CN103102940A - Combined process for hydrotreatment of heavy oil - Google Patents
Combined process for hydrotreatment of heavy oil Download PDFInfo
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Abstract
The invention relates to a combined process for hydrotreatment of heavy oil. According to the invention, fluidized bed reactors and a fixed bed reactor are combined together; raw oil and hydrogen enter from the bottom of the fluidized bed reactors and undergo a hydrogenation reaction under hydrogenation conditions of a fluidized bed; reacted materials are discharged from the top of the fluidized bed reactor, enter into the fixed bed reactor and undergo a hydrogenation reaction under hydrogenation conditions of a fixed bed, and a liquid material obtained in the fixed bed reactor is used as raw oil for a catalytic cracking unit; at least two tandem fluidized bed reactors are arranged, and a first fluidized bed reactor and a second fluidized bed reactor are switchable. For the fluidized bed reactors provided by the invention, arrangement of an on-line catalyst feeding and discharging system is not needed, so investment for equipment can be obviously reduced; the fluidized bed reactors can cooperate with the fixed bed reactor, so a running period of the equipment can be effectively prolonged, and a high-quality raw material is provided for the catalytic cracking unit.
Description
Technical field
The present invention relates to a kind of combined technical method of mink cell focus hydrotreatment, this technique is that ebullated bed and fixed-bed process organically combine, and produces catalytically cracked material.
Background technology
Oil is one of widely used important energy source of mankind nowadays, yet, because the reserve of earth oil is fixed, wherein inferior heavy oil accounts for the larger proportion of crude oil reserve, therefore, having effectively utilized limited petroleum resources, particularly taken full advantage of the inferior heavy oil resource, is the challenge that the refining of petroleum scientific worker faces.Residual oil is oil remaining residue after distillation processing, its ratio accounts for 50% before refining of petroleum, because residual oil is of poor quality, impurity and imperfect component content are high, difficulty of processing is large, causes residual oil Ceng Zuowei boiler oil to be burnt, and not only wastes limited resources, and environment has been caused pollution, how rationally utilizing mink cell focus (inferior heavy oil or residual oil etc.) is the important topic that petroleum refining industry faces.
The heavy-oil hydrogenation treatment process mainly contains fixed bed, ebullated bed, suspension bed and moving-bed.Fixed bed is because of its technology maturation, and is simple to operate and be widely applied.But fixed bed hydrogenation technique has strict restriction to metal in raw material and carbon residue content.Boiling bed hydrogenation technique is because catalyzer can add online and discharge, be conducive to keep higher catalyst activity and long-term operation, strong to adaptability to raw material, processing scheme is flexible, can the higher inferior raw material of processing metal foreign matter content, as inferior heavy oil or vacuum residuum etc.This technology not only can be used for hydrotreatment, can be used for simultaneously residual hydrocracking, and application prospect is very wide.
The Residue Hydrotreating Technology technology trends is single process residual oils/heavy oil technique, to the Combined art transition, realizes with the friendly product of process for cleanly preparing production environment the yield of maximum ground increase intermediate oil, the output of minimizing last running.Take full advantage of the characteristics of each technique, the exploitation combination process comes realize target.For example HRI and Lummus company have all developed boiling bed hydrogenation reactor and fixed bed hydrogenation reactor serial connection technology, and main purpose is that the light-end products that the boiling bed hydrogenation cracking is produced are directly refining to satisfy specification of quality.
Difference according to process raw material oil and purpose product, the ebullated bed reactor part can be divided into single reactor or several parallel series (several series that be arranged in parallel are mainly the scale problems of solving device), each series comprises several tandem reactors, the identical catalyzer of can packing in different reactor also can load different catalyzer.Ebullated bed reactor quality product out is slightly poor, needs further hydrotreatment.When the different catalyzer of three reactor charge, common one be anti-hydrodemetallation (HDM) (HDM) catalyzer of larger aperture, two anti-and three anti-be (hydrogenating desulfurization) HDS and hydrogenation conversion catalyst than high-ratio surface.When using two reactors, also can an anti-high activated catalyst that adopts, make the raw material mid-boiling point have 50% to be converted into boiling point lower than the hydro carbons of 524 ℃ (975 °F) higher than the hydro carbons of 524 ℃ (975 °F), the part desulphurization reaction occurs simultaneously; The two anti-lower catalyzer of activity that use make the hydrocracking total conversion rate reach certain level, simultaneously further desulfurization.Three reactors in series generally can reach required reaction effect.
CN101591563A discloses the combination process of a kind of boiling bed hydrogenation and fixed bed hydrogenation.This technique comprises at least one three-phase fluidized bed reactor and at least one fixed-bed reactor, stock oil with enter three-phase fluidized bed reactor after hydrogen mixes, contact with hydrogenation catalyst and carry out hydrogenation reaction.From three-phase fluidized bed reactor out gas phase and liquid phase enters respectively the lightweight oil fixed bed and the mink cell focus fixed bed is processed.
USP6270654 discloses a kind of shortening process that adopts the multistage boiling bed reactor.Adopt the ebullating bed reactor system of online displacement in this patent, the catalyzer replacement rate of first step ebullated bed reactor is 0.05-0.5Lb/Bbl.Being used for the active metallic content that the catalyzer of the first step and second stage reactor contains is 5-20wt%, and the catalyzer pore volume is 0.4-1.2mL/g, and surface-area is 100-400m
2/ g, mean pore size is 8-25nm.Reactive metal is Mo-Co or the Mo-Ni(second stage).The catalyzer that second stage reactor draws off adds in first reactor.Multistage hydrogenation process can increase filling and the liquid volume of catalyzer, reduces simultaneously the gas holdup in each reactor, therefore can improve the validity of technique.
USP4576710 discloses a kind of preparation of Hydrobon catalyst of residual oil raw material.This patent adopts two ebullated bed reactors, each sends former reactor from the spent catalyst that reactor draws off back to after regenerating, perhaps second reactor added live catalyst, and the catalyzer of second reactor first reactor of packing into, and the catalyzer in first reactor all abandoned originally.Reactive metal is Co, Mo, Ni, W and composition thereof.Carrier is aluminum oxide, silicon oxide and composition thereof.
USP4457831 discloses the secondary hydroconversion process of the hydrocarbon raw material that adopts the residual oil circulation.First step reactor uses the catalyzer of suitable diameter, transforms to produce hydrocarbon gas and liquid distillate under medium reaction conditions, and wherein lighter liquid distillate is product after separating, and residual gas and heavier liquid distillate are mixed into second stage ebullated bed reactor.Second stage reactor comprises the larger diameter catalyzer, is relatively producing the low boiling point hydrocarbon cut under severe condition.Part vacuum distillation tower substrate is sent into the productive rate that second stage ebullating bed reactor increases transformation efficiency and improves liquid hydrocarbon.Active metal component is Co, Mo, Ni, W and composition thereof.Carrier is aluminum oxide, silicon oxide and composition thereof.
USP3809644 discloses a kind of employing Multi-stage boiling bed hydrogenation process, this technique is to produce low sulphur fuel oil by the petroleum residual oil of high-sulfur and high metal content, final stage reactor used catalyst is taken out join in reactor the last period, obviously the activity of extending catalyst and useful life thereof.This technique comprises three reactors, first reactor charge catalyst for demetalation wherein, second reactor charge demetalization and desulfurization catalyst, the 3rd reactor charge desulfurization catalyst.Catalyzer adopts Mo-Co/Al
2O
3And Mo-Ni/Al
2O
3, pore volume is 0.4-0.65mL/g, is preferably 0.5-0.6 mL/g.
Above-mentioned boiling bed hydrogenation reactor all uses catalyzer to add online heat-extraction system, invest higher because ebullated bed adds heat-extraction system online, it is calculated that, the investment that catalyzer adds heat-extraction system online accounts for half left and right of boiling bed hydrogenation system gross investment, and the fault that occurs during operation is mainly adding heat-extraction system.Existing boiling bed process is mainly emphasized higher transformation efficiency, obtains more light liquid phase product, and the light liquid phase product is processed to improve the quality of products through follow-up fixed bed hydrogenation device.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of combination process of mink cell focus hydrotreatment, this technique is that ebullated bed and fixed-bed process are organically combined, and produces catalytically cracked material.This combination process investment is lower, can guarantee to synchronize with catalytic cracking running period, for catalytic cracking provides qualified stock oil.
The combined technical method of mink cell focus hydrotreatment of the present invention, comprise following content: ebullated bed reactor and fixed-bed reactor combination, stock oil and hydrogen enter bottom ebullated bed reactor, carry out hydrogenation reaction under the boiling bed hydrogenation condition, reacting rear material is discharged from reactor head and is entered fixed-bed reactor, carry out hydrogenation reaction under the fixed bed hydrogenation condition, the liquid phase material that fixed-bed reactor obtain is as the stock oil of catalytic cracking unit.
The ebullated bed reactor of at least 2 series connection of setting of the present invention, be First ebullated bed reactor (hereinafter to be referred as R101), second ebullated bed reactor (hereinafter to be referred as R102), but and the 3rd ebullated bed reactor (hereinafter to be referred as R103) of choice for use, R101 and R102 are the blocked operation mode, when namely operating, R101 or R102 switch and more catalyst changeout of reactive system, then switch back reactive system.When using three ebullated bed reactors, specifically can loop by following three kinds of modes: (1) reaction mass passes through R101-R102-R103 successively; (2) cut out R101 and carry out catalyst updating, reaction mass is successively by R102-R103, and more after raw catalyst, reaction mass passes through R101-R102-R103 to R101 successively; (3) cut out R102 and carry out catalyst change, reaction mass is successively by R101-R103, and more after raw catalyst, reaction mass passes through R101-R102-R103 to R102 successively.
In the inventive method, described series connection refers to that reaction mass is successively by described 2 or 3 ebullated bed reactors.Industrial scale according to device also can arrange two or more reaction train simultaneously, and each series comprises ebullated bed reactor and the fixed-bed reactor of at least 2 series connection as above.
In the inventive method, fixed-bed reactor can arrange 1～2 that series connection is used.
In the inventive method, R101 loads Hydrodemetalation catalyst, R102 filling Hydrodemetalation catalyst or filling Hydrobon catalyst, and R103 loads Hydrobon catalyst.Fixed-bed reactor filling Hydrobon catalyst and/or hydrodenitrogenation catalyst.The catalyzer that above-mentioned ebullated bed reactor and fixed-bed reactor use can be commercial catalyst, also can be by the existing method preparation in this area.
In the inventive method, ebullated bed reactor R101, R102, R103 do not arrange catalyzer and add online heat-extraction system, save facility investment.Press catalyst deactivation speed the switching time of R101 or R102 and determine, R101 switched catalyzer of renewal in general 3 ~ 9 months, and R102 can switch catalyzer of renewal in general 5 ~ 18 months, specifically can specifically determine according to the requirement of reaction.Because material carries out the qualitative response of hydrogenation removing impurities by R101 and R102, R103 and fixed-bed reactor can keep the running period grown, as can reach about 3 years.
In the inventive method, high pressure low temperature reactor R104 preferably is set, the pressure rating of R104 identical with reactive system (pressure-losses of ignoring Flow of Goods and Materials), the temperature of R104 is 150 ~ 300 ℃, R104 is adjusted to required operational condition before R101 or R102 need more raw catalyst.When R101 or R102 cut out reactive system, the catalyzer in R101 or R102 is entered in R104 fast, reduce reactor required time of catalyst changeout more, reduce because switch impact on reactive system.After adopting R104, can reduce the catalyst updating time more than 50%.
In the inventive method, the volume of three ebullated bed reactors is preferably identical, the reaction effect that operational condition can reach according to character and the requirement of raw material is determined, reaction pressure is generally 8 ~ 25MPa, hydrogen to oil volume ratio is generally 100:1 ~ 1000:1, total liquid volume air speed (LHSV, liquid volume inlet amount and total catalyst volume ratio) is generally 0.1～5.0h
-1, the R101 temperature of reaction is generally 370～420 ℃, and the R102 temperature of reaction is generally 370～420 ℃, and the R103 temperature of reaction is generally 380～430 ℃.In the inventive method, compare with existing residual oil ebullating bed reactor, the residual oil of not having relatively high expectations is converted into the transformation efficiency of light-end products, and main purpose is demetalization, desulfurization etc., the raw material that requires to obtain meeting the catalytic cracking unit amount of finger, so reaction conditions comparatively relaxes.
In the inventive method, R101 or R102 cut out reactive system when carrying out catalyst updating, in order not affect reaction effect, can reduce the inlet amount of reaction raw materials, the 50%-80%(quality as the raw material inlet amount can be reduced to normal running the time).Also can reach by the mode of suitable raising temperature of reaction the normal reaction effect.
In the inventive method, R101 uses the character of catalyzer to be: specific surface is 80～200m
2/ g, bore dia〉hole of 20nm accounts for 40% of total pore volume at least, and the average pore diameter of catalyzer is more than 20nm, to be preferably 22 ~ 40nm; By weight, catalyzer contains VI B family metal oxide (as MoO
3) 1.0%～10.0%, be preferably 1.5%～8.5%, contain group VIII metal oxide compound (as NiO or CoO) 0.1%～8.0%, preferably 0.5%～5.0%.
The catalyzer that R102 uses is can R101 identical, also can be different.The catalyst property that R102 uses is: specific surface is 80～300m
2/ g, bore dia〉hole of 20nm accounts for 20% of total pore volume at least, and the average pore diameter of catalyzer is more than 12nm, to be preferably 12 ~ 30nm; By weight, catalyzer contains VI B family metal oxide (as MoO
3) 1.0%～15.0%, be preferably 1.5%～13%, contain group VIII metal oxide compound (as NiO or CoO) 0.1%～8.0%, preferably 1.0%～5.0%.Can contain auxiliary agent, be selected from following several element: B, Ca, F, Mg, P, Si, Ti etc., auxiliary agent content is 0%～5.0%, the auxiliary element weighing scale.
The catalyst property that R103 uses is: catalyst specific surface is 180～300m
2/ g, bore dia〉hole of 20nm accounts for 10% of total pore volume at least, and the average pore diameter of catalyzer is more than 9nm, to be preferably 9 ~ 15nm.Catalyzer contains VI B family metal oxide (as MoO
3) 3.0%～20.0%, be preferably 6.0%～18.0%, contain VIII family metal oxide (as NiO or CoO) 0.3%～8.0%, preferably 0.5%～5.0%.Contain at least a auxiliary agent, be selected from following several element: B, Ca, F, Mg, P, Si, Ti etc., auxiliary agent content is 0.5%～5.0%, auxiliary agent is in element wt.
The granules of catalyst of three ebullated bed reactor uses is spherical, and diameter is 0.1～0.8mm, is preferably 0.1～0.6mm; Abrasion index≤2.0wt%.
According to required hydrotreatment degree, a fixed bed hydrogenation reactor can be set, the use of connecting with above-mentioned ebullated bed reactor of a plurality of fixed bed hydrogenation reactors also can be set, 1～2 fixed-bed reactor of operated by rotary motion get final product.Fixed bed hydrogenation is processed and can be adopted the commodity fixed bed hydrogenation to process catalyzer, as the FZC-20 of Fushun Petrochemical Research Institute's development and production, and FZC-30, one or more of FZC-40 etc. are used in conjunction with.Fixed bed hydrogenation is processed catalyzer also can be by the existing method preparation in this area.The fixed bed hydrogenation treatment condition are generally: temperature of reaction is 350～420 ℃, and reaction pressure is 8～25MPa, hydrogen to oil volume ratio 100:1 ~ 1000:1, and liquid volume air speed (LHSV) is 0.3～2.0h
-1
The inventive method can be processed the inferior heavy oil raw material, and the heavy hydrocarbon feedstocks as boiling range＞500 ℃ contains sulphur, nitrogen, bituminous matter and a large amount of metal (as V, Fe, Ni, Ca, Na etc.) compound, metal content＞100 μ g/g.
The generation oil that obtains after processing through the inventive method is converted into the transformation efficiency of light-end products generally lower than 50%, and preferably lower than 30%, sulphur content is generally lower than 0.5wt%, and preferably lower than 0.3wt%, metal content is lower than 30 μ g/g, preferably lower than 20 μ g/g.
The present invention adopts and does not add the multistage boiling bed residual hydrocracking technique of heat-extraction system with catalyzer, has greatly reduced facility investment, has reduced the possibility that accidents happened; By modes such as suitable switching or use standby reactor, adjusting operation conditions, realize that not adopting catalyzer to add online the heat-extraction system boiling bed process still can keep the requirement of long period steady running.Adopting this boiling bed hydrogenation system for handling to process with fixed bed hydrogenation combines, impurity in more can effective elimination stock oil, because ebullated bed reactor has removed a large amount of metals and bituminous matter, extended the runtime of fixed bed, for follow-up processing provides qualified raw material simultaneously.
Description of drawings
Fig. 1 is the inventive method process flow diagram.
Wherein: 1-valve one, 2-valve two, 3-valve three, 4-valve four, 5-valve five, 6-valve six, 7-valve seven, 8-valve eight, 9-valve nine, 10-valve ten, 11-valve 11,12-valve 12.
Embodiment
Further illustrate the solution of the present invention and effect below by a kind of embodiment.
The ebullating bed reactor unit of the inventive method arranges 3 of reactors, the first and second changeable operations of reactor, and the 3rd reactor does not switch, and reaches the purpose of displacement catalyzer, and fixed bed arranges a reactor, realizes long-term operation; Find through research, above-mentioned three ebullated bed reactors and a fixed-bed reactor series connection are used, and the process unit cycle of operation can reach 3 years, realizes synchronizeing with catalytic cracking unit shutting down.While boiling bed residual oil hydrogenator is not established catalyzer and is added online heat-extraction system, reduces investment outlay.
Boiling bed hydrogenation is established 3 reactors (R-101, R102 and R103) of series connection use successively, and the high pressure low temperature reactor (R104) (being used for the reactor blocked operation) of 1 same volume is set.Do not establish catalyzer and add online heat-extraction system, reduce investment outlay.Fixed-bed reactor arrange a reactor R-1, carry out hydrotreatment after ebullated bed R103.During to latter stage, cut out this reactor when the catalyst runs of R101, reaction feed is successively by other reactors; After the reactor R101 that cuts out draws off catalyzer, loading catalyst again; After the R101 reactor is incorporated system into, excision the second reactor R102 after operation for some time, reaction feed is successively by R101-R103-R-1; After the reactor R102 that cuts out draws off catalyzer, again load live catalyst; Then incorporate system into, reaction feed is successively by R101-R202-R103-R-1.
Specifically as shown in Figure 1:
(1) when R101, R102, R103, R-1 use fully, in flow process, valve five, valve six, valve eight, valve nine are opened, and valve 11, valve 12 are closed; Valve one, valve two, valve three, valve four, valve seven, valve ten are closed;
(2) when switching the R101 reactor, valve 11, valve eight, valve nine are opened, and valve five, valve six, valve 12 are closed; At this moment, clean the R101 reactor, valve one, valve two, valve four are opened the circulation of lowering the temperature, are unloaded agent, and valve three, valve ten, valve seven are closed;
(3) when switching the R102 reactor, valve five, valve six, valve 12 are opened, and valve eight, valve nine, valve 11 are closed; At this moment, clean the R102 reactor, valve one, valve ten, valve seven, valve three are opened the circulation of lowering the temperature, are unloaded agent, and valve four, valve two are closed.
The catalyzer that uses in the present invention can adopt existing method preparation according to performance need, prepares as prior aries such as reference US7074740, US5047142, US4549957, US4328127, CN200710010377.5.
The preparation process of boiling bed hydrogenation treatment catalyst is at first to prepare micro-spherical catalyst carrier, the hydrogenation active metals component that then adopts the pickling process load to need.The preparation process of support of the catalyst is as follows: the support of the catalyst feed product that humidity is suitable is made the particle of suitable size, and then with this particle spheroidizing, spherical carrier of catalyst is made in coccoid is dry, roasting.
The drying of support of the catalyst and roasting can be adopted condition well known to those skilled in the art, can adopt seasoning or dry under 80～150 ℃ as drying, and roasting is 600～1000 ℃ of roastings 1～6 hour.Pickling process supported active hydrogenation metal component can adopt method well known to those skilled in the art to carry out, and as the active metal salt wiring solution-forming with needs, with the solution impregnated catalyst carrier that contains active metal salt, then dry, roasting obtains final catalyzer.The drying process of catalyzer adopts seasoning or is dry under 60～150 ℃, and the roasting process of catalyzer was 400～600 ℃ of roastings 1～6 hour.
Catalyzer makes reactive metal and metal promoter change sulphided state into vulcanizing for before the heavy feed stock hydrogenation reaction, and sulfuration can be adopted vulcanization process known by the technical staff.
Further explain technical characterictic of the present invention below by embodiment, but be not limited to embodiment, the percentage composition of not pointing out benchmark wherein by weight percentage.Specific surface area of catalyst, pore volume, can adopt N by several bore dias
2Determination of adsorption method, the bore dia pore volume more than 20nm adopts mercury penetration method to measure.
Embodiment 1
The catalyzer preparation
Prepare a kind of spherical carrier of catalyst, mean pore size is 24nm, and spherical particle diameters is 0.1-0.3mm.Prepare according to a conventional method Mo-Ni solution, in solution with MoO
3The content of weighing scale is 8.00%, take the content of NiO weighing scale as 1.80%.Obtain final catalyzer R101-C with this solution by the above-mentioned carrier of incipient impregnation method dipping, its character is as shown in table 1.
The preparation mean pore size is the spherical carrier of catalyst of 15nm, and the spherical catalyst particle is 0.1-0.3mm.Prepare according to a conventional method Mo-Ni-P solution, in solution with MoO
3The content of weighing scale is 13.00%, take the content of NiO weighing scale as 2.50%, take the content of P weighing scale as 1.00%.Obtain final catalyzer R102-C with this solution by the above-mentioned carrier of incipient impregnation method dipping, its character is as shown in table 1.
The preparation mean pore size be the spherical carrier of catalyst of 12nm, the spherical catalyst particle is 0.1-0.3mm, prepares according to a conventional method Mo-Ni-P solution, in solution with MoO
3The content of weighing scale is 18.00%, take the content of NiO weighing scale as 2.50%, take the content of P weighing scale as 1.00%.Obtain final catalyzer R103-C with this solution by the above-mentioned carrier of incipient impregnation method dipping, its character is as shown in table 1.
Fixed bed catalyst adopts full scale plant to use the commercial catalyst FZC-40 of Fushun Petrochemical Research Institute's development and production, and its character sees Table 1.
The main physico-chemical property of table 1 embodiment catalyzer.
| Project | R101-C | R102-C | R103-C | FZC-40 |
| MoO 3, quality % | 7.82 | 12.85 | 18.04 | 22.5 |
| NiO(CoO), quality % | 1.69 | 2.18 | 2.37 | 9.3 |
| P, quality % | - | 1.05 | 0.98 | - |
| Abrasion index, quality % | ＜2.0 | ＜2.0 | ＜2.0 | - |
| Particle diameter, mm | 0.1-0.3 | 0.1-0.3 | 0.1-03 | 4.0 |
| Pore volume, mL/g | 1.57* | 0.68 | 0.67 | 0.40 |
| Specific surface, m 2/g | 136 | 175 | 239 | 195 |
| Pore distribution〉20nm accounts for total pore volume % | 48.02 | 25.14 | 13.51 | 9.82 |
| Average pore diameter | 25nm | 15nm | 11nm | 8nm |
* mercury penetration method is measured
Boiling bed hydrogenation reactor of the present invention is a kind of three-phase fluidized bed reactor, the ebullated bed reactor that can adopt CN02109404.7, CN200610134154.5 and CN200710012680.9 etc. to announce can satisfy the gas, liquid, solid three-phase and separate in ebullated bed reactor.
In selection embodiment 1, R101-C, R102-C and R103-C catalyzer join respectively in the 1L three-phase fluidized bed reactor of three series connection, the FZC-40 catalyzer is encased in R-1 in fixed-bed reactor, under the existence of hydrogen, carry out vacuum residuum hydrotreatment test.Testing selected Vacuum Residue Properties is: 520 ℃ of boiling ranges
+, sulphur content is 2.60 quality %, metal (Ni+V+Fe) content is 253 μ g/g, the CCR(carbon residue) and content is 12.1 quality %, asphalt content is 5.9 quality %.
Test conditions and evaluation result see Table 2.
Product property after processing condition in table 2 embodiment 2 and hydrogenation.
| Reactor | R101 | R102 | R103 | R-1 |
| Processing condition | ? | ? | ? | ? |
| Temperature of reaction/℃ | 400 | 395 | 390 | 390 |
| Reaction pressure/MPa | 15 | 15 | 15 | 15 |
| Air speed/h -1 | 1.2 | 1.2 | 1.2 | 0.80 |
| Hydrogen to oil volume ratio | 900:1 | 900:1 | 900:1 | 900:1 |
| Generate oil nature | ? | ? | ? | ? |
| S, quality % | 1.75 | 0.88 | 0.38 | 0.15 |
| （Ni+V+Fe），μg/g | 110.21 | 54.78 | 11.15 | 8.91 |
| CCR, quality % | 11.01 | 9.12 | 7.56 | 5.52 |
| Bituminous matter (C7 insolubles), quality % | 2.0 | 1.0 | 0.3 | <0.1 |
As can be seen from Table 2: the product that adopts combination process to obtain can be used as the raw material of catalytic cracking, and the transformation efficiency of residual oil raw material lighting is 35% left and right.
Embodiment 3
The HDM catalyst runs of boiling bed hydrogenation R101 reactor generated oil nature and can not meet the demands (seeing Table 3) after half a year, showed that catalyzer can not meet the demands, must change.
Excision R101 reactor, fresh feed and hydrogen directly enter the R102 reactor; Fresh feed this moment is the 70%(quality of original charging).The R101 reactor that cuts out is kept reaction pressure, introduces recycle hydrogen and quenching oil, to keep the fluidisation of beds, prevents catalysis glare bed.When the R101 reactor temperature is down to 200 ℃ of left and right, enter high pressure low temperature reactor R104 at voltage-controlled lower catalyzer with reactor; The R104 inner catalyst draws off after fully washing, and waits for operation next time.After catalyzer in the R101 reactor enters R104, prepare catalyst loading.With the live catalyst live catalyst low pressure storage tank that ground arranges of packing into, with rear substitution to the hydrogen state; Reactor head arranges the live catalyst pressure pan, and at first this pressure pan cuts off with reactor, under low pressure utilizes hydrogen that the surface storage tank inner catalyst is transported to this pressure pan; The pressure pan high reactor pressure that boosts is subsequently opened bottom valve, and with the catalyzer reactor of packing into, repetitive operation is until with the reactor of all packing into of the catalyzer in the catalyst tank of ground.
During switching, the processing condition of R102, R103 and R-1 and product property see Table 3.
Processing condition and product property during switching in table 3 embodiment 3.
| Reactor | R101 | R102 | R103 | R-1 |
| Processing condition | Before the R101 excision | After the R101 excision | After the R101 excision | After the R101 excision |
| Temperature of reaction/℃ | 420 | 405 | 400 | 393 |
| Reaction pressure/MPa | 15 | 15 | 15 | 15 |
| Air speed/h -1 | 1.2 | 0.84 | 0.84 | 0.30 |
| Hydrogen to oil volume ratio | 900:1 | 900:1 | 900:1 | 900:1 |
| Generate oil nature | ? | ? | ? | ? |
| S, quality % | 2.39 | 1.21 | 0.61 | 0.23 |
| （Ni+V+Fe），μg/g | 221 | 62.35 | 34.16 | 18.98 |
| CCR, quality % | 11.81 | 10.23 | 8.02 | 6.21 |
| Bituminous matter (C7 insolubles), quality % | 5.0 | 1.2 | 0.5 | <0.1 |
As can be seen from Table 3: when the R101 blocked operation carries out, enter the feed flow rates of R102 and R-1 reaction and the temperature of reaction of raising R102, R103 and R-1 reactor by reduction, can generate qualified catalytically cracked material.
Embodiment 4
The R101 reactor is incorporated operation into: before the R101 reactor was incorporated system into, pressure was adjusted to standard atmosphere pressure, temperature 200 ℃ of left and right; Introduce gradually 20% fresh feed, improve temperature of reaction, the fresh feed load is increased to 100% gradually; With the rising of temperature of reaction, increase gradually resid feed to 100% load.This moment, technique was undertaken by the flow process of multistage boiling bed heavy oil, residual hydrocracking technique, and after the R101 reactor switches, each reactor process condition and product property see Table 4.
Processing condition and product property during switching in table 4 embodiment 4.
| Reactor | R101 | R102 | R103 | R-1 |
| Processing condition | After R101 incorporates into | After R101 incorporates into | After R101 incorporates into | After R101 incorporates into |
| Temperature of reaction/℃ | 400 | 400 | 393 | 390 |
| Reaction pressure/MPa | 15 | 15 | 15 | 15 |
| Air speed/h -1 | 1.2 | 1.2 | 1.2 | 0.80 |
| Hydrogen to oil volume ratio | 900:1 | 900:1 | 900:1 | 900:1 |
| Generate oil nature | ? | ? | ? | ? |
| S, quality % | 1.82 | 0.98 | 0.43 | 0.20 |
| （Ni+V+Fe），μg/g | 118.51 | 65.21 | 24.54 | 15.98 |
| CCR, quality % | 11.12 | 9.52 | 8.01 | 5.89 |
| Bituminous matter (C7 insolubles), quality % | 1.9 | 1.1 | 0.4 | <0.1 |
As can be seen from Table 4: after R101 displacement catalyzer was incorporated system into, the product that R-1 obtains was the acceptable material of catalytic cracking.
After each reactor normal operation 1000h in embodiment 4, processing condition and the product property of each reactor are as shown in table 5.
Processing condition and the quality product of table 5 device running 1000h.
| Reactor | R101 | R102 | R103 | R-1 |
| Temperature of reaction/℃ | 408 | 415 | 400 | 395 |
| Reaction pressure/MPa | 15 | 15 | 15 | 15 |
| Air speed/h -1 | 1.2 | 1.2 | 1.2 | 0.80 |
| Hydrogen to oil volume ratio | 900:1 | 900:1 | 900:1 | 900:1 |
| Generate oil nature | ? | ? | ? | ? |
| S, quality % | 1.85 | 0.95 | 0.40 | 0.25 |
| （Ni+V+Fe），μg/g | 120.01 | 68.12 | 28.32 | 18.66 |
| CCR, quality % | 11.35 | 9.35 | 8.22 | 6.16 |
| Bituminous matter (C7 insolubles), quality % | 2.0 | 0.9 | 0.3 | <0.1 |
As can be seen from Table 5: after each reactor normal operation 1000h, stability is better, and not too large change of quality product is suitable for catalytically cracked material.
Claims (10)
1. the combined technical method of a mink cell focus hydrotreatment, comprise following content: ebullated bed reactor and fixed-bed reactor combination, stock oil and hydrogen enter bottom ebullated bed reactor, carry out hydrogenation reaction under the boiling bed hydrogenation condition, reacting rear material is discharged from reactor head and is entered fixed-bed reactor, carry out hydrogenation reaction under the fixed bed hydrogenation condition, the liquid phase material that fixed-bed reactor obtain is as the stock oil of catalytic cracking unit; It is characterized in that arranging the ebullated bed reactor of at least 2 series connection, be that the First ebullated bed reactor is that R101, second ebullated bed reactor are R102, and but the 3rd ebullated bed reactor of choice for use is R103, wherein R101 and R102 are the blocked operation mode, when namely operating, R101 or R102 switch and more catalyst changeout of reactive system, then switch back reactive system.
2. in accordance with the method for claim 1, it is characterized in that: using three ebullated bed reactors is R101, R102 and R103, and the operating method of ebullated bed reactor loops by following three kinds of modes: (1) reaction mass passes through R101-R102-R103 successively; (2) cut out R101 and carry out catalyst updating, reaction mass is successively by R102-R103, and more after raw catalyst, reaction mass passes through R101-R102-R103 to R101 successively; (3) cut out R102 and carry out catalyst change, reaction mass is successively by R101-R103, and more after raw catalyst, reaction mass passes through R101-R102-R103 to R102 successively.
3. it is characterized in that in accordance with the method for claim 1: fixed-bed reactor arrange 1～2 that series connection is used.
4. in accordance with the method for claim 1, it is characterized in that: R101 loads Hydrodemetalation catalyst, R102 filling Hydrodemetalation catalyst or filling Hydrobon catalyst, R103 loads Hydrobon catalyst, fixed-bed reactor filling Hydrobon catalyst and/or hydrodenitrogenation catalyst.
5. in accordance with the method for claim 1, it is characterized in that: ebullated bed reactor R101, R102, R103 do not arrange catalyzer and add online heat-extraction system, the R101 reactor switched catalyzer of renewal in 3 ~ 9 months, and the R102 reactor can switch catalyzer of renewal in 5 ~ 18 months.
6. in accordance with the method for claim 1, it is characterized in that: high pressure low temperature reactor R104 is set, the pressure rating of R104 is identical with reactive system, the temperature of R104 is 150 ~ 300 ℃, R104 is before R101 or R102 need more raw catalyst, be adjusted to required operational condition, when R101 or R102 cut out reactive system, the catalyzer in R101 or R102 entered in R104 fast.
7. in accordance with the method for claim 1, it is characterized in that: the ebullated bed reactor reaction pressure is 8 ~ 25MPa, and hydrogen to oil volume ratio is 100:1 ~ 1000:1, and total liquid volume air speed is 0.1～5.0h
-1, the R101 temperature of reaction is 370～420 ℃, and the R102 temperature of reaction is 370～420 ℃, and the R103 temperature of reaction is 380～430 ℃; The fixed bed hydrogenation temperature of reaction is 350～420 ℃, and reaction pressure is 8～25MPa, hydrogen to oil volume ratio 100:1 ~ 1000:1, and the liquid volume air speed is 0.3～2.0h
-1
8. it is characterized in that in accordance with the method for claim 1: it is 80～200m that R101 uses the specific surface of catalyzer
2/ g, bore dia〉hole of 20nm accounts for 40% of total pore volume at least, and the average pore diameter of catalyzer is more than 20nm, and by weight, catalyzer contains VI B family metal oxide 1.0%～10.0%, contains group VIII metal oxide compound 0.1%～8.0%.
9. it is characterized in that in accordance with the method for claim 1: R102 uses the character of catalyzer to be: specific surface is 80～300m
2/ g, bore dia〉hole of 20nm accounts for 20% of total pore volume at least, and the average pore diameter of catalyzer is more than 12nm, and by weight, catalyzer contains VI B family metal oxide 1.0%～15.0%, contains group VIII metal oxide compound 0.1%～8.0%.
10. it is characterized in that in accordance with the method for claim 1: it is 180～300m that R103 uses the specific surface of catalyzer
2/ g, bore dia〉hole of 20nm accounts for 10% of total pore volume at least, and the average pore diameter of catalyzer is more than 9nm, and by weight, catalyzer contains VI B family metal oxide 3.0%～20.0%, contains VIII family metal oxide 0.3%～8.0%.
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