CN104974792A - Fluidized bed hydrogenation system and hydrogenation method - Google Patents
Fluidized bed hydrogenation system and hydrogenation method Download PDFInfo
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- CN104974792A CN104974792A CN201410128269.8A CN201410128269A CN104974792A CN 104974792 A CN104974792 A CN 104974792A CN 201410128269 A CN201410128269 A CN 201410128269A CN 104974792 A CN104974792 A CN 104974792A
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Abstract
The invention discloses a fluidized bed hydrogenation system and hydrogenation method. The system comprises a fluidized bed hydrogenation reactor and a middle separation tank, wherein a raw material inlet and a circulating oil inlet are formed at the bottom of the fluidized bed hydrogenation reactor; an exit at the top of the fluidized bed hydrogenation reactor is connected with the middle separation tank; an exit pipeline at the bottom of the middle separation tank is divided into two parts; and one part is connected with the bottom of the fluidized bed hydrogenation reactor while the other part is combined with the top pipeline of the middle separation tank and delivered outside. According to the system and method disclosed by the invention, one part of liquid phase at the bottom of the middle separation tank is used as an entrance for the circulating oil to return to the fluidized bed reactor, a circulating cup in traditional boiling bed or suspended bed reactor is saved, effective space of the fluidized bed reactor is increased, the utilization rate of the catalyst is improved, the limited filling quantity of catalyst is increased, and the operation and maintenance of the device are facilitated.
Description
Technical field
The present invention relates to field of hydrogenation, furtherly, relate to a kind of fluidized-bed hydrogenation system and method for hydrotreating.
Background technology
Along with the change weight of crude oil, become bad, deep processing technology that is heavy, residual oil has become the emphasis of petroleum resources exploitation, and the Residue Hydrotreating Technology of current industrial extensive employing mainly contains fixed bed and ebullated bed two kinds.When processing (high-sulfur, high carbon residue, high metal) residual oil inferior, fixed bed hydrogenation can run into beds coking that high thermopositive reaction causes, solids gathers the bed pressure drop caused and increases and the problem such as poisoning of catalyst.Boiling bed hydrogenation then avoids the problem of fixed bed hydrogenation, can adapt to well process poor residuum, simultaneously the long period steady running of energy assurance device.
Floating bed hydrogenation is also the important chemical reaction process of a kind of heavy oil lighting, have a wide range of applications in refining of petroleum, Coal Chemical Industry and chemical industry, fixed bed and boiling bed hydrogenation have obtained a large amount of industrial application, and suspension bed is in the commerical test stage in heavy oil upgrading.
Reactor is one of the most key equipment of direct coal liquefaction process, and be a gas, solid, liquid three-phase slurries state reaction system, suspension bed has achieved industrialized production at gelatin liquefaction manufacture field, and obtains industrial application checking.
Fluidized-bed is a general designation to ebullated bed and suspension bed, and the catalyzer referred to exists a kind of kinestate in reaction system, is divided into ebullated bed and suspension bed according to the existence form of catalyzer in reactor.
Ebullated bed, suspension bed are all a kind of forms in fluidization, at present, boiling bed hydrogenation is the business-like technology of comparative maturity, floating bed hydrogenation technology is in the commercial exploitation stage, and these technology are all adopt the inner-loop reactor with circulation cup realize boiling or suspend, and this form causes structure of reactor complicated, reactor useful space utilization ratio is low, facility investment is large, and the utilization ratio of catalyzer is not high, is inconvenient to safeguard and overhaul.
Summary of the invention
For solving produced problem in prior art, the invention provides a kind of fluidized-bed hydrogenation system and method for hydrotreating.Technical process of the present invention is simple, easy to operate; The raw material of various different mal-condition can be adapted to.
An object of the present invention is to provide a kind of fluidized-bed hydrogenation system.
Comprise: fluidized-bed hydrogenation reactor and middle separating tank; Fluidized-bed hydrogenation reactor bottom is provided with material inlet and turning oil import, separating tank in the middle of the outlet of fluidized-bed hydrogenation reactor head connects, bottom middle separating tank, outlet line is divided into two, one connects fluidized-bed hydrogenation reactor bottom, sends out-of-bounds after another and middle separating tank overhead line merge.
Wherein,
Described fluidized-bed hydrogenation reactor is upflowing fluidized-bed reactor.
The beds of fluidized-bed hydrogenation reactor is ebullated bed or suspension bed.
It is taper bottom described middle separating tank.Preferred: the tapering of middle separating tank bottom pyramidal is 15 ~ 60 degree.The liquid phase residence time is 2-8min.
The benefit of pyramidal structure increases the flow velocity of liquid, prevents liquid in the coking at wall place.Fluid retention time is mainly controlled by liquid level, and in the design process, the space size of point flow container liquid phase section determines the residence time of liquid.
The pipeline connecting fluidized-bed reactor bottom middle separating tank is provided with circulating oil pump.
Fluidized-bed hydrogenation reactor can be separate unit or more than two serial or parallel connections.
Two of object of the present invention is to provide a kind of fluidized-bed hydrogenation method.
Comprise:
Stock oil and hydrogen enter from the reaction feed mouth bottom described fluidized-bed reactor, and through hydrogenation reaction, reaction product is discharged from top reacting product outlet, enter middle point flow container; Reaction product is divided in flow container in centre and is carried out flash distillation; As the liquid phase of last running, discharge from middle separatory pot bottom, be divided into two-way, the turning oil entrance of fluidized-bed hydrogenation reactor is delivered on a road; All the other liquid-phase products merge into final reacting product with the gas phase of the lighting end of discharging from middle separatory tank top.
Described stock oil is at least one in residual oil, liquefied coal coil, coal slurry or coal tar;
Described hydrogen comes from device for producing hydrogen, catalytic reforming unit, ethylene cracker, the PSA hydrogen gas recovering device at least one separately in gained hydrogen.
Fluidized-bed hydrogenation reaction conditions can adopt common hydrogenation conditions in this area, in the present invention, and can be preferred:
The operational condition pressure of described fluidized-bed hydrogenation reactor is 10.0 ~ 21.0MPa, temperature 350 ~ 470 DEG C, stock oil liquid hourly space velocity 0.1 ~ 2.0h
-1; Preferred pressure is 12.0 ~ 20.0MPa, temperature 360 ~ 460 DEG C, stock oil liquid hourly space velocity 0.4 ~ 1.5h
-1;
The volume ratio of hydrogen/stock oil is 100:1 ~ 1200:1, is preferably 200:1 ~ 1000:1;
The weight ratio of turning oil and stock oil is 0.5:1 ~ 4:1, is preferably 1.5:1 ~ 3:1.
The present invention specifically can by the following technical solutions:
Described middle separatory pot bottom liquid-phase outlet line is provided with circulating oil pump, is connected with the turning oil entrance bottom fluidized-bed reactor through this circulating oil pump.
Described fluidized-bed reactor is upflowing, and if reactor is ebullated bed, in it, the catalyzer of filling remains certain material level; If reactor is suspension bed, catalyzer is in the reaction product dispersed with nano-form, reaction following response product outflow reactor.
Described stock oil and hydrogen enter from the reaction feed mouth bottom described fluidized-bed reactor, and through hydrofining or the cracking reaction of desulfurization, denitrogenation, deoxidation, olefin saturated, aromatic saturation, impurity removal etc., reaction product is discharged from top reacting product outlet;
Middle point flow container entrance is directly entered without the operation such as heat exchange, step-down after described reaction product flows out from reactor, reaction product is divided in flow container in centre and is carried out flash distillation, liquid phase as last running is discharged from middle separatory pot bottom, and the gas phase of a part of liquid phase and lighting end is discharged from middle separatory tank top and merged as final product; Another part, through boosting, delivers to the turning oil entrance of fluidized-bed reactor.
The present invention uses the external liquid circulation that middle separating tank achieves fluidized-bed reactor.Ebullated bed or floating bed hydrogenation technology is realized by liquefaction outer circulation.All the effect adopting reactor internal recycle to reach ebullated bed and suspension bed at present both at home and abroad, compare with suspended-bed reactor internal recycle with the ebullated bed of routine, the present invention is by a part of entrance being back to fluidized-bed reactor as turning oil of the liquid phase of middle separatory pot bottom, eliminate the circulation cup in traditional ebullated bed or suspended-bed reactor, add the useful space of fluidized-bed reactor, improve the utilization ratio of catalyzer, add the limited loadings of catalyzer, at utmost realize hydrogenation reaction, facilitate the operation and maintenance of device simultaneously.
Apparatus of the present invention are simple, and the cycle of operation is long, easy to maintenance, investing with the obvious advantage.
Accompanying drawing explanation
Fig. 1 fluidized-bed hydrogenation system schematic of the present invention
Description of reference numerals:
1-raw material, 2-hydrogen, 3-reaction feed, 4-fluidized-bed hydrogenation reactor, 5-reaction product, 6-middle point flow container, 7-gas phase, 8-middle point flow container outlet liquid phases, 9-liquid-phase product, 10-final reacting product, 11-circulating oil pump, 12-turning oil.
Embodiment
Below in conjunction with embodiment, further illustrate the present invention.
Embodiment
As shown in Figure 1, a kind of fluidized-bed hydrogenation system.
Comprise: fluidized-bed hydrogenation reactor 4 and middle separating tank 6; Material inlet and turning oil import is provided with bottom fluidized-bed hydrogenation reactor 4, separating tank in the middle of fluidized-bed hydrogenation reactor 4 top exit connects, middle separating tank 6 outlet at bottom pipeline is divided into two, one connects bottom fluidized-bed hydrogenation reactor 4, sends out-of-bounds after another and middle separating tank 6 overhead line merge.
Wherein,
Described fluidized-bed hydrogenation reactor 4 is upflowing fluidized-bed reactor.
The beds of fluidized-bed hydrogenation reactor 4 is ebullated bed.
Be taper bottom described middle separating tank, tapering is 30 degree.
The pipeline connecting fluidized-bed reactor bottom middle separating tank 6 is provided with circulating oil pump 11.
Raw material 1 after boosting, intensification is mixed into reaction feed 3 with hydrogen 2, then enters fluidized-bed reactor 4 from bottom to top, the pressure 13.5MPa of fluidized-bed reactor, temperature 380 DEG C, hydrogen to oil volume ratio 252:1; Under above operational condition, raw material carries out hydrofining or the cracking reactions such as a series of hydrodenitrification, deoxidation, desulfurization, alkene and aromatic saturation under the effect of catalyzer; Reaction product 5 directly enters middle point flow container 6 without the operation such as heat exchange, step-down after leaving from fluidized-bed reactor 4 top.Reaction product carries out flash distillation in this point of flow container, after the gas phase 7 that tank deck flashes off mixes with liquid-phase product 9, enters follow-up heat exchange, separating unit process as final reacting product 10.The liquid phase 8 of middle separatory pot bottom separates a part and boosts as turning oil 12 through circulating oil pump 11, returns fluidized-bed reactor turning oil entrance.
Claims (10)
1. a fluidized-bed hydrogenation system, is characterized in that described system comprises:
Fluidized-bed hydrogenation reactor and middle separating tank; Fluidized-bed hydrogenation reactor bottom is provided with material inlet and turning oil import, separating tank in the middle of the outlet of fluidized-bed hydrogenation reactor head connects, bottom middle separating tank, outlet line is divided into two, one connects fluidized-bed hydrogenation reactor bottom, sends out-of-bounds after another and middle separating tank overhead line merge.
2. fluidized-bed hydrogenation system as claimed in claim 1, is characterized in that:
Described fluidized-bed hydrogenation reactor is upflowing fluidized-bed reactor.
3. fluidized-bed hydrogenation system as claimed in claim 2, is characterized in that:
The beds of fluidized-bed hydrogenation reactor is ebullated bed or suspension bed.
4. fluidized-bed hydrogenation system as claimed in claim 1, is characterized in that:
It is taper bottom described middle separating tank.
5. fluidized-bed hydrogenation system as claimed in claim 4, is characterized in that:
The tapering of described middle separating tank bottom pyramidal is 15 ~ 60 degree.
6. fluidized-bed hydrogenation system as claimed in claim 1, is characterized in that:
The pipeline connecting fluidized-bed reactor bottom middle separating tank is provided with circulating oil pump.
7. fluidized-bed hydrogenation system as claimed in claim 1, is characterized in that:
Fluidized-bed hydrogenation reactor is separate unit or more than two serial or parallel connections.
8. adopt a method of hydrotreating for the fluidized-bed hydrogenation system as described in one of claim 1 ~ 7, it is characterized in that described method comprises:
Stock oil and hydrogen enter from the reaction feed mouth bottom described fluidized-bed reactor, and through hydrogenation reaction, reaction product is discharged from top reacting product outlet, enter middle point flow container; Reaction product is divided in flow container in centre and is carried out flash distillation; As the liquid phase of last running, discharge from middle separatory pot bottom, be divided into two-way, the turning oil entrance of fluidized-bed hydrogenation reactor is delivered on a road; All the other liquid-phase products merge into final reacting product with the gas phase of the lighting end of discharging from middle separatory tank top.
9. method of hydrotreating as claimed in claim 8, is characterized in that:
Described stock oil is at least one in residual oil, liquefied coal coil, coal slurry or coal tar;
Described hydrogen comes from device for producing hydrogen, catalytic reforming unit, ethylene cracker, the PSA hydrogen gas recovering device at least one separately in gained hydrogen.
10. method of hydrotreating as claimed in claim 8, is characterized in that:
The operational condition pressure of described fluidized-bed hydrogenation reactor is 10.0 ~ 21.0MPa, temperature 350 ~ 470 DEG C, stock oil liquid hourly space velocity 0.1 ~ 2.0h
-1; Preferred pressure is 12.0 ~ 20.0MPa, temperature 360 ~ 460 DEG C, stock oil liquid hourly space velocity 0.4 ~ 1.5h
-1;
The volume ratio of hydrogen/stock oil is 400:1 ~ 1200:1, is preferably 500:1 ~ 1000:1;
The weight ratio of turning oil and stock oil is 0.5:1 ~ 4:1, is preferably 1.5:1 ~ 3:1.
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Cited By (1)
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| CN114181034A (en) * | 2020-09-15 | 2022-03-15 | 中国石油化工股份有限公司 | Alkylation reaction system and method for aromatic hydrocarbon with more than eight carbon atoms |
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