytic cracking fractionating tower 14, and catalytic cracking fractionating tower obtains liquefied gas 15, gasoline 16 and heavy distillate 17, and heavy distillate 17 comprises diesel oil, recycle stock and the slurry oil in conventional catalytic cracking unit.The ebullating bed reactor effluent enters fixed-bed reactor after can entering strainer 18 or sump again, removes solid impurity that may exist etc.Said apparatus is the technical process of a series, according to the requirement of unit scale, can be set up in parallel two or more series.
For further illustrating main points of the present invention, adopt the flow process of Fig. 1, enumerate following examples, but do not limit its scope.
Embodiment 1
The present embodiment adopts solvent deasphalting, ebullated bed and fixed bed, catalytic cracking combined technique to carry out residuum hydroconversion.at first residual oil raw material is evenly mixed in static mixer with pentane solvent, then enter two sections solvent deasphalting units, obtain deasphalted oil and de-oiled asphalt, be mixed into the boiling bed hydrogenation treatment unit with hydrogen after the de-oiled asphalt preheating, carry out hydrogenation reaction under prepared boiling bed hydrogenation catalyst and processing condition, remove the sulphur in raw material, nitrogen, the heteroatomss such as metal, making simultaneously asphaltenes conversion is colloid or small molecules more, reduce product viscosity, hydrogenation products is isolated to the liquid phase upgrading and generates oil, this upgrading generation oil is mixed into the fixed bed hydrogenation device with deasphalted oil and reacts, obtain generating oil under fixed bed grating catalyzer and reaction conditions.This generation oil enters the further cracking of catalytic cracking unit and is converted into dry gas, catalytically cracked gasoline and catalytic cracking last running, and the catalytic cracking heavy distillate is carried out hydrogenation through being mixed into de-oiled asphalt after filtering in ebullated bed reactor.
Wherein the reaction conditions of solvent deasphalting, boiling bed hydrogenation, fixed bed hydrogenation, catalytic cracking sees Table 1, and experimental result sees Table 2.
Boiling bed hydrogenation treatment catalyst can adopt existing method preparation according to performance need, prepares as prior aries such as reference US7074740, US5047142, US4549957, US4328127, CN200710010377.5.The character specific surface area 142m of catalyst A
2/ g, pore volume 1.45mL/g(mercury penetration method), the pore volume of bore dia 30～300nm accounts for the 52%(mercury penetration method of total pore volume) and, MoO
3Content is that 6.02%, NiO content is 1.54%, and spherical particle diameters is 0.4mm.The character of catalyst B is specific surface area 239m
2/ g, pore volume 0.67mL/g(nitrogen adsorption method), the pore volume in 5-20nm hole accounts for 78%,〉pore volume in 20nm hole is 0.16mL/g, MoO
3Content is that 12.58%, CoO content is 2.34%, and spherical particle diameters is 0.4mm.Embodiment 1 ebullated bed reactor uses catalyst A, embodiment 2 to use catalyst A and catalyst B volume ratio to be the mixed catalyst of 1:0.4.In the ebullated bed reactor charging, catalytic cracking last running accounts for 40% of weight.
Fixed bed catalyst employing full scale plant uses commercial catalyst FZC-28, FZC-30 and the FZC-41 of Fushun Petrochemical Research Institute's development and production, fixed-bed reactor loading catalyst FZC-28, FZC-30 and FZC-41, and the admission space ratio is 3:2:1.
Catalytic cracking catalyst is the catalyzer that 3,500,000 ton/years of heavy oil catalytically cracking equipments of Dalian Company use, and is industrial equilibrium catalyst.Its fresh dose consists of: 95wt%LBO-16 olefine lowering catalyst+5wt%LBO-A improves octane enhancing additive.
Table 1 feedstock property.
| Project | Data |
| Density (20 ℃)/Kgm -3 | 1001.2 |
| Viscosity/mm 2/s（100℃） | 265 |
| Sulphur, wt% | 3.81 |
| Carbon residue, wt% | 15.15 |
| Ni/ μg·g -1 | 47.91 |
| V/ μg·g -1 | 134.11 |
| Fe/ μg·g -1 | 8.84 |
Table 2 combination process test conditions.
| Project | Embodiment |
| The solvent de-asphalting process condition | ? |
| Temperature/℃ | 190 |
| Pressure/MPa | 4.2 |
| Solvent ratio, v/v | 8 |
| The deasphalted oil yield, wt% | 45 |
| The deasphalted oil metal content, μ g/g | 34 |
| The boiling bed hydrogenation technique condition | ? |
| Temperature of reaction/℃ | 410 |
| Reaction pressure/MPa | 15 |
| Volume space velocity/h -1 | 0.7 |
| Hydrogen to oil volume ratio, v/v | 900:1 |
| Ebullated bed product metal content, μ g/g | 65 |
| The fixed bed hydrogenation processing condition | ? |
| Temperature of reaction/℃ | 385 |
| Reaction pressure/MPa | 15 |
| Volume space velocity/h -1 | 0.55 |
| Hydrogen to oil volume ratio, v/v | 900:1 |
| The catalytic cracking process condition | ? |
| Temperature of reaction/℃ | 505 |
| The finish ratio, weight ratio | 7.5 |
Table 3 residual hydrogenation generates oil nature.
| Project | Embodiment |
| Density (20 ℃), g/cm 3 | 925.8 |
| Viscosity (100 ℃), mm 2.s -1 | 20.15 |
| Sulphur, wt% | 0.29 |
| Carbon residue, wt% | 4.72 |
| Ni＋V+Fe，μg.g -1 | 13.14 |
The product distribution * that table 4 combination process is total.
| Project | Embodiment |
| Dry gas, wt% | 3.97 |
| Liquefied gas, wt% | 22.67 |
| Gasoline, wt% | 65.86 |
| Coke, wt% | 6.05 |
* take residual oil raw material weight as 100% calculating
Embodiment 2
Compare with embodiment 1, ebullated bed reactor makes spent mixed catalyst.The fixed bed permanent stability are good, and concrete knot sees Table 4, wherein 3 ℃ of each temperature raisings of fixed-bed reactor in 5000,8000,12000 hours.
Table 5 fixed bed hydrogenation reactive system stability result.
| Embodiment | Embodiment 1 | Embodiment 2 |
| Runtime, hour | Final oily metal content (μ the g/g)/fixed bed reaction system's total pressure drop (MPa) that generates | Final oily metal content (μ the g/g)/fixed bed reaction system's total pressure drop (MPa) that generates |
| 500 | 13.1/0.08 | 11.0/0.08 |
| 5000 | 13.0/0.12 | 10.9/0.11 |
| 8000 | 12.7/0.13 | 11.5/0.12 |
| 12000 | 13.5/0.14 | 11.2/0.12 |
Can find out from above-mentioned fixed bed reaction Systems balanth experimental result, the inventive method can realize the long period steady running of fixed bed hydrogenation treatment unit, can estimate according to development trend, the inventive method can realize the steady running of 2～3 years, obviously be longer than present fixed bed residual hydrogenation equipment 1 year with the interior fortune cycle, and be not subjected to the restriction of raw material sources quality, can realize and the same cycleoperation of catalytic cracking unit, be conducive to the collaborative running of two covering devices.
Claims (10)
1. a residual oil transforms combined technical method, it is characterized in that comprising the steps:
(1) residual oil raw material enters solvent deasphalting unit, obtains deasphalted oil and de-oiled asphalt;
(2) de-oiled asphalt that obtains in step (1) and the heavy distillate of catalytic cracking unit are mixed into the boiling bed hydrogenation treatment unit, under hydrogen and boiling bed hydrogenation treatment catalyst exist, carry out boiling bed hydrogenation and process;
(3) the boiling bed hydrogenation processing reaction effluent that step (2) is obtained mixes with deasphalted oil, then enter the fixed bed hydrogenation treatment unit, process under the catalyzer existence at hydrogen and fixed bed hydrogenation, be fixed bed hydroprocessing and process, the generation oil that fixed bed hydrogenation processing reaction effluent obtains is as the raw material of catalytic cracking unit;
(4) the catalytic cracking reaction effluent is isolated catalytic cracking last running after dry gas, liquefied gas and catalytically cracked gasoline and is mixed with de-oiled asphalt and carry out boiling bed hydrogenation and process.
2. it is characterized in that in accordance with the method for claim 1: the metal content in the inferior heavy oil raw material in step (1) is at least 120 μ g/g.
3. in accordance with the method for claim 1, it is characterized in that: the service temperature of solvent deasphalting is 60～250 ℃, pressure is 1.0～5.0MPa, solvent and inferior heavy oil volume feed are 1.0:1～10.0:1, solvent deasphalting unit is controlled index, in deasphalted oil, the content of heptane insolubles is less than 1.5wt%, and the deasphalted oil weight yield is 20%-85%, and in deasphalted oil, metal content is lower than 80 μ g/g.
4. in accordance with the method for claim 1, it is characterized in that: an ebullated bed reactor is set in step (2), and boiling bed hydrogenation processing reaction temperature is 350～430 ℃, and reaction pressure is 8～25MPa, hydrogen to oil volume ratio 100:1 ~ 1000:1, the liquid volume air speed is 0.3～5.0h
-1, after the boiling bed hydrogenation processing reaction in product liquid metal content require lower than 120 μ g/g.
5. in accordance with the method for claim 1, it is characterized in that: boiling bed hydrogenation treatment catalyst uses the boiling bed hydrogenation catalyst that contains more macropore, and the specific surface of catalyzer is 80～200m
2/ g, the pore volume of bore dia 30～300nm accounts for 35%～60% of total pore volume, and the average pore diameter of catalyzer is more than 20nm, and in catalyzer, by weight, catalyzer contains VI B family metal oxide 1.0%～10.0%, contains group VIII metal oxide compound 0.1%～8.0%.
6. in accordance with the method for claim 5, it is characterized in that: the mixed catalyst that uses two kinds of catalyzer in the boiling bed hydrogenation treatment reactor, it is the mixed catalyst of catalyst A and catalyst B, described catalyst A and catalyst B mixed volume are than being 1:0.1 ~ 1:2, catalyst A is the described boiling bed hydrogenation catalyst that contains more macropore, and the character of catalyst B is: catalyst specific surface is 180～300m
2/ g, bore dia accounts for 70% of total pore volume at least in the hole of 5～20nm, bore dia〉the shared pore volume in hole of 20nm is not less than 0.1mL/g, by weight, catalyzer contains VI B family metal oxide 3.0%～25.0%, contains VIII family metal oxide 0.3%～8.0%, in oxide weight, the catalyst B hydrogenation active metals is higher 1 ~ 18 percentage point than catalyst A hydrogenation active metals content, and catalyst A and catalyst B particle are spherical, and the particle flat footpath diameter of catalyst A and catalyst B is identical.
7. it is characterized in that in accordance with the method for claim 1: the metal content in the liquid phase feeding that middle fixed bed hydrogenation is processed is lower than 80 μ g/g.
8. in accordance with the method for claim 1, it is characterized in that: the temperature of reaction that fixed bed hydrogenation is processed is 350～420 ℃, and reaction pressure is 8～25MPa, hydrogen to oil volume ratio 100:1 ~ 1000:1, and the liquid volume air speed is 0.2～2.0h
-1
9. in accordance with the method for claim 1, it is characterized in that: the catalytic cracking double distilled is divided into initial boiling point the last running of 170～220 ℃, comprises catalytic cracking diesel oil, heavy catalytic cycle oil and slurry oil.
10. in accordance with the method for claim 1, it is characterized in that: catalytic cracking unit operant response temperature is 450～600 ℃, catalyzer and stock oil weight ratio 2:1～30:1, and with 0.1～15 second duration of contact of catalyzer, pressure 0.1～0.5MPa.
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| US10836967B2 (en) | 2017-06-15 | 2020-11-17 | Saudi Arabian Oil Company | Converting carbon-rich hydrocarbons to carbon-poor hydrocarbons |
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| CN114763491A (en) * | 2021-01-11 | 2022-07-19 | 中国石油化工股份有限公司 | Method for improving operation stability of fluidized bed hydrogenation device |
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| CN115895718A (en) * | 2022-11-10 | 2023-04-04 | 陕西延长石油（集团）有限责任公司 | Deoiled asphalt hydrocracking treatment method |
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