A kind of combined technical method and system handling low grade oilsTechnical field
The present invention relates to a kind of low grade oils lightening method and systems, more particularly to a kind of inferior using hydrotreatingThe combined technical method and processing system of oil product.
Background technique
Currently, it will be in hold that demand of the refined products market to oil products such as steam coal bavins, which is especially the demand to motor petrol, both at home and abroadThe continuous trend risen, and the demand to heavy oil products such as heavy fuel oils is then on a declining curve.Meanwhile crude oil in the worldMatter is deteriorated increasingly, and environmental regulation is increasingly stringent, and increasingly strict requirement is proposed to oil quality.Therefore, how relatively to pass throughReasonable cost of helping realizes that heavy oil lighting and petrol and diesel oil product quality persistently upgrade and has become oil refining industry concern both at home and abroadFocus.
The main purpose of residual hydrocracking technique is to keep sulphur, nitrogen, metal in residual oil raw material etc. miscellaneous by hydrotreatingMatter content is greatly reduced, the undesirable components hydro-conversion such as condensed-nuclei aromatics, colloid, asphalitine, improves hydrogen-carbon ratio, reduces carbon residue and containsAmount, make its cracking performance be improved significantly.Fixed bed residual hydrogenation technology is a kind of heavy oil deep processing technology, equipped with spyDetermine in the fixed bed reactors of catalyst, under the hydro condition of high temperature and pressure, desulfurization is carried out to normal pressure or decompression residuum, is taken offNitrogen, demetalization etc. are one of the important means of residual oil weight-lightenings to obtain light-end products to the maximum extent.Fixed bed residual oil addsHydrogen technology is with its liquid product yield height, and good product quality, production chains are strong, and waste, waste material are few, environmental-friendly, invests backThe advantages that report rate is high, has been more and more widely used.
The setting of fixed bed residual hydrocracking process reaction part reactor is generally connected by multiple reactors or bedIt uses, requires to optimize the dosage form of catalyst according to the property of original oil, reaction condition and purpose product, according to different physicalMatter, catalyst activity and all kinds of catalyst ratios carry out grading loading.Fixed bed residual hydrogenation technology although having many advantages, such as,But in process of production, but it is easy to appear the phenomenon that reactor pressure drop increases.Industrial operation shows that reactor pressure drop increasesOne of an important factor for being confining device full production and long-term operation.Especially more reactor series connection, preposition is anti-Answer device to react load due to assuming responsibility for 70% or more demetalization, metal sulfide is deposited on catalyst bed, into operation afterInevitably there is pressure drop rapid growth in phase, and subsequent reactor is since demetalization load is obviously relatively low, pressure drop increase compared withSlowly.This affects the cycle of operation and the device of device there have been front reactor and the distribution of rear portion reactor load are unevenStable operation.
CN103059928A discloses a kind of hydrotreater and its application and process for hydrogenating residual oil.The invention mentionsFor a kind of and its processing unit, which includes primary concatenated plus hydrogen insured unit and main hydrotreating unit.Described addsHydrogen protection location includes in parallel main hydrogenation protecting reactor and spare hydrogenation protecting reactor, and main hydrogenation protecting reactorVolume is greater than stand-by protection reactor.In hydroprocessing processes, main hydrogenation protecting reactor and spare hydrogenation protecting reactorIt is used alternatingly.Main hydrogenation protecting reactor and spare hydrogenation protecting reactor handover operation can be processed height by the processThe residual oil of calcium high metal content, the disadvantage is that the reactor that left unused, increasing investment reduces reactor utilization rate, and cannotLead reactor pressure drop growing concern is solved from not catching up with.
CN1393515A discloses a kind of method of residual hydrocracking.This method is in heavy resid hydrogenation reaction systemFirst reactor add one or more feed inlets, change simultaneously original catalyst grade and match, when an anticatalyst bedWhen pressure drop designs 0.4~0.8 times of pressure drop for device, next feed inlet is successively used instead, while original feed inlet can be into circulationThe miscella of oil or recycle oil and original oil can be effectively prevented bed pressure drop with the technique and extend the operation cycle of device,And the processing capacity of device can be increased, help to improve flow distribution.The disadvantage is that inductor manufacturing cost increases, make initialPressure drop increases, and device inner volume utilization rate reduces etc..
CN103059931A discloses a kind of method of residual hydrocracking.This method is in hydrotreating reaction conditionUnder, residual oil raw material and hydrogen once pass through concatenated more reactors, when device operation 700~4000 it is small when after carry out shunting behaviourMake, reduce an anti-inlet amount or keep an anti-inlet amount constant, increase that one is anti-and the last one reactor among each reactorInlet amount, increased feed residue intermediate reactor entrance inject.This method is delayed by changing each anti-feed loadingThe growth of pressure drop is solved, but cannot fundamentally change the growth trend of lead reactor pressure drop, from the point of view of industrial actual motion, pressure dropThe design upper limit can be quickly reached once increasing, and changes the stable operation that each anti-entrance charging is unfavorable for device.
CN1119397C discloses a kind of hydrogenation and catalystic cracking combined process for residual oil, in this method, residual oilEnter residual hydrogenation equipment together with clarified oil, reacted in the presence of hydrogen and hydrogenation catalyst, heavy-cycle oil is being catalyzedIt is recycled inside cracking unit；Resulting slurry oil is reacted through the isolated clarified oil of separator, is back to hydrogenation plant.But oilSlurry enters residual hydrocracking device, and the easy green coke object in slurry oil will will increase the carbon deposit of hydrogenation catalyst, reduces plus hydrogen is urgedThe hydrogenation activity of agent and operation cycle, and heavy-cycle oil is inside catalytic cracking unit.Therefore, the method is to reduction cokeYield, raising product quality are limited.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of combined technical methods and system for handling low grade oils.The process process is simple, it is only necessary to carry out simple modifications to existing apparatus, so that it may substantially extend the operation cycle of device,And the utilization efficiency of catalyst can be made to realize and maximized.The method of the present invention splits fixed bed hydrogenation processing and boiling bed hydrogenationChange organic assembling, heavy oil feedstock can guarantee maximum journey using boiling bed hydrogenation cracking processing after fixed bed hydrogenation modifiesDegree obtains light-end products.
Existing heavy Oil Hydrotreating Processes, all reactors use concatenated process flow, it is therefore desirable to anti-in FirstDevice is answered to load a large amount of protective agent to deposit the impurity and dirt in raw material, operation will lead in First protection reactor in this wayFor the antigravity system of filling since activity is lower, demetalization load is lower, has arrived device end-of-run reactor in some casesPressure drop is still very low, so that the ability that is de-, holding metallic compound of monolithic catalyst reduces.If improving its catalyst activity againIt will cause the rapid growth of pressure drop, shorten the cycle of operation, and subsequent catalyst performance plays completely not yet, keeps FirstProtection reactor catalyst activity appropriate be difficult to control, and during residual hydrogenation equipment whole service there are it is many becauseElement such as Fe in urgent shutting down, feedstock property fluctuation or raw material, Ca impurity increases suddenly, therefore common practice is stillIt is to maintain an anti-protection lower reactivity of reactor catalyst, main function intercepts and deposit the impurity and dirt in raw materialObject only carries out lower demetalization reaction, and the usually reactor reaction temperature rise is lower, and pressure drop maintains in the whole service periodIn lower level, this requires that loading a large amount of catalyst for demetalation in subsequent demetalization reactor is substantially carried out de- goldBelong to reaction and provide enough spaces to accommodate the metallic compound of hydrogenation and removing and carbon distribution, inevitably causes in this wayThe demetalization reactor deposits a large amount of metal, and demetalization reaction load is larger, usually the reactor reaction temperature rise highest, to the greatest extentPipe initial operating stage reactor pressure decrease is lower, but the pressure drop to operation to the mid-term or later period pressure drop reactor at first increasesIt is long, and growth is most fast, becomes the principal element for restricting the cycle of operation.
The present invention provides a kind of combined technical method for handling low grade oils, and the process includes the following contents:
(1) heavy oil feedstock, fixed bed hydrogenation processing reaction zone generate after oil is mixed with hydrogen and enter boiling bed hydrogenation crackingReaction zone is reacted, and obtains dry gas, liquefied gas, gasoline, diesel oil and heavy distillat after reaction effluent separation；
(2) heavy distillat obtained in step (1) is successively passed through the fixed bed hydrogenation pretreatment reaction area being arranged in series and is consolidatedFixed bed hydrotreating reaction area, the generation oil that fixed bed hydrogenation processing reaction zone obtains enter boiling bed hydrogenation cracking reaction area；
Wherein, fixed bed hydrogenation pretreatment reaction area includes at least two weighted BMO spaces reactions being arranged in parallelDevice, when the pressure drop of any one weighted BMO spaces reactor in fixed bed hydrogenation pretreatment reaction area reaches predetermined value,The weighted BMO spaces reactor that pressure drop reaches predetermined value is cut out from fixed bed hydrogenation pretreatment reaction area, and by the fixationBed hydroprocessing pretreatment reaction area, the pressure drop reach the weighted BMO spaces reactor of predetermined value and the fixed bed hydrogenation is handled insteadArea is answered to be connected in turn in series, wherein the predetermined value designs the 50%~80% of the upper limit for pressure drop, preferably60%~70%.
In the combined technical method of the processing low grade oils, in the reaction initial stage, the fixed bed hydrogenation is located in advanceManaging reaction zone includes 2~6, preferably includes 3~4 weighted BMO spaces reactors being arranged in parallel.
In the preferred case, when the pressure drop of a weighted BMO spaces reactor reaches the predetermined value, this plus hydrogen is pre-Treatment reactor is cut out from fixed bed hydrogenation pretreatment reaction area, which is named as to cut out plus hydrogenPreatreating reactors I, and by fixed bed hydrogenation pretreatment reaction area, the weighted BMO spaces reactor I cut out and instituteIt states fixed bed hydrogenation processing reaction zone to be connected in turn in series, at this time the weighted BMO spaces reactor I cut outCharging be all weighted BMO spaces reactors in parallel reaction effluent；When the pressure drop of next weighted BMO spaces reactor reachesWhen to the predetermined value, which is cut out from fixed bed hydrogenation pretreatment reaction area, this plus hydrogen is pre-Treatment reactor is named as the weighted BMO spaces reactor II cut out, and by fixed bed hydrogenation pretreatment reaction area, describedThe weighted BMO spaces reactor II, the weighted BMO spaces reactor I cut out that cut out and fixed bed hydrogenation processing reactionArea is connected in turn in series；In the manner described above, until all weighted BMO spaces reactors are all with stringThe mode of connection connects.
In the combined technical method of the processing low grade oils, all in fixed bed hydrogenation pretreatment reaction area plus hydrogenThe pressure drop of preatreating reactors does not reach predetermined value simultaneously, two neighboring anti-closest to the weighted BMO spaces for reaching pressure drop predetermined valueThe time difference for answering device to reach its pressure drop predetermined value is not less than the 20% of the whole device cycle of operation, preferably 20%~60%.
In the combined technical method of the processing low grade oils, setting and/or catalyst bed by operating conditionIt is predetermined that the difference of property makes in fixed bed hydrogenation pretreatment reaction area each weighted BMO spaces reactor not reach pressure drop simultaneouslyValue, for example, can by control catalyst packing height different in each weighted BMO spaces reactor, different inlet amounies,Different Catalyst packing density is used under the conditions of different feed properties, different operating conditions and identical filling heightOne of or various ways when making each weighted BMO spaces reactor difference in fixed bed hydrogenation pretreatment reaction area to realizeReach pressure drop predetermined value.
In the combined technical method of the processing low grade oils, when by controlling phase in each weighted BMO spaces reactorWith filling height under the conditions of by the way of different Catalyst packing density to realize when, locate in advance in the fixed bed hydrogenationIn each weighted BMO spaces reactor for managing reaction zone parallel connection, maximum loading density can be 400kg/m3~600kg/m3, preferablyFor 450kg/m3~550kg/m3；Minimum loading density can be 300kg/m3~550kg/m3, preferably 350kg/m3~450kg/m3.Preferably, the Catalyst packing density difference of the immediate two weighted BMO spaces reactors of loading density is50kg/m3~200kg/m3, preferably 80kg/m3~150kg/m3.The difference loading density can be urged by different types ofThe realization of agent grading loading, such as can be by hydrogenation protecting agent, Hydrodemetalation catalyst, Hydrobon catalyst with differentRatio realizes that the Catalyst packing density in each weighted BMO spaces reactor is different.
In the combined technical method of the processing low grade oils, when by controlling in each weighted BMO spaces reactor notWith inlet amount mode come when realizing, the ratio between the feed volume air speed of the immediate two weighted BMO spaces reactors of inlet amountIt can be 1.1 ~ 3:1, preferably 1.1 ~ 1.5:1.
In the combined technical method of the processing low grade oils, when by controlling in each weighted BMO spaces reactor notWith feed properties mode come when realizing, the tenor difference of the immediate two weighted BMO spaces reactors of feed propertiesIt can be the 5 μ g/g of μ g/g ~ 50, preferably 10 μ of μ g/g ~ 30 g/g.
In the combined technical method of the processing low grade oils, when by controlling in each weighted BMO spaces reactor notWith operating condition mode come when realizing, control operating pressure and the immediate two weighted BMO spaces reactors of volume space velocityOperating condition in, operation temperature difference can be 2 DEG C ~ 30 DEG C, preferably 5 DEG C ~ 20 DEG C, or control operating pressure and operationIn the operating condition of the immediate two weighted BMO spaces reactors of temperature, volume space velocity difference is 0.1 h -1~10 h-1, preferablyFor 0.2 h -1~5 h -1。
In the combined technical method of the processing low grade oils, according to Flow of Goods and Materials direction, each weighted BMO spaces are anti-It answers and successively loads hydrogenation protecting agent, Hydrodemetalation catalyst and optional Hydrobon catalyst in device；Each plus hydrogen is located in advanceReason reactor can set according to itself process conditions and not load Hydrobon catalyst, can also be set according to itself process conditionsA certain proportion of Hydrobon catalyst is loaded after Hydrodemetalation catalyst；The reactor in the hydrotreating reaction area is successivelyLoad Hydrobon catalyst and hydrodenitrogeneration carbon residue reforming catalyst.
In the combined technical method of the processing low grade oils, the operation item in fixed bed hydrogenation pretreatment reaction areaPart are as follows: temperature is 370 DEG C~420 DEG C, preferably 380 DEG C~400 DEG C；Pressure be 10MPa~25MPa, preferably 15MPa~20MPa；Hydrogen to oil volume ratio is 300~1500, preferably 500~800；Volume space velocity is 0.15h when raw material oil liquid-1~2h-1,Preferably 0.3h-1~1h-1.The residual hydrogenation that the average reaction temperature of weighted BMO spaces reaction zone is apparently higher than the prior art is de-The reaction temperature of metallic reactors, the residuum hydrogenating and metal-eliminating reaction temperature of the prior art are usually 350 DEG C~390 DEG C.WeThe fixed bed hydrogenation pretreatment reaction area of method middle front part setting eliminates pressure drop and increases limits device by the optimization of process flowThe unfavorable factor in steady running period can operate at high temperature, and what in addition relatively high reaction temperature was conducive to be loaded urgesThe performance of agent system performance is conducive to the removing of the hydro-conversion and impurity of macromolecular.
In the combined technical method of the processing low grade oils, the fixed bed hydrogenation processing reaction zone may include 1~5 hydrotreating reactors being arranged in series preferably include 1~2 hydrotreating reactor being arranged in series.
In the combined technical method of the processing low grade oils, the operating condition of the fixed bed hydrogenation processing reaction zoneAre as follows: temperature is 370 DEG C~430 DEG C, preferably 380 DEG C~410 DEG C；Pressure be 10MPa~25MPa, preferably 15MPa~20MPa；Hydrogen to oil volume ratio is 300~1500, preferably 400~800；Volume space velocity is 0.15h when raw material oil liquid-1~0.8h-1, preferably 0.2h-1~0.6h-1。
In the combined technical method of the processing low grade oils, the heavy oil feedstock can selected from atmospheric residue and/orDecompression residuum.The heavy oil feedstock can mix refining straight-run gas oil and/or decompressed wax oil, or can mix refining secondary operation wax oilAnd/or FCC recycle oil.
It is described processing low grade oils combined technical method in, boiling bed hydrogenation cracking reaction area can be set 1 withOn boiling bed hydrogenation cracker, be preferably provided with 1 or 2 boiling bed hydrogenation cracker being arranged in series, series connection is setSet the boiling bed hydrogenation cracker for referring to that reaction mass passes sequentially through setting.Boiling bed hydrogenation cracker can be using existingThere is the conventional fluidized bed reactor in technology.The reaction condition in boiling bed hydrogenation cracking reaction area can be according to feed properties and anti-Conversion requirements are answered specifically to determine, generally are as follows: reaction temperature is 380~450 DEG C, preferably 390~430 DEG C；Reaction pressure is12~25MPa, preferably 14.0~16MPa；Hydrogen to oil volume ratio 500:1 ~ 1000:1, preferably 600:1~900:1；Liquid bulkProduct air speed (LHSV) is 0.3~5.0h-1, preferably 0.3~2.0h-1；Boiling bed hydrogenation processing control conversion ratio is with maximum metaplasiaProduce lighting oil product main target.
The present invention also provides a kind of systems for handling low grade oils, and the system comprises boiling bed hydrogenation cracking reactionsArea, fixed bed hydrogenation pretreatment reaction area, fixed bed hydrogenation processing reaction zone, sensing unit and control unit, the heavy oil are formerMaterial is connect through feeding line with boiling bed hydrogenation cracking reaction area feed inlet, after the separation of boiling bed hydrogenation cracking reaction area's effluentObtain dry gas, liquefied gas, gasoline, diesel oil and heavy distillat；Wherein double distilled lease making pipeline and fixed bed hydrogenation pretreatment reaction areaFeeding line connection, the generation oil of fixed bed hydrogenation processing reaction zone through pipeline and boiling bed hydrogenation cracking reaction area intoMaterial mouth connection；
Wherein, fixed bed hydrogenation pretreatment reaction area and fixed bed hydrogenation processing reaction zone are sequentially connected in series setting, instituteStating fixed bed hydrogenation pretreatment reaction area includes at least two weighted BMO spaces reactors, and any one weighted BMO spaces reactsThe discharge port of device and the feed inlet of the feed inlet of other weighted BMO spaces reactors and fixed bed hydrogenation processing reaction zone are equalIt is connected by the pipeline with control valve, wherein the sensing unit is used to detect the pressure in each weighted BMO spaces reactorDrop, described control unit for receiving the pressure drop signal from the sensing unit, and according to the pressure drop signal control with it is eachThe corresponding control valve of weighted BMO spaces reactor, so that when any one in each weighted BMO spaces reactor parallel with one anotherWhen the pressure drop of weighted BMO spaces reactor reaches predetermined value, pressure drop is reached into the weighted BMO spaces reactor of predetermined value from adding hydrogen pre-Cut out in processing reaction zone, and fixed bed hydrogenation pretreatment reaction area, the pressure drop are reached into predetermined value plus hydrogen locate in advanceReason reactor, the hydrotreating reaction area are connected in turn in series.
In processing low grade oils system of the present invention, fixed bed hydrogenation pretreatment reaction area includes 3~6, excellentIt is selected as 3~4 weighted BMO spaces reactors being arranged in parallel；The fixed bed hydrogenation processing reaction zone includes that 1~5 series connection is setThe hydrotreating reactor set preferably includes 1~2 hydrotreating reactor being arranged in series, the boiling bed hydrogenation crackingReaction zone includes 1 or more boiling bed hydrogenation cracker, preferably includes 1 or 2 boiling bed hydrogenation cracking being arranged in seriesReactor.
In processing low grade oils system of the present invention, described control unit is believed according to the pressure drop from the sensing unitNumber corresponding with each weighted BMO spaces reactor control valve of control, so that:
When the pressure drop of a weighted BMO spaces reactor reaches the predetermined value, by the weighted BMO spaces reactor from admittedlyIt is cut out in fixed bed weighted BMO spaces reaction zone, which is named as to the weighted BMO spaces reactor I cut out,And fixed bed hydrogenation pretreatment reaction area, the weighted BMO spaces reactor I cut out, the fixed bed hydrogenation are handledReaction zone is connected in turn in series；
When the pressure drop of next weighted BMO spaces reactor reaches the predetermined value, by the weighted BMO spaces reactor fromFixed bed hydrogenation pretreatment reaction is cut out in area, which is named as to the weighted BMO spaces reactor cut outII, and by fixed bed hydrogenation pretreatment reaction area, the weighted BMO spaces reactor II cut out, it is described cut out plus hydrogenPreatreating reactors I, fixed bed hydrogenation processing reaction zone are connected in turn in series；
In the manner described above, until all weighted BMO spaces reactors are all connected in series to.
Compared with prior art, the combined technical method of the processing low grade oils provided by the invention and system haveFollowing advantage:
It (1) include multiple weighted BMO spaces reactors in parallel in fixed bed hydrogenation pretreatment reaction area, so that wholeA catalyst system takes off/holds metal ability and is increased dramatically.
(2) in heavy oil hydrogenation treatment method of the present invention, when the pressure drop of a weighted BMO spaces reactor rises toWhen predetermined value, it is cut out from fixed bed hydrogenation pretreatment reaction area, and by the change of process flow, keep its pressure drop no longer fastSpeed increases, but slowly increases can control in range until device is stopped work, and then makes some weighted BMO spaces reactorPressure drop will not restrict the cycle of operation of whole device.
(3) in heavy oil hydrogenation treatment method of the present invention, by will be each in fixed bed hydrogenation pretreatment reaction areaTo solve weighted BMO spaces reactor pressure decrease quick from the adjustment for being parallel to series connection handover operation mode for weighted BMO spaces reactorThe problem of growth, while increasing the operating flexibility and raw material adaptability of device.
(4) big by setting weighted BMO spaces reactor parallel form in heavy oil hydrogenation treatment method of the present inventionThe appearance amount of metal that width increases catalyst system enables the growth of device pressure drop to be controlled so that the stability of system enhancesSystem extends the device cycle of operation.
(5) heavy oil hydrogenation treatment method of the present invention can utmostly realize the synchronous inactivation of all kinds of catalyst, fromAnd the operational efficiency of device is improved, it increases economic efficiency.
(6) in heavy oil hydrogenation treatment method of the present invention, by weighted BMO spaces reaction zone catalyst performanceWith optimizing and revising for technological parameter, the cooperation of carbon residue catalyst is taken off with subsequent high activity desulfurization, so that improving whole catalysisDesulfurization takes off carbon residue performance and is guaranteed while de-/appearance metal ability of agent.
(7) the characteristics of present invention passes through fixed bed and bubbling bed combined process, has not only played respective technique, but also the two is hadThe combination of machine improves the light oil yield of device on the whole, increases economic efficiency.
Detailed description of the invention
Fig. 1 is the combined technical method and system schematic of processing low grade oils of the present invention.
Fig. 2 is that fixed bed hydrogenation pretreatment is anti-in the combined technical method and system of processing low grade oils of the present inventionArea and fixed bed hydrogenation is answered to handle reaction zone schematic diagram.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specificEmbodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges orValue should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectivelyIt can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or moreNew numberical range, these numberical ranges should be considered as specific open herein.
In the combined technical method and system of processing low grade oils of the present invention, the predetermined value designs for pressure dropThe 50%~80% of the upper limit, for example, 50%, 52%, 54%, 55%, 56%, 57%, 58%, 60%, 61%, 62%, 63%, 64%, 65%, 66%,67%, 68%, 69%, 70%, 71%, 72%, 74%, 75%, 76%, 78%, 80% and in them range composed by any two value itBetween arbitrary value.In the preferred case, the predetermined value designs the 60%~70% of the upper limit for pressure drop.In the present invention, the pressureThe drop design upper limit refers to the maximum value of reactor pressure decrease, and when reactor pressure decrease reaches the value, reaction system needs to stop work, describedIt is usually the .0MPa of 0.7 MPa ~ 1 that pressure drop, which designs the upper limit,.
In the combined technical method and system of processing low grade oils of the present invention, all weighted BMO spaces reactionsThe pressure drop of device does not reach predetermined value simultaneously.In the preferred case, two neighboring to locate in advance closest to reach pressure drop predetermined value plus hydrogenThe time difference that reason reactor reaches its pressure drop predetermined value is not less than the 20% of the whole service period, preferably whole service period20-60%, for example, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%.In the present invention, the whole service period isRefer to heavy-oil hydrogenation processing system from bringing into operation to the time experienced of stopping work.
In the combined technical method and system of processing low grade oils of the present invention, the fixed bed hydrogenation pretreatmentHydrogenation protecting agent can be loaded in each weighted BMO spaces reactor of reaction zone, Hydrodemetalation catalyst, hydrodesulfurization are urgedOne of agent is a variety of, can be loaded in the reactor of the fixed bed hydrogenation processing reaction zone Hydrobon catalyst andOne of hydrodenitrogeneration carbon residue reforming catalyst is a variety of.
In a preferred embodiment, it according to Flow of Goods and Materials direction, is successively loaded in each weighted BMO spaces reactorHydrogenation protecting agent, Hydrodemetalation catalyst and optional Hydrobon catalyst；The reaction in the hydrotreating reaction areaDevice successively loads Hydrobon catalyst and hydrodenitrogeneration carbon residue reforming catalyst.It is filled according to the catalyst of the preferred embodimentEmbankment formula, so that de-/appearance metal ability of whole system is increased dramatically, while the adjustment matched by catalyst grade is so that eachThe pressure drop of a weighted BMO spaces reactor increases in control range.In fixed bed hydrogenation pretreatment reaction area it is in parallel each plusThe catalyst system of hydrogen pretreatment reactor filling with it is de-/hold based on metal function so that while demetalization performance boost, by forceChange the ability to the hydro-conversion of such as gum asphalt of macromolecular in raw material, establishes base for successive depths desulfurization and the conversion of carbon residuePlinth, so that hydrodesulfurizationreaction reaction zone is conducive to further deep reaction, therefore, compared with routine techniques, side of the present inventionAlthough the ratio of Hydrodemetalation catalyst improves in method, the hydro-conversion of whole desulphurizing activated and carbon residuePerformance is not only improved without reducing instead.
In the present invention, the hydrogenation protecting agent, the Hydrodemetalation catalyst, the Hydrobon catalyst and instituteStating hydrodenitrogeneration carbon residue reforming catalyst all can be the conventional use of catalyst of fixed bed heavy-oil hydrogenation treatment process.These are urgedAgent usually with porous refractory inorganic oxide (such as aluminium oxide) for carrier, group VIB and/or group VIII metal (such as W, Mo,Co, Ni etc.) oxide be active component, be selectively added the catalyst of the elements such as various other auxiliary agents such as P, Si, F, B.For example, the FZC series heavy oil hydrogenating treatment catalyst produced by Sinopec Group's catalyst branch.
In the present invention, the ebullated bed of catalyst this field routine used in the boiling bed hydrogenation cracker addsHydrogen catalyst, generally using aluminium oxide as carrier, particle is spherical shape, and diameter is 0.1~0.8mm, preferably 0.1~0.6mm, millDamage≤2.0wt%, catalyst specific surface are 100~300m2/ g, bore dia at least account for the 70% of total pore volume in the hole of 5~20nm；WithPoidometer, catalyst contain VI B family metal oxide (such as MoO3) 12.0%~30.0%, preferably 15.0%~25.0%, contain VIII raceMetal oxide (such as NiO or CoO) 0.5%~10.0%, preferably 2.0%~8.0%.Containing at least one auxiliary agent, selected from as followsSeveral elements: B, Ca, F, Mg, P, Si, Ti etc., auxiliary agent content are 1.0%~8.0%.
In the combined technical method and system of processing low grade oils of the present invention, the heavy oil feedstock be can be oftenBallast oil or decompression residuum, usually also containing one of straight-run gas oil, decompressed wax oil, secondary operation wax oil and FCC recycle oilOr it is a variety of.The property of the heavy oil feedstock can be with are as follows: sulfur content is not more than 4 weight %, and nitrogen content is not more than 0.7 weight %, metalContent (Ni+V) is not more than 120 μ g/g, and carbon residue is not more than 17 weight %, and asphalt content is not more than 5 weight %.
Below with reference to Fig. 1, Fig. 2 to it is of the present invention processing low grade oils combined technical method and system in carry out intoOne step explanation, but it is not thereby limiting the invention.
As shown in Figure 1 and Figure 2, heavy-oil hydrogenation processing system and heavy-oil hydrogenation processing method of the present invention includeFollowing content: heavy oil feedstock M1, fixed bed hydrogenation processing reaction zone, which generates after oil M2 is mixed with hydrogen M3, enters boiling bed hydrogenationCracking reaction area R3 is reacted, and dry gas M4, liquefied gas M5, gasoline M6, diesel oil M7 and heavy distillat M8 are obtained after separation, described heavyFraction M8 enters the fixed bed hydrogenation pretreatment reaction area R1 being arranged in series through pipeline and fixed bed hydrogenation handles reaction zone R2, instituteState fixed bed hydrogenation processing reaction zone R2 generation oil M2 mixed with heavy oil feedstock M1 after be used as boiling bed hydrogenation cracking reaction areaThe charging of R3.Fixed bed hydrogenation pretreatment reaction area R1 as shown in Figure 2 includes that three weighted BMO spaces being arranged in parallel are anti-Device is answered, respectively weighted BMO spaces reactor A, weighted BMO spaces reactor B, weighted BMO spaces reactor C, described plus hydrogen is located in advanceManage reactor A, weighted BMO spaces reactor B, weighted BMO spaces reactor C feed inlet respectively with feeding line 1, feeding line2 and feeding line 3 connect, three tunnels of the outlet of the weighted BMO spaces reactor A point, the first via is through pipeline 6 and weighted BMO spacesThe feed inlet of reactor B connects, and the second tunnel is connect through pipeline 7 with the feed inlet of weighted BMO spaces reactor C, and third road is through pipeline10 connect with the feed inlet of hydrotreating reactor D；Three tunnels of the outlet of the weighted BMO spaces reactor B point, the first via is through pipeLine 4 is connect with the feed inlet of weighted BMO spaces reactor A, and the second tunnel obtains feed inlet through pipeline 5 and weighted BMO spaces reactor C and connectsIt connects, third road is connect through pipeline 11 with the feed inlet of hydrotreating reactor D；The outlet of the weighted BMO spaces reactor C pointThree tunnels, the first via are connect through pipeline 8 with the feed inlet of weighted BMO spaces reactor A, and the second tunnel is anti-through pipeline 9 and weighted BMO spacesThe feed inlet of device B is answered to connect, third road is connect through pipeline 12 with the feed inlet of hydrotreating reactor D；It is arranged on the pipeline 1There is valve 101, valve 102 is provided on the pipeline 2, valve 103 is provided on the pipeline 3, is provided on the pipeline 4Valve 104 is provided with valve 105 on the pipeline 5, valve 106 is provided on the pipeline 6, is provided with valve on the pipeline 7Door 107 is provided with valve 108 on the pipeline 8, valve 109 is provided on the pipeline 9, is provided with valve on the pipeline 10Door 1010 is provided with valve 1011 on the pipeline 11, valve 1012, the hydrotreating reaction is provided on the pipeline 12The generation oil M2 that device obtains enters boiling bed hydrogenation reactor after mixing with heavy oil feedstock M1 and carries out cracking reaction.Described plus hydrogen is pre-It is each provided in treatment reactor A, the weighted BMO spaces reactor B and the weighted BMO spaces reactor C for monitoringThe sensing unit (not shown) of pressure drop, and the heavy-oil hydrogenation processing system further includes that control unit (is not shown in figureOut), for receiving the pressure drop signal from the sensing unit, and it is anti-with each weighted BMO spaces according to pressure drop signal controlAnswer the corresponding valve of device.
In above-mentioned heavy-oil hydrogenation processing system, weighted BMO spaces reactor A, weighted BMO spaces reactor B and add hydrogen it is pre-Treatment reactor C can be inactivated in any order, it is preferred to use following six kinds of modes switch over operation:
Mode 1: according to weighted BMO spaces reactor A, weighted BMO spaces reactor B, the sequence of weighted BMO spaces reactor CReach pressure drop predetermined value.
(1) when going into operation, pipeline 1, pipeline 2, pipeline 3, pipeline 10, pipeline 11, the valve 101 on pipeline 12, valve 102,Valve 103, valve 1010, valve 1011, valve 1012 are opened, pipeline 4, pipeline 5, pipeline 6, pipeline 7, pipeline 8, on pipeline 9Valve 104, valve 105, valve 106, valve 107, valve 108, valve 109 close；
(2) it is reacted with sensing unit detection weighted BMO spaces reactor A, weighted BMO spaces reactor B and weighted BMO spacesThe pressure drop of device C is reacted when the pressure drop of weighted BMO spaces reactor A reaches predetermined value from the weighted BMO spaces are corresponded toThe pressure drop signal of the sensing unit of device A passes to control unit, and control unit is received to execute after the signal and be adjusted to valveControl specifically closes valve 101, the valve 1011 of pipeline 11 and the valve 1012 of pipeline 12 of feeding line 1, opens pipeline 8On valve 108 and pipeline 4 on valve 104 so that weighted BMO spaces reaction zone (including weighted BMO spaces reactor B and plusHydrogen pretreatment reactor C), weighted BMO spaces reactor A and hydrodesulfurizationreaction reaction zone form series connection, complete at this time once by parallel connectionTo concatenated handover operation；
(3) it when the pressure drop of weighted BMO spaces reactor B reaches predetermined value, is reacted from the weighted BMO spaces are corresponded toThe pressure drop signal of the sensing unit of device B passes to control unit, and control unit is received to execute after the signal and be adjusted to valveControl specifically closes the valve 102 of feeding line 2, the valve 108 of pipeline 8, the valve 109 on pipeline 9 is opened, so that plus hydrogenPreatreating reactors C, weighted BMO spaces reactor B, weighted BMO spaces reactor A and hydrodesulfurizationreaction reaction zone form series connection, thisWhen complete the 2nd time by being parallel to concatenated handover operation；
(4) when the pressure drop of weighted BMO spaces reactor C reaches the design upper limit, entire reaction system needs shutdown process.
Mode 2: according to weighted BMO spaces reactor A, weighted BMO spaces reactor C, weighted BMO spaces reactor B sequenceReach pressure drop predetermined value.
(1) when going into operation, pipeline 1, pipeline 2, pipeline 3, pipeline 10, pipeline 11, the valve 101 on pipeline 12, valve 102,Valve 103, valve 1010, valve 1011, valve 1012 are opened, pipeline 4, pipeline 5, pipeline 6, pipeline 7, pipeline 8, on pipeline 9Valve 104, valve 105, valve 106, valve 107, valve 108, valve 109 close；
(2) it is reacted with sensing unit detection weighted BMO spaces reactor A, weighted BMO spaces reactor B and weighted BMO spacesThe pressure drop of device C is reacted when the pressure drop of weighted BMO spaces reactor A reaches predetermined value from the weighted BMO spaces are corresponded toThe pressure drop signal of the sensing unit of device A passes to control unit, and control unit is received to execute after the signal and be adjusted to valveControl specifically closes valve 101, the valve 1011 of pipeline 11 and the valve 1012 of pipeline 12 of feeding line 1, opens pipeline 8On valve 108 and pipeline 4 on valve 104 so that weighted BMO spaces reaction zone (including weighted BMO spaces reactor B and plusHydrogen pretreatment reactor C), weighted BMO spaces reactor A and hydrodesulfurizationreaction reaction zone form series connection, complete at this time once by parallel connectionTo concatenated handover operation；
(3) it when the pressure drop of weighted BMO spaces reactor C reaches predetermined value, is reacted from the weighted BMO spaces are corresponded toThe pressure drop signal of the sensing unit of device C passes to control unit, and control unit is received to execute after the signal and be adjusted to valveControl specifically closes the valve 103 of feeding line 3, the valve 104 of pipeline 4, the valve 105 on pipeline 5 is opened, so that plus hydrogenPreatreating reactors B, weighted BMO spaces reactor C, weighted BMO spaces reactor A and hydrodesulfurizationreaction reaction zone form series connection, thisWhen complete the 2nd time by being parallel to concatenated handover operation；
(4) when the pressure drop of weighted BMO spaces reactor C reaches predetermined value, entire reaction system needs shutdown process.
Mode 3: according to weighted BMO spaces reactor B, weighted BMO spaces reactor C, weighted BMO spaces reactor A sequenceReach pressure drop predetermined value.
(1) when going into operation, pipeline 1, pipeline 2, pipeline 3, pipeline 10, pipeline 11, the valve 101 on pipeline 12, valve 102,Valve 103, valve 1010, valve 1011, valve 1012 are opened, pipeline 4, pipeline 5, pipeline 6, pipeline 7, pipeline 8, on pipeline 9Valve 104, valve 105, valve 106, valve 107, valve 108, valve 109 close；
(2) it is reacted with sensing unit detection weighted BMO spaces reactor A, weighted BMO spaces reactor B and weighted BMO spacesThe pressure drop of device C is reacted when the pressure drop of weighted BMO spaces reactor B reaches predetermined value from the weighted BMO spaces are corresponded toThe pressure drop signal of the sensing unit of device B passes to control unit, and control unit is received to execute after the signal and be adjusted to valveControl specifically closes valve 102, the valve 1010 of pipeline 10 and the valve 1012 of pipeline 12 of feeding line 2, opens pipeline 9On valve 109 and pipeline 6 on valve 106 so that weighted BMO spaces reaction zone (including weighted BMO spaces reactor A and plusHydrogen pretreatment reactor C), weighted BMO spaces reactor B and hydrodesulfurizationreaction reaction zone form series connection, complete at this time once by parallel connectionTo concatenated handover operation；
(3) it when the pressure drop of weighted BMO spaces reactor C reaches predetermined value, is reacted from the weighted BMO spaces are corresponded toThe pressure drop signal of the sensing unit of device C passes to control unit, and control unit is received to execute after the signal and be adjusted to valveControl specifically closes the valve 103 of feeding line 3, the valve 106 of pipeline 6, the valve 107 on pipeline 7 is opened, so that plus hydrogenPreatreating reactors A, weighted BMO spaces reactor C, weighted BMO spaces reactor B and hydrodesulfurizationreaction reaction zone form series connection, thisWhen complete the 2nd time by being parallel to concatenated handover operation；
(4) when the pressure drop of weighted BMO spaces reactor A reaches predetermined value, entire reaction system needs shutdown process.
Mode 4: according to weighted BMO spaces reactor B, weighted BMO spaces reactor A, the sequence of weighted BMO spaces reactor CReach pressure drop predetermined value.
(1) when going into operation, pipeline 1, pipeline 2, pipeline 3, pipeline 10, pipeline 11, the valve 101 on pipeline 12, valve 102,Valve 103, valve 1010, valve 1011, valve 1012 are opened, pipeline 4, pipeline 5, pipeline 6, pipeline 7, pipeline 8, on pipeline 9Valve 104, valve 105, valve 106, valve 107, valve 108, valve 109 close；
(2) it is reacted with sensing unit detection weighted BMO spaces reactor A, weighted BMO spaces reactor B and weighted BMO spacesThe pressure drop of device C is reacted when the pressure drop of weighted BMO spaces reactor B reaches predetermined value from the weighted BMO spaces are corresponded toThe pressure drop signal of the sensing unit of device B passes to control unit, and control unit is received to execute after the signal and be adjusted to valveControl specifically closes valve 102, the valve 1010 of pipeline 10 and the valve 1012 of pipeline 12 of feeding line 2, opens pipeline 9On valve 109 and pipeline 6 on valve 106 so that weighted BMO spaces reaction zone (including weighted BMO spaces reactor A and plusHydrogen pretreatment reactor C), weighted BMO spaces reactor B and hydrodesulfurizationreaction reaction zone form series connection, complete at this time once by parallel connectionTo concatenated handover operation；
(3) it when the pressure drop of weighted BMO spaces reactor A reaches predetermined value, is reacted from the weighted BMO spaces are corresponded toThe pressure drop signal of the sensing unit of device A passes to control unit, and control unit is received to execute after the signal and be adjusted to valveControl specifically closes the valve 101 of feeding line 1, the valve 109 of pipeline 9, the valve 108 on pipeline 8 is opened, so that plus hydrogenPreatreating reactors C, weighted BMO spaces reactor A, weighted BMO spaces reactor B and hydrodesulfurizationreaction reaction zone form series connection, thisWhen complete the 2nd time by being parallel to concatenated handover operation；
(4) when the pressure drop of weighted BMO spaces reactor C reaches predetermined value, entire reaction system needs shutdown process.
Mode 5: according to weighted BMO spaces reactor C, weighted BMO spaces reactor B, the sequence of weighted BMO spaces reactor AReach pressure drop predetermined value.
(1) when going into operation, pipeline 1, pipeline 2, pipeline 3, pipeline 10, pipeline 11, the valve 101 on pipeline 12, valve 102,Valve 103, valve 1010, valve 1011, valve 1012 are opened, pipeline 4, pipeline 5, pipeline 6, pipeline 7, pipeline 8, on pipeline 9Valve 104, valve 105, valve 106, valve 107, valve 108, valve 109 close；
(2) it is reacted with sensing unit detection weighted BMO spaces reactor A, weighted BMO spaces reactor B and weighted BMO spacesThe pressure drop of device C is reacted when the pressure drop of weighted BMO spaces reactor C reaches predetermined value from the weighted BMO spaces are corresponded toThe pressure drop signal of the sensing unit of device C passes to control unit, and control unit is received to execute after the signal and be adjusted to valveControl specifically closes valve 103, the valve 1010 of pipeline 10 and the valve 1011 of pipeline 11 of feeding line 3, opens pipeline 7On valve 107 and pipeline 5 on valve 105 so that weighted BMO spaces reaction zone (including weighted BMO spaces reactor A and plusHydrogen pretreatment reactor B), weighted BMO spaces reactor C and hydrodesulfurizationreaction reaction zone form series connection, complete at this time once by parallel connectionTo concatenated handover operation；
(3) it when the pressure drop of weighted BMO spaces reactor B reaches predetermined value, is reacted from the weighted BMO spaces are corresponded toThe pressure drop signal of the sensing unit of device B passes to control unit, and control unit is received to execute after the signal and be adjusted to valveControl specifically closes the valve 102 of feeding line 2, the valve 107 of pipeline 7, the valve 106 on pipeline 6 is opened, so that plus hydrogenPreatreating reactors A, weighted BMO spaces reactor B, weighted BMO spaces reactor C and hydrodesulfurizationreaction reaction zone form series connection, thisWhen complete the 2nd time by being parallel to concatenated handover operation；
(4) when the pressure drop of weighted BMO spaces reactor A reaches predetermined value, entire reaction system needs shutdown process.
Mode 6: according to weighted BMO spaces reactor C, weighted BMO spaces reactor A, the sequence of weighted BMO spaces reactor BReach pressure drop predetermined value.
(1) when going into operation, pipeline 1, pipeline 2, pipeline 3, pipeline 10, pipeline 11, the valve 101 on pipeline 12, valve 102,Valve 103, valve 1010, valve 1011, valve 1012 are opened, pipeline 4, pipeline 5, pipeline 6, pipeline 7, pipeline 8, on pipeline 9Valve 104, valve 105, valve 106, valve 107, valve 108, valve 109 close；
(2) it is reacted with sensing unit detection weighted BMO spaces reactor A, weighted BMO spaces reactor B and weighted BMO spacesThe pressure drop of device C is reacted when the pressure drop of weighted BMO spaces reactor C reaches predetermined value from the weighted BMO spaces are corresponded toThe pressure drop signal of the sensing unit of device C passes to control unit, and control unit is received to execute after the signal and be adjusted to valveControl specifically closes valve 103, the valve 1010 of pipeline 10 and the valve 1011 of pipeline 11 of feeding line 3, opens pipeline 7On valve 107 and pipeline 5 on valve 105 so that weighted BMO spaces reaction zone (including weighted BMO spaces reactor A and plusHydrogen pretreatment reactor B), weighted BMO spaces reactor C and hydrodesulfurizationreaction reaction zone form series connection, complete at this time once by parallel connectionTo concatenated handover operation；
(3) it when the pressure drop of weighted BMO spaces reactor A reaches predetermined value, is reacted from the weighted BMO spaces are corresponded toThe pressure drop signal of the sensing unit of device A passes to control unit, and control unit is received to execute after the signal and be adjusted to valveControl specifically closes the valve 101 of feeding line 1, the valve 105 of pipeline 5, the valve 104 on pipeline 4 is opened, so that plus hydrogenPreatreating reactors B, weighted BMO spaces reactor A, weighted BMO spaces reactor C and hydrodesulfurizationreaction reaction zone form series connection, thisWhen complete the 2nd time by being parallel to concatenated handover operation；
(4) when the pressure drop of weighted BMO spaces reactor B reaches predetermined value, entire reaction system needs shutdown process.
Illustrate effect of the invention below with reference to specific embodiment, it is used in embodiment of the present invention and comparative exampleRaw material includes three kinds, and respectively raw material A, raw material B, raw material C, specific nature is shown in Table 1, and boiling bed hydrogenation cracking reaction area is set1 boiling bed hydrogenation cracker is set, the catalyst loaded in the boiling bed hydrogenation cracker is boiling bed hydrogenationCatalyst.
Boiling bed hydrogenation catalyst prepares the spherical carrier of catalyst that average pore size is 13nm, and spherical catalyst particles are0.1-0.3mm, other catalyst preparation process are carried out referring to US7074740 and CN200710010377.5 method.Routinely sideMethod prepares Mo-Co-P solution, MoO in solution3Quality meter content is 18.00%, and content is that 3.50%, P mass contains in terms of CoO massAmount is 1.05%.Above-mentioned carrier is impregnated by incipient impregnation method with the solution and obtains final catalyst F, and specific nature is detailed in table8.Boiling bed hydrogenation reactor of the present invention be a kind of three-phase fluidized bed reactor, can using CN02109404.7,The fluidized bed reactor that CN200610134154.5 and CN200710012680.9 etc. is announced can satisfy gas, liquid, solid three-phaseIt is separated in fluidized bed reactor.It is added in 1L three-phase fluidized bed reactor using catalyst F and catalysis, in the presence of hydrogenUnder, carry out residual hydrocracking test.
The type of feed of catalyst is shown in Table 2 in the Examples 1 to 4, the filling side of catalyst in the comparative example 1~4Formula is shown in Table 3, and the reaction condition of the Examples 1 to 4 is shown in Table 4, and the reaction condition of the comparative example 1~4 is shown in Table 5, the implementationThe reaction result of example 1~4 and comparative example 1~4 is shown in Table 6.Using conventional tandem process, other difference in the comparative example 1-4It is corresponding identical as Examples 1 to 4.Weighted BMO spaces reactor A described in the embodiment of the present invention, weighted BMO spaces reactor B,Weighted BMO spaces reactor C is pattern, the identical reactor of size, reactor A, reactor B, reactor in the comparative exampleC is pattern, the identical reactor of size.
Embodiment 1
Weighted BMO spaces reactor A, weighted BMO spaces reactor B described in embodiment 1, in weighted BMO spaces reactor C allUsing raw material A, the weighted BMO spaces reactor A, weighted BMO spaces reactor B, the catalyst of weighted BMO spaces reactor C are totalLoading amount, feed properties and inlet amount are identical, and the weighted BMO spaces reactor A, weighted BMO spaces reactor B plus hydrogen are pre-Treatment reactor C, hydrotreating reactor D catalyst loaded in the way of in table 2, the operating condition is shown in Table 4, specificallyReaction result is shown in Table 6, and boiling bed hydrogenation generates oil nature and is shown in Table 7.
Embodiment 2
In embodiment 2, the weighted BMO spaces reactor A, weighted BMO spaces reactor B, in weighted BMO spaces reactor CRaw material B is all used, specific nature is shown in Table 1, and each anti-Feed space velocities are different, volume space velocity when the weighted BMO spaces reactor A liquidFor 0.20h-1, volume space velocity is 0.32h when weighted BMO spaces reactor B liquid-1, volume space velocity when weighted BMO spaces reactor C liquidFor 0.44h-1.Weighted BMO spaces reactor A, weighted BMO spaces reactor B are urged using identical in weighted BMO spaces reactor CAgent type of feed, catalyst loading pattern are shown in Table 2, and the operating condition of each reactor is shown in Table 4, and specific reaction result is shown inTable 6.
Embodiment 3
It is former using being used in raw material A, weighted BMO spaces reactor B in the weighted BMO spaces reactor A in embodiment 3Expect to use raw material C in B, weighted BMO spaces reactor C, raw material property is shown in Table 1.The weighted BMO spaces reactor A plus hydrogenPreatreating reactors B, the inlet amount of weighted BMO spaces reactor C are identical, the weighted BMO spaces reactor A, weighted BMO spacesIdentical catalyst loading pattern is used in reactor B, weighted BMO spaces reactor C, catalyst loading pattern is shown in Table 2, describedThe operating condition of each reactor is shown in Table 4, and specific reaction result is shown in Table 6.
Embodiment 4
In embodiment 4, the weighted BMO spaces reactor A, weighted BMO spaces reactor B, in weighted BMO spaces reactor CUsing raw material C as charging, and inlet amount is identical.The weighted BMO spaces reactor A average reaction temperature be 372 DEG C,Weighted BMO spaces reactor B average reaction temperature is 378 DEG C, weighted BMO spaces reactor C average reaction temperature is 383 DEG C, addsThe average reaction temperature of hydrogen treatment reactor D is 382 DEG C, and catalyst loading pattern is shown in Table 2, and the operating condition is shown in Table 4, specificallyReaction result is shown in Table 6.
Comparative example 1
Also 4 reactors, respectively reactor A, reactor B, reactor C, reactor D, reactor are used in comparative example 1A, reactor B, reactor C are connected in the form of being sequentially connected in series with reactor D.Raw materials used A property is shown in Table 1 in comparative example 1,The inlet amount and feed properties of reactor A are identical with the total feed of embodiment 1 and feed properties.It is the reactor A, anti-Answer the catalyst inventory of device B, reactor C and reactor D weighted BMO spaces reactor A corresponding with embodiment, weighted BMO spacesReactor B, weighted BMO spaces reactor C, hydrotreating reactor D are identical, but the loadings of various species catalyst areDifference is loaded in the way of in table 3, and the operating condition is shown in Table 5, and specific reaction result is shown in Table 6.
Comparative example 2
Also 4 reactors, respectively reactor A, reactor B, reactor C, reactor D, reactor are used in comparative example 2A, reactor B, reactor C are connected in the form of being sequentially connected in series with reactor D.Raw material B is used in comparative example 2, property is shown in Table1, reactor A entrance is identical with the total inlet amount of embodiment 2 and feed properties.The reactor A, reactor B, reactorThe catalyst inventory of C and reactor D weighted BMO spaces reactor A corresponding with embodiment 2, adds weighted BMO spaces reactor BHydrogen pretreatment reactor C, hydrotreating reactor D are identical, but the loadings of various species catalyst are different, according to tableMode in 3 is loaded, and the operating condition is shown in Table 5.
Comparative example 3
Also 4 reactors, respectively reactor A, reactor B, reactor C, reactor D, reactor are used in comparative example 3A, reactor B, reactor C are connected in the form of being sequentially connected in series with reactor D.Comparative example 3 uses raw material A, raw material B, raw material CEqual proportion mixed raw material, reactor A, reactor B, reactor C and reactor D use concatenated form, reactor A in comparative exampleEntrance is identical as the total inlet amount of embodiment 3 and mixed feeding property.The reactor A, reactor B, reactor C and reactorThe catalyst inventory of D weighted BMO spaces reactor A corresponding with embodiment, weighted BMO spaces reactor B, weighted BMO spaces reactionDevice C, hydrotreating reactor D are identical, but the loadings of various species catalyst are different, fill in the way of in table 3It fills out, the operating condition is shown in Table 5.
Comparative example 4
Also 4 reactors, respectively reactor A, reactor B, reactor C, reactor D, reactor are used in comparative example 4A, reactor B, reactor C are connected in the form of being sequentially connected in series with reactor D.Comparative example 4 uses raw material C, and property is shown in Table 1,Reactor A, reactor B, reactor C and reactor D use concatenated form in comparative example, and reactor A entrance and embodiment 4 are totalInlet amount it is identical with feed properties.The reactor A, reactor B, reactor C and reactor D catalyst inventory and realityIt applies example and corresponds to weighted BMO spaces reactor A, weighted BMO spaces reactor B, weighted BMO spaces reactor C, hydrotreating reactor DIt is identical, but the loadings of various species catalyst are different, load in the way of in table 3, the operating condition is shown in Table5。
1 feedstock property of table
Catalyst loading pattern in 2 Examples 1 to 4 of table
Catalyst loading pattern in 3 comparative example 1~4 of table
The reaction condition of 4 Examples 1 to 4 of table
The reaction condition of 5 comparative example 1~4 of table
6 steady running period of table and residual hydrogenation generate oil nature
7 boiling bed residual oil of table is hydrogenated to oil nature
The main physico-chemical property of 8 boiling-bed catalyst of table