CN103102940B - A kind of combined technical method of mink cell focus hydrotreatment - Google Patents
A kind of combined technical method of mink cell focus hydrotreatment Download PDFInfo
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Abstract
The present invention relates to a kind of combined technical method of mink cell focus hydrotreatment, comprise following content: ebullated bed reactor and fixed-bed reactor combine, stock oil and hydrogen enter bottom ebullated bed reactor, hydrogenation reaction is carried out under boiling bed hydrogenation condition, reacting rear material is discharged from reactor head and is entered fixed-bed reactor, under fixed bed hydrogenation condition, carry out hydrogenation reaction, the liquid phase material that fixed-bed reactor obtain is as the stock oil of catalytic cracking unit; Arrange the ebullated bed reactors of at least 2 series connection, wherein First and second are changeable operating method.Ebullated bed reactor of the present invention does not need to arrange catalyzer and adds heat-extraction system online, and facility investment can obviously reduce, and coordinates with fixed-bed reactor simultaneously, can effective prolong operating period, for catalytic cracking unit provides high quality raw material.
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, but, reserve due to earth oil is fixing, wherein inferior heavy oil accounts for the larger proportion of crude oil reserve, therefore, having effectively utilized limited petroleum resources, particularly made full use of inferior heavy oil resource, is the challenge that 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 high, difficulty of processing is large, causes residual oil Zeng Zuowei boiler oil to be burnt, not only wastes limited resources, and pollution is caused to environment, how Appropriate application mink cell focus (inferior heavy oil or residual oil etc.) is the important topic that petroleum refining industry faces.
Heavy-oil hydrogenation treatment process mainly contains fixed bed, ebullated bed, suspension bed and moving-bed.Fixed bed is because of its technology maturation, 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 can add online and discharge due to catalyzer, be conducive to maintaining 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 residual hydrocracking simultaneously, and application prospect is very wide.
Residue Hydrotreating Technology technology trends is single process residual oils/heavy oil technique, and to Combined art transition, realize with the friendly product of process for cleanly preparing production environment, maximum ground increases the yield of intermediate oil, reduces the output of last running.Make full use of the feature of each technique, exploitation combination process carrys out realize target.Such as HRI and Lummus company all develops boiling bed hydrogenation reactor and fixed bed hydrogenation reactor serial connection technology, and main purpose is that the light-end products that boiling bed hydrogenation cracking is produced are directly refining to meet specification of quality.
According to the difference of process raw material oil and object product, ebullated bed reactor part can be divided into single reactor or several parallel series the scale problem of solving device (several series that be arranged in parallel mainly), each series comprises several tandem reactors, identical catalyzer can be loaded in different reactor, also can load different catalyzer.Ebullated bed reactor quality product is out slightly poor, needs further hydrotreatment.When the catalyzer that three reactor charge are different, usual one be anti-hydrodemetallation (HDM) (HDM) catalyzer of larger aperture, two anti-and three anti-be (hydrogenating desulfurization) HDS compared with high-ratio surface and hydrogenation conversion catalyst.When use two reactors, also one instead can adopt high activated catalyst, make raw material mid-boiling point have 50% to be converted into the hydro carbons of boiling point lower than 524 DEG C (975 °F) higher than the hydro carbons of 524 DEG C (975 °F), simultaneously generating portion desulphurization reaction; Two instead use active lower catalyzer, make hydrocracking total conversion rate reach certain level, simultaneously desulfurization further.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, enters three-phase fluidized bed reactor, contact carry out hydrogenation reaction with hydrogenation catalyst after stock oil mixes with hydrogen.From three-phase fluidized bed reactor gas phase out with liquid phase enters lightweight oil fixed bed respectively and mink cell focus fixed bed processes.
USP6270654 discloses a kind of catalytic hydrogenation adopting multistage boiling bed reactor.Adopt the ebullating bed reactor system of online displacement in this patent, the catalyst replacement speed of first step ebullated bed reactor is 0.05-0.5Lb/Bbl.The active metallic content contained for the catalyzer in the first step and second stage reactor is 5-20wt%, and catalyzer pore volume is 0.4-1.2mL/g, and surface-area is 100-400m
2/ g, mean pore size is 8-25nm.Active 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 the gas holdup in each reactor simultaneously, 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 spent catalyst drawn off from reactor sends former reactor back to after regeneration, or live catalyst is added to second reactor, and the catalyzer of second reactor is loaded first reactor, and the catalyzer in original first reactor all abandons.Active metal is Co, Mo, Ni, W and composition thereof.Carrier is aluminum oxide, silicon oxide and composition thereof.
USP4457831 discloses the secondary hydrogenation conversion process of the hydrocarbon raw material adopting residual oil circulation.First step reactor uses the catalyzer of suitable diameter, and transform under medium reaction conditions and produce hydrocarbon gas and liquid distillate, wherein lighter liquid distillate is product after being separated, and residual gas and heavier fluid cut are mixed into second stage ebullated bed reactor.Second stage reactor comprises larger diameter catalyzer, produces low boiling point hydrocarbon cut under relative severe condition.Part reduced pressure bottoms sends 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 produces low sulphur fuel oil by the petroleum residual oil of high-sulfur and high metal content, final stage reactor used catalyst is taken out to be joined in reactor the last period, can the obviously activity of extending catalyst and useful life thereof.This technique comprises three reactors, wherein first reactor charge catalyst for demetalation, 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 0.5-0.6mL/g.
Above-mentioned boiling bed hydrogenation reactor all uses catalyzer to add heat-extraction system online, invest higher because ebullated bed adds heat-extraction system online, according to calculating, about the investment that catalyzer adds heat-extraction system online accounts for the half of boiling bed hydrogenation system gross investment, and the fault occurred during operation is mainly adding heat-extraction system.Existing boiling bed process mainly emphasizes higher transformation efficiency, obtains more light liquid phase product, light liquid phase product through the process of follow-up fixed bed hydrogenation device to improve the quality of products.
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 organically combined ebullated bed and fixed-bed process, produces catalytically cracked material.The investment of this combination process is lower, can ensure that running period is synchronous with catalytic cracking, 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 combine, stock oil and hydrogen enter bottom ebullated bed reactor, hydrogenation reaction is carried out under boiling bed hydrogenation condition, reacting rear material is discharged from reactor head and is entered fixed-bed reactor, under fixed bed hydrogenation condition, carry out hydrogenation reaction, the liquid phase material that fixed-bed reactor obtain is as the stock oil of catalytic cracking unit.
The present invention arranges the ebullated bed reactor of at least 2 series connection, i.e. First ebullated bed reactor (hereinafter referred to as R101), second ebullated bed reactor (hereinafter referred to as R102), and can the 3rd ebullated bed reactor (hereinafter referred to as R103) of choice for use, R101 and R102 is blocked operation mode, namely during operation, R101 or R102 switches out reactive system more catalyst changeout, then switches back reactive system.When use three ebullated bed reactors, specifically can circulate by following three kinds of modes and carry out: (1) reaction mass passes through R101-R102-R103 successively; (2) cut out R101 and carry out catalyst updating, reaction mass is successively by after R102-R103, R101 more raw catalyst, and reaction mass passes through R101-R102-R103 successively; (3) cut out R102 and carry out catalyst change, reaction mass is successively by after R101-R103, R102 more raw catalyst, and reaction mass passes through R101-R102-R103 successively.
In the inventive method, described series connection refers to reaction mass successively by described 2 or 3 ebullated bed reactors.According to the industrial scale of device, also can arrange two or more reaction train, each series comprises ebullated bed reactor and the fixed-bed reactor of at least 2 series connection as above simultaneously.
In the inventive method, fixed-bed reactor can arrange 1 ~ 2 of series connection use.
In the inventive method, R101 loads Hydrodemetalation catalyst, and R102 loads 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 by the existing method preparation in this area.
In the inventive method, ebullated bed reactor R101, R102, R103 do not arrange catalyzer and add heat-extraction system online, save facility investment.The switching time of R101 or R102 is determined by catalyst deactivation speed, and R101 switches renewal catalyzer in general 3 ~ 9 months, and R102 can switch renewal catalyzer for general 5 ~ 18 months, specifically specifically can 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 longer running period, as can reach about 3 years.
In the inventive method, preferably arrange high pressure low temperature reactor R104, the pressure rating of R104 is identical with reactive system (ignoring the pressure-losses of Flow of Goods and Materials), and the temperature of R104 is 150 ~ 300 DEG C, R104 needs, more before raw catalyst, to be adjusted to required operational condition at R101 or R102.When R101 or R102 cuts out reactive system, the catalyzer in R101 or R102 is entered in R104 fast, reduce the time of reactor more needed for catalyst changeout, reduce because switch the impact on reactive system.After adopting R104, the catalyst updating time more than 50% can be reduced.
In the inventive method, the volume of three ebullated bed reactors is preferably identical, the reaction effect that operational condition can reach according to the character of raw material and requirement 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, R101 temperature of reaction is generally 370 ~ 420 DEG C, and R102 temperature of reaction is generally 370 ~ 420 DEG C, and R103 temperature of reaction is generally 380 ~ 430 DEG C.In the inventive method, compared with existing residual oil ebullating bed reactor, do not require that higher crude conversion is the transformation efficiency of light-end products, main purpose is demetalization, desulfurization etc., to obtain the raw material meeting the requirement of the catalytic cracking unit amount of finger, therefore reaction conditions comparatively relaxes.
In the inventive method, R101 or R102 cuts out reactive system when carrying out catalyst updating, in order to not affect reaction effect, can reduce the inlet amount of reaction raw materials, as feedstock amount being reduced to 50%-80%(quality during normal running).Also normal reaction effect can be reached by the mode suitably improving temperature of reaction.
In the inventive method, the character of R101 use catalyzer is: specific surface is 80 ~ 200m
2/ g, the hole of bore dia >20nm at least accounts for 40% of total pore volume, and the average pore diameter of catalyzer is more than 20nm, is 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%, containing group VIII metal oxide compound (as NiO or CoO) 0.1% ~ 8.0%, preferably 0.5% ~ 5.0%.
The catalyzer that R102 uses can R101 identical, also can be different.The catalyst property that R102 uses is: specific surface is 80 ~ 300m
2/ g, the hole of bore dia >20nm at least accounts for 20% of total pore volume, and the average pore diameter of catalyzer is more than 12nm, is preferably 12 ~ 30nm; By weight, catalyzer contains VI B family metal oxide (as MoO
3) 1.0% ~ 15.0%, be preferably 1.5% ~ 13%, containing 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%, auxiliary element weighing scale.
The catalyst property that R103 uses is: catalyst specific surface is 180 ~ 300m
2/ g, the hole of bore dia >20nm at least accounts for 10% of total pore volume, and the average pore diameter of catalyzer is more than 9nm, is preferably 9 ~ 15nm.Catalyzer contains VI B family metal oxide (as MoO
3) 3.0% ~ 20.0%, be preferably 6.0% ~ 18.0%, containing VIII family metal oxide (as NiO or CoO) 0.3% ~ 8.0%, preferably 0.5% ~ 5.0%.Containing at least one auxiliary agent, be selected from following several element: B, Ca, F, Mg, P, Si, Ti etc., auxiliary agent content is 0.5% ~ 5.0%, and 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, multiple fixed bed hydrogenation reactor also can be set and connect with above-mentioned ebullated bed reactor and use, 1 ~ 2 fixed-bed reactor is generally set.Fixed bed hydrogenation process can adopt commodity fixed bed hydrogenation process catalyzer, as the FZC-20 of Fushun Petrochemical Research Institute's development and production, FZC-30, FZC-40 etc. one or more with the use of.Fixed bed hydrogenation process catalyzer also can by the existing method preparation in this area.Fixed bed hydrogenation treatment condition are generally: temperature of reaction is 350 ~ 420 DEG C, and reaction pressure is 8 ~ 25MPa, hydrogen to oil volume ratio 100:1 ~ 1000:1, and liquid volume air speed (LHSV) is 0.3 ~ 2.0h
-1.
The inventive method can process inferior heavy oil raw material, as the heavy hydrocarbon feedstocks of boiling range > 500 DEG C, containing sulphur, nitrogen, bituminous matter and a large amount of metal (as V, Fe, Ni, Ca, Na etc.) compound, metal content > 100 μ g/g.
Obtain after the inventive method process generation oil, the transformation efficiency being converted into light-end products is generally lower than 50%, and preferably lower than 30%, sulphur content is generally lower than 0.5wt%, preferably lower than 0.3wt%, metal content lower than 30 μ g/g, preferably lower than 20 μ g/g.
The present invention adopts the multistage boiling bed residual hydrocracking technique not adding heat-extraction system with catalyzer, greatly reduces facility investment, decreases the possibility that accidents happened; By suitable switching or use the mode such as standby reactor, adjustment operational condition, the requirement realizing not adopting catalyzer to add online heat-extraction system boiling bed process still can maintain long period steady running.This boiling bed hydrogenation system for handling is adopted to combine with fixed bed hydrogenation process, more can impurity in effective elimination stock oil, simultaneously because ebullated bed reactor is stripped of a large amount of metals and bituminous matter, extend the runtime of fixed bed, for follow-up processing provides qualified raw material.
Accompanying drawing explanation
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
The solution of the present invention and effect is further illustrated below by a kind of embodiment.
The ebullating bed reactor unit of the inventive method arranges reactor 3, the changeable operation of the first and second reactors, and the 3rd reactor does not switch, and reach the object of displacement catalyzer, 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 use, and the process unit cycle of operation can reach 3 years, realizes shutting down synchronous with catalytic cracking unit.Boiling bed residual oil hydrogenator does not establish catalyzer to add heat-extraction system online simultaneously, reduces investment outlay.
Boiling bed hydrogenation establishes 3 reactors (R-101, R102 and R103) used of connecting successively, arranges the high pressure low temperature reactor (R104) (for reactor blocked operation) of 1 same volume.Do not establish catalyzer to add heat-extraction system online, reduce investment outlay.Fixed-bed reactor arrange a reactor R-1, after ebullated bed R103, carry out hydrotreatment.When the catalyst runs of R101 is to latter stage, cut out this reactor, reaction feed is successively by other reactors; After the reactor R101 cut out draws off catalyzer, loading catalyst again; After R101 reactor is incorporated to system, excise the second reactor R102 after running for some time, reaction feed is successively by R101-R103-R-1; After the reactor R102 cut out draws off catalyzer, again load live catalyst; Then be incorporated to system, reaction feed is successively by R101-R202-R103-R-1.
Specifically as shown in Figure 1:
(1) when R101, R102, R103, R-1 use completely, 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 R101 reactor, valve 11, valve eight, valve nine are opened, and valve five, valve six, valve 12 are closed; Now, cleaning R101 reactor, valve one, valve two, valve four are opened and are carried out down cycles, unload agent, and valve three, valve ten, valve seven are closed;
(3) when switching R102 reactor, valve five, valve six, valve 12 are opened, and valve eight, valve nine, valve 11 are closed; Now, cleaning R102 reactor, valve one, valve ten, valve seven, valve three are opened and are carried out down cycles, unload agent, and valve four, valve two are closed.
The catalyzer used in the present invention can adopt existing method to prepare according to performance need, as prepared with reference to prior aries such as US7074740, US5047142, US4549957, US4328127, CN200710010377.5.
The preparation process of boiling bed hydrogenation treatment catalyst first prepares micro-spherical catalyst carrier, then adopts the hydrogenation active metals component that pickling process load needs.The preparation process of support of the catalyst is as follows: the particle of suitable size made by catalyst support material material humidity be suitable for, and then by this particle spheroidizing, spherical carrier of catalyst is made in coccoid is dry, roasting.
The drying of support of the catalyst and roasting can adopt condition well known to those skilled in the art, and as drying can adopt seasoning or drying at 80 ~ 150 DEG C, roasting is 600 ~ 1000 DEG C 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 that will need, with the solution impregnated catalyst carrier containing active metal salt, then dry, roasting obtains final catalyzer.The drying process of catalyzer adopts seasoning or drying at 60 ~ 150 DEG C, and the roasting process of catalyzer was 400 ~ 600 DEG C of roastings 1 ~ 6 hour.
Catalyzer carried out sulfuration before for heavy feed stock hydrogenation reaction, and make active metal and metal promoter change sulphided state into, sulfuration can adopt vulcanization process known by the technical staff.
State technical characteristic of the present invention further below by embodiment, but be not limited to embodiment, the percentage composition not pointing out benchmark wherein by weight percentage.Specific surface area of catalyst, pore volume, a few bore dia can adopt N
2determination of adsorption method, bore dia adopts mercury penetration method to measure at the pore volume of more than 20nm.
Embodiment 1
Catalyst preparing
Prepare a kind of spherical carrier of catalyst, mean pore size is 24nm, and spherical particle diameters is 0.1-0.3mm.Prepare Mo-Ni solution according to a conventional method, with MoO in solution
3the content of weighing scale is 8.00%, with the content of NiO weighing scale for 1.80%.Flood above-mentioned carrier with this solution by incipient impregnation method and obtain final catalyzer R101-C, its character is as shown in table 1.
Preparation mean pore size is the spherical carrier of catalyst of 15nm, and spherical catalyst particles is 0.1-0.3mm.Prepare Mo-Ni-P solution according to a conventional method, with MoO in solution
3the content of weighing scale is 13.00%, with the content of NiO weighing scale for 2.50%, with the content of P weighing scale for 1.00%.Flood above-mentioned carrier with this solution by incipient impregnation method and obtain final catalyzer R102-C, its character is as shown in table 1.
Preparation mean pore size is the spherical carrier of catalyst of 12nm, and spherical catalyst particles is 0.1-0.3mm, prepares Mo-Ni-P solution according to a conventional method, with MoO in solution
3the content of weighing scale is 18.00%, with the content of NiO weighing scale for 2.50%, with the content of P weighing scale for 1.00%.Flood above-mentioned carrier with this solution by incipient impregnation method and obtain final catalyzer R103-C, 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 is in 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
Embodiment 2
Boiling bed hydrogenation reactor of the present invention is a kind of three-phase fluidized bed reactor, the ebullated bed reactor that CN02109404.7, CN200610134154.5 and CN200710012680.9 etc. announce can be adopted, gas, liquid, solid three-phase can be met and be separated in ebullated bed reactor.
R101-C, R102-C and R103-C catalyzer in embodiment 1 is selected to join in the 1L three-phase fluidized bed reactor of three series connection respectively, FZC-40 catalyzer is encased in R-1 in fixed-bed reactor, in the presence of hydrogen gas, vacuum residuum hydrotreatment test is carried out.The selected Vacuum Residue Properties of test is: boiling range 520 DEG C
+, sulphur content is 2.60 quality %, and metal (Ni+V+Fe) content is 253 μ g/g, CCR(carbon residue) and content is 12.1 quality %, asphalt content is 5.9 quality %.
Test conditions and evaluation result are in 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/DEG C | 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 adopting combination process to obtain can as the raw material of catalytic cracking, and the transformation efficiency of residual oil raw material lighting is about 35%.
Embodiment 3
After HDM catalyst runs half a year of boiling bed hydrogenation R101 reactor, generate oil nature and can not meet the demands (see table 3), show that catalyzer can not meet the demands, must change.
Excision R101 reactor, fresh feed and hydrogen directly enter R102 reactor; Now fresh feed is the 70%(quality of original charging).The R101 reactor cut out maintains reaction pressure, introduces recycle hydrogen and quenching oil, to maintain the fluidisation of beds, prevents catalysis glare bed.When R101 reactor temperature is down to about 200 DEG C, enter high pressure low temperature reactor R104 at the voltage-controlled lower catalyzer by reactor; After R104 inner catalyst fully washs, draw off, wait for subsequent operation.After catalyzer in R101 reactor enters R104, prepare catalyst loading.Live catalyst is loaded the live catalyst low pressure storage tank that ground is arranged, with rear substitution to hydrogen state; Reactor head arranges live catalyst pressure pan, and first this pressure pan cuts off with reactor, under low pressure utilizes hydrogen that surface storage tank inner catalyst is transported to this pressure pan; Pressure pan boosts high reactor pressure subsequently, and open bottom valve, catalyzer is loaded reactor, repetitive operation is until all load reactor by the catalyzer in the catalyst tank of ground.
During switching, the processing condition of R102, R103 and R-1 and product property are in table 3.
Processing condition and product property during switching in table 3 embodiment 3.
| Reactor | R101 | R102 | R103 | R-1 |
| Processing condition | Before R101 excision | After R101 excision | After R101 excision | After R101 excision |
| Temperature of reaction/DEG C | 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 R101 blocked operation carries out, by reducing the feed flow rates entering R102 and R-1 reaction and the temperature of reaction improving R102, R103 and R-1 reactor, qualified catalytically cracked material can be generated.
Embodiment 4
R101 reactor is incorporated to operation: before R101 reactor is incorporated to system, pressure adjusting to standard atmosphere pressure, temperature about 200 DEG C; Introduce the fresh feed of 20% gradually, improve temperature of reaction, fresh feed load is increased to 100% gradually; With the rising of temperature of reaction, increase resid feed gradually to 100% load.Now technique is undertaken by the flow process of multistage boiling bed heavy oil, residual hydrocracking technique, and after R101 reactor switches, each reactor process condition and product property are in table 4.
Processing condition and product property during switching in table 4 embodiment 4.
| Reactor | R101 | R102 | R103 | R-1 |
| Processing condition | After R101 is incorporated to | After R101 is incorporated to | After R101 is incorporated to | After R101 is incorporated to |
| Temperature of reaction/DEG C | 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 is incorporated to system, the product that R-1 obtains is the acceptable material of catalytic cracking.
Embodiment 5
After each reactor normal operation 1000h in embodiment 4, processing condition and the product property of each reactor are as shown in table 5.
The processing condition of table 5 device running 1000h and quality product.
| Reactor | R101 | R102 | R103 | R-1 |
| Temperature of reaction/DEG C | 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 quality product not too large change, is suitable for catalytically cracked material.
Claims (6)
1. the combined technical method of a mink cell focus hydrotreatment, comprise following content: ebullated bed reactor and fixed-bed reactor combine, stock oil and hydrogen enter bottom ebullated bed reactor, hydrogenation reaction is carried out under boiling bed hydrogenation condition, reacting rear material is discharged from reactor head and is entered fixed-bed reactor, under fixed bed hydrogenation condition, carry out hydrogenation reaction, 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 is set, i.e. First ebullated bed reactor and R101, second ebullated bed reactor and R102, and the 3rd ebullated bed reactor and R103, it is characterized in that R101 and R102 is blocked operation mode, namely during operation, R101 or R102 switches out reactive system more catalyst changeout, then reactive system is switched back, wherein
As use three ebullated bed reactors and R101, R102 and R103, the operating method of ebullated bed reactor circulates by following three kinds of modes and carries out: (1) reaction mass passes through R101-R102-R103 successively; (2) cut out R101 and carry out catalyst updating, reaction mass is successively by after R102-R103, R101 more raw catalyst, and reaction mass passes through R101-R102-R103 successively; (3) cut out R102 and carry out catalyst change, reaction mass is successively by after R101-R103, R102 more raw catalyst, and reaction mass passes through R101-R102-R103 successively,
R101 uses the specific surface of catalyzer to be 80 ~ 200m
2/ g, the hole of bore dia >20nm at least accounts for 40% of total pore volume, 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%, containing group VIII metal oxide compound 0.1% ~ 8.0%; The character of R102 use catalyzer is: specific surface is 80 ~ 300m
2/ g, the hole of bore dia >20nm at least accounts for 20% of total pore volume, 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%, containing group VIII metal oxide compound 0.1% ~ 8.0%; R103 uses the specific surface of catalyzer to be 180 ~ 300m
2/ g, the hole of bore dia >20nm at least accounts for 10% of total pore volume, 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%, containing VIII family metal oxide 0.3% ~ 8.0%.
2. in accordance with the method for claim 1, it is characterized in that: fixed-bed reactor arrange 1 ~ 2 of series connection use.
3. in accordance with the method for claim 1, it is characterized in that: R101 loads Hydrodemetalation catalyst, R102 loads Hydrodemetalation catalyst or filling Hydrobon catalyst, R103 loads Hydrobon catalyst, fixed-bed reactor filling Hydrobon catalyst and/or hydrodenitrogenation catalyst.
4. 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 heat-extraction system online, R101 reactor switches renewal catalyzer in 3 ~ 9 months, and R102 reactor switches renewal catalyzer in 5 ~ 18 months.
5. 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 DEG C, R104 needs more before raw catalyst at R101 or R102, be adjusted to required operational condition, when R101 or R102 cuts out reactive system, the catalyzer in R101 or R102 entered in R104 fast.
6. in accordance with the method for claim 1, it is characterized in that: ebullated bed reactor reaction pressure is 8 ~ 25MPa, hydrogen to oil volume ratio is 100:1 ~ 1000:1, and total liquid volume air speed is 0.1 ~ 5.0h
-1, R101 temperature of reaction is 370 ~ 420 DEG C, and R102 temperature of reaction is 370 ~ 420 DEG C, and R103 temperature of reaction is 380 ~ 430 DEG C; Fixed bed hydrogenation temperature of reaction is 350 ~ 420 DEG C, and reaction pressure is 8 ~ 25MPa, hydrogen to oil volume ratio 100:1 ~ 1000:1, and liquid volume air speed is 0.3 ~ 2.0h
-1.
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| CN108070402B (en) * | 2016-11-15 | 2020-03-17 | 中国石油化工股份有限公司 | Boiling bed-fixed bed combined process start-up method |
| CN108102705B (en) * | 2016-11-25 | 2019-08-06 | 中国石油化工股份有限公司 | A kind of heavy oil lightening method |
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| CN101591563A (en) * | 2009-06-25 | 2009-12-02 | 中国石油化工集团公司 | The combination process of a kind of boiling bed hydrogenation and fixed bed hydrogenation |
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