CN103102945B - A kind of inferior heavy oil working method - Google Patents
A kind of inferior heavy oil working method Download PDFInfo
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Abstract
The invention discloses a kind of inferior heavy oil working method, comprise the steps: that (1) inferior heavy oil raw material enters solvent deasphalting unit, obtain deasphalted oil and de-oiled asphalt; (2) de-oiled asphalt that step (1) obtains is entered boiling bed hydrogenation treatment unit, under hydrogen and boiling bed hydrogenation treatment catalyst exist, carry out boiling bed hydrogenation process; (3) boiling bed hydrogenation processing reaction effluent step (2) obtained and deasphalted oil are mixed into fixed bed hydrogenation treatment unit, under hydrogen and fixed bed hydrogenation process catalyzer exist, be fixed bed hydroprocessing process, the generation oil that fixed bed hydrogenation processing reaction effluent obtains is as the raw material of catalytic cracking unit.Compared with prior art, the inventive method raw material sources are extensive, and plant investment is low, and running is stable, and the operational cycle is long, removes to maximum the impurity in raw material, for catalytic cracking unit provides high quality raw material.
Description
Technical field
The present invention relates to a kind of inferior heavy oil working method, be specially adapted to the poor residuum that heavy metal content is higher, be the working method combining decarburization and hydrogenation technique, specifically solvent deasphalting, ebullated bed and fixed bed three kinds of technological processs organically combined the working method of effectively process inferior heavy oil.
Background technology
Along with the increase of crude oil heaviness, in poor quality degree, and market is to the change 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.Its cracking will be not still lower boiling product by the processing treatment of inferior heavy oil, as petroleum naphtha, intermediate oil and pressure reduction gas wet goods, but also will improve their hydrogen-carbon ratio, and the Basic Ways of therefore its processing is adopt hydrogenation or decarburization two kinds of methods substantially.Decarbonization process comprises coking, solvent deasphalting, heavy oil fluid catalytic cracking etc.; Hydrogenation comprises hydrocracking, hydrofining etc.Hydrogenation method can hydrocracking residual oil, and improve the productive rate of liquid product, and can also remove heteroatoms wherein, quality product is not bad.Current residual hydrogenation has developed fixed bed, ebullated bed, suspension bed and moving-bed four kinds of technology types.Wherein fixed-bed conversion rate lower (generally lower than 35%), is mainly catalytic cracking unit and provides high quality raw material; Ebullated bed transformation efficiency higher (generally higher than 60%), can obtain a large amount of light-end products, but light-end products need further process just can obtain qualified product; Suspension bed can obtain higher transformation efficiency (generally higher than 80%), but device stability is poor, is still difficult at present realize industrial operation; Moving-bed is between fixed bed and ebullated bed, and Problems existing is that device is complicated, and operation is solid difficult.
Being high value-added product the crude conversion of cheapness, is the lifeline of petroleum refining industry.The utilization ratio improving vacuum residuum is to greatest extent 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 obtained is good hydrotreated feed.Residue Hydrotreating Technology liquid yield is high, in product structure, quality product and environmental protection, all have obvious advantage.
Solvent de-asphalting process is by selecting suitable solvent and processing condition, make the bituminous matter in residual oil and oil carry out appropriateness to be separated, and make metal in residual oil, sulphur, nitride major part or partial concentration in bituminous matter, the foreign matter contents such as the bituminous matter in deasphalted oil and heavy metal significantly reduce, and can pass through the technique deep processings such as hydrotreatment, hydrocracking, hydrogenation and catalystic cracking.
USP7214308 discloses the technological process that a kind of solvent deasphalting and ebullated bed are effectively combined.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 ebullated bed system to process respectively, design and operation conditions optimization according to feedstock property.Wherein deasphalted oil ebullated bed reactor operational condition: stagnation pressure 3.45 ~ 20.69MPa, temperature of reaction 388 ~ 438 DEG C, liquid volume air speed 0.2 ~ 1.5h
-1.De-oiled asphalt ebullated bed reactor operational condition: stagnation pressure 10 ~ 20.69MPa, temperature of reaction 399 ~ 454 DEG C, liquid air speed 0.1 ~ 1.0h
-1.Require that this technique total conversion rate is 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 ebullated bed reactor local coking of processing de-oiled asphalt, thus affect device smooth operation.
CN200710157792.3 discloses a kind of combination process processing poor residuum.The method comprises residual oil raw material and enters solvent deasphalting unit, obtain deasphalted oil and de-oiled asphalt, the deasphalted oil of gained enters boiling bed hydrogenation device and processes, obtain light ends and hydrogenation tail oil goes catalytic cracking unit to process, and the light ends obtained thus and slurry oil, at least part of slurry oil and de-oiled asphalt are mixed into 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 boiling bed hydrogenation device.The method does not give full play to the ability of ebullated bed and suspension bed processing poor residuum, and floating bed hydrogenation technology is still difficult to normal commercial application at present due to stability problem, brings solid difficulty also to the method practical application.
CN1393525A discloses the method for the combined processing high-sulfur high-metal residual oil of a kind of solvent deasphalting, fixed bed hydrogenation process and catalytic cracking.Residual oil obtains deasphalted oil and de-oiled asphalt through solvent extraction, wherein deasphalted oil and optional heavy catalytic cycle oil send into fixed bed hydrogenation treatment unit upgrading, hydrogenation tail oil sends into catalytic cracking unit cracking, in its product, all or part of heavy cycle oil is circulated to fixed bed hydrogenation treatment unit, and all or part of catalytic slurry loops back solvent deasphalting unit.There is following problem in this method, containing catalytic cracking catalyst powder in one catalytic slurry, be easily carried in deasphalted oil by solvent extraction, after 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 blocking; 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., as pitch blending stock or oil fuel, can only cause the wasting of resources.
Because inferior heavy oil adds man-hour, its volume space velocity is lower, and therefore the multiple reactors in series of general needs uses (series connection use refers to reaction mass successively by each reactor), arranges more than 2 or 2 parallel series simultaneously.Therefore, inferior heavy oil hydrogenation unit generally comprises multiple reactor, for the device of year amount of finish 2,000,000 tons of scales, usually needs 8 reactors by current device fabrication level.For ebullated bed reactor, each reactor all needs a set of catalyzer to add heat-extraction system online, the investment that this cover catalyzer adds heat-extraction system is online very high (about assessment accounts for the half of boiling bed hydrogenation device gross investment), and complicated operation, the failure rate of appearance is also the highest.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of inferior heavy oil working method, be mainly catalytic cracking unit and provide high-quality charging, raw material sources are extensive, and plant investment is low, and running is stable, and the operational cycle is long, removes to maximum the impurity in raw material.
Inferior heavy oil working method of the present invention, comprises the steps:
(1) inferior heavy oil raw material enters solvent deasphalting unit, obtains deasphalted oil and de-oiled asphalt;
(2) de-oiled asphalt that step (1) obtains is entered boiling bed hydrogenation treatment unit, under hydrogen and boiling bed hydrogenation treatment catalyst exist, carry out boiling bed hydrogenation process;
(3) boiling bed hydrogenation processing reaction effluent step (2) obtained and deasphalted oil are mixed into fixed bed hydrogenation treatment unit, under hydrogen and fixed bed hydrogenation process catalyzer exist, be fixed bed hydroprocessing process, the generation oil that fixed bed hydrogenation processing reaction effluent obtains is as the raw material of catalytic cracking unit.
The inferior heavy oil raw material related in step (1) comprises the inferior heavy oil in vacuum residuum that crude distillation obtains or other source, and the metal content in inferior heavy oil raw material is at least 120 μ g/g, is preferably 180 more than μ g/g, most preferably is 220 more than 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 enter from the upper and lower of solvent deasphalting unit respectively, in extraction tower, carry out counter current contact, also first can enter extraction tower again by pre-mixing and be separated.In the present invention, the operational condition of solvent deasphalting is generally: temperature is 60 ~ 250 DEG C, and pressure is 1.0 ~ 5.0MPa, and agent oil volume ratio (solvent and inferior heavy oil volume feed) is 1.0:1 ~ 10.0:1; Preferable temperature is 60 ~ 200 DEG C, and pressure is 2.5 ~ 5.0MPa, and agent oil volume is than being 4.0:1 ~ 8.0:1.Solvent deasphalting operation adopts old process, can be that single hop also can be two sections.
Solvent deasphalting unit Con trolling index is, in deasphalted oil (DAO), the content of heptane insolubles is generally less than 1.5wt%, is preferably less than 0.5wt%; And DAO weight yield is generally 20%-85%, preferred 20%-60%, requires that in DAO, metal content is lower than 80 μ g/g, preferably lower than 50 μ g/g simultaneously.
Relate to ebullated bed reactor in step (2) and conventional ebullated bed reactor of the prior art can be adopted.An ebullated bed reactor can be set, 2 ebullated bed reactors be arranged in series also can be set, be arranged in series and refer to the reactor of reaction mass successively by arranging.Boiling bed hydrogenation treatment condition can require specifically to determine according to feedstock property and reaction conversion ratio, are generally: temperature of reaction is 350 ~ 430 DEG C, best 380 ~ 430 DEG C; 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
-1.Boiling bed hydrogenation process not with transformation efficiency (lighting) and desulfurization removing nitric for major objective, but be that fixed bed hydrogenation process provides qualified charging for major objective with demetalization, after boiling bed hydrogenation processing reaction, in product liquid, metal content requires lower than 120 μ g/g, preferably lower than 90 μ g/g, most preferably lower than 60 μ g/g.
Owing to containing a large amount of resin and asphalts in the de-oiled asphalt of boiling bed hydrogenation treatment unit processing, and bitum chemical structure is very complicated, is made up of polymerization aromatic hydrocarbons, alkane chain, naphthenic ring, and molecular weight is very large, mean molecule size about 6 ~ 9nm.Also containing heteroatomss such as sulphur, nitrogen, metals in structure of asphaltene, in crude oil, the metal of 80% ~ 90% is all enriched in bituminous matter.These impurity all " are hidden " deeply at intramolecule, and needing could imurity-removal under the operational condition of harshness.Bituminous matter is relevant with the aperture of used catalyst in the rate of decomposition of hydrogenation process.Catalyzer aperture is at least greater than 10nm, and bituminous matter is likely diffused in catalyzer duct.Therefore more macropore must be had to boiling-bed catalyst.This boiling bed hydrogenation catalyst specific surface is 80 ~ 200m
2the pore volume of/g, bore dia 30 ~ 300nm accounts for 35% ~ 60%(mercury penetration method of total pore volume), the average pore diameter of catalyzer is more than 20nm, is 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% ~ 6.5%, containing 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, and particle diameter is 0.1 ~ 0.8mm.
The mixed catalyst of two kinds of catalyzer is preferably used in boiling bed hydrogenation treatment reactor of the present invention, the i.e. 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), namely the mixed volume of catalyst A and catalyst B is than being 1:0.1 ~ 1:2, is preferably 1:0.2 ~ 1:0.5.Catalyst A and the above-mentioned boiling bed hydrogenation catalyst containing more macropore.Wherein the character of catalyst B is: catalyst specific surface is 180 ~ 300m
2/ g, bore dia at least accounts for 70% of total pore volume in the hole of 5 ~ 20nm, and shared by the hole of bore dia >20nm, pore volume 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%, containing VIII family metal oxide (as NiO or CoO) 0.3% ~ 8.0%, preferably 0.5% ~ 5.0%.Containing at least one 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 than catalyst A hydrogenation active metals content 1 ~ 18 percentage point, preferably high 3 ~ 15 percentage points.Catalyst A and catalyst B particle are spherical, and diameter is 0.1 ~ 0.8mm, are preferably 0.1 ~ 0.6mm; Wearing and tearing≤2.0wt%.Catalyst A is identical with the particle of catalyst B flat footpath diameter.
The deasphalted oil mixture of the reaction effluent that the raw material used in the fixed bed hydrogenation treating processes related in step (3) is ebullated bed and step (1), also can add other and be suitable for adopting fixed bed to carry out the heavy feed stock processed.Metal content in the liquid phase feeding of fixed bed hydrogenation process will lower than 80 μ g/g, preferably lower than 50 μ g/g, to protect the longer operational cycle.Fixed bed hydrogenation process uses the combination catalyst system of this area routine, generally comprise Hydrodemetalation catalyst, Hydrobon catalyst and hydrodenitrogenation catalyst etc., these catalyzer are all generally if aluminum oxide is for carrier with porous refractory inorganic oxide, group vib and/or group VIII metal such as the oxide compound of W, Mo, Co, Ni etc. are active ingredient, optionally add other various auxiliary agent as the catalyzer of the elements such as P, Si, F, B, serial heavy, the residual oil hydrocatalyst of the FZC such as developed by Fushun Petrochemical Research Institute.
Fixed bed hydrogenation treatment condition are generally: temperature of reaction is 350 ~ 420 DEG C, 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
-1.According to required hydrotreatment degree and unit scale, a fixed bed hydrogenation reactor can be set, also multiple fixed bed hydrogenation reactor can be set.
The generation oil obtained after fixed bed hydrogenation process can such as, as the high quality raw material of subsequent technique, catalytic cracking.
Of the present invention have advantage:
1, solvent deasphalting, boiling bed hydrogenation and fixed bed hydrogenation technique are organically combined, hydrogenation technique and decarbonization process are organically combined, the scope of application of the raw material expanded, more heavy, vacuum residuum feed etc. more inferior can be processed, particularly can process the higher inferior raw material of metals content impurity.
2, this combination process possesses the technological merit of decarburization and hydrogenation technique simultaneously, is not only subsequent technique and provides high quality raw material, can reduce overall cost of ownership again.Ebullated bed reactor generally only arranges one, and its object is that fixed bed hydrogenation reactor carries out raw materials pretreatment, needs the operation object of higher conversion different, combine the comprehensive advantage of fixed bed and ebullated bed from current boiling bed residual oil hydrogen addition technology.Ebullated bed reactor uses the mixed catalyst of suitable character catalyzer, improves boiling bed hydrogenation processing reaction effect.
3, this combination process takes full advantage of solvent de-asphalting process byproduct de-oiled asphalt, achieves and utilizes residual oil raw material to greatest extent.Ebullating bed reactor effluent viscosity greatly reduces, and just need can not reach the requirement of fixed bed hydrogenation technique to raw material at use thinner, improve the processing power of device with deasphalted oil after mixing.
4, this combination process is stripped of most of metal, sulphur, nitrogen, carbon residue and the bituminous matter in residual oil, reduces the viscosity of oil product, for subsequent machining technology provides high quality raw material.
Accompanying drawing explanation
Fig. 1 is poor residuum processing process schematic diagram of the present invention.
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 (or several can be arranged in series), 10-fixed-bed reactor reaction effluent.
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 can mix by oil pipeline feeding static mixer 3 respectively, solvent deasphalting unit 4 sent into by the material mixed, solvent deasphalting operation can be one-part form also can be two-part, obtain deasphalted oil (DAO) 5 and de-oiled asphalt 6, boiling bed hydrogenation reactor 8 is mixed into hydrogen 7 after de-oiled asphalt 6 preheating, hydrogenation reaction is carried out under the boiling bed hydrogenation catalyst loading above-mentioned preparation and processing condition, remove the heteroatoms such as metal, sulphur, make asphaltenes conversion be colloid or more small molecules, reduce product viscosity.Ebullating bed reactor effluent and deasphalted oil are mixed into fixed bed hydrogenation reactor 9, hydrogenation reaction is carried out under fixed bed grating catalyzer and reaction conditions, obtain reaction effluent 10, further separation obtains gas phase and loops back reactive system, be separated the liquid phase that obtains directly as catalytic cracking unit raw material, liquid phase also can enter fractionating system and fractionate out hydrogenated residue and enter catalytic cracking unit.Ebullating bed reactor effluent enters fixed-bed reactor after can entering strainer or sump again, removes the solid impurity etc. that may exist.Said apparatus is a serial technical process, 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, adopting the flow process of Fig. 1, enumerating following examples, but do not limit its scope.
Embodiment 1
The present embodiment adopts solvent deasphalting, ebullated bed and fixed bed combination process to carry out residual hydrocracking.First the Homogeneous phase mixing in static mixer by residual oil raw material and pentane solvent, then two sections of solvent deasphalting units are entered, obtain deasphalted oil and de-oiled asphalt, boiling bed hydrogenation treatment unit is mixed into hydrogen after de-oiled asphalt preheating, hydrogenation reaction is carried out under prepared boiling bed hydrogenation catalyst and processing condition, remove the sulphur in raw material, nitrogen, the heteroatomss such as metal, make asphaltenes conversion be colloid or more small molecules simultaneously, reduce product viscosity, hydrogenation reaction effluent and deasphalted oil are mixed into fixed bed hydrogenation device and react, obtain generating oil under fixed bed grating catalyzer and reaction conditions.Wherein feedstock property is in table 1, and the processing condition of solvent deasphalting, boiling bed hydrogenation, fixed bed hydrogenation are in table 2, and experimental result is in table 3, and table 3 data can be found out, the generation oil obtained is the catalytically cracked material of high-quality.
Boiling bed hydrogenation treatment catalyst can adopt existing method to prepare according to performance need, as prepared with reference to prior aries such as 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), MoO
3content is 8.02%, 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 method), the pore volume that the pore volume in 5-20nm hole accounts for 78%, >20nm hole is 0.16mL/g, MoO
3content is 14.58%, CoO content is 2.34%, and spherical particle diameters is 0.4mm.Embodiment 1 ebullated bed reactor uses catalyst A, and embodiment 2 uses the mixed catalyst that catalyst A and catalyst B volume ratio are 1:0.4.
Fixed bed adopts two reactors used of connecting, catalyzer adopts full scale plant to use commercial catalyst FZC-28, FZC-30 and FZC-41 of Fushun Petrochemical Research Institute's development and production, anti-loading catalyst FZC-28 and FZC-30 of fixed bed one, filling ratio is 2:1, anti-loading catalyst FZC-30 and FZC-41 of fixed bed two, filling ratio is 3:1.
table 1 feedstock property.
| Project | Data |
| Density (20 DEG C)/Kgm -3 | 981.2 |
| Viscosity/mPas(100 DEG C) | 265 |
| Sulphur, wt% | 2.51 |
| Carbon residue, wt% | 12.15 |
| Ni/ μg·g -1 | 44.19 |
| V/ μg·g -1 | 244.11 |
| Fe/ μg·g -1 | 9.54 |
| Four composition is analyzed, wt% | |
| Stable hydrocarbon | 43.20 |
| Aromatic hydrocarbon | 26.4 |
| Colloid | 24.5 |
| Bituminous matter | 5.9 |
table 2 combination process test conditions.
| Project | Data |
| Solvent de-asphalting process condition | |
| Temperature (tower top), DEG C | 190 |
| Pressure, MPa | 4.2 |
| Solvent ratio, v/v | 8 |
| Deasphalted oil yield, wt% | 45 |
| Deasphalted oil metal content, μ g/g | 34 |
| Boiling bed hydrogenation technique condition | |
| Temperature of reaction, DEG C | 400 |
| Reaction pressure, MPa | 15 |
| Volume space velocity, h -1 | 0.5 |
| Hydrogen to oil volume ratio, v/v | 900:1 |
| Ebullated bed transformation efficiency, wt% | 25 |
| Ebullated bed product metal content, μ g/g | 92 |
| Fixed bed hydrogenation processing condition | |
| One is instead/bis-anti- | |
| Temperature of reaction/DEG C | 380/390 |
| Reaction pressure/MPa | 15 |
| Volume space velocity/h -1 | 0.35 |
| Hydrogen to oil volume ratio, v/v | 800:1 |
table 3 test-results.
| Final generation oil nature | Data |
| Density (20 DEG C)/Kgm -3 | 925.1 |
| Viscosity/mPas(100 DEG C) | 30.14 |
| Sulphur, wt% | 0.25 |
| Carbon residue, wt% | 2.14 |
| Ni/ μg·g -1 | 4.15 |
| V/ μg·g -1 | 11.26 |
| Fe/μg·g -1 | 0.35 |
| Four composition is analyzed, wt% | |
| Stable hydrocarbon | 65.8 |
| Aromatic hydrocarbon | 22.7 |
| Colloid | 10.8 |
| Bituminous matter | 0.7 |
Embodiment 2
Compared with embodiment 1, ebullated bed reactor makes spent mixed catalyst.Fixed bed permanent stability are good, specifically tie in table 4, wherein each temperature raising of fixed-bed reactor in 5000,8000,12000 hours 3 DEG C.
table 4 fixed bed hydrogenation reactive system stability result.
| Embodiment | Embodiment 1 | Embodiment 2 |
| Runtime, hour | The oily metal content of final generation (μ g/g)/fixed bed reaction total system pressure falls (MPa) | The oily metal content of final generation (μ g/g)/fixed bed reaction total system pressure falls (MPa) |
| 500 | 15.8/0.06 | 13.5/0.06 |
| 1000 | 17.6/0.08 | 14.7/0.08 |
| 3000 | 18.2/0.09 | 15.4/0.09 |
| 5000 | 17.5/0.10 | 14.2/0.10 |
| 8000 | 19.1/0.12 | 13.5/0.12 |
| 12000 | 18.7/0.13 | 13.1/0.13 |
As can be seen from the stability experiment result of above-mentioned fixed bed reaction system, 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 the fortune cycle of current fixed bed residual hydrogenation equipment within 1 year, and not by the quantitative limitation of raw material sources matter, the same cycleoperation with catalytic cracking unit can be realized, be conducive to the collaborative running of two covering devices.
Claims (8)
1. an inferior heavy oil working method, is characterized in that comprising the steps:
(1) inferior heavy oil raw material enters solvent deasphalting unit, obtains deasphalted oil and de-oiled asphalt;
(2) de-oiled asphalt that step (1) obtains is entered boiling bed hydrogenation treatment unit, under hydrogen and boiling bed hydrogenation treatment catalyst exist, carry out boiling bed hydrogenation process, wherein, an ebullated bed reactor is only set;
(3) boiling bed hydrogenation processing reaction effluent step (2) obtained and deasphalted oil are mixed into fixed bed hydrogenation treatment unit, under hydrogen and fixed bed hydrogenation process catalyzer exist, be fixed bed hydroprocessing process, the generation oil that fixed bed hydrogenation processing reaction effluent obtains is as the raw material of catalytic cracking unit;
Boiling bed hydrogenation treatment catalyst uses the boiling bed hydrogenation catalyst containing 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%, containing group VIII metal oxide compound 0.1% ~ 8.0%.
2. in accordance with the method for claim 1, it is characterized in that: the inferior heavy oil feed metal content described 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 operational condition of the solvent deasphalting in step (1) is: temperature is 60 ~ 250 DEG C, pressure is 1.0 ~ 5.0MPa, and solvent and inferior heavy oil volume feed are 1.0:1 ~ 10.0:1.
4. in accordance with the method for claim 1, it is characterized in that: step (1) solvent deasphalting unit Con trolling index is that in deasphalted oil, the content of heptane insolubles is less than 1.5wt%, deasphalted oil weight yield is 20%-85%.
5. in accordance with the method for claim 1, it is characterized in that: boiling bed hydrogenation processing reaction temperature is 350 ~ 420 DEG C, reaction pressure is 8 ~ 25MPa, hydrogen to oil volume ratio 100:1 ~ 1000:1, and liquid volume air speed is 0.3 ~ 5.0h
-1, after boiling bed hydrogenation process, in product liquid, metal content controls lower than 120 μ g/g.
6. in accordance with the method for claim 1, it is characterized in that: boiling bed hydrogenation processing reaction temperature is 380 ~ 430 DEG C, reaction pressure is 8.0 ~ 16MPa, hydrogen to oil volume ratio 500:1 ~ 1000:1, and liquid volume air speed is 0.3-2.0h
-1, after boiling bed hydrogenation process, in product liquid, metal content requires lower than 90 μ g/g.
7. in accordance with the method for claim 1, it is characterized in that: the mixed catalyst using two kinds of catalyzer in boiling bed hydrogenation treatment reactor, the i.e. 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 containing more macropore, and the character of catalyst B is: catalyst specific surface is 180 ~ 300m
2/ g, bore dia at least accounts for 70% of total pore volume in the hole of 5 ~ 20nm, shared by the hole of bore dia >20nm, pore volume is not less than 0.1mL/g, by weight, catalyzer is containing VI B family metal oxide 3.0% ~ 25.0%, containing VIII family metal oxide 0.3% ~ 8.0%, in oxide weight, catalyst B hydrogenation active metals is higher than catalyst A hydrogenation active metals content 1 ~ 18 percentage point, catalyst A and catalyst B particle are spherical, and catalyst A is identical with the particle of catalyst B flat footpath diameter.
8. in accordance with the method for claim 1, it is characterized in that: the metal content in the liquid phase feeding of fixed bed hydrogenation process in step (3) is lower than 80 μ g/g, the temperature of reaction of fixed bed hydrogenation process is 350 ~ 420 DEG C, reaction pressure is 8 ~ 25MPa, hydrogen to oil volume ratio 100:1 ~ 1000:1, liquid volume air speed is 0.2 ~ 2.0h
-1.
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| US6207041B1 (en) * | 1997-10-14 | 2001-03-27 | Institut Francais Du Petrole | Process for converting heavy crude oil fractions, comprising an ebullating bed hydroconversion step and a hydrotreatment step |
| CN1735678A (en) * | 2002-12-06 | 2006-02-15 | 阿尔伯麦尔荷兰有限公司 | Hydro processing of hydrocarbon using a mixture of catalysts |
| CN101376834A (en) * | 2007-08-27 | 2009-03-04 | 中国石油化工股份有限公司 | Bubbling bed combined process |
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| US7279090B2 (en) * | 2004-12-06 | 2007-10-09 | Institut Francais Du Pe'trole | Integrated SDA and ebullated-bed process |
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| US6207041B1 (en) * | 1997-10-14 | 2001-03-27 | Institut Francais Du Petrole | Process for converting heavy crude oil fractions, comprising an ebullating bed hydroconversion step and a hydrotreatment step |
| CN1735678A (en) * | 2002-12-06 | 2006-02-15 | 阿尔伯麦尔荷兰有限公司 | Hydro processing of hydrocarbon using a mixture of catalysts |
| CN101376834A (en) * | 2007-08-27 | 2009-03-04 | 中国石油化工股份有限公司 | Bubbling bed combined process |
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