CN101724453A - Hydrogenation method of heavy hydrocarbon multi-segment fluidized bed - Google Patents
Hydrogenation method of heavy hydrocarbon multi-segment fluidized bed Download PDFInfo
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Abstract
The invention discloses a hydrogenation method of a heavy hydrocarbon multi-segment fluidized bed. The technical process comprises the steps of: mixing thick heavy hydrocarbon raw materials with gas phase material flow which is discharged from a fluidized bed hydrogenation-desulfuration reactor and a hydrogenation-denitrification reactor to enter into a hydrogenation-demetalization reactor; cooling and purifying reacted gas phase material flow to be taken as recycle hydrogen; mixing the demetallized liquid phase material flow with hydrogen to enter into the fluidized bed hydrogenation-desulfuration reactor; mixing the desulfurated liquid phase material flow with hydrogen to enter into the hydrogenation-desulfuration reactor; and leading the denitrified liquid phase material flow to enter into a separating device. The technology adopts a new reactor assembly mode to machine heavy oil raw materials with high viscosity and bad quality, can provide a new flexible, high-efficiency and energy-saving operation mode, organically combines the performances of the raw materials with the characteristic of each hydrogenation reaction, makes full use of reaction heating on the premise that a device is guaranteed to be stably operated, provides a product with good quality, and can flexibly adjust the operation process according to the requirement of a refinery.
Description
Technical field
The present invention relates to a kind of hydrogenation method of heavy hydrocarbon multi-segment fluidized bed, particularly heavy hydrocarbon feeds such as inferior heavy oil, residual oil carries out the hydrogenation method of operations such as boiling bed hydrogenation demetalization, boiling bed hydrogenation desulfurization, boiling bed hydrogenation denitrogenation.
Background technology
Along with the variation of petroleum products demand structure in the exploitation energetically of heavy crude and the world wide, market maintains sustained and rapid growth to the demand of light-weight fuel oil and the demand of heavy fuel oil (HFO) is reduced rapidly, and the deep process technology of heavy oil has become the emphasis of petroleum refining industry's development.The boiling bed hydrogenation technology has characteristics such as adaptability to raw material is wide, flexible operation, transformation efficiency height, good product quality, is one of important means of processing heavy hydrocarbon feeds.Conventional ebullated bed processing technology is used a plurality of reactors in series usually, hydrodemetallation (HDM) is housed in the reactor successively, hydrogenating desulfurization and hydrodenitrogenation catalyst, raw material with carry out hydrodemetallation (HDM), hydrogenating desulfurization and hydrodenitrification reaction by above-mentioned reactor in turn after hydrogen mixes.The reaction pattern of this routine can not be given full play to the handiness of ebullated bed reactor, the service temperature of ebullated bed reactor is higher simultaneously, be generally 410～460 ℃, this need be higher from the effusive material temperature of process furnace, even reach more than 410 ℃, but also need to use hot hydrogen carrier further to promote feeding temperature, could guarantee to enter the satisfied required temperature index of product requirement that reaches of stream temperature of reactor.And usually, adopt process furnace heating petroleum to control the furnace outlet temperature usually and be lower than 360～375 ℃.If temperature is too high, serious cracking and the reaction of condensation green coke can take place in macromolecular substance in the petroleum and condensed-nuclei aromatics, and the charging quality is poor more heavily more, macromolecular substance and condensed-nuclei aromatics cracking condensation green coke reaction Shaoxing opera is strong in the raw material, thereby the tube coking that causes process furnace, influence the heat-transfer effect of boiler tube, under the serious situation even cause device to be stopped work.And,, then need a large amount of hydrogen because hot hydrogen carrier thermal capacitance is low by the further temperature raising of hot hydrogen carrier, will increase the power consumption of heat energy consumption and compressor like this.Simultaneously in the boiling bed hydrogenation reaction of routine, the raw material that bituminous matter and condensed-nuclei aromatics content are high at first enters the hydrodemetallation (HDM) reactor because the viscosity of raw material is big, then raw material and hydrogen to contact effect relatively poor, mass transfer and heat-transfer effect are bad, and the hydrodemetallation (HDM) effect is undesirable.The gas-liquid phase reaction logistics of hydrodemetallation (HDM) is in turn by hydrogenating desulfurization and hydrodenitrification reactor simultaneously, because the transformation efficiency of boiling bed hydrogenation is higher, the light constituent that generates is more, the part light constituent is gaseous state under reaction conditions, reduced the hydrogen dividing potential drop of hydrogenating desulfurization and hydrodenitrification, thereby influence the hydrogenation effect, closely influence quality product.How rationally carry out process design and at energy-conservation, production high-quality liquid fuel or for downstream unit provides charging under the condition efficiently, and the characteristic that can give full play to ebullated bed device flexible operating is the important developing direction in this area according to feedstock property.
US6270654 has introduced and has used ebullated bed to carry out the multistage Catalytic processes of heavy hydrocarbon feeds hydrogenation, its flow process is: heavy hydrocarbon feeds mixes the back enters first no gas-liquid separation equipment with upflowing ebullated bed reactor with hydrogen, the logistics of coming out from reactor head enters outside phase separator, and isolated gas enters the gas sweetening district.Isolated partially liq loops back the ratio of expansion that first reactor (is anti-) is kept catalyzer through pump, another part liquid and second ebullated bed reactor (two is anti-) that enters inner gas-liquid separation after hydrogen mixes.Two anti-desulfurization degrees are 65-70wt%.The logistics of coming out from two anti-tops enters phase separator, and the hydrogen-containing gas that comes out from the separator top is removed carbonic acid gas through the gas purification device, loops back one anti-and two anti-behind ammonia and the hydrogen sulfide.The frequent decompression separation tower of liquid that comes out from separator bottom obtains lighter hydrocarbons and vacuum gas oil and tail oil, and a part of tail oil effluxes, and it is one anti-that a part loops back.
Summary of the invention
At the deficiencies in the prior art, the invention provides the multi-segment fluidized bed hydrogenation method of a kind of heavy hydrocarbon feeds, the inventive method can effectively be utilized the heat release of hydrogenating desulfurization and hydrodenitrification device reaction, improve the hydrodemetallation (HDM) temperature of reactor, suitably reduce the raw material Heating temperature, strengthen the gas-liquid of the demetalization reactor mixing contact effect between solid simultaneously, improve the hydrogen dividing potential drop of hydrogenating desulfurization and hydrodenitrification device, improve the hydrogenation reaction effect.
Hydrogenation method of heavy hydrocarbon multi-segment fluidized bed of the present invention comprises following process:
A) be mixed into boiling bed hydrogenation demetalization reactor after the heavy hydrocarbon feeds preheating with from the gas phase of boiling bed hydrogenation desulfurization and boiling bed hydrogenation denitrification reactor;
B) be used for boiling bed hydrogenation desulfurization and boiling bed hydrogenation denitrification reaction as recycle hydrogen after the isolated gas phase separation of step a) boiling bed hydrogenation demetalization reactor purifies;
C) liquid phase stream and the hydrogen of the outflow of step a) boiling bed hydrogenation demetalization reactor are mixed into the boiling bed hydrogenation desulphurization reactor;
D) effusive liquid phase stream of step c) boiling bed hydrogenation desulphurization reactor and hydrogen are mixed into the boiling bed hydrogenation denitrification reactor, and boiling bed hydrogenation denitrification reactor liquid phase effluent enters tripping device;
E) isolated gas phase of boiling bed hydrogenation denitrification reactor and boiling bed hydrogenation desulphurization reactor are isolated all or part of boiling bed hydrogenation demetalization reactor that enters of gas phase.
In the inventive method, the described heavy hydrocarbon feeds of step a) comprises one or more in the inferior raw materials such as long residuum, vacuum residuum, deasphalted oil, oil sands bitumen, consistency crude oil, coal tar and gelatin liquefaction heavy oil.Wherein boiling bed hydrogenation demetalization, hydrogenating desulfurization and hydrodenitrification reactor refer to be equipped with respectively the conventional ebullated bed reactor of hydrodemetallation (HDM), hydrogenating desulfurization and hydrodenitrogenation catalyst, as the ebullated bed reactor of band gas, liquid, solid triphase separator in the reactor, wherein the gas phase of reaction back generation is discharged from reactor respectively through different outlets with liquid phase.The boiling bed hydrogenation catalyst for demetalation is the hydrotreating catalyst of this area routine, and wherein the activity of such catalysts metal can be in nickel, cobalt, molybdenum or the tungsten one or more.Can comprise by weight percentage as the catalyzer composition: nickel or cobalt are 0.5%～8% (calculating by its oxide compound), molybdenum or tungsten are 1%～10% (calculating by its oxide compound), and carrier can be in aluminum oxide, silicon oxide, aluminium oxide-silicon oxide or the titanium oxide one or more.The shape of catalyzer is extrudate or sphere, and bulk density is 0.3～0.8g/cm
3, particle diameter (spherical diameter or bar shaped diameter) is 0.3～1.0mm, specific surface area is 80～120m
2/ g.The demetallated reaction conditions of boiling bed hydrogenation is: reaction pressure 6～30MPa, and temperature of reaction is 350～500 ℃, air speed is 0.1～5h
-1, hydrogen to oil volume ratio is 400～2000.
Hydrogen and light hydrocarbons in the isolated gas phase of step b) boiling bed hydrogenation demetalization reactor, through refrigerated separation, obtain the light hydrocarbons product, hydrogen-rich gas is through being used for the boiling bed hydrogenation desulfurization and the boiling bed hydrogenation denitrification reaction of process of the present invention as recycle hydrogen behind the depriving hydrogen sulphide, the additional new hydrogen of reactive system also can add in the recycle hydrogen.
Catalyzer in the boiling bed hydrogenation desulphurization reactor described in the step c) is the hydrotreating catalyst of this area routine, and wherein the activity of such catalysts metal can be in nickel, cobalt, molybdenum or the tungsten one or more.Can comprise by weight percentage as the catalyzer composition: nickel or cobalt are 0.1%～12% (calculating by its oxide compound), molybdenum or tungsten are 5%～15% (calculating by its oxide compound), and carrier can be in aluminum oxide, silicon oxide, aluminium oxide-silicon oxide or the titanium oxide one or more.The shape of catalyzer is extrudate or sphere, and bulk density is 0.4～0.9g/cm
3, particle diameter (spherical diameter or bar shaped diameter) is 0.08～0.8mm, specific surface area is 100～200m
2/ g.The demetallated reaction conditions of boiling bed hydrogenation is: reaction pressure 6～30MPa, and temperature of reaction is 350～500 ℃, air speed is 0.1～5h
-1, hydrogen to oil volume ratio is 400～2000.The reaction conditions of boiling bed hydrogenation desulfurization is: reaction pressure 6～30MPa, and temperature of reaction is 350～500 ℃, air speed is 0.1～5h
-1, hydrogen to oil volume ratio is 400～2000.The liquid phase stream of boiling bed hydrogenation demetalization reactor can enter the boiling bed hydrogenation desulphurization reactor after increasing, flow smoothly to promote material.
Catalyzer in the boiling bed hydrogenation denitrification reactor described in the step d) is the hydrotreating catalyst of this area routine, and wherein the activity of such catalysts metal can be in nickel, cobalt, molybdenum or the tungsten one or more.Can comprise by weight percentage as the catalyzer composition: nickel or cobalt are 1%～20% (calculating by its oxide compound), molybdenum or tungsten are 5%～30% (calculating by its oxide compound), and carrier can be in aluminum oxide, silicon oxide, aluminium oxide-silicon oxide or the titanium oxide one or more.The shape of catalyzer is extrudate or sphere, and bulk density is 0.4～0.9g/cm
3, particle diameter (spherical diameter or bar shaped diameter) is 0.08～0.6mm, specific surface area is 100～300m
2/ g.The reaction conditions of boiling bed hydrogenation denitrogenation is: reaction pressure 6～30MPa, and temperature of reaction is 350～500 ℃, air speed is 0.1～5h
-1, hydrogen to oil volume ratio is 400～2000.Water distilling apparatus described in the step d) comprises atmospheric and vacuum tower, isolates light hydrocarbons such as petroleum naphtha, diesel oil distillate.
According to the needs of boiling bed hydrogenation demetalization reaction process to gas volume, the isolated gas phase of boiling bed hydrogenation desulphurization reactor can all enter ebullated bed demetalization reactor, also can partly enter ebullated bed demetalization reactor, concrete amount can be determined according to the operational condition of ebullated bed demetalization reactor.When the isolated gas phase of boiling bed hydrogenation desulphurization reactor partly enters boiling bed hydrogenation demetalization reactor, remainder can enter the boiling bed hydrogenation denitrification reactor, recycles after also can handling jointly with the isolated gas phase of boiling bed hydrogenation demetalization reactor.
In the multistage boiling bed hydrogenation technique of heavy hydrocarbon of the present invention; hydrodemetallation (HDM) reactor, hydrodesulphurisatioreactors reactors and hydrodenitrification reactor are can be according to the needs of unit scale or working depth in parallel respectively or connect a plurality of (parallel connection refers to that liquid phase material enters different reactor respectively, and series connection refers to that liquid phase material passes through different reactors successively).For example, in order to reach the purpose that the degree of depth transforms and takes off impurity, two the hydrodenitrification reactors of can connecting; Deep desulfuration if desired, two hydrodesulphurisatioreactors reactors of then can connecting.
In the inventive method, unconverted tail oil can all or part ofly loop back boiling bed hydrogenation demetalization reactor or boiling bed hydrogenation desulphurization reactor, also can be used as the charging of catalytic cracking unit.
Compared with prior art, the advantage of ebullated bed complete processing of the present invention is:
(1) adopt high temperature gaseous stream and the heavy hydrocarbon feedstocks of hydrogenating desulfurization and hydrodenitrification to be mixed into the hydrodemetallation (HDM) reactor, can preheating material, reduce the thermal load of raw materials furnace and heating, saving heat energy makes full use of the hydrogenation reaction heat release, assurance device running period.
(2) condensed-nuclei aromatics and asphalt content height in the heavy hydrocarbon feeds, viscosity is big, is unfavorable for mass-and heat-transfer.Adopt the gaseous stream of hydrogenating desulfurization and hydrodenitrification to be circulated to the hydrodemetallation (HDM) reactor, can guarantee under reaction conditions, the turbulent flow back-mixing is effective in the reactor, help fully contacting of the interior raw material of reactor and gas and catalyzer, thereby help the alternate transmission of quality and heat, promote reaction to carry out.
(3) adopt recycle hydrogen respectively with hydrogenating desulfurization and hydrodenitrification logistics hybrid reaction, can improve the hydrogen dividing potential drop under the reaction conditions, help the carrying out of hydrogenation reaction, the fine hydrogenated products are provided.
(4) adopt part or all of hydrodenitrification tail oil circulation, can increase conversion of raw material, improve the yield of light weight fluid product.
(5) whole technological process adopts new operator scheme processing high viscosity inferior heavy oil raw material, performance and each hydrogenation reaction feature of charging are organically combined, can make full use of the existing energy, the fine quality product is provided, and can require to adjust flexibly operating process according to the refinery.
(6) reaction conditionss such as hydrodemetallation (HDM) reaction pair hydrogen dividing potential drop that remove inorganic metal compound and simple organometallic compound require lower, the present invention uses through hydrogenating desulfurization and the reacted gas phase of hydrodenitrification and originates as the hydrogen of hydrodemetallation (HDM), do not influence the hydrodemetallation (HDM) reaction on the one hand, needing to help the reaction conditions hydrogenating desulfurization and the hydrodenitrification process of harshness on the other hand, optimized the integrated operation condition.
Description of drawings
Fig. 1 is a kind of block diagram of the flexible ebullated bed complete processing of the present invention.
Embodiment
For further setting forth concrete feature of the present invention, will be illustrated in conjunction with the accompanying drawings.
In conjunction with the accompanying drawings 1, a kind of technological process of the present invention is:
Through the heavy hydrocarbon feeds of heating in pipeline 1 and pipeline 15 hydrogenating desulfurization and after the hydrodenitrification reactant gases mixes, enter boiling bed hydrogenation demetalization reactor 2 with upflowing and carry out hydrodemetallation (HDM) and react.Reacted gas-liquid logistics flows out from reactor respectively, and wherein gaseous stream can recycle through the hydrogen-rich gas that pipeline 3 obtains behind cooling and purifying, and the liquid that condensation is got off enters atmospheric and vacuum distillation unit and obtains gasoline, diesel oil distillate; Liquid phase stream mixes with hydrogen in the pipeline 7 through pipeline 4, enters boiling bed hydrogenation desulphurization reactor 5 with upflowing and carries out hydrodesulfurization reaction.Gaseous stream behind the hydrodesulfurization reaction is discharged from reactor through pipeline 6, is circulated to hydrodemetallation (HDM) reactor 5 through pipeline 15; Liquid phase stream is discharged from reactor through pipeline 8, enters boiling bed hydrogenation denitrification reactor 9 with upflowing after mixing with the hydrogen of pipeline 11 and carries out the hydrodenitrification reaction.Reacted gaseous stream is discharged from reactor through pipeline 10, is circulated to boiling bed hydrogenation demetalization reactor 2 through pipeline 15; Liquid phase stream enters tripping device 12, isolated part or all of heavy constituent or be circulated to boiling bed hydrogenation demetalization reactor through pipeline 16, or discharge through pipeline 14 and to obtain petrol and diesel oil product and fine catalysis charging with isolated light constituent through water distilling apparatus.
For further specifying the solution of the present invention and effect, enumerate following examples.The per-cent that wherein relates to all is weight percentage.
The residual oil raw material character that test is used is listed in table 1.This residual oil raw material carbon residue is 18.3% as shown in Table 1, and metal content is 328.9 μ g.g
-1, bituminous matter is 13.4%, and S content is 2.5%, and N content is 0.6%, is with the unmanageable inferior raw material of ordinary method.
Embodiment
Present embodiment be the ebullated bed complete processing a kind of embodiment, the operating process synoptic diagram is with reference to accompanying drawing 1.
Technological process is: be heated to through process furnace 360 ℃ raw material (required Heating temperature is low about 40 ℃ than traditional technology) in pipeline 1 and pipeline 15 440 ℃ of hydrogenating desulfurizations and after the hydrodenitrification reactant gases mixes, enter boiling bed hydrogenation demetalization reactor 2 with upflowing and carry out the hydrodemetallation (HDM) reaction, wherein reaction conditions sees Table 2.Reacted gas-liquid logistics flows out from reactor respectively, and wherein gaseous stream recycles through the hydrogen-rich gas that pipeline 3 obtains behind cooling and purifying, and the liquid that condensation is got off enters atmospheric and vacuum distillation unit and obtains gasoline, diesel oil distillate; Liquid phase stream mixes with hydrogen in the pipeline 7 through pipeline 4, enters boiling bed hydrogenation desulphurization reactor 5 with upflowing and carries out hydrodesulfurization reaction, and reaction conditions sees Table 2.Gaseous stream behind the hydrodesulfurization reaction is discharged from reactor through pipeline 6, is circulated to hydrodemetallation (HDM) reactor 5 through pipeline 15; Liquid phase stream is discharged from reactor through pipeline 8, enters boiling bed hydrogenation denitrification reactor 9 with upflowing after mixing with the hydrogen of pipeline 11 and carries out the hydrodenitrification reaction, and reaction conditions sees Table 2.Reacted gaseous stream is discharged from reactor through pipeline 10, is circulated to boiling bed hydrogenation demetalization reactor 2 through pipeline 15; Liquid phase stream enters tripping device 12, and isolated heavy constituent all enter atmospheric and vacuum distillation unit through pipeline 14 discharges with isolated light constituent and obtain gasoline, diesel oil distillate and catalytic cracking unit charging.
The boiling bed hydrogenation catalyst for demetalation that process of the test is used as microspheroidal with the tungsten-nickel catalyzator of aluminum oxide as carrier, wherein contain WO in the catalyzer
3Be 6wt%, containing NiO is 2wt%.The bulk density of catalyzer is 0.60g/cm
3, surface-area is 110m
2/ g, the granules of catalyst mean diameter is 0.7mm.
The boiling bed hydrogenation desulfurization catalyst that process of the test is used as microspheroidal with the molybdenum-nickel catalyzator of aluminum oxide as carrier, wherein contain MoO in the catalyzer
3Be 14wt%, containing NiO is 6wt%.The bulk density of catalyzer is 0.78g/cm
3, surface-area is 200m
2/ g, the granules of catalyst mean diameter is 0.3mm.
The boiling bed hydrogenation denitrification catalyst that process of the test is used as microspheroidal with the molybdenum-nickel catalyzator of aluminum oxide as carrier, wherein contain MoO in the catalyzer
3Be 20wt%, containing NiO is 8wt%.The bulk density of catalyzer is 0.85g/cm
3, surface-area is 290m
2/ g, the granules of catalyst mean diameter is 0.3mm.
Reaction conditions and the results are shown in sees Table 2 and table 3.
Comparative example
Use conventional technological process to carry out ebullated bed heavy oil hydrogenation demetal, hydrogenating desulfurization and hydrodenitrification reaction.
Technological process is: be heated to 400 ℃ raw material through process furnace and enter boiling bed hydrogenation demetalization reactor with upflowing after hydrogen mixes, reacted logistics is discharged from reactor head, enter the boiling bed hydrogenation desulphurization reactor with upflowing, enter the boiling bed hydrogenation denitrification reactor from the effusive reactant flow of reactor head with upflowing, reaction back logistics is discharged from reactor head and is entered atmospheric and vacuum distillation unit, obtain gasoline, diesel oil and catalytic cracking charging.Reaction conditions and result see Table 2 and table 3 respectively.Use therein raw material is identical with embodiment 1 with hydrodemetallation (HDM), hydrogenating desulfurization and hydrodenitrogenation catalyst.
Table 1 test residual oil raw material character
| Project | Data |
| Density (20 ℃), kg.m -3 | ??1007.8 |
| Carbon residue, wt% | ??18.3 |
| Viscosity (100 ℃), mm 2/s | ??576.7 |
| Condensation point, ℃ | ??40 |
| Ultimate analysis, wt% | |
| ??C/H | ??86.3/10.7 |
| ??S/N | ??2.5/0.6 |
| Metallic element, μ g.g -1 | |
| ??Fe/Ni/V | ??2.9/38.6/287.4 |
| Four proximate analyses, wt% | |
| Stable hydrocarbon | ??29.0 |
| Project | Data |
| Aromatic hydrocarbon | ??33.1 |
| Colloid | ??24.5 |
| Bituminous matter | ??13.4 |
Table 2 reaction conditions
| Numbering | Embodiment | Comparative example |
| Boiling bed hydrogenation demetalization reaction conditions: | ||
| Temperature of reaction, ℃ | ??410 | ??410 |
| Reaction pressure, MPa | ??15 | ??15 |
| Reaction velocity, h -1 | ??3.5 | ??3.5 |
| Hydrogen to oil volume ratio | About 1500 (gas and oil volume ratio *) | ??700 |
| Boiling bed hydrogenation desulphurization reaction condition: | ||
| Temperature of reaction, ℃ | ??440 | ??440 |
| Reaction pressure, MPa | ??15 | ??15 |
| Hydrogen to oil volume ratio | ??700 | ??700 |
| Reaction velocity, h -1 | ??3.0 | ??3.0 |
| Boiling bed hydrogenation denitrification reaction condition: | ||
| Temperature of reaction, ℃ | ??440 | ??440 |
| Reaction pressure, MPa | ??15 | ??15 |
| Hydrogen to oil volume ratio | ??700 | ??700 |
| The total reaction air speed, h -1 | ??2.5 | ??2.5 |
* the gas and oil volume ratio is the volume ratio of gas phase and stock oil, contains the light hydrocarbons that a large amount of ebullating bed reactors generate in the gas phase except that hydrogen.
Table 3 reaction result
| Numbering | Embodiment | Comparative example |
| Gasoline | ||
| ?S/μg.g-1 | ??47 | ??150 |
| ?N/μg.g-1 | ??2.1 | ??10.7 |
| Yield, wt% | ??15.5 | ??13.3 |
| Diesel oil | ||
| ?S/μg.g-1 | ??70 | ??240 |
| ?N/μg.g-1 | ??21.7 | ??42.1 |
| Yield, % | ??47.5 | ??45.7 |
| FCC charging (ebullated bed processing tail oil) | ||
| ??S，wt％ | ??0.24 | ??0.7 |
| ??N，wt％ | ??0.054 | ??0.091 |
| Metal (Ni+V)/μ g.g-1 | ??6 | ??15 |
| Carbon residue, wt% | ??0.2 | ??0.4 |
| Yield, wt% | ??37.0 | ??41.0 |
Claims (10)
1. hydrogenation method of heavy hydrocarbon multi-segment fluidized bed comprises following process:
A) be mixed into boiling bed hydrogenation demetalization reactor after the heavy hydrocarbon feeds preheating with from the gas phase of boiling bed hydrogenation desulfurization and boiling bed hydrogenation denitrification reactor;
B) be used for boiling bed hydrogenation desulfurization and boiling bed hydrogenation denitrification reaction as recycle hydrogen after the isolated gas phase separation of step a) boiling bed hydrogenation demetalization reactor purifies;
C) liquid phase stream and the hydrogen of the outflow of step a) boiling bed hydrogenation demetalization reactor are mixed into the boiling bed hydrogenation desulphurization reactor;
D) effusive liquid phase stream of step c) boiling bed hydrogenation desulphurization reactor and hydrogen are mixed into the boiling bed hydrogenation denitrification reactor, and boiling bed hydrogenation denitrification reactor liquid phase effluent enters tripping device;
E) isolated gas phase of boiling bed hydrogenation denitrification reactor and boiling bed hydrogenation desulphurization reactor are isolated all or part of boiling bed hydrogenation demetalization reactor that enters of gas phase.
2. it is characterized in that in accordance with the method for claim 1: the described heavy hydrocarbon feeds of step a) comprises one or more of long residuum, vacuum residuum, deasphalted oil, oil sands bitumen, consistency crude oil, coal tar and gelatin liquefaction heavy oil inferior raw material.
3. in accordance with the method for claim 1, it is characterized in that: the demetallated reaction conditions of boiling bed hydrogenation is: reaction pressure 6～30MPa, and temperature of reaction is 350～500 ℃, air speed is 0.1～5h
-1, hydrogen to oil volume ratio is 400～2000; The reaction conditions of boiling bed hydrogenation desulfurization is: reaction pressure 6～30MPa, and temperature of reaction is 350～500 ℃, air speed is 0.1～5h
-1, hydrogen to oil volume ratio is 400～2000; The reaction conditions of boiling bed hydrogenation denitrogenation is: reaction pressure 6～30MPa, and temperature of reaction is 350～500 ℃, air speed is 0.1～5h
-1, hydrogen to oil volume ratio is 400～2000.
4. in accordance with the method for claim 1, it is characterized in that: boiling bed hydrogenation catalyst for demetalation composition is pressed oxide compound and is calculated, and comprise by weight percentage: nickel or cobalt are 0.5%～8%, and molybdenum or tungsten are 1%～10%.
5. in accordance with the method for claim 1, it is characterized in that: boiling bed hydrogenation desulfurization catalyst composition is pressed oxide compound and is calculated, and comprise by weight percentage: nickel or cobalt are 0.1%～12%, and molybdenum or tungsten are 5%～15%.
6. in accordance with the method for claim 1, it is characterized in that: boiling bed hydrogenation denitrification catalyst composition is pressed oxide compound and is calculated, and comprise by weight percentage: nickel or cobalt are 1%～20%, and molybdenum or tungsten are 5%～30%.
7. it is characterized in that in accordance with the method for claim 1: the ebullated bed reactor of band gas, liquid, solid triphase separator in the reactor is used in the boiling bed hydrogenation reaction.
8. in accordance with the method for claim 1, it is characterized in that: hydrogen and light hydrocarbons in the isolated gas phase of step b) boiling bed hydrogenation demetalization reactor, through refrigerated separation, obtain the light hydrocarbons product, hydrogen-rich gas is used for boiling bed hydrogenation desulfurization and boiling bed hydrogenation denitrification reaction through behind the depriving hydrogen sulphide as recycle hydrogen.
9. it is characterized in that in accordance with the method for claim 1: hydrodemetallation (HDM) reactor, hydrodesulphurisatioreactors reactors and hydrodenitrification reactor are in parallel respectively or connect a plurality of.
10. in accordance with the method for claim 1, it is characterized in that: all or part of boiling bed hydrogenation demetalization reactor or the boiling bed hydrogenation desulphurization reactor of looping back of unconverted tail oil, perhaps as the charging of catalytic cracking unit.
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| CN102465009A (en) * | 2010-11-04 | 2012-05-23 | 中国石油化工股份有限公司 | Multistage boiling bed heavy oil hydrogenation treatment method |
| CN103059928A (en) * | 2011-10-24 | 2013-04-24 | 中国石油化工股份有限公司 | Hydrotreating device and application thereof as well as residual oil hydrotreating method |
| CN103102938A (en) * | 2011-11-10 | 2013-05-15 | 中国石油化工股份有限公司 | Fluidized bed hydrotreatment method |
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