CN104974792B - A kind of fluidized-bed hydrogenation system and method for hydrotreating - Google Patents
A kind of fluidized-bed hydrogenation system and method for hydrotreating Download PDFInfo
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- CN104974792B CN104974792B CN201410128269.8A CN201410128269A CN104974792B CN 104974792 B CN104974792 B CN 104974792B CN 201410128269 A CN201410128269 A CN 201410128269A CN 104974792 B CN104974792 B CN 104974792B
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Abstract
The invention discloses a kind of fluidized-bed hydrogenation system and method for hydrotreating.System includes：Fluidized-bed hydrogenation reactor and middle knockout drum；Fluidized-bed hydrogenation reactor bottom is provided with material inlet and circulation oil inlet, knockout drum in the middle of fluidized-bed hydrogenation reactor head outlet connection, middle knockout drum bottom outlet line is divided into two, one connection fluidized-bed hydrogenation reactor bottom, another with centre knockout drum overhead line merge after send out out-of-bounds.The present invention is back to the entrance of fluidized-bed reactor by a liquid phase part for middle point of flow container bottom as recycle oil, eliminate the circulation cup in traditional ebullated bed or suspended-bed reactor, add the useful space of fluidized-bed reactor, improve the utilization rate of catalyst, the limited loadings of catalyst are added, while facilitating the operation and maintenance of device.
Description
Technical field
The present invention relates to field of hydrogenation, furtherly, it is related to a kind of fluidized-bed hydrogenation system and method for hydrotreating.
Background technology
With the change weight of crude oil, deteriorate, weight, the deep processing technology of residual oil have become the weight of petroleum resources exploitation
Point, current industrial widely used Residue Hydrotreating Technology mainly has two kinds of fixed bed and ebullated bed.When processing is inferior（High-sulfur,
High carbon residue, high metal）During residual oil, fixed bed hydrogenation can run into beds coking caused by highly exothermic reaction, solids product
The problems such as bed pressure drop increase caused by poly- and catalyst poisoning.The problem of boiling bed hydrogenation then avoids fixed bed hydrogenation, can
To be well adapted for processing poor residuum, while can guarantee that the long period steady running of device.
Floating bed hydrogenation is also a kind of important chemical reaction process of heavy oil lighting, in PETROLEUM PROCESSING, coal chemical industry and change
Industrial and commercial bank's industry has a wide range of applications, and fixed bed and boiling bed hydrogenation have obtained substantial amounts of commercial Application, and suspension bed is in heavy oil
The commerical test stage is in processing.
Reactor is one of the most key equipment of direct coal liquefaction process, is a gas, solid, liquid three-phase slurries
State reaction system, suspension bed has been realized in industrialized production in coal liquefaction manufacture field, and has obtained commercial Application checking.
Fluid bed is a general designation to ebullated bed and suspension bed, and the catalyst referred to has a kind of motion in reaction system
State, is divided into ebullated bed and suspension bed according to existence form of the catalyst in reactor.
Ebullated bed, suspension bed are all a kind of forms in fluidization, at present, and boiling bed hydrogenation is the business of comparative maturity
The technology of industry, floating bed hydrogenation technology is in the commercial development stage, and these technologies are all to use the interior circulation with circulation cup
Formula reactor seethes with excitement or suspended to realize, this form causes structure of reactor complicated, and reactor useful space utilization rate is low, if
Standby investment is big, and the utilization rate of catalyst is not high, it has not been convenient to safeguards and overhauls.
The content of the invention
To solve produced problem in the prior art, the invention provides a kind of fluidized-bed hydrogenation system and method for hydrotreating.
The technological process of the present invention is simple, easy to operate；It is adapted to the raw material of various different mal-conditions.
An object of the present invention is to provide a kind of fluidized-bed hydrogenation system.
Including：Fluidized-bed hydrogenation reactor and middle knockout drum；Fluidized-bed hydrogenation reactor bottom is provided with material inlet
With circulation oil inlet, the middle knockout drum of fluidized-bed hydrogenation reactor head outlet connection, middle knockout drum bottom outlet line point
Into two, a connection fluidized-bed hydrogenation reactor bottom, another merge with centre knockout drum overhead line after send out out-of-bounds.
Wherein,
The fluidized-bed hydrogenation reactor is up flow type fluidized-bed reactor.
The beds of fluidized-bed hydrogenation reactor are ebullated bed or suspension bed.
The middle knockout drum bottom is taper.It is preferred that：The taper of middle knockout drum bottom pyramidal is 15~60 degree.Liquid phase
Residence time is 2-8min.
The benefit of pyramidal structure increases the flow velocity of liquid, prevents coking of the liquid at wall.Fluid retention time is main
It is to be controlled by liquid level, the space size of middle point of flow container liquid phase section determines the residence time of liquid in the design process.
Oil circulating pump is provided with the pipeline of middle knockout drum bottom connection flow fluidized bed reactor.
Fluidized-bed hydrogenation reactor can be separate unit or more than two serial or parallel connections.
The second object of the present invention is to provide a kind of fluidized-bed hydrogenation method.
Including：
Feedstock oil enters with hydrogen from the reaction feed mouthful of the fluidized-bed reactor bottom, hydrogenated reaction, reaction production
Thing is discharged from top reacting product outlet, into centre point flow container；Reaction product is flashed in the flow container of centre point；It is used as weight
The liquid phase of cut, from the discharge of centre point flow container bottom, is divided into two-way, the recycle oil that fluidized-bed hydrogenation reactor is delivered to all the way enters
Mouthful；Remaining liquid-phase product from the gas phase of the light fraction of discharge at the top of middle point of flow container with merging into final reacting product.
Described feedstock oil is at least one of residual oil, liquefied coal coil, coal slurry or coal tar；
It is each that described hydrogen comes from device for producing hydrogen, catalytic reforming unit, ethylene cracker, PSA hydrogen gas recovering devices
From at least one of gained hydrogen.
Fluidized-bed hydrogenation reaction condition can be used in common hydrogenation conditions in this area, the present invention, preferably：
The operating condition pressure of described fluidized-bed hydrogenation reactor is 10.0~21.0MPa, and 350~470 DEG C of temperature is former
0.1~2.0h of the oily liquid hourly space velocity (LHSV) of material-1；It is preferred that pressure is 12.0~20.0MPa, 360~460 DEG C of temperature, feedstock oil liquid hourly space velocity (LHSV)
0.4~1.5h-1；
The volume ratio of hydrogen/feedstock oil is 100:1~1200:1, preferably 200:1~1000:1；
The weight ratio of recycle oil and feedstock oil is 0.5:1~4:1, preferably 1.5:1~3:1.
The present invention can specifically use following technical scheme：
Oil circulating pump is provided with the flow container bottom liquid phases egress line of the centre point, it is anti-by the oil circulating pump and fluid bed
The circulation oil-in of device bottom is answered to connect.
Described fluidized-bed reactor is up flow type, and such as reactor is ebullated bed, and catalyst of filling remains one in it
Fixed material position；Such as reactor is suspension bed, and catalyst is dispersed in the reaction product with nano-form, reaction following reaction production
Thing outflow reactor.
The feedstock oil enters with hydrogen from the reaction feed mouthful of the fluidized-bed reactor bottom, through desulfurization, denitrogenation, takes off
The hydrofinishing or cracking reaction of oxygen, alkene saturation, aromatic hydrocarbons saturation, impurity removal etc., reaction product go out from top reaction product
Mouth discharge；
Described reaction product is directly entered a middle point flow container without processes such as heat exchange, decompressions after reactor outflow and entered
Mouthful, reaction product is flashed in the flow container of centre point, divides the discharge of flow container bottom, a part from centre as the liquid phase of heavy distillat
Liquid phase and the gas phase of light fraction are incorporated as final product from discharge at the top of the flow container of centre point；Another part is boosted, delivers to stream
The circulation oil-in of fluidized bed reactor.
The present invention is that knockout drum realizes the external liquid circulation of fluidized-bed reactor in the middle of borrowing.By liquefy outer circulation come
Realize ebullated bed or floating bed hydrogenation technology.All it is both at home and abroad at present that ebullated bed and suspension bed are reached using reactor interior circulation
Effect, compared with conventional ebullated bed and suspended-bed reactor interior circulation, the liquid phase one that the present invention passes through middle point of flow container bottom
Part is back to the entrance of fluidized-bed reactor as recycle oil, eliminates following in traditional ebullated bed or suspended-bed reactor
Ring cup, adds the useful space of fluidized-bed reactor, improves the utilization rate of catalyst, add the limited filling of catalyst
Amount, at utmost realizes hydrogenation reaction, while facilitating the operation and maintenance of device.
Apparatus of the present invention are simple, and the cycle of operation is long, easy to maintenance, investing it is with the obvious advantage.
Brief description of the drawings
The fluidized-bed hydrogenation system schematic of Fig. 1 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 phase, 9-liquid-phase product, 10- final reacting products, 11-oil circulating pump,
12-recycle oil.
Embodiment
With reference to embodiment, the present invention is further illustrated.
Embodiment
As shown in figure 1, a kind of fluidized-bed hydrogenation system.
Including：Fluidized-bed hydrogenation reactor 4 and middle knockout drum 6；The bottom of fluidized-bed hydrogenation reactor 4 is provided with raw material and entered
Knockout drum, the middle outlet at bottom pipe of knockout drum 6 in the middle of mouth and circulation oil inlet, the connection of the top exit of fluidized-bed hydrogenation reactor 4
Line is divided into two, a bottom of connection fluidized-bed hydrogenation reactor 4, another merge with the centre overhead line of knockout drum 6 after give
Outside out-of-bounds.
Wherein,
The fluidized-bed hydrogenation reactor 4 is up flow type fluidized-bed reactor.
The beds of fluidized-bed hydrogenation reactor 4 are ebullated bed.
The middle knockout drum bottom is taper, and taper is 30 degree.
Oil circulating pump 11 is provided with the pipeline of the middle bottom of knockout drum 6 connection fluidized-bed reactor.
Raw material 1 after boosting, heating is mixed into reaction feed 3 with hydrogen 2, then enters fluidized-bed reaction from bottom to top
Device 4, the pressure 13.5MPa of fluidized-bed reactor, 380 DEG C of temperature, hydrogen to oil volume ratio 252:1；Under above operating condition, raw material
A series of hydrofinishings such as hydrodenitrogenerations, deoxidation, desulfurization, alkene and aromatic hydrocarbons saturation are carried out in the presence of catalyst or cracking is anti-
Should；Reaction product 5 is directly entered middle point of flow container 6 after being left from the top of fluidized-bed reactor 4 without processes such as heat exchange, decompressions.
Reaction product is flashed in this point of flow container, after the gas phase 7 that tank deck is flashed off is mixed with liquid-phase product 9, is used as end reaction
Product 10 enters follow-up heat exchange, separative element processing.The liquid phase 8 of centre point flow container bottom separates a part through oil circulating pump 11
Boosting returns to fluidized-bed reactor circulation oil-in as recycle oil 12.
Claims (14)
1. a kind of fluidized-bed hydrogenation system, it is characterised in that the system includes：
Fluidized-bed hydrogenation reactor and middle knockout drum without built-in circulation cup；Fluidized-bed hydrogenation reactor bottom is provided with raw material
Knockout drum, middle knockout drum bottom outlet in the middle of import and circulation oil inlet, fluidized-bed hydrogenation reactor head outlet connection
Line is divided into two, a connection fluidized-bed hydrogenation reactor bottom, another merge with middle knockout drum overhead line after submitting
Out-of-bounds；
The middle knockout drum bottom is taper.
2. fluidized-bed hydrogenation system as claimed in claim 1, it is characterised in that：
The fluidized-bed hydrogenation reactor is up flow type fluidized-bed reactor.
3. fluidized-bed hydrogenation system as claimed in claim 2, it is characterised in that：
The beds of fluidized-bed hydrogenation reactor are ebullated bed or suspension bed.
4. fluidized-bed hydrogenation system as claimed in claim 1, it is characterised in that：
The taper of the middle knockout drum bottom pyramidal is 15~60 degree.
5. fluidized-bed hydrogenation system as claimed in claim 1, it is characterised in that：
Oil circulating pump is provided with the pipeline of middle knockout drum bottom connection flow fluidized bed reactor.
6. fluidized-bed hydrogenation system as claimed in claim 1, it is characterised in that：
Fluidized-bed hydrogenation reactor is separate unit or more than two serial or parallel connections.
7. the method for hydrotreating of a kind of fluidized-bed hydrogenation system using as described in one of claim 1~6, it is characterised in that described
Method includes：
Feedstock oil and hydrogen enter from the reaction feed mouthful of the fluidized-bed reactor bottom, hydrogenated reaction, reaction product from
Top reacting product outlet discharge, into centre point flow container；Reaction product is flashed in the flow container of centre point；It is used as heavy distillat
Liquid phase, from the discharge of centre point flow container bottom, be divided into two-way, the circulation oil-in of fluidized-bed hydrogenation reactor delivered to all the way；Its
Remaining liquid-phase product from the gas phase of the light fraction of discharge at the top of middle point of flow container with merging into final reacting product.
8. method of hydrotreating as claimed in claim 7, it is characterised in that：
Described feedstock oil is at least one of residual oil, liquefied coal coil, coal slurry or coal tar；
Described hydrogen comes from device for producing hydrogen, catalytic reforming unit, ethylene cracker, PSA hydrogen gas recovering devices each institute
Obtain at least one of hydrogen.
9. method of hydrotreating as claimed in claim 7, it is characterised in that：
The operating condition pressure of described fluidized-bed hydrogenation reactor is 10.0~21.0MPa, 350~470 DEG C of temperature, feedstock oil
0.1~2.0h of liquid hourly space velocity (LHSV)-1；
The volume ratio of hydrogen/feedstock oil is 400:1~1200:1；
The weight ratio of recycle oil and feedstock oil is 0.5:1~4:1.
10. method of hydrotreating as claimed in claim 9, it is characterised in that：
The pressure is 12.0~20.0MPa.
11. method of hydrotreating as claimed in claim 9, it is characterised in that：
The temperature is 360~460 DEG C.
12. method of hydrotreating as claimed in claim 9, it is characterised in that：
0.4~1.5h of the feedstock oil liquid hourly space velocity (LHSV)-1。
13. method of hydrotreating as claimed in claim 9, it is characterised in that：
The volume ratio of the hydrogen/feedstock oil is 500:1~1000:1.
14. method of hydrotreating as claimed in claim 9, it is characterised in that：
The weight ratio of the recycle oil and feedstock oil is 1.5:1~3:1.
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| CN102533324A (en) * | 2010-12-20 | 2012-07-04 | 中国石油化工股份有限公司 | Hydrogenation combined process |
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| CN102120934B (en) * | 2010-01-12 | 2014-01-15 | 中国石油化工集团公司 | Circulating liquid phase hydrogenation method |
| CN102533327A (en) * | 2010-12-23 | 2012-07-04 | 冯刚 | Single-stage inferior gasoline fraction hydrotreatment process method |
| CN103571533B (en) * | 2012-07-20 | 2015-09-09 | 中国石油化工集团公司 | A kind of coal tar hydrogenating system and method |
| CN103468285B (en) * | 2013-09-13 | 2015-12-09 | 神木富油能源科技有限公司 | In pulverized coal pyrolysis, coalite tar produces the method for oil fuel |
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