CN110003937A - Boiling bed hydrogenation method - Google Patents
Boiling bed hydrogenation method Download PDFInfo
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- CN110003937A CN110003937A CN201910342694.XA CN201910342694A CN110003937A CN 110003937 A CN110003937 A CN 110003937A CN 201910342694 A CN201910342694 A CN 201910342694A CN 110003937 A CN110003937 A CN 110003937A
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- fluidized bed
- catalyst
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
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- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
This disclosure relates to a kind of boiling bed hydrogenation method, comprising: (a) makes the mixture of feedstock oil, hydrogen supply agent, recycle oil and hydrogen first pass through fluidized bed reactor I, fluidized bed reactor II offline standby connected in parallel；(b) when the catalyst activity in I significantly reduces, it is cut out, while switching pipeline and II is cut into process flow from process flow, the mixture is made to pass through II；(c) low activity catalyst drawn off in I is regenerated, and the catalyst after regeneration is still back to I；(d) when the catalyst activity in II significantly reduces, II is cut out, while switching pipeline and I is cut into process flow from process flow, the raw mixture is made to pass through I；(e) low activity catalyst drawn off in II is regenerated, and the catalyst after regeneration is still back to II；And (f) repeat step (b) to (e).
Description
Technical field
The disclosure belongs to chemical field, is related to a kind of flexible hydrogenation method, especially with boiling bed technique carry out residual oil,
The hydrogenation method of heavy oil and bio-oil.Specifically, a kind of this disclosure relates to boiling bed hydrogenation method.
Background technique
Hydrogen addition technology can be divided into fixed bed hydrogenation, floating bed hydrogenation, moving bed according to the catalyst bed difference used
Add hydrogen and boiling bed hydrogenation etc..So far, boiling bed hydrogenation technology has raw material due to using catalyst to add drainage technique online
The features such as wide adaptability, the operation cycle is long, flexible operation, so that the technology rapidly develops, but the online plus heat-extraction system of catalyst
Cost of investment is high, and operating procedure is complicated, while fluidized bed reactor continually adds row's catalyst to increase operation difficulty online, holds
The fluctuation for easily causing logistics composition and flow regime in reactor increases the operation difficulty of entire fluidized bed device, in addition by
Be in full back-mixing state in gas-solid-liquid logistics in fluidized bed reactor, thus the fresh catalyst being added online and inactivated or
The catalyst of partial inactivation uniformly mixes, and when progress decaying catalyst discharges online, makes part still urging with catalytic activity
Agent and decaying catalyst are discharged from the catalyst exit line line of reactor simultaneously, cannot efficiently use the activity of catalyst, wave
Take resource.Device long-term operation how was not only can guarantee, but also operating process can be simplified and can guarantee final product quality, under
It is the major issue for being worth explore and study that trip device, which provides high-quality charging or production qualified products,.
United States Patent (USP) USRE.25770 discloses the specific steps of boiling bed process: feedstock oil and hydrogen are from reactor bottom
Into distributor by a distribution grid and thereon makes uniform gas-liquid distribution, keeps catalyst bed swollen using the liquid stream of rising
It is swollen, and keep good back-mixing, realize isothermal reaction and reduce pressure drop.A part of product is recycled to provide foot with a centrifugal pump
Enough amount of liquid expand catalyst bed.Circulation cup is set in reactor head to separate gas in circulating liquid to reduce
Gas entrainment.Discharge a small amount of catalyst from reactor head supplement and reactor bottom daily to maintain certain activity, thus
Need not stop work more catalyst changeout.The patent adds heat-extraction system to carry out adding for fluidized bed reactor fresh catalyst online using catalyst
The exclusion of decaying catalyst after entering and reacting, which increases investment and operating cost, and increases operation difficulty.
U.S. Patent application US 5417846A proposes a kind of fixed bed protection reactor parallel connection switching thinking, with protection
Subsequent hydrodemetallization main reactor.When heavy hydrocarbon fixed bed hydrogenation demetalization-desulfurization, impurity in heavy hydrocarbon feeds with metal and
The form of coking gradually accumulates on a catalyst, makes catalyst failure and quickly obstruction, reduces catalyst life, lead to device
It cannot maintain long-term operation.This application before hydrodemetallization main reactor in parallel two fixed beds protection reactor R1a and
Any one reactor work in R1b, R1a and R1b, another offline standby, after the reactor catalyst in work fails,
The reactor is cut out, spare reactor is cut；The reactor cut out is connect with catalyst regeneration system, carries out useless agent again
It is raw；It is in operating status due in above-mentioned handoff procedure, always maintaining a fixed bed protection reactor, therefore handoff procedure
In, the influence to subsequent main reactor is smaller, and can guarantee the longer cycle of operation.It is disadvantageous in that, fixed bed protection
Catalyst reactor level of deactivation is uneven, and often inactivation, blocking occurs in overlying catalyst bed, and lower catalyst agent is still
Have certain activity, still, since the whole pressure drop of catalyst bed increases and has to cut out displacement, catalyst is caused to make
Use cost increase.
Therefore, for above-mentioned defect in the prior art, there is an urgent need in the art to develop a kind of flexible hydrogenation technique side
Method to can not only keep the technical advantage of fluidized bed reactor, but also can save the online plus heat-extraction system of fluidized bed reactor,
It can guarantee that properties of product meet scheduled index request simultaneously, and require simplification of flowsheet, it is easily operated.
Summary of the invention
Present disclose provides a kind of novel boiling bed hydrogenation methods, to overcome the defect of the prior art.
On the one hand, present disclose provides a kind of boiling bed hydrogenation methods, method includes the following steps:
(a) mixture of feedstock oil, hydrogen supply agent, recycle oil and hydrogen is made to first pass through fluidized bed reactor I, it is anti-with ebullated bed
Answer the fluidized bed reactor II offline standby of device I parallel connection；
(b) when in the fluidized bed reactor I catalyst activity significantly reduce when, by the fluidized bed reactor I from
It is cut out in boiling bed hydrogenation technique process, while switching pipeline and fluidized bed reactor II is cut into boiling bed hydrogenation technique process,
The mixture of the feedstock oil, hydrogen supply agent, recycle oil and hydrogen is set to pass through fluidized bed reactor II；
(c) low activity catalyst drawn off in the fluidized bed reactor I is regenerated, the catalysis of activity recovery after regeneration
Agent is still back to the fluidized bed reactor I；
(d) when the catalyst activity in fluidized bed reactor II significantly reduces, by fluidized bed reactor II from ebullated bed
It is cut out in hydrogenation technique process, while switching pipeline and fluidized bed reactor I is cut into boiling bed hydrogenation technique process, make the original
Expect that the mixture of oil, hydrogen supply agent, recycle oil and hydrogen passes through fluidized bed reactor I；
(e) low activity catalyst drawn off in the fluidized bed reactor II is regenerated, and activity recovery urges after regeneration
Agent is still back to the fluidized bed reactor II；And
(f) step (b) to (e) is repeated.
In one preferred embodiment, the feedstock oil is containing in aerobic, sulphur, nitrogen, chlorine and metal impurities atom
One or more macromolecule hydrocarbons.
In another preferred embodiment, the catalyst activity, which reduces, significantly refers to the anti-device exit oil of ebullated bed
Rate of oxygen be greater than 8wt%.
In another preferred embodiment, the catalyst activity, which reduces, significantly refers to the anti-device exit oil of ebullated bed
Tenor be greater than 20 μ g/g.
In another preferred embodiment, the catalyst activity, which reduces, significantly refers to the anti-device exit oil of ebullated bed
Carbon left be greater than 10wt%.In another preferred embodiment, the fluidized bed reactor I and fluidized bed reactor II
Operating condition are as follows: pressure be 10~20MPa, temperature be 380~450 DEG C, the weight hourly space velocity of reaction is in 0.2~4h-1；Institute
Fluidized bed reactor I and fluidized bed reactor II filling is stated using active carbon as the microspheroidal hydrogenation catalyst of carrier, wherein activity
Metallic element is iron, nickel, molybdenum or platinum, and particle diameter is 0.2~1.2mm；The operation cycle of the fluidized bed reactor I and II sets
It is calculated as 1~6 month；The fluidized bed reactor I and II has three phase separation structure.
In another preferred embodiment, the weight fraction ratio of the recycle oil and the feedstock oil is 2~10, institute
State recycle oil from the feedstock oil add hydrogen after hot high score oil；The weight fraction ratio of the hydrogen supply agent and the feedstock oil is
0.25~2, the hydrogen supply agent from the feedstock oil add hydrogen after diesel oil distillate oil.
In another preferred embodiment, in step (c) and step (e), by the low activity catalyst
Solvent eddy flow extraction-hot hydrogen is carried out to mention to realize regeneration with activity recovery；In step (f), step (b) to (e) 1- is repeated
10 times.
In another preferred embodiment, the solvent eddy flow extraction is using a kind of solvent selected from the group below: methanol,
Ethyl alcohol, sulfolane, triethylene glycol and tetraethylene glycol.
In another preferred embodiment, the low activity catalyst is regenerated in catalyst regeneration system,
The following steps are included:
(i) it is kept in after low activity catalyst is drawn off in the fluidized bed reactor；
(ii) low activity catalyst is mixed with solvent, forms the homogeneous mixture of catalysed particulate and solvent；
(iii) micro- eddy flow extraction is carried out to the homogeneous mixture of catalysed particulate obtained by step (ii) and solvent to wash, utilize micro- rotation
The mechanical stripping of insoluble material in outlet catalyst is realized in the rotation of particle in flow field；
(iv) under an atmosphere of hydrogen, make the work being oxidized on the catalyst granules washed in step (iii) by micro- eddy flow extraction
Property metal reduction and regeneration, and can return to fluidized bed reactor recycling；And
(v) solvent obtained by step (iii) is sent into rectifying column and carries out rectifying, the oil isolated mutually recycles, a part
Solvent is mixed with low activity catalyst again, is recycled, and another part solvent returns to rectifying column.
On the other hand, present disclose provides a kind of boiling bed hydrogenation methods, method includes the following steps:
(a) mixture of feedstock oil, hydrogen supply agent, recycle oil and hydrogen first passes through fluidized bed reactor I and carries out adding hydrogen, obtains
Hydrogenated products pass sequentially through thermal high flash column, air cooler, cold high pressure separator, high pressure hot separator and cold low separator
Gas-liquid separation and boiling range segmentation are carried out, hot high score oil a part of acquisition returns to the fluidized bed reactor I as recycle oil, obtains
The diesel oil distillate oil a part obtained is back to fluidized bed reactor I as hydrogen supply agent；The ebullated bed in parallel with fluidized bed reactor I
Reactor II offline standby；
(b) when in the fluidized bed reactor I catalyst activity significantly reduce when, by the fluidized bed reactor I from
It is cut out in boiling bed hydrogenation technique process, while switching pipeline and fluidized bed reactor II is cut into boiling bed hydrogenation technique process,
The mixture of the feedstock oil, hydrogen supply agent, recycle oil and hydrogen is set to pass through fluidized bed reactor II；
(c) low activity catalyst drawn off in the fluidized bed reactor I is regenerated, the catalysis of activity recovery after regeneration
Agent is still back to the fluidized bed reactor I；
(d) when the catalyst activity in fluidized bed reactor II significantly reduces, by fluidized bed reactor II from ebullated bed
It is cut out in hydrogenation technique process, while switching pipeline and fluidized bed reactor I is cut into boiling bed hydrogenation technique process, make the original
Expect that the mixture of oil, hydrogen supply agent, recycle oil and hydrogen passes through fluidized bed reactor I；
(e) low activity catalyst drawn off in the fluidized bed reactor II is regenerated, and activity recovery urges after regeneration
Agent is still back to the fluidized bed reactor II；And
(f) step (b) to (e) is repeated.
In one preferred embodiment, the low activity catalyst is regenerated in catalyst regeneration system, packet
Include following steps:
(i) low activity catalyst is drawn off in the fluidized bed reactor, is temporarily stored into surge tank；
(ii) low activity catalyst mix with solvent by star-shaped discharge valve, formation catalysed particulate and solvent
Homogeneous mixture；
(iii) homogeneous mixture of catalysed particulate obtained by step (ii) and solvent is sent into cyclone separator, is carried out micro-
Eddy flow extraction is washed, and the mechanical stripping of insoluble material in outlet catalyst is realized using the rotation of particle in micro- eddy flow field；
(iv) it will be sent into catalyst storage tank by the catalyst granules that micro- eddy flow extraction is washed in step (iii), in atmosphere of hydrogen
Under make the active metal being oxidized on catalyst granules restore and regeneration, and can pass through charging spout return fluidized bed reactor circulation
It uses；And
(v) solvent obtained by step (iii) is sent into rectifying column and carries out rectifying, the oil isolated mutually recycles, a part
Solvent is mixed with low activity catalyst again, is recycled, and another part solvent returns to rectifying column.
In another preferred embodiment, in step (f), step (b) to (e) is repeated 1-10 times.
In another preferred embodiment, the solvent is selected from the group: methanol, ethyl alcohol, sulfolane, triethylene glycol and four
Glycol.
The utility model has the advantages that
Compared with prior art, the advantages of the flexible plus hydrogen of the disclosure are as follows:
(1) heat-extraction system is added using the conventional ebullated bed of the method replacement of two fluidized bed reactor parallel connections online, can be kept away
Exempt from discharge of the active catalyst from reaction system, catalyst activity is made to be not fully exerted.It simultaneously can also be to avoid due to reaction
Device frequent progress catalyst adds the fluctuation of row's operation bring reaction temperature, pressure and logistics composition online, and it is difficult to reduce operation
Degree reduces equipment investment, streamline operation.
(2) method for using two fluidized bed reactor parallel connections, needs at any time according to more catalyst changeout by two ebullated beds
Any reactor in reactor cuts out the boiling bed process flow system of operation, and a remaining reactor is cut ebullated bed
It is run in process flow system, this operation can guarantee the continuity of entire ebullated bed operating system, guarantee device
Long-term operation.Operating process can be simplified while playing the advantages that fluidized bed reactor adaptability to raw material is strong, guarantee to produce
Quality.
(3) simultaneously use catalyst on-line regeneration system, be able to extend catalyst service life, reduce catalyst at
This, reduces waste discharge when more catalyst changeout, improves resource reclaim, is conducive to environmental protection.
Detailed description of the invention
Fig. 1 is the flow diagram according to the boiling bed hydrogenation method of one preferred embodiment of the disclosure.
Fig. 2 be according to a kind of working state schematic representation of the boiling bed hydrogenation method of one preferred embodiment of the disclosure,
Wherein, reactor I is opened, and reactor II is closed, and regenerative system closes.
Fig. 3 be according to a kind of working state schematic representation of the boiling bed hydrogenation method of one preferred embodiment of the disclosure,
Wherein, reactor I is opened, and reactor II is closed, and regenerative system is opened.
Fig. 4 be according to a kind of working state schematic representation of the boiling bed hydrogenation method of one preferred embodiment of the disclosure,
Wherein, reactor I is opened, and reactor II is closed, and regenerative system is opened.
Specific embodiment
Present inventor adds row after extensive and in-depth study, for original conventional fluidized bed reactor online
The defect of the height of cost of investment present in system, operating procedure complexity is developed a kind of using two fluidized bed reactor parallel connections
The process raw material mode of oil of the operation mode of switching replaces original conventional fluidized bed reactor and adds the flexible of heat-extraction system online
Hydrogenation technique, it is strong both to have played fluidized bed reactor adaptability to raw material, reactor isothermal operation, device long-term operation it is excellent
Point, and equipment investment cost can be saved simultaneously, simplify operating process, avoids adding the operation of row's bring online due to catalyst not
Ballast, and the effective active of catalyst can be made full use of, reduce operating cost.It joined catalyst on-line regeneration system simultaneously
System, is able to extend catalyst service life, reduces the cost of catalyst, reduce waste discharge when more catalyst changeout, improves
Resource reclaim is conducive to environmental protection.
Technical concept of the invention is as follows:
It is alternately carried out the hydro-conversion of feedstock oil using two fluidized bed reactors in parallel, is packed into two reactors
Hydrogenation catalyst of the same race, when the catalyst activity in fluidized bed reactor I significantly reduces, by the reactor from entire ebullated bed
It is cut out in hydrogenation technique process, is switched to fluidized bed reactor II and continues hydroprocessing, guarantee continuously running for device.It urges
Agent returns to fluidized bed reactor I through catalyst on-line regeneration, regenerated catalyst.When the catalyst in fluidized bed reactor II is living
Property significantly reduce when, which is cut out from entire boiling bed hydrogenation technique process, be switched to fluidized bed reactor I continuation
Hydroprocessing is carried out, guarantees continuously running for device.For catalyst through catalyst on-line regeneration, it is anti-that regenerated catalyst returns to ebullated bed
Answer device II.
In the first aspect of the disclosure, a kind of boiling bed hydrogenation method is provided, method includes the following steps:
(a) mixture of feedstock oil, hydrogen supply agent, recycle oil and hydrogen is made to first pass through fluidized bed reactor I, it is anti-with ebullated bed
Answer the fluidized bed reactor II offline standby of device I parallel connection；
(b) when in the fluidized bed reactor I catalyst activity significantly reduce when, by the fluidized bed reactor I from
It is cut out in boiling bed hydrogenation technique process, while switching pipeline and fluidized bed reactor II is cut into boiling bed hydrogenation technique process,
The mixture of the feedstock oil, hydrogen supply agent, recycle oil and hydrogen is set to pass through fluidized bed reactor II；
(c) low activity catalyst drawn off in the fluidized bed reactor I is regenerated, the catalysis of activity recovery after regeneration
Agent is still back to the fluidized bed reactor I；
(d) when the catalyst activity in fluidized bed reactor II significantly reduces, by fluidized bed reactor II from ebullated bed
It is cut out in hydrogenation technique process, while switching pipeline and fluidized bed reactor I is cut into boiling bed hydrogenation technique process, make the original
Expect that the mixture of oil, hydrogen supply agent, recycle oil and hydrogen passes through fluidized bed reactor I；
(e) low activity catalyst drawn off in the fluidized bed reactor II is regenerated, and activity recovery urges after regeneration
Agent is still back to the fluidized bed reactor II；And
(f) step (b) to (e) is repeated 1-10 times.
In the disclosure, the fluidized bed reactor that cuts out draws off decaying catalyst, passes through the solvent to decaying catalyst
Eddy flow extraction washes-and hot hydrogen mentions reduction activity recovery, decaying catalyst activation recovering, then is packed into fluidized bed reactor；Its
In, the activity that the catalyst activity significantly reduces the catalyst referred in the reactor is not able to satisfy downstream reactor or device
Charging index request.
In the disclosure, the feedstock oil is containing one of aerobic, sulphur, nitrogen, chlorine and metal impurities atom or a variety of
Macromolecule hydrocarbon；Boiling bed hydrogenation upgrading catalyst reactor inactivates replacement standard according to the property of the reactor effluent stream
Mass-energy is no to meet particular requirement.
In the disclosure, the catalyst activity significantly reduces containing for the exit oil for referring to fluidized bed reactor I or II
Oxygen rate is to be greater than 20 μ g/g or carbon left greater than 10wt% greater than 8wt% or containing amount of metal.
In the disclosure, the raw material is mainly feedstock oil；Wherein, boiling bed hydrogenation reactor refers to conventional ebullating bed reactor
Device, i.e., with the fluidized bed reactor of gas-liquid-solid three-phase separator, wherein the gas phase and liquid phase that generate after reaction are through different outlets point
It is not discharged from reactor.
In the disclosure, the operating condition of the fluidized bed reactor I and fluidized bed reactor II are as follows: pressure be 10~
20MPa, temperature are 380~450 DEG C, and the weight hourly space velocity of reaction is in 0.2~4h-1。
In the disclosure, the fluidized bed reactor I and fluidized bed reactor II filling is using active carbon as the microballoon of carrier
Shape hydrogenation catalyst, wherein active metallic element is iron, nickel, molybdenum or platinum, and particle diameter is 0.2~1.2mm.
In the disclosure, the operation cycle of the fluidized bed reactor I and II is designed as 1~6 month.
In the disclosure, the fluidized bed reactor I and II has three phase separation structure.
In the disclosure, the weight fraction ratio of the recycle oil and the feedstock oil is 2~10, the recycle oil from
The feedstock oil adds the hot high score oil after hydrogen.
In the disclosure, the weight fraction ratio of the hydrogen supply agent and the feedstock oil is 0.25~2, and the hydrogen supply agent comes from
Diesel oil distillate oil after the feedstock oil adds hydrogen.
In the disclosure, the solvent eddy flow extraction uses a kind of solvent selected from the group below: methanol, ethyl alcohol, sulfolane, three
Glycol and tetraethylene glycol.
In the disclosure, the low activity catalyst is regenerated in catalyst regeneration system, comprising the following steps:
(i) low activity catalyst is drawn off in the fluidized bed reactor, is temporarily stored into surge tank；
(ii) low activity catalyst mix with solvent by star-shaped discharge valve, formation catalysed particulate and solvent it is equal
Even mixture；
(iii) homogeneous mixture of catalysed particulate and solvent obtained by step (ii) is sent into cyclone separator, through micro- eddy flow
Extraction is washed, and the mechanical stripping of insoluble material in outlet catalyst is realized using the high speed rotation of particle in micro- eddy flow field；
(iv) enter catalyst storage tank by the catalyst granules that micro- eddy flow extraction is washed obtained in step (iii), in hydrogen
Under atmosphere, the active metal being oxidized on the catalyst granules is set to restore and regenerate, and ebullated bed can be returned to by charging spout
Reactor cycles use；And
(v) solvent obtained by step (iii) is sent into rectifying column and carries out rectifying, the oil isolated mutually recycles, a part
Solvent is mixed with low activity catalyst again, is recycled, and another part solvent returns to rectifying column.
In the second aspect of the disclosure, a kind of boiling bed hydrogenation method is provided, method includes the following steps:
(a) mixture of feedstock oil, hydrogen supply agent, recycle oil and hydrogen first passes through fluidized bed reactor I and carries out adding hydrogen, obtains
Hydrogenated products pass sequentially through thermal high flash column, air cooler, cold high pressure separator, high pressure hot separator and cold low separator
Gas-liquid separation and boiling range segmentation are carried out, hot high score oil a part of acquisition returns to the fluidized bed reactor I as recycle oil, obtains
The diesel oil distillate oil a part obtained is back to fluidized bed reactor I as hydrogen supply agent；The ebullated bed in parallel with fluidized bed reactor I
Reactor II offline standby；
(b) when in the fluidized bed reactor I catalyst activity significantly reduce when, by the fluidized bed reactor I from
It is cut out in boiling bed hydrogenation technique process, while switching pipeline and fluidized bed reactor I is cut into boiling bed hydrogenation technique process, made
The feedstock oil, hydrogen supply agent, recycle oil and hydrogen mixture only pass through fluidized bed reactor II；
(c) low activity catalyst drawn off in the fluidized bed reactor I is regenerated, the catalysis of activity recovery after regeneration
Agent is still back to the fluidized bed reactor I；
(d) when the catalyst activity in fluidized bed reactor II significantly reduces, by fluidized bed reactor II from ebullated bed
It is cut out in hydrogenation technique process, while switching pipeline and fluidized bed reactor II is cut into boiling bed hydrogenation technique process, made described
Feedstock oil, hydrogen supply agent, recycle oil and hydrogen mixture only pass through fluidized bed reactor I；
(e) low activity catalyst drawn off in the fluidized bed reactor II is regenerated, and activity recovery urges after regeneration
Agent is still back to the fluidized bed reactor II；And
(f) step (b) to (e) is repeated 1-10 times.
For the specific features that the disclosure is further described, will be described with reference to the appended drawings.
Fig. 1 is the flow diagram according to the boiling bed hydrogenation method of one preferred embodiment of the disclosure.Such as Fig. 1 institute
Show, device used in this method includes: fluidized bed reactor I20 and fluidized bed reactor II21, thermal high flash tank 22, heat
High-pressure separator 23, cold high pressure separator 25, circulating pump 26, cold low separator 27, surge tank 33, star-like unloads air cooler 24
Expect valve 34, cyclone separator 35, rectifying column 36, catalyst storage tank 37 and charging spout 39 and valve 4,5,6,7,8,9,10,11,
12,13,14,15,16,17,18,19,40；All valves 4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19,
40 is fully open；Hydrogen in air accumulator 1 enters reactor from the bottom fluidized bed reactor I20 through valve 4, the original in head tank 2
Material oil through valve 5 enters reactor from the side inlet of fluidized bed reactor I20, and the hydrogen supply agent in head tank 3 is through valve 6 from ebullated bed
The side inlet of reactor I20 enters reactor, and the hot high score oil a part obtained in high pressure hot separator 23 is as recycle oil
Enter fluidized bed reactor I20 from reactor bottom through pump 26 and valve 12, is carried out under boiling bed hydrogenation reaction condition plus hydrogen is anti-
It answers, for reactant stream after three phase separator separates, gas phase enters thermal high flash tank 22 through valve 7, and liquid phase is from reactor side
It exporting and enters high pressure hot separator 23 by valve 10, hot high score oil a part of acquisition passes through the compression of pump 26 as recycle oil,
Enter reactor from the bottom fluidized bed reactor II20 by valve 12, another part enters cold low separator 27, through cold low
After the processing of separator 27, low-pressure separation gas 30, diesel oil distillate oil 29 and waste water 28,29 1 points of the diesel oil distillate oil of acquisition are isolated
Portion is back to fluidized bed reactor I20 as hydrogen supply agent；Enter the gas phase of cold high pressure separator 25 through excessive by air cooler 24
From hydrogen 32 can be used as recycle hydrogen through air compressor machine compression, and waste water 31 is discharged；
When entire boiling bed hydrogenation device operates 1~6 month, the solid-holding amount of boiling bed hydrogenation catalyst reaches capacity,
The activity of catalyst is no longer satisfied running requirements at this time, opening valve 8,9,11,13,14,15,16,18, close valve 4,5,6,
7,10,12, the fluidized bed reactor I20 equipped with decaying catalyst is cut out into device, fluidized bed reactor II21 cuts ebullated bed
It is run in process flow system；Offline fluidized bed reactor I20 draws off the catalyst of inactivation from catalyst outlet, is drawn off
Catalyst enters surge tank 33 through valve 16, then from surge tank 33 through star-shaped discharge valve 34, after mixing with solvent, into cyclonic separation
Device 35 is washed through micro- eddy flow extraction, the machine of insoluble material in outlet catalyst is realized using the high speed rotation of particle in micro- eddy flow field
Tool stripping process, the catalyst granules isolated are supplied through the hydrogen in air accumulator 1 by valve 40 in catalyst storage tank 37
It gives, reduction activity recovery is mentioned by hot hydrogen, the liquid phase isolated enters rectifying column 36 and carries out rectifying, and oily phase 38 is discharged, gasification
Solvent after condenser condenses, a part of solvent is mixed with decaying catalyst again, be recycled, another part return essence
Tower 36 is evaporated, the catalyst to the inactivation in fluidized bed reactor I20 is drawn off completely, and the regenerated catalyst in catalyst storage tank 37 is logical
It crosses charging spout 39 and enters reactor from fluidized bed reactor I20 top catalyst entrance through valve 18；
When entire boiling bed hydrogenation device runs to 1~6 month, in fluidized bed reactor II 21 at this time plus hydrogen is urged
The hydrocon version functionality of agent has reached limiting value, its product that reruns will not be able to satisfy II 21 exit of fluidized bed reactor
The particular requirement of oil, opening valve 4,5,6,7,10,12,17,19 simultaneously close off valve 8,11,13,14,15,16,18, make equipped with mistake
The fluidized bed reactor II21 of catalyst living is offline, and fluidized bed reactor I is cut in boiling bed process flow system and run；Offline
Fluidized bed reactor I21 the catalyst of inactivation is drawn off from catalyst outlet, the catalyst drawn off enters surge tank through valve 17
33, then from surge tank 33 through star-shaped discharge valve 34, after being mixed with solvent, into cyclone separator 35, wash, utilize through micro- eddy flow extraction
The mechanical stripping process of insoluble material in outlet catalyst, the catalysis isolated are realized in the high speed rotation of particle in micro- eddy flow field
Agent particle mentions reduction activity recovery through hot hydrogen in catalyst storage tank 37, and the liquid phase isolated enters rectifying column 36 and carries out essence
It evaporates, oily phase 38 is discharged, and after condenser condenses, a part of solvent is mixed with decaying catalyst the solvent of gasification again, circulation
It uses, another part returns to rectifying column 36, and the catalyst to the inactivation in fluidized bed reactor I21 is drawn off completely, catalyst storage
The charging spout 39 that is regenerated catalyst through in tank 37 enters reaction from fluidized bed reactor I21 top catalyst entrance through valve 19
Device.
Fig. 2 be according to a kind of working state schematic representation of the boiling bed hydrogenation method of one preferred embodiment of the disclosure,
Wherein, reactor I is opened, and reactor II is closed, and regenerative system closes.As shown in Fig. 2, device used in this method includes: ebullated bed
Reactor I20 and fluidized bed reactor II21, thermal high flash tank 22, high pressure hot separator 23, air cooler 24, cold anticyclone separation
Device 25, circulating pump 26, cold low separator 27, surge tank 33, star-shaped discharge valve 34, cyclone separator 35, rectifying column 36, catalysis
Agent storage tank 37 and charging spout 39 and valve 4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19,40；Initial work
Making state is that fluidized bed reactor I20 is in parallel with fluidized bed reactor II21, and fluidized bed reactor II21 cuts out ebullated bed work
Skill flow system, offline standby；Valve 4,5,6,7,10,12,40 is opened, valve 8,9,11,13,14,15,16,17,18,19
Closing (is not related to cutting out reactor to use subsequent surge tank 33, star-shaped discharge valve 34, cyclone separator 35, catalyst storage tank
37, rectifying column 36 (oily phase 38 is discharged) and charging spout 39)；Hydrogen in air accumulator 1 is through valve 4 from the bottom fluidized bed reactor I20
Into reactor, the feedstock oil in head tank 2 enters reactor, head tank from the side inlet of fluidized bed reactor I20 through valve 5
Hydrogen supply agent in 3 enters reactor from the side inlet of fluidized bed reactor I20 through valve 6, obtains in high pressure hot separator 23
Hot high score oil a part enters fluidized bed reactor I20 from reactor bottom through pump 26 and valve 12 as recycle oil, in ebullated bed
Hydrogenation reaction is carried out under hydrogenation conditions, after three phase separator separates, gas phase enters thermal high through valve 7 and dodges reactant stream
Steaming pot 22, liquid phase enter high pressure hot separator 23 by valve 10 from reactor side exit, and hot high score oil a part of acquisition is made
It is recycle oil by the compression of pump 26, enters reactor from the bottom fluidized bed reactor I20 by valve 12, another part enters cold
Low pressure separator 27 isolates low-pressure separation gas 30, diesel oil distillate oil 29 and waste water 28 after the processing of cold low separator 27,
Oily 29 1 branches of the diesel oil distillate of acquisition are back to fluidized bed reactor I20 as hydrogen supply agent；Enter cold height by air cooler 24
Press the gas phase of separator 25 by separation, hydrogen 32 can be used as recycle hydrogen through air compressor machine compression, and waste water 31 is discharged.
Fig. 3 be according to a kind of working state schematic representation of the boiling bed hydrogenation method of one preferred embodiment of the disclosure,
Wherein, reactor I is opened, and reactor II is closed, and regenerative system is opened.As shown in figure 3, device used in this method includes: ebullated bed
Reactor I20 and fluidized bed reactor II21, thermal high flash tank 22, high pressure hot separator 23, air cooler 24, cold anticyclone separation
Device 25, circulating pump 26, cold low separator 27, surge tank 33, star-shaped discharge valve 34, cyclone separator 35, rectifying column 36, catalysis
Agent storage tank 37 and charging spout 39 and valve 4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19,40；Wherein, valve
Door 8,9,11,13,14,15,16,18,40 is opened, and valve 4,5,6,7,10,12,17,19 is closed；When entire boiling bed hydrogenation fills
When setting operating 1~6 month, the solid-holding amount of boiling bed hydrogenation catalyst reaches capacity, and the activity of catalyst cannot expire at this time
Sufficient running requirements, opening valve 8,9,11,13,14,15,16,18 close valve 4,5,6,7,10,12, and decaying catalyst will be housed
Fluidized bed reactor I20 cuts out device, runs in fluidized bed reactor II21 incision boiling bed process flow system；Offline boiling
The catalyst that a reactor I20 draws off inactivation from catalyst outlet is risen, the catalyst drawn off enters surge tank 33 through valve 16, then
From surge tank 33 through star-shaped discharge valve 34, after being mixed with solvent, into cyclone separator 35, is washed through micro- eddy flow extraction, utilize micro- rotation
The mechanical stripping process of insoluble material in outlet catalyst, the catalyst particles isolated are realized in the high speed rotation of particle in flow field
Grain is supplied through the hydrogen in air accumulator 1 by valve 40 in catalyst storage tank 37, mentions reduction activity recovery by hot hydrogen,
The liquid phase isolated enters rectifying column 36 and carries out rectifying, and oily phase 38 is discharged, and the solvent of gasification is after condenser condenses, a part
Solvent is mixed with decaying catalyst again, is recycled, and another part returns to rectifying column 36, in fluidized bed reactor I20
The catalyst of inactivation is drawn off completely, is regenerated catalyst through charging spout 39 through valve 18 from ebullating bed reactor in catalyst storage tank 37
Device I20 top catalyst entrance enters reactor；
Preceding step are as follows: the hydrogen in air accumulator 1 enters reactor, head tank from the bottom fluidized bed reactor I20 through valve 4
Feedstock oil in 2 enters reactor from the side inlet of fluidized bed reactor I20 through valve 5, and the hydrogen supply agent in head tank 3 is through valve 6
Enter reactor from the side inlet of fluidized bed reactor I20, the hot high score oil a part obtained in high pressure hot separator 23 is made
For recycle oil through pump 26 and valve 12 enter fluidized bed reactor I20 from reactor bottom, under boiling bed hydrogenation reaction condition into
Row hydrogenation reaction, for reactant stream after three phase separator separates, gas phase enters thermal high flash tank 22 through valve 7, and liquid phase is from anti-
Device side exit is answered to enter high pressure hot separator 23 by valve 10, hot high score oil a part of acquisition passes through pump 26 as recycle oil
Compression, enter reactor from the bottom fluidized bed reactor II20 by valve 12, another part enters cold low separator 27, warp
After the processing of cold low separator 27, low-pressure separation gas 30, diesel oil distillate oil 29 and waste water 28, the diesel oil distillate oil of acquisition are isolated
29 1 branches are back to fluidized bed reactor I20 as hydrogen supply agent；Enter the gas phase of cold high pressure separator 25 by air cooler 24
By separation, hydrogen 32 can be used as recycle hydrogen through air compressor machine compression, and waste water 31 is discharged.
Fig. 4 be according to a kind of working state schematic representation of the boiling bed hydrogenation method of one preferred embodiment of the disclosure,
Wherein, reactor I is opened, and reactor II is closed, and regenerative system is opened.As shown in figure 4, device used in this method includes: ebullated bed
Reactor I20 and fluidized bed reactor II21, thermal high flash tank 22, high pressure hot separator 23, air cooler 24, cold anticyclone separation
Device 25, circulating pump 26, cold low separator 27, surge tank 33, star-shaped discharge valve 34, cyclone separator 35, rectifying column 36, catalysis
Agent storage tank 37 and charging spout 39 and valve 4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19,40；Wherein, valve
Door 4,5,6,7,10,12,17,19,40 is opened, and valve 8,9,11,13,14,15,16,18 is closed；When entire boiling bed hydrogenation fills
It sets when running to 1~6 month, the hydrocon version functionality of the hydrogenation catalyst in fluidized bed reactor II 21 at this time has reached
Limiting value, its product that reruns will not be able to satisfy the particular requirement of II 21 exit of fluidized bed reactor oil, opening valve 4,5,6,
7,10,12,17,19, valve 8,11,13,14,15,16,18 is simultaneously closed off, the fluidized bed reactor equipped with decaying catalyst is made
II21 is offline, and fluidized bed reactor I is cut in boiling bed process flow system and run；Offline fluidized bed reactor I21 is from urging
Agent exports the catalyst for drawing off inactivation, and the catalyst drawn off enters surge tank 33 through valve 17, then from surge tank 33 through star-like
Discharge valve 34 after mixing with solvent, into cyclone separator 35, is washed through micro- eddy flow extraction, utilizes the high speed of particle in micro- eddy flow field
The mechanical stripping process of insoluble material in outlet catalyst is realized in rotation, and the catalyst granules isolated is in catalyst storage tank 37
Middle to mention reduction activity recovery through hot hydrogen, the liquid phase isolated enters rectifying column 36 and carries out rectifying, and oily phase 38 is discharged, gasification it is molten
After condenser condenses, a part of solvent is mixed with decaying catalyst again for agent, is recycled, and another part returns to rectifying column
36, the catalyst to the inactivation in fluidized bed reactor I21 is drawn off completely, and being regenerated catalyst through in catalyst storage tank 37 adds
Hopper 39 enters reactor from fluidized bed reactor I21 top catalyst entrance through valve 19.
Preceding step are as follows: the hydrogen in air accumulator 1 enters reactor, head tank from the bottom fluidized bed reactor I20 through valve 4
Feedstock oil in 2 enters reactor from the side inlet of fluidized bed reactor I20 through valve 5, and the hydrogen supply agent in head tank 3 is through valve 6
Enter reactor from the side inlet of fluidized bed reactor I20, the hot high score oil a part obtained in high pressure hot separator 23 is made
For recycle oil through pump 26 and valve 12 enter fluidized bed reactor I20 from reactor bottom, under boiling bed hydrogenation reaction condition into
Row hydrogenation reaction, for reactant stream after three phase separator separates, gas phase enters thermal high flash tank 22 through valve 7, and liquid phase is from anti-
Device side exit is answered to enter high pressure hot separator 23 by valve 10, hot high score oil a part of acquisition passes through pump 26 as recycle oil
Compression, enter reactor from the bottom fluidized bed reactor II20 by valve 12, another part enters cold low separator 27, warp
After the processing of cold low separator 27, low-pressure separation gas 30, diesel oil distillate oil 29 and waste water 28, the diesel oil distillate oil of acquisition are isolated
29 1 branches are back to fluidized bed reactor I20 as hydrogen supply agent；Enter the gas phase of cold high pressure separator 25 by air cooler 24
By separation, hydrogen 32 can be used as recycle hydrogen through air compressor machine compression, and waste water 31 is discharged.
Embodiment
The disclosure is further described below with reference to specific embodiment.It should be appreciated, however, that these embodiments are only used for
The bright disclosure is without constituting the limitation to disclosure range.The test method of actual conditions is not specified in the following example, usually
According to normal conditions, or according to the normal condition proposed by manufacturer.Unless otherwise indicated, all percentage and number be by weight
Meter.
Embodiment 1
One, device name
30000 tons/year of sawdust pyrolysis oil boiling bed hydrogenation device for deoxidizing
Two, process flow
As shown in Fig. 2, original operating state is that fluidized bed reactor I20 is in parallel with fluidized bed reactor II21, and boils
Bed reactor II21 cuts out boiling bed process flow system offline standby；Hydrogen (flow 1666.7m in air accumulator 13/ h is pure
Degree 85%, pressure 14.5MPa, temperature 50 C) through valve 4 enter reactor from the bottom fluidized bed reactor I20, in head tank 2
Sawdust pyrolysis oil raw material (3.5 ton/hours of flow, 3.3m3/ h, pressure 15.0MPa, 20 DEG C of temperature, density 1.05g/cm3) through valve 5
Enter reactor from the side inlet of fluidized bed reactor I20, and hydrogen supply agent in head tank 3 (1.75 ton/hours of flow, temperature
20 DEG C) through valve 6 enter reactor from the side inlet of fluidized bed reactor I20, the hot high score obtained in high pressure hot separator 23
Oily a part enters boiling from reactor bottom through pump 26 and valve 12 as recycle oil (17.5 ton/hours of flow, 350 DEG C of temperature)
Bed reactor I20, carries out hydrogenation deoxidation reaction, reactant stream under the conditions of reaction pressure 14.5MPa, 400 DEG C of reaction temperature
After three phase separator separates, gas phase enters thermal high flash tank 22 through valve 7, and liquid phase enters from reactor side exit through valve 10
High pressure hot separator 23, hot high score oil a part of acquisition as recycle oil by pump 26 compression, by valve 12 from ebullated bed
The bottom reactor I20 enters reactor, and another part enters cold low separator 27, after the processing of cold low separator 27, point
Low-pressure separation gas 30, diesel oil distillate oil 29 and waste water 28 are separated out, oily 29 1 branches of the diesel oil distillate of acquisition return as hydrogen supply agent
To fluidized bed reactor I20；Pass through separation by the gas phase that air cooler 24 enters cold high pressure separator 25, hydrogen 32 is through air compressor machine
Compression can be used as recycle hydrogen, and waste water 31 is discharged；Wherein, fractionated products mass percent in diesel oil distillate oil: naphtha 5%,
Aviation kerosine fraction 45%, diesel oil 40%, weight bavin 10%.
As shown in figure 3, when entire boiling bed hydrogenation device operates 1~6 month, the appearance of boiling bed hydrogenation dehydrogenation catalyst
The quantity of slag reaches capacity, and the activity of catalyst is no longer satisfied running requirements at this time, i.e. the exit fluidized bed reactor I20 oil
Rate of oxygen is greater than 8wt%, and opening valve 8,9,11,13,14,15,16,18 closes valve 4,5,6,7,10,12, will urge equipped with inactivation
The fluidized bed reactor I20 of agent cuts out device, runs in fluidized bed reactor II21 incision boiling bed process flow system；From
The fluidized bed reactor I20 of line draws off the dehydrogenation catalyst of inactivation from catalyst outlet, and the catalyst drawn off enters surge tank
33, then from surge tank 33 through star-shaped discharge valve 34, after being mixed with solvent, into cyclone separator 35, wash, utilize through micro- eddy flow extraction
The mechanical stripping process of insoluble material in outlet catalyst, the catalysis isolated are realized in the high speed rotation of particle in micro- eddy flow field
Agent particle mentions reduction activity recovery through hot hydrogen in catalyst storage tank 37, and the liquid phase isolated enters rectifying column 36 and carries out essence
It evaporates, after condenser condenses, a part of solvent is mixed with decaying catalyst the solvent of gasification again, is recycled, another portion
Divide return rectifying column 36, the catalyst to the inactivation in fluidized bed reactor I20 is drawn off completely, the regeneration in catalyst storage tank 37
Catalyst passes through star-shaped discharge valve, is entered instead through valve 18 from I 20 top catalyst entrance of fluidized bed reactor by charging spout 39
Answer device.
As shown in figure 4, when entire boiling bed hydrogenation device runs to 1~6 month, fluidized bed reactor II 21 at this time
In the hydrocon version functionality of hydrogenation deoxidation catalyst have reached limiting value, it is anti-that its product that reruns will not be able to satisfy ebullated bed
The particular requirement of the exit device II21 oil is answered, i.e. the rate of oxygen of the exit fluidized bed reactor II21 oil is greater than 8wt%, opening valve
4,5,6,7,10,12,17,19, valve 8,11,13,14,15,16,18 is simultaneously closed off, keeps the ebullated bed equipped with decaying catalyst anti-
It answers device II21 offline, is run in fluidized bed reactor I20 incision boiling bed process flow system.
Three, main device equipment
Hydrogenation deoxidation reactor I20, II21 are selected from fluidized bed reactor；
Cold high pressure separator 25 is selected from vertical gravity equipment；
Cold low separator 27 is selected from horizontal gravitational settling equipment.
Four, implementation result
Using the method for two fluidized bed reactor parallel connections, this operation guarantees the company of entire ebullated bed operating system
Continuous property, the technical process after improving enable to the device cycle of operation to extend to 18 months by 6 months.Catalyst is online again
Raw system makes decaying catalyst have activity again, and the 80% of activation recovering to fresh catalyst；For contained by catalyst
The overall recovery of oil reaches 90% or more.
Embodiment 2
One, device name
10000 tons/year of sludge crack oil boiling bed hydrogenation device for deoxidizing
Two, process flow
As shown in Fig. 2, original operating state is that fluidized bed reactor I20 is in parallel with fluidized bed reactor II21, and boils
Bed reactor II21 cuts out boiling bed process flow system offline standby；Hydrogen (flow 875m in air accumulator 13/ h, purity
85%, pressure 13.5MPa, temperature 50 C) through valve 4 enter reactor from the bottom fluidized bed reactor I20, the dirt in head tank 2
Mud cracked oil raw material (1.2 ton/hours of flow, 1.25m3/ h, pressure 14.0MPa, 20 DEG C of temperature, density 0.96g/cm3) through valve 5
Enter reactor from the side inlet of fluidized bed reactor I20, and hydrogen supply agent in head tank 3 (0.6 ton/hour of flow, temperature 20
DEG C) through valve 6 enter reactor from the side inlet of fluidized bed reactor I20, the hot high score oil obtained in high pressure hot separator 23
A part enters ebullated bed from reactor bottom through pump 26 and valve 12 as recycle oil (3.6 ton/hours of flow, 330 DEG C of temperature)
Reactor I20 carries out hydrogenation deoxidation reaction, reactant stream warp under the conditions of reaction pressure 13.5MPa, 380 DEG C of reaction temperature
After three phase separator separation, gas phase enters thermal high flash tank 22 through valve 7, and liquid phase enters heat through valve 10 from reactor side exit
High-pressure separator 23, hot high score oil a part of acquisition passes through the compression of pump 26 as recycle oil, anti-from ebullated bed by valve 12
The bottom device I20 is answered to enter reactor, another part enters cold low separator 27, after the processing of cold low separator 27, separation
Low-pressure separation gas 30 out, diesel oil distillate oil 29 and waste water 28, oily 29 1 branches of the diesel oil distillate of acquisition are back to as hydrogen supply agent
Fluidized bed reactor I20；Pass through separation by the gas phase that air cooler 24 enters cold high pressure separator 25, hydrogen 32 is through air compressor machine pressure
Contracting can be used as recycle hydrogen, and waste water 31 is discharged；Wherein, fractionated products mass percent in diesel oil distillate oil: naphtha 10%, boat
Empty kerosene distillate 55%, diesel oil 25%, weight bavin 10%.
As shown in figure 3, when entire boiling bed hydrogenation device operates 1~6 month, the appearance of boiling bed hydrogenation dehydrogenation catalyst
The quantity of slag reaches capacity, and the activity of catalyst is no longer satisfied running requirements at this time, i.e. the exit fluidized bed reactor I20 oil
Rate of oxygen is greater than 8wt%, and opening valve 8,9,11,13,14,15,16,18 closes valve 4,5,6,7,10,12, will urge equipped with inactivation
The fluidized bed reactor I20 of agent cuts out device, runs in fluidized bed reactor II21 incision boiling bed process flow system；From
The fluidized bed reactor I20 of line draws off the dehydrogenation catalyst of inactivation from catalyst outlet, and the catalyst drawn off enters surge tank
33, then from surge tank 33 through star-shaped discharge valve 34, after being mixed with solvent, into cyclone separator 35, wash, utilize through micro- eddy flow extraction
The mechanical stripping process of insoluble material in outlet catalyst, the catalysis isolated are realized in the high speed rotation of particle in micro- eddy flow field
Agent particle mentions reduction activity recovery through hot hydrogen in catalyst storage tank 37, and the liquid phase isolated enters rectifying column 36 and carries out essence
It evaporates, after condenser condenses, a part of solvent is mixed with decaying catalyst the solvent of gasification again, is recycled, another portion
Divide return rectifying column 36, the catalyst to the inactivation in fluidized bed reactor I20 is drawn off completely, the regeneration in catalyst storage tank 37
Catalyst passes through star-shaped discharge valve, is entered instead through valve 18 from fluidized bed reactor I20 top catalyst entrance by charging spout 39
Answer device.
As shown in figure 4, when entire boiling bed hydrogenation device runs to 1~6 month, fluidized bed reactor II 21 at this time
In the hydrocon version functionality of hydrogenation deoxidation catalyst have reached limiting value, it is anti-that its product that reruns will not be able to satisfy ebullated bed
The particular requirement of the exit device II21 oil is answered, i.e. the rate of oxygen of the exit fluidized bed reactor II21 oil is greater than 8wt%, opening valve
4,5,6,7,10,12,17,19, valve 8,11,13,14,15,16,18 is simultaneously closed off, keeps the ebullated bed equipped with decaying catalyst anti-
It answers device II19 offline, is run in fluidized bed reactor I20 incision boiling bed process flow system.
Three, main device equipment
Hydrogenation deoxidation reactor I20, II21 are selected from fluidized bed reactor；
Cold high pressure separator 25 is selected from vertical gravity equipment；
Cold low separator 27 is selected from horizontal gravitational settling equipment.
Four, implementation result
Using the method for two fluidized bed reactor parallel connections, this operation guarantees the company of entire ebullated bed operating system
Continuous property, the technical process after improving enable to the device cycle of operation to extend to 18 months by 6 months.Catalyst is online again
Raw system makes decaying catalyst have activity again, and the 80% of activation recovering to fresh catalyst；For contained by catalyst
The overall recovery of oil reaches 90% or more.
Embodiment 3
One, device name
10000 tons/year of residual oil boiling bed hydrogenation devices
Two, process flow
As shown in Fig. 2, original operating state is that fluidized bed reactor I20 is in parallel with fluidized bed reactor II21, and boils
Bed reactor II21 cuts out boiling bed process flow system offline standby；Hydrogen (flow 875m in air accumulator 13/ h, purity
85%, pressure 13.5MPa, temperature 50 C) through valve 4 enter reactor from the bottom fluidized bed reactor I20, the slag in head tank 2
Oily raw material (1.2 ton/hours of flow, 1.36m3/ h, pressure 14.0MPa, 20 DEG C of temperature, density 0.88g/cm3) through valve 5 from boiling
The side inlet of bed reactor I20 enters reactor, (0.6 ton/hour of flow, 20 DEG C of temperature) of hydrogen supply agent warp in head tank 3
Valve 6 enters reactor from the side inlet of fluidized bed reactor I20, the hot high score oil a part obtained in high pressure hot separator 23
Enter fluidized bed reactor from reactor bottom through pump 26 and valve 12 as recycle oil (3.6 ton/hours of flow, 420 DEG C of temperature)
I20 carries out hydrogenation reaction under the conditions of reaction pressure 16.0MPa, 420 DEG C of reaction temperature, and reactant stream is through three phase separator
After separation, gas phase enters thermal high flash tank 22 through valve 7, and liquid phase enters high pressure hot separator through valve 10 from reactor side exit
23, the hot high score of acquisition oil a part as recycle oil by pump 26 compression, by valve 12 from the bottom fluidized bed reactor I20
Into reactor, another part enters cold low separator 27, after the processing of cold low separator 27, isolates low-pressure separation gas
30, diesel oil distillate oil 29 and waste water 28, oily 29 1 branches of the diesel oil distillate of acquisition are back to fluidized bed reactor as hydrogen supply agent
I20；Pass through separation by the gas phase that air cooler 24 enters cold high pressure separator 25, hydrogen 32 can be used as through air compressor machine compression and follow
Ring hydrogen, waste water 31 are discharged；Wherein, fractionated products mass percent in diesel oil distillate oil: naphtha 10%, aviation kerosine fraction
55%, diesel oil 25%, weight bavin 10%.
As shown in figure 3, when entire boiling bed hydrogenation device operates 1~6 month, boiling bed hydrogenation catalyst for demetalation
Solid-holding amount reaches capacity, and the activity of catalyst is no longer satisfied running requirements, the i.e. exit fluidized bed reactor I20 oil at this time
Tenor be greater than 10-20 μ g/g or carbon left and be greater than 10wt%, opening valve 8,9,11,13,14,15,16,18 closes valve
4,5,6,7,10,12, the fluidized bed reactor I20 equipped with decaying catalyst is cut out into device, fluidized bed reactor II21 incision
It is run in boiling bed process flow system；Offline fluidized bed reactor I20 draws off the hydrogenation catalyst of inactivation from catalyst outlet
Agent, the catalyst drawn off enter surge tank 33, then from surge tank 33 through star-shaped discharge valve 34, after mixing with solvent, into rotation
Stream separator 35 is washed through micro- eddy flow extraction, realizes insoluble object in outlet catalyst using the high speed rotation of particle in micro- eddy flow field
The mechanical stripping process of matter, the catalyst granules isolated mention reduction activity recovery through hot hydrogen in catalyst storage tank 37, point
The liquid phase separated out enter rectifying column 36 carry out rectifying, the solvent of gasification after condenser condenses, a part of solvent again with mistake
Catalyst mixing living, is recycled, another part returns to rectifying column 36, the catalyst to the inactivation in fluidized bed reactor I20
It draws off completely, the regenerated catalyst in catalyst storage tank 37 passes through star-shaped discharge valve, by charging spout 39 through valve 18 from ebullated bed
Reactor I20 top catalyst entrance enters reactor.
As shown in figure 4, when entire boiling bed hydrogenation device runs to 1~6 month, fluidized bed reactor II 21 at this time
In the hydrocon version functionality of Hydrodemetalation catalyst have reached limiting value, its product that reruns will not be able to satisfy ebullated bed
The particular requirement of the exit reactor II21 oil, the i.e. tenor of the exit fluidized bed reactor II21 oil are greater than 20 μ g/g
Or carbon left is greater than 10wt%, opening valve 4,5,6,7,10,12,17,19 simultaneously closes off valve 8,11,13,14,15,16,18,
Keep the fluidized bed reactor II19 equipped with decaying catalyst offline, fluidized bed reactor I20 cuts boiling bed process flow system
Middle operation.
Three, main device equipment
Hydrogenator I20, II21 are selected from fluidized bed reactor；
Cold high pressure separator 25 is selected from vertical gravity equipment；
Cold low separator 27 is selected from horizontal gravitational settling equipment.
Four, implementation result
Using the method for two fluidized bed reactor parallel connections, this operation guarantees the company of entire ebullated bed operating system
Continuous property, the technical process after improving enable to the device cycle of operation to extend to 18 months by 6 months.Catalyst is online again
Raw system makes decaying catalyst have activity again, and the 80% of activation recovering to fresh catalyst；For contained by catalyst
The overall recovery of oil reaches 90% or more.
Above-mentioned listed embodiment is only the preferred embodiment of the disclosure, not is used to limit the implementation model of the disclosure
It encloses.Equivalence changes and modification made by i.e. all contents according to disclosure claim, all should be the technology model of the disclosure
Farmland.
It is incorporated herein by reference in all documents of disclosure topic note, it is independent just as each document
It is incorporated as with reference to such.In addition, it should also be understood that, those skilled in the art can after having read the above-mentioned teaching content of the disclosure
To make various changes or modifications to the disclosure, such equivalent forms equally fall within model defined by the application the appended claims
It encloses.
Claims (11)
1. a kind of boiling bed hydrogenation method, method includes the following steps:
(a) mixture of feedstock oil, hydrogen supply agent, recycle oil and hydrogen is made to first pass through fluidized bed reactor I, with fluidized bed reactor
The fluidized bed reactor II offline standby of I parallel connection；
(b) when the catalyst activity in the fluidized bed reactor I significantly reduces, by the fluidized bed reactor I from boiling
It is cut out in bed hydroprocessing process flow, while switching pipeline and fluidized bed reactor II is cut into boiling bed hydrogenation technique process, make institute
The mixture for stating feedstock oil, hydrogen supply agent, recycle oil and hydrogen passes through fluidized bed reactor II；
(c) low activity catalyst drawn off in the fluidized bed reactor I is regenerated, and the catalyst of activity recovery is still after regeneration
It is back to the fluidized bed reactor I；
(d) when the catalyst activity in fluidized bed reactor II significantly reduces, by fluidized bed reactor II from boiling bed hydrogenation
It is cut out in process flow, while switching pipeline and fluidized bed reactor I is cut into boiling bed hydrogenation technique process, make the raw material
Oil, hydrogen supply agent, recycle oil and hydrogen mixture pass through fluidized bed reactor I；
(e) low activity catalyst drawn off in the fluidized bed reactor II is regenerated, the catalyst of activity recovery after regeneration
Still it is back to the fluidized bed reactor II；And
(f) step (b) to (e) is repeated.
2. the method as described in claim 1, which is characterized in that the feedstock oil is containing aerobic, sulphur, nitrogen, chlorine and metal impurities
One of atom or a variety of macromolecule hydrocarbons.
3. the method as described in claim 1, which is characterized in that the catalyst activity reduction significantly refers to: the anti-device of ebullated bed
The rate of oxygen of exit oil is greater than 8wt%.
4. the method as described in claim 1, which is characterized in that the catalyst activity reduction significantly refers to: the anti-device of ebullated bed
It is greater than 10wt% that the tenor of exit oil, which is greater than 20 μ g/g or the carbon left of the anti-device exit oil of ebullated bed,.
5. the method as described in claim 1, which is characterized in that the behaviour of the fluidized bed reactor I and fluidized bed reactor II
Make condition are as follows: pressure is 10~20MPa, and temperature is 380~450 DEG C, and the weight hourly space velocity of reaction is in 0.2~4h-1；The boiling
It rises a reactor I and fluidized bed reactor II to load using active carbon as the microspheroidal hydrogenation catalyst of carrier, wherein active metal
Element is iron, nickel, molybdenum or platinum, and particle diameter is 0.2~1.2mm；The operation cycle of the fluidized bed reactor I and II is designed as
1~6 month；The fluidized bed reactor I and II has three phase separation structure.
6. the method as described in claim 1, which is characterized in that the weight fraction ratio of the recycle oil and the feedstock oil is 2
~10, the recycle oil from the feedstock oil add hydrogen after hot high score oil；The weight of the hydrogen supply agent and the feedstock oil
Score ratio be 0.25~2, the hydrogen supply agent from the feedstock oil add hydrogen after diesel oil distillate oil.
7. the method as described in claim 1, which is characterized in that in step (c) and step (e), by the low activity
Catalyst carries out solvent eddy flow extraction-hot hydrogen and mentions to realize regeneration with activity recovery；In step (f), step (b) is repeated extremely
(e) 1-10 times.
8. the method for claim 7, which is characterized in that the solvent eddy flow extraction is using a kind of selected from the group below molten
Agent: methanol, ethyl alcohol, sulfolane, triethylene glycol and tetraethylene glycol.
9. method according to claim 8, which is characterized in that the low activity catalyst carries out in catalyst regeneration system
Regeneration, comprising the following steps:
(i) it is kept in after low activity catalyst is drawn off in the fluidized bed reactor；
(ii) low activity catalyst is mixed with solvent, forms the homogeneous mixture of catalysed particulate and solvent；
(iii) micro- eddy flow extraction is carried out to the homogeneous mixture of catalysed particulate obtained by step (ii) and solvent to wash, utilize micro- eddy flow field
The mechanical stripping of insoluble material in outlet catalyst is realized in the rotation of middle particle；
(iv) under an atmosphere of hydrogen, make the activity gold being oxidized on the catalyst granules washed in step (iii) by micro- eddy flow extraction
Belong to reduction and regeneration, and can return to fluidized bed reactor recycling；And
(v) solvent obtained by step (iii) is sent into rectifying column and carries out rectifying, the oil isolated mutually recycles, a part of solvent
Again it mixes, is recycled with low activity catalyst, another part solvent returns to rectifying column.
10. a kind of boiling bed hydrogenation method, method includes the following steps:
(a) mixture of feedstock oil, hydrogen supply agent, recycle oil and hydrogen first passes through fluidized bed reactor I (20) and carries out adding hydrogen, obtains
Hydrogenated products pass sequentially through thermal high flash column (22), air cooler (24), cold high pressure separator (25), high pressure hot separator
(23) and cold low separator (27) carries out gas-liquid separation and boiling range segmentation, and hot high score oil a part of acquisition is returned as recycle oil
The fluidized bed reactor I is returned, diesel oil distillate oil a part of acquisition is back to fluidized bed reactor I as hydrogen supply agent；With boiling
Rise a fluidized bed reactor II offline standby for reactor I parallel connection；
(b) when the catalyst activity in the fluidized bed reactor I significantly reduces, by the fluidized bed reactor I from boiling
It is cut out in bed hydroprocessing process flow, while switching pipeline and fluidized bed reactor II is cut into boiling bed hydrogenation technique process, make institute
The mixture for stating feedstock oil, hydrogen supply agent, recycle oil and hydrogen passes through fluidized bed reactor II；
(c) low activity catalyst drawn off in the fluidized bed reactor I is regenerated, and the catalyst of activity recovery is still after regeneration
It is back to the fluidized bed reactor I；
(d) when the catalyst activity in fluidized bed reactor II significantly reduces, by fluidized bed reactor II from boiling bed hydrogenation
It is cut out in process flow, while switching pipeline and fluidized bed reactor I is cut into boiling bed hydrogenation technique process, make the raw material
Oil, hydrogen supply agent, recycle oil and hydrogen mixture pass through fluidized bed reactor I；
(e) low activity catalyst drawn off in the fluidized bed reactor II is regenerated, the catalyst of activity recovery after regeneration
Still it is back to the fluidized bed reactor II；And
(f) step (b) to (e) is repeated.
11. method as claimed in claim 10, which is characterized in that the low activity catalyst in catalyst regeneration system into
Row regeneration, comprising the following steps:
(i) low activity catalyst is drawn off in the fluidized bed reactor, is temporarily stored into surge tank (33)；
(ii) low activity catalyst mix with solvent by star-shaped discharge valve (34), formation catalysed particulate and solvent
Homogeneous mixture；
(iii) homogeneous mixture of catalysed particulate obtained by step (ii) and solvent is sent into cyclone separator (35), is carried out micro-
Eddy flow extraction is washed, and the mechanical stripping of insoluble material in outlet catalyst is realized using the rotation of particle in micro- eddy flow field；
(iv) catalyst storage tank (37) will be sent by the catalyst granules that micro- eddy flow extraction is washed in step (iii), in atmosphere of hydrogen
Under make the active metal being oxidized on catalyst granules restore and regeneration, and can pass through charging spout (39) return fluidized bed reactor
It is recycled；And
(v) solvent obtained by step (iii) is sent into rectifying column (36) and carries out rectifying, the oil isolated mutually recycles, a part
Solvent is mixed with low activity catalyst again, is recycled, and another part solvent returns to rectifying column.
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| CN115093880A (en) * | 2022-07-31 | 2022-09-23 | 中国石油化工股份有限公司 | Mixed bubble flow fluidized bed residual oil hydrogenation process and device |
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