CN1107699C - Low-grade heavy oil and residual oil treating method - Google Patents
Low-grade heavy oil and residual oil treating method Download PDFInfo
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- CN1107699C CN1107699C CN 00110719 CN00110719A CN1107699C CN 1107699 C CN1107699 C CN 1107699C CN 00110719 CN00110719 CN 00110719 CN 00110719 A CN00110719 A CN 00110719A CN 1107699 C CN1107699 C CN 1107699C
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Abstract
The present invention discloses a treating method for poor-quality heavy oil and residual oil. An expanded bed reactor is combined with a movable bed reactor; thus, the utilization ratio of hydrogenation catalysts is improved, the operation severity level of a downstream device is greatly decelerated under the condition of the same demetallization ratio, and great economic benefits are obtained.
Description
The present invention relates to the treatment process of heavy hydrocarbon, especially the higher heavy hydrocarbon hdyrotreating methods inferior of detrimental impurity content such as S, N, metal.
Heavy and to the increase day by day of light-end products demand along with becoming day by day of crude oil, the heavy oil lighting has become oil refining worker's main task.The heavy-oil hydrogenation upgrading is one of main method of heavy oil lighting, and it not only can slough detrimental impurity such as metal in the residual oil, sulphur, nitrogen in a large number, the low boiling component that can also make heavily, slag oil crack becomes high value.
Prove that according to test and industrial operation the reason of the easy inactivation of catalyzer is that metal deposition and sedimentation of coke cause in the residual hydrocracking device.For hydrogenation unit, metal deposition is the major cause of hydrogenation catalyst inactivation.Therefore, when surpassing the heavy oil residue of 100ppm (weight),, also need very big fixed-bed reactor, just can reach satisfied on-stream time even adopt the high catalyzer of metals capacity with hydrogen addition technology processing metal content.In this case, reactor assembly that can on-stream more catalyst changeout just has very big advantage.At present, the reactor assembly of the more catalyst changeout of industrial application has: ebullated bed (expanded bed) reactor, moving-bed or bunker reactor etc.Ebullated bed (expanded bed) hydrogenation technique is representative with the H-oil technology of U.S. HRI company exploitation and the LC-Fining technology of ABB Lummus Crest company exploitation respectively; The moving-bed hydrogenation technique is representative with the HYCON of Dutch Shell company and the OCR technology of U.S. Chevron company, the HYCON technology of wherein Dutch Shell company is downflow system, raw material and catalyzer be coflow from top to bottom, in industrialization in 1989,1,300,000 tons of working abilities, the OCR technology of U.S. Chevron company is reverse-flow, raw material flows from bottom to top, catalyzer but flowed from top to bottom, and both carry out counter current contact, and it has realized industrialization in 1992.
Ebullated bed and downflow system moving-bed compare, following as can be seen characteristics: the dirty slag capacity of the dirty slag volume ratio moving-bed system of (1) ebullated bed is big; (2) if keep same catalyzer rate of displacement, the catalyzer average activity level of ebullated bed can be hanged down; (3) for demetalization (being higher than the reaction of zero level), the catalyst activity in the moving-bed is more better than the utilization in the ebullated bed reactor; (4) ebullated bed allows to operate under comparatively high temps, can more effectively utilize reactor volume.But document (" residual hydrogenation Progress in technique and prospect ", annual meeting in 1993 report of refining of petroleum association of Chinese Petroleum Society (CPS)) points out that ebullated bed is because of existing the fluid air-teturning mixed phenomenon, and catalyst concentration not high (the general only 60V% of suitable fixed bed), so difficulty reaches deep removal residual oil impurity, for keeping the impurity removal degree of depth preferably, need to keep higher reaction pressure (generally＞15MPa), also need adopt a plurality of reactors in series systems and consume more catalyzer, so that increase tooling cost.Simultaneously, back-mixing also can make a part of live catalyst discharge (accounting for 30%) with spent catalyst, has increased the consumption of catalyzer, and therefore, the downflow system moving-bed is better than ebullated bed.Moving-bed is divided into two kinds: a kind ofly be and flow down streaming, another kind is the reverse-flow of stock oil upper reaches, document (Beijing international petroleum refining in 1991 and petrochemical complex proceeding, 208～216) once the catalyzer consumption of cocurrent flow type moving-bed and reverse-flow moving-bed was compared, draw when metal content in the resid feed increases, it is minimum to use reverse-flow movable bed catalyst consumption.Adopt reverse-flow charging and remove to be contaminated with metals the most serious catalyzer, can increase the metal bearing capacity of catalyzer, the save catalyst expense of maximum.
United States Patent (USP) 5076908,5302357,5409598,5472928,5492617,5498327, CN1659164A etc. have all proposed some improvement to OCR technology, but sum up and get up to still have following shortcoming: (1) has more peripheral high-low pressure container and catalyzer translating eqipment, makes the device one-time investment bigger; (2) polluted the most serious catalyzer generation fouling for preventing by metal impurities, hinder the displacement of catalyzer, the ratio of expansion of catalyzer reduces catalyst density about 10% in the OCR technology, has influenced the impurity removal percentage of residual oil or has increased the operating severity that installs.(3) for preventing that fouling of catalyst from influencing displacement, the catalyzer frequency of replacement of OCR is higher, and the appearance metal potentiality of catalyzer are performance fully not, causes the utilization ratio of catalyzer not high, has increased the investment of catalyzer.
In order to solve the deficiency in the above-mentioned existing residual oil moving-bed hydrotreatment technology, the object of the present invention is to provide a kind of inferior heavy, process for hydrogenating residual oil, give full play to the performance of catalyzer, reduce the inversion frequency of catalyzer, simplify the operation.
Technical scheme of the present invention is as follows:
After heavily, the parallel feeding of residual oil and hydrogen is heated through process furnace, mode with the upper reaches enters expanded bed reactor, and then enters moving-burden bed reactor in the mode at upper reaches, when this catalyst reactor is not replaced, belong to fixed bed operation, thereby realize hydrocracking heavy, residual oil raw material.After the expanded bed reactor catalyst activity loses, under the device state of not stopping work it is discharged, deciding the output of catalyzer according to the level of deactivation of catalyzer is part or all (accounting for the 5%-100% of expanded bed reactor catalyzer total amount).Required catalyzer is replenished by the bottom catalyzer of moving-burden bed reactor again, and the catalyzer that moving-burden bed reactor lacks is replenished by the live catalyst that adds to above the beds.
Expanded bed reactor of the present invention, catalyzer ratio of expansion wherein, are preferably within the scope of 15～20V% preferably at 10～25V% at 5～25V%; The loading amount of catalyzer is 10～50V% of expanded bed and moving-burden bed reactor catalyzer total amount, preferably at 20～45V%, is preferably within the scope of 25～35V%; Operational condition is: hydrogen pressure 1.0～20.0MPa, be preferably 5.0～18.0MPa, and that best is 8.0～16.0MPa; 340～427 ℃ of temperature are preferably 360～420 ℃, and best is 360～400 ℃; Volume space velocity 1.0～17.5h during liquid
-1, be preferably 1.0～12.5h
-1, that best is 1.0～10h
-1Hydrogen to oil volume ratio 300～2500 is preferably 400～2000, and best is 500～1500.The main purpose of this expanded bed is to take off colloid, bituminous matter and the olefines of the metallic iron class that easily causes the hydrogenation catalyst fouling and easily coking, catalyzer in the moving-burden bed reactor can be turned round the long period, and be unlikely in replacement process, to discharge smoothly because of fouling.The another one purpose is to give full play to the appearance dirt potentiality of hydrogenation catalyst used therein.Catalyzer in this expanded bed is at first together by S, N, metal impurities, the particularly residual oil raw material of metallic pollution maximum contact, make between the decreasing ratio 20～45% of S, metal (especially Ni, V), more fortunately between 25～40%, be preferably in 35～40% between (decreasing ratio is a benchmark with the device charging).
The ratio of expansion of catalyzer is controlled between 0～5% in the moving-burden bed reactor of the present invention, is preferably zero.Its process conditions is: hydrogen pressure 1.0～20.0MPa, be preferably 5.0～18.0MPa, and that best is 8.0～16.0MPa; 340～427 ℃ of temperature are preferably 350～420 ℃, and best is 360～420 ℃; Volume space velocity 0.5～7.5h during liquid
-1, be preferably 0.5～6h
-1, that best is 0.5～4.5h
-1Hydrogen to oil volume ratio 300～2500 is preferably 400～2000, and best is 500～1500.
Ratio of expansion described in the present invention is meant that the charge level difference of altitude after the charge level height after catalyzer expands loads naturally with catalyzer loads the ratio of charge level height afterwards naturally with catalyzer.
Employed catalyzer is meant and has the catalyzer that holds metal impurities and hydrodemetallation (HDM), desulfurization, takes off carbon residue, nitrogen removal performance in above-mentioned two reactors, this class catalyzer generally is to be carrier with porous refractory inorganic oxides such as aluminum oxide, with VIB (as W, Mo) and/or group VIII (as Co, Ni) metal component is the catalyzer of active ingredient, can certainly optionally add the IA that is selected from the periodic table of elements and/or the basic metal of IIA, or add auxiliary agents such as P, Si.
Expanded bed of the present invention and moving-bed combination process can adapt to the different needs of refinery neatly.For example, a scheme is can tell gas, gasoline fraction, diesel oil distillate, hydrogenated residue through after separating through the reaction product after the moving-burden bed reactor processing, they is handled respectively again; Perhaps another scheme is that reaction product after moving-burden bed reactor is handled directly enters fixed bed residual hydrogenation reactive system and handles, and the present invention preferentially recommends this scheme.So at different needs, in expanded bed of the present invention and the moving-bed COMBINED PROCESS, the coupling of corresponding technological conditions and catalyst loading, different catalysts can be done corresponding adjustment.When for example adopting first kind of above-mentioned scheme, volume space velocity reduces in the time of can be with the feeding liquid of expanded bed and moving-burden bed reactor, the ratio of Hydrodemetalation catalyst filling can reduce relatively in the moving-burden bed reactor, can adorn some hydrogenating desulfurizations accordingly, hydrogenation takes off carbon residue, hydrodenitrogenation catalyst even hydrocracking catalyst more.As when adopting second kind of scheme, the main task of expanded bed and moving-burden bed reactor is to remove metallic impurity, so comparable first kind of scheme height of volume space velocity during liquid, and the filling ratio of Hydrodemetalation catalyst in the increasing moving-burden bed reactor, even all load Hydrodemetalation catalyst, and the pore distribution situation of the catalyzer of adorning preferably can satisfy following requirement in expanded bed and the moving-bed: diameter accounts for 5% (better be 5%～10%, preferably 10%～15%) of pore volume at least greater than the macropore of 100nm; Surface-area (BET, nitrogen adsorption method) is at 50m
2/ g～200m
2Between/the g, be preferably at 80m
2/ g～150m
2/ g, best is at 100m
2/ g～120m
2/ g, can several apertures in the scope of about 15～60nm, pore volume (mercury penetration method) is at 0.7～1.2cm
3Between/the g, average particulate diameter 1.5～7.5mm is preferably at 1.5～7.0mm, and best is at 1.5～5.5mm.This aluminum oxide can prepare with any method in common.For example, preparing the method for catalyst oxidation alumina supporter of the present invention can be referring to the United States Patent (USP) the 4179408th (date of publication on December 18th, 1979) of the United States Patent (USP) of Laine etc. No. 4392987 (12 days July nineteen eighty-three of date of publication) and Sanchez etc.After this, can be by pickling process or kneading method commonly used in any suitable method, particularly catalyst preparation technology, the catalyst component that the catalyzer of this beds is required joins on the alumina supporter.Be applicable to that catalyst component of the present invention has vib metal (especially molybdenum and tungsten) and/or VIII family metal (especially cobalt and nickel).The amount of catalyst component (by the metal oxide compound) is preferably between about 2.5～13.5%, and the kind of catalyzer is one or more, and particle shape can be shapes such as cylindrical, bar shaped, sphere, elliposoidal, but preferably spherical, elliposoidal.
The generation oil of moving-burden bed reactor can enter residual hydrocracking reactive systems such as ebullated bed, suspension bed, fixed bed and carry out hydrotreatment again, preferred fixed bed residual hydrocracking reactive system.The generation oil of moving-burden bed reactor directly enters fixed bed residual hydrogenation reactive system and carries out hydrotreatment, residual oil behind the upgrading separates from entering Separate System of Water-jet after reactive system comes out, hydrogenous gas phase Returning reacting system after purifying recycles, liquid phase then enters separation column and carries out fractionation, the light ends fractionation that fractionation obtains goes out device respectively, residue oil fraction at the bottom of the tower can go downstream unit to continue processing, and also Returning reacting system carries out hydrotreatment again.
The operational condition of described fixed bed residual hydrocracking system is generally: temperature of reaction 340-420 ℃, and preferably 360-410 ℃; Reaction pressure is 8.0-20.0MPa, and that best is 8.0-15.0MPa; Hydrogen to oil volume ratio is 500-2000, and that best is 700-1500; Volume space velocity is 0.2-2.5h during liquid
-1, be preferably 0.2-2.0h
-1, that best is 0.2-1.5h
-1The heavy residual oil hydrocatalyst that is adopted be meant have weight, the single catalyst or the series catalyst of residuum hydrogenating and metal-eliminating, hydrogenating desulfurization, hydrodenitrification and hydrocracking function.These catalyzer generally all are to be carrier with porous refractory inorganic oxides such as aluminum oxide, the oxide compound of group vib and/or VIII family metal such as W, Mo, Co, Ni etc. is an active ingredient, the catalyzer that optionally adds other various auxiliary agents such as P, Si, elements such as F, B, for example CEN, the FZC series of being produced by Fushun Petrochemical Research Institute pilot scale base weighs, residuum hydrogenating and metal-eliminating catalyst, and ZTN, the ZTS catalyst series produced by first fertilizer plant of Qilu Petrochemical company just belong to this class catalyzer.At present in fixed bed residual hydrogenation technology, it often is the supporting use of multiple catalyzer, Hydrodemetalation catalyst, Hydrobon catalyst, hydrodenitrogenation catalyst are wherein arranged, and the filling order generally is that stock oil is contacted with hydrodemetallation (HDM), hydrogenating desulfurization, hydrodenitrification, hydrocracking catalyst successively.Technology with these several catalyst mix fillings is also arranged certainly.For the present invention, also can be according to situations such as the composition of raw material, foreign matter contents, and the metal in preceding two reactors removes situation, suitably adjust the ratio of catalyzer such as hydrogenation metal, hydrodenitrification, hydrogenating desulfurization, removal of ccr by hydrotreating, for example, can suitably reduce the loading amount of catalyst for demetalation or not adorn Hydrodemetalation catalyst etc., also can increase the conversion that hydrocracking catalyst carries out the higher degree of residual oil.
The present invention is applicable to normal slag and the pre-treatment that subtracts slag, is particularly useful for the poor residuum hydrotreatment of high metal, high carbon residue, high condensed ring material.
Compared with prior art, characteristics of the present invention are: by adopting the combination of expanded bed reactor and moving-burden bed reactor, not only can improve the utilization ratio of hydrogenation catalyst, and under the situation of identical demetallization per, can also slow down the operating severity of downstream unit greatly, obtain bigger economic benefits.
Fig. 1 is a schematic flow sheet of the present invention.
For further specifying all main points of the present invention, be elaborated below in conjunction with drawings and Examples.
As shown in Figure 1, the parallel feeding 1 of residual oil and hydrogen enters in the process furnace 2 heats, enter expanded bed reactor 4 through pipeline 3 afterwards, resultant of reaction 5 directly enters moving-burden bed reactor 6 with the form at upper reaches through pipeline, and reaction end back resultant 7 enters existing residue fixed-bed hydrogenation reaction system 8 through pipeline and further carries out hydrogenation reaction.Resultant 9 behind the hydrogenation goes out reactive system and enters downstream separation, fractionation plant, finally goes out product.Behind the catalyst deactivation of expanded bed 4, the displacement of beginning hydrogenation catalyst, decaying catalyst is discharged by pipeline 11 and is entered high pressure vessel 24, and the pressure of high pressure vessel 24 is by advancing hydrogen 23 and emptying 21 is controlled, and last spent catalyst 22 is discharged and is handled through pipeline.The catalyzer that expanded bed 4 lacks is replenished through pipeline 12 by the catalyzer in the moving-burden bed reactor 6, and moving-burden bed reactor 6 insufficient catalyzer are replenished through pipeline 13 by live catalyst.The pressure of live catalyst container 25 is by advancing hydrogen 14 and emptying 15 is controlled, and live catalyst adds through pipeline 16.Adding live catalyst to moving-burden bed reactor 6 is tube line 10, and carries through the moving-bed generation oil 7 that pump 18 boosts.The displacement of hydrogenation catalyst has two kinds of schemes: (1), live catalyst add to earlier in the moving-burden bed reactor 6, discharge the catalyzer of expanded bed reactor 4 again, and the catalyzer of last moving-burden bed reactor 6 adds in the expanded bed reactor 4.(2), the catalyzer of expanded bed reactor 4 discharges earlier, when the catalyzer of moving-burden bed reactor 6 added to expanded bed reactor 4, live catalyst added in the moving-burden bed reactor 6.Expanded bed reactor 4 has two kinds of substitute modes during the catalyzer displacement: (1), isolation displacement.(2), one displacement.Wherein isolating displacement is that expanded bed reactor is isolated from reactive system, and resid feed directly enters moving-burden bed reactor 6 through pipeline 19, and without expanded bed reactor 4, the pressure of expanded bed reactor 4 is by advancing hydrogen 20 and emptying 17 is controlled; The one displacement is exactly that resid feed still is introduced into expanded bed reactor, replaces under the state of expanded bed reactor work.
Embodiment 1～5, comparative example 1
This test mainly is a performance of investigating the present invention and single OCR moving-burden bed reactor.The physico-chemical property of the catalyzer that this test is used sees Table-1, and stock oil main character character sees Table-2.Test all is to turn round on the 200ml packaged unit.The inventory of expanded bed and two reactor catalysts of moving-bed is 200ml in the embodiment of the invention, the loaded catalyst of the single reaction vessel of single OCR moving bed reaction system is 200ml just in the comparative example, and single OCR moving-burden bed reactor operation is that stock oil autoreactor bottom enters, upwards flow, catalyzer is intermittently discharged, and the catalyzer of first reactor is the 33V% of second reactor in the reactive system of the present invention.In whole operation process, adopt their generation oil sample and analysis.Running period is by single OCR moving-burden bed reactor catalyzer of four times metathetical time smoothly.Single OCR moving-burden bed reactor displacement catalyzer four times be total to the 120ml catalyzer, and the present invention is replaced catalyzer twice, altogether the 80ml catalyzer.Say that from the catalyzer consumption the present invention is better than the OCR moving-burden bed reactor.Operation condition in the operation process the results are shown in Table-3 with generating oil analysis, and impurity removal percentage of the present invention as can be seen from the table is higher than the OCR moving-burden bed reactor.
The spherical range estimation of table-1 catalyzer physico-chemical property project catalyst analysis method shape diameter, mm 2.5 slide calliper rule pore volumes, ml/g 1.1 nitrogen cryogenic absorption specific surface areas, m
2/ g 105 nitrogen cryogenic absorption tap densities, g/ml 0.43 graduated cylinder method Nio w% 2.53MoO
3W% 5.36 can several apertures, and nm 45
The main character of table-2 stock oils
| Project | Stock oil |
| Elementary composition | |
| S，w％ | 2.79 |
| N，w％ | 3014 |
| CCR，w％ | 15.67 |
| Ni+V，μg/g | 117.3 |
| Four components | |
| Saturated part, w% | 14.5 |
| Fragrance part, w% | 34.8 |
| Colloid, w% | 47.2 |
| Bituminous matter, w% | 3.5 |
Table-3 operation conditions and generation oil analysis result
| Comparative example and embodiment | Comparative example 1 | Embodiment 1 | Embodiment 2 | |||
| * | ** | * | ** | * | ** | |
| Expanded bed | ||||||
| Temperature, ℃ | 370 | 380 | ||||
| Air speed, h -1 | 1.0 | 3.0 | ||||
| Hydrogen-oil ratio | 700 | 800 | ||||
| Pressure, MPa | 10.0 | 12.0 | ||||
| Ratio of expansion | 15％ | 15％ | ||||
| OCR | Moving-bed | |||||
| Temperature, ℃ | 385 | 370 | 380 | |||
| Air speed, h -1 | 1.65 | 0.5 | 1.5 | |||
| Hydrogen-oil ratio | 1000 | 700 | 800 | |||
| Pressure, MPa | 15.0 | 10.0 | 10.0 | |||
| Ratio of expansion | 8％ | 2％ | 2％ | |||
| Generate oil nature | ||||||
| S，w％ | 1.28 | 1.40 | 1.68 | 1.63 | 1.31 | 1.37 |
| N，w％ | 2566 | 2763 | 2700 | 2897 | 2596 | 2733 |
| Ni+V，μg/g | 19.38 | 27.16 | 30.65 | 38.5 | 20.61 | 27.63 |
| Four components | ||||||
| Saturated part, w% | 32.6 | 28.7 | 30.2 | 25.6 | 32.6 | 28.6 |
| Fragrance part, w% | 30.6 | 32.0 | 31.5 | 33.2 | 30.4 | 32.5 |
| Colloid, w% | 35.9 | 38.1 | 37.1 | 39.5 | 36.0 | 37.5 |
| Bituminous matter, w% | 0.9 | 1.2 | 1.2 | 1.7 | 1.0 | 1.4 |
Continuous table-3 operation conditions and generation oil analysis result
| Embodiment | Embodiment 3 | Embodiment 4 | Embodiment 5 | |||
| * | ** | * | ** | * | ** | |
| Expanded bed | ||||||
| Temperature, ℃ | 385 | 390 | 395 | |||
| Air speed, h -1 | 5.0 | 7.0 | 8.0 | |||
| Hydrogen-oil ratio | 1000 | 1200 | 1400 | |||
| Pressure, MPa | 13.0 | 14.0 | 15.0 | |||
| Ratio of expansion | 17％ | 17％ | 19％ | |||
| Moving-bed | ||||||
| Temperature, ℃ | 385 | 390 | 395 | |||
| Air speed, h -1 | 2.5 | 3.5 | 4.0 | |||
| Hydrogen-oil ratio | 1000 | 1200 | 1400 | |||
| Pressure, MPa | 13.0 | 14.0 | 15.0 | |||
| Generate oil nature | 3％ | 3％ | 4％ | |||
| S，w％ | 1.25 | 1.33 | 1.10 | 1.15 | 0.85 | 0.93 |
| N，w％ | 2516 | 2698 | 2400 | 2443 | 2298 | 2313 |
| Ni+V，μg/g | 16.94 | 23.21 | 11.6 | 14.6 | 8.7 | 9.5 |
| Four components | ||||||
| Saturated part, w% | 34.2 | 30.9 | 40.3 | 37.2 | 44.6 | 41.5 |
| Fragrance part, w% | 28.2 | 31.8 | 27.6 | 29.3 | 25.8 | 27.6 |
| Colloid, w% | 34.7 | 36.2 | 31.2 | 32.6 | 28.7 | 30.0 |
| Bituminous matter, w% | 0.9 | 1.1 | 0.9 | 0.9 | 0.9 | 0.9 |
In the table
*Be meant the sampling analysis before single OCR moving-burden bed reactor is replaced catalyzer for the first time, the sampling time of stream oriented device is identical.
*All that are meant a running period of stream oriented device generate oily average properties analysis.
Claims (7)
1, a kind of inferior heavy, residual oil treatment process, after comprising the parallel feeding process process furnace heating of weight, residual oil and hydrogen, the mode with the upper reaches of it is characterized in that at first enters expanded bed reactor and contacts with catalyzer, and then enter moving-burden bed reactor in the mode at upper reaches and contact with catalyzer, realize the hydrocracking of described heavy, residual oil raw material; After described expanded bed reactor catalyst activity loses, under the state that device is not stopped work it is discharged, catalyst system therefor is replenished by the catalyzer of described moving-burden bed reactor again, and the catalyzer that moving-burden bed reactor lacks is replenished by live catalyst; Operational condition in the above-mentioned expanded bed reactor is: the catalyzer ratio of expansion is at 5～25V%, the loading amount of catalyzer is 10～50V% of expanded bed and moving-burden bed reactor catalyzer total amount, hydrogen pressure 1.0～20.0MPa, 340～427 ℃ of temperature, volume space velocity 1.0～17.5h during liquid
-1, hydrogen to oil volume ratio 300～2500; The operational condition of above-mentioned moving-burden bed reactor is: the ratio of expansion of catalyzer is controlled between 0～5V%, hydrogen pressure 1.0～20.0MPa, 340～427 ℃ of temperature, volume space velocity 0.5～7.5h during liquid
-1, hydrogen to oil volume ratio 300～2500.
2, according to the described inferior heavy of claim 1, residual oil treatment process, the reactant that it is characterized in that described moving-burden bed reactor directly enters fixed bed residual hydrocracking system and handles, entering Separate System of Water-jet then separates, hydrogeneous gas phase Returning reactor after purifying recycles, and liquid phase then enters separation column and separates.
3, according to the described inferior heavy of claim 1, residual oil treatment process, it is characterized in that in described expanded bed and the moving-burden bed reactor that catalyzer is is carrier with the porous refractory inorganic oxides, is the catalyzer of active ingredient with VIB and/or group VIII metal component.
4, according to the described inferior heavy of claim 1, residual oil treatment process, it is characterized in that the described resultant answer reactor that moves directly enters fixed bed residual hydrogenation system and handles, to be diameter account for 5% of pore volume greater than the macropore of 100nm to the pore volume distribution of described expanded bed and movable bed catalyst at least, and surface-area is at 50m
2/ g～200m
2Between/the g, can several apertures in the scope of 15～60nm, pore volume is at 0.7～1.2cm
3Between/the g, average particulate diameter 1.5～7.5mm.
5, according to the described inferior heavy of claim 1, residual oil treatment process, it is characterized in that the operational condition in the described expanded bed reactor is: the catalyzer ratio of expansion is at 10～25V%, the loading amount of catalyzer is 20～45V% of expanded bed and moving-burden bed reactor catalyzer total amount, hydrogen pressure 5.0～18.0MPa, 360～420 ℃ of temperature, volume space velocity 1.0～12.5h during liquid
-1, hydrogen to oil volume ratio 400～2000.
6, according to the described inferior heavy of claim 1, residual oil treatment process, it is characterized in that the operational condition of described moving-burden bed reactor is: the ratio of expansion of catalyzer is 0, hydrogen pressure 5.0～18.0MPa, 350～420 ℃ of temperature, volume space velocity 0.5～6h during liquid
-1, hydrogen to oil volume ratio 400～2000.
7, according to the described inferior heavy of claim 2, residual oil treatment process, the operational condition that it is characterized in that described fixed bed residual hydrocracking system is: temperature of reaction 340-420 ℃, reaction pressure 8.0-16MPa, hydrogen to oil volume ratio is 500-2000, volume space velocity is 0.2-2.5h during liquid
-1, described catalyzer is to be carrier with the aluminum oxide, is the catalyzer of active ingredient to be selected from VIB and/or VIII metallic element.
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| CN102234534B (en) * | 2010-04-28 | 2014-01-15 | 中国石油化工股份有限公司 | Method for processing inferior heavy oil |
| CN103045302B (en) * | 2011-10-17 | 2015-02-18 | 中国石油化工股份有限公司 | Method for grading catalysts for hydrotreatment |
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