CN105585400B - A kind of method by low-carbon alkanes preparing low-carbon olefins - Google Patents
A kind of method by low-carbon alkanes preparing low-carbon olefins Download PDFInfo
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- CN105585400B CN105585400B CN201410557715.7A CN201410557715A CN105585400B CN 105585400 B CN105585400 B CN 105585400B CN 201410557715 A CN201410557715 A CN 201410557715A CN 105585400 B CN105585400 B CN 105585400B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y02P20/584—Recycling of catalysts
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Abstract
The invention discloses a kind of method by low-carbon alkanes preparing low-carbon olefins, this method includes：Low-carbon alkanes are subjected to reaction preparing low-carbon olefins in the presence of dehydrogenation in a fluidized bed reactor；Reclaimable catalyst returns reactor after locking hopper is regenerated into fluid bed regenerator, then by lock hopper cycle.The method of the present invention, compared with fixed bed and moving bed process, the activity of catalyst is more stable, and due to multiple reactors and intermediate heater need not be set, construction and the operating cost of device are reduced, and because the processes such as reaction, coke burning regeneration are carried out in different individual regions respectively, pass through the use of locking hopper, can flexible modulation reactor and regenerator operating pressure, it is entirely avoided contact of the hydrogen-containing gas streams with oxygen flow, more securely and reliably.Using the method for the present invention, not only operating process is simple, continuous, can also accomplish that reduced investment, treating capacity are big and safe.
Description
Technical field
The present invention relates to a kind of method by low-carbon alkanes preparing low-carbon olefins.
Background technology
Low-carbon alkene is the base stock for producing petrochemical, for producing polypropylene, methyl tertiary butyl ether(MTBE), higher octane
It is worth the products such as gasoline component, alkylate oil and rubber.Although the demand growth of these products is quickly, the acquisition canal of low-carbon alkene
Road is limited, it is necessary to a large amount of imports.C containing more than 10v% in China's major part casing-head gas2 +Alkane resource, moreover page in recent years
The exploitation of rock gas resource is gradually brought into schedule with utilizing.Therefore, with the exploration energetically and exploitation of shale gas resource, it is contemplated that
It will be enriched very much to the source of low-carbon alkanes and yield.Therefore, greatly develop except catalytic cracking and steam cracking by-product low-carbon
Dehydrogenating low-carbon alkane technology outside alkene is very important.
The reaction of dehydrogenating low-carbon alkane preparing low-carbon olefins is the endothermic reaction, thermodynamical equilibrium be present, it is de- that high temperature is advantageous to this
Hydrogen reaction is carried out.To reach certain conversion ratio and selectivity, reaction also needs to suitable catalyst.The catalyst is necessary to ensure that
Higher feed stock conversion and target product selectivity, should also trying one's best, it is secondary anti-to reduce isomerization, cracking, polymerization and aromatisation etc.
Should, these are all the decisions such as catalyst the Nomenclature Composition and Structure of Complexes.
Catalyst formulation for dehydrogenating low-carbon alkane preparing low-carbon olefins is too numerous to enumerate, as noble metal catalyst system,
Transition metal oxide and metal composite oxide system, heteropolyacid catalyst system and molecular sieve catalyst system etc..More
Patent, which describes, uses chromium oxide as active component or the catalyst of co-catalyst, such as US 2956030 and US 2945823.US
The numerous patents such as 4056576 all disclose carries out dehydrating alkanes reaction using the catalyst containing gallium oxide.US 4914075 is public
Cloth is a kind of to carry out dehydrating alkanes reaction methods using containing the catalyst of noble metal platinum and gallium oxide, and describes coke burning regeneration
Catalyst afterwards needs chlorination to redistribute active metal component.GB 2162082A disclose one kind and use chromium oxide/oxidation
Al catalysts are used for C3~C5 alkane catalytic dehydrogenating reactions；The synthetic method of the catalyst uses equi-volume impregnating, is different from
Alumina support is impregnated in excessive chromium solution；According to embodiment introduction in patent, the alkane transformations of the process for synthetic catalyst
Rate and corresponding olefine selective all greatly improve.
Having been carried out the dehydrogenating low-carbon alkane technique of industrial applications at present has Lummus Catofin techniques, UOP
The STAR techniques of Oleflex, Phillips company and the FBD-4 techniques of Italian Snamprogetti companies.However, at present I
The device that state's dehydrogenating low-carbon alkane is in industrialized production is less.To find out its cause, the investment of mainly foreign technology is high and produces
Technological service guarantee of the enterprise to the later stage has misgivings.Therefore, it is fine to develop dehydrogenating low-carbon alkane preparing low-carbon olefins new technology
Outlet.
For Lummus Catofin techniques using 4 groups of fixed bed reactors being arranged in juxtaposition, catalyst is chromium oxide/Al2O3,
When the raw materials technology uses iso-butane, iso-butane conversion ratio has reached 60% and selective isobutene is more than 90%, is to be at present
Only target alkene yield highest in dehydrogenation of isobutane technique；The reaction and regeneration of the technique are that interval is carried out, i.e., device is transported
The reactor having during turning carries out course of reaction, and some reactors carry out catalyst regeneration process, it is seen that the efficiency drop of device
It is low.UOP Oleflex techniques use the moving-burden bed reactor and noble metal catalyst Pt/Al of 3 groups of series connection2O3, technique includes
Reaction, continuous catalyst regenerating and Product recycling three parts, about 650 DEG C or so of reaction temperature.US 3978150 discloses shifting
Dynamic bed alkane dehydrogenation process.The advantages of Oleflex techniques is that reactor operation is continuous, it is not necessary to is made instead for the regeneration of catalyst
Should stop, iso-butane can be made to be converted into the overall selectivity of isobutene and reach 91%~93%, but the investment of the process unit compared with
Greatly.The former Soviet Union carries out iso-butane (and normal butane or iso-butane and normal butane using aluminium chromic acid catalyst and boiling bed process
Mixture) dehydrogenation, the method effect is good, and the conversion ratio of iso-butane is 50%~55%, and the selectivity for being converted into isobutene is 82%
~86%.
Summarizing existing patent and non-patent literature can show that fixed-bed dehydrogenation and moving bed dehydrogenation respectively have feature, also respectively
There is shortcoming.Fixed-bed process is multiple fixed bed reactors circulate operations, relatively frequently in reaction and regenerative process conversion；The mistake
Each reactor of journey is intermittently operated, and therefore, to reach continuous feed operation, multiple reactor is used simultaneously；The process
Major defect is that reactor operating mode is being aoxidized and frequently changed in reducing environment, and the temperature change of reactor is very complicated；In addition
It is worth noting that reactant is more than outlet temperature by the inlet temperature of fixed bed.Moving bed process process uses multiple
Moving-burden bed reactor, wherein catalyst slowly flow downward in the reactor；Reaction institute's calorific requirement is carried by multiple intermediate heating furnaces
For；Catalyst after regeneration is sent to first reactor, then flow to last reactor successively；The problem of technique
It is equally to be also required to multiple reactors and intermediate heating furnace, equipment investment is larger, and another is potentially prone to how to keep each
The stability of catalyst reactor activity.
To reduce the stability of investment, the continuity of raising technique and catalyst activity, a kind of possible solution
It is that the reaction of dehydrogenating low-carbon alkane preparing low-carbon olefins is carried out using the technique similar to fluid catalytic cracking (FCC), that is, adopts
With a reactor and a regenerator and realize successive reaction-regenerative operation.But if using the thinking, there can be two
Significant problem needs to solve：First, due to being hydrogen atmosphere (dehydrogenation reaction can produce hydrogen) in reactor, and be in regenerator
Oxygen-containing atmosphere (catalyst coke burning regeneration needs oxygen), the air-flow of reactor and regenerator must be well isolated to ensure technique
Security；Second, during using a reactor, to reach and fixed bed or moving bed process identical treating capacity, it is necessary to
Increase the size of reactor, this can equally increase investment and cost.
EP0894781 A1 and US7235706 B2 disclose a kind of using corresponding paraffins dehydrogenation preparing low-carbon olefins
Method, this method use dense-phase fluidized bed reaction-regeneration system, and reaction temperature is 450~800 DEG C, and reaction pressure is 0.1~
3atm, volume space velocity are 100~1000h-1, the catalyst composition that two pieces patent uses is different, and the former catalytic component is oxygen
Change chromium, tin oxide, potassium oxide, carrier is silica modified aluminum oxide, and the catalytic component of the latter is gallium oxide, metal
Platinum, potassium oxide, carrier are similarly silica modified aluminum oxide；Catalyst after carbon deposit is regenerated using dense-phase fluidized bed；It is to be generated
Catalyst and it is regenerated catalyst through U-tube and is shifted between reactor and regenerator.Asked existing for the method for this two patents
Topic is：Reactor and be reducing atmosphere (hydrogen atmosphere) for the reductor of reclaimable catalyst reduction, and regenerator burns
Regeneration is oxygen-containing atmosphere, is not well isolated from the two, very big potential safety hazard be present；In addition, by U-tube by reactor
It is connected with regenerator, the operating pressure of reactor and regenerator is identical, can not neatly regulate and control reactor and regenerator
Operating pressure.
The content of the invention
It is an object of the invention to provide a kind of method by low-carbon alkanes preparing low-carbon olefins, this method can overcome use
Problem present in fluidized-bed reaction-regenerative system preparing low-carbon olefins technique, the security of technique is on the one hand able to ensure that, more
Further aspect is that the treating capacity of device can be improved in the case of same reactor size.
To achieve these goals, the present invention provides a kind of method by low-carbon alkanes preparing low-carbon olefins, this method bag
Include：Continuously the low-carbon alkanes after preheating are contacted with dehydrogenation in a fluidized bed reactor and occurred under dehydrogenation condition
Dehydrogenation reaction, produce the reclaimable catalyst of oil gas and carbon distribution rich in low-carbon alkene；Oil gas and reclaimable catalyst are separated, will be divided
Oil gas from after is sent into product separation and recovery system, and reclaimable catalyst is continuously drawn from reactor；It will be drawn from reactor
Reclaimable catalyst be delivered to reclaimable catalyst receiver after, then reclaimable catalyst head tank is delivered to by locking hopper, so
Fluid bed regenerator is delivered to from reclaimable catalyst head tank afterwards, and carries out coke burning regeneration under an oxygen-containing atmosphere in a regenerator,
Obtain regenerated catalyst；After regenerated catalyst is continuously drawn out into regenerated catalyst receiver from regenerator, then pass through locking
Hopper is delivered to regenerated catalyst head tank, and is continuously returned in the reactor from regenerated catalyst head tank.
Preferably, this method also includes：By the regenerated catalyst being delivered in regenerated catalyst head tank in reducing atmosphere
Lower carry out reduction treatment, obtains reducing catalyst, then continuously returns to the reducing catalyst in the reactor.
Preferably, wherein the low-carbon alkanes are in ethane, propane, iso-butane, normal butane, pentane and isopentane
One or more.
Preferably, wherein the low-carbon alkanes are selected from natural gas condensate, natural gas liquid, catalytic cracking liquefied gas, oil
At least one of field gas condensed liquid and shale gas condensed liquid.
Preferably, wherein the fluidized-bed reactor is bubbling fluidized bed reactor or turbulent fluidized bed reactor.
Preferably, wherein the fluidized-bed reactor has the internal baffle of layered arrangement.
Preferably, wherein the internal baffle is board-like grid, the every 20~150cm of board-like grid installs one layer, from most lower
The bottom surface of panel type grid to the distance between top surface of board-like grid topmost is the 20% of reactor inner space total height
~70%.
Preferably, wherein separating oil gas and reclaimable catalyst by metal sintered filter.
Preferably, wherein the dehydrogenation contains active component and carrier；The active component be metal platinum or
Chromium oxide, the carrier are aluminum oxide；On the basis of the gross weight of catalyst, the content of the metal platinum for 0.01 heavy %~
1.0 heavy %, or the content of the chromium oxide is the 1.0 heavy % in weight %~30, the content of the carrier is aequum.
Preferably, wherein the condition of the dehydrogenation reaction is：500~700 DEG C, 0.1~3MPa of reaction pressure of reaction temperature,
Low-carbon alkanes volume space velocity 100~2000 hours-1, catalyst residence times 1~30 minute.
Preferably, wherein the condition of the dehydrogenation reaction is：530~600 DEG C of reaction temperature, reaction pressure 0.4~
2.0MPa, low-carbon alkanes volume space velocity 200~500 hours-1, catalyst residence times 3~8 minutes.
Preferably, wherein the condition of the coke burning regeneration is：Temperature is 550~750 DEG C, and pressure is 0.1~0.5MPa, is urged
The agent residence time is 5~60 minutes；Described oxygen-containing atmosphere is with air, the air or oxygen rich gas that are diluted with nitrogen
As fluidizing agent.
Preferably, wherein the condition of the reduction treatment is：Temperature is 500~600 DEG C, and pressure is 0.4~2.0MPa, is urged
The agent residence time is 1~10 minute；Described reducing atmosphere is to be used as fluidizing agent using hydrogeneous reduction logistics；The reduzate
Stream is not oxygenous and containing 50~100 volume % hydrogen, and contains 0~50 volume % refinery dry gas.
Preferably, this method also includes：Control the reaction pressure in reactor at least higher than the regeneration pressure in regenerator
0.3MPa。
Preferably, wherein by the oil gas contained by the reclaimable catalyst logistics in reclaimable catalyst receiver with hydrogen stripped extremely
The reactor.
Preferably, this method also includes：By through the isolated unreacted lower alkanes of the product separation and recovery system
Hydrocarbon is back in the reactor as raw material.
The method of the low-carbon alkanes preparing low-carbon olefins of the present invention and the method for existing low-carbon alkanes preparing low-carbon olefins
Compare, major advantage is as follows：
1st, carbon deposition catalyst continuously can be transferred to regenerator from reactor and be regenerated, and be catalyzed in fluidized-bed reactor
Agent activity kept stable, this is different from fixed bed and moving bed process；
2nd, the use of fluidization reaction-regeneration system eliminates the use of multiple reactors and intermediate heater, with fixation
Bed is compared with moving bed process can be greatly reduced construction and operating cost；
3rd, dehydrogenation reaction institute's calorific requirement is directly transmitted to reactant by the regenerated catalyst of heat, and the strong mixing of gas-solid avoids
Such as the appearance of focus in fixed-bed operation；
4th, importantly, being urged by the use of locking hopper, reactor and for the regeneration of regenerated catalyst reduction
The reducing atmosphere (hydrogen atmosphere) of agent head tank can be well isolated from the oxygen-containing atmosphere of the coke burning regeneration of regenerator, can
Ensure the safe operation of technique；
5th, moreover, by the use of locking hopper, the operation of reactor and regenerator can neatly be adjusted
Pressure, that is to say, that the operating pressure of reactor in the case where keeping regenerator normal pressure or low pressure operation, can be improved, from
And the treating capacity of device can be improved in the case where not increasing reactor size.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Brief description of the drawings
Accompanying drawing is for providing a further understanding of the present invention, and a part for constitution instruction, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings：
Fig. 1 is shown according to a kind of flow of the method for the low-carbon alkanes preparing low-carbon olefins of embodiment of the present invention
It is intended to；
Fig. 2 is the method according to a kind of low-carbon alkanes preparing low-carbon olefins of further embodiment of the present invention
Schematic flow sheet；
Fig. 3 is the top view and front view of a kind of embodiment of the internal baffle (i.e. board-like grid) in Fig. 2.
Description of reference numerals
The reclaimable catalyst receiver of 1 fluidized-bed reactor, 2 fluid bed regenerator 3
The regenerated catalyst receiver of 4 locking hopper, 5 reclaimable catalyst head tank 6
The pipeline of 7 pipeline, 8 pipeline, 9 pipeline, 10 pipeline, 11 pipeline 12
The control valve of 13 pipeline, 14 pipeline, 15 control valve, 16 control valve 17
The pipeline of 18 control valve, 19 control valve, 20 control valve, 21 pipeline 22
The pipeline of 23 pipeline, 24 pipeline, 25 pipeline, 26 pipeline 27
The pipeline of 28 pipeline, 29 pipeline, 30 pipeline 31
40 regenerated catalyst head tank, 41 pipeline, 42 pipeline, 50 board-like grid
Embodiment
The embodiment of the present invention is described in detail below in conjunction with accompanying drawing.It should be appreciated that this place is retouched
The embodiment stated is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The present invention provides a kind of method by low-carbon alkanes preparing low-carbon olefins, and this method includes：After continuously preheating
Low-carbon alkanes contacted in a fluidized bed reactor with dehydrogenation and dehydrogenation reaction occur under dehydrogenation condition, generation is rich in
The oil gas of low-carbon alkene and the reclaimable catalyst of carbon distribution；Oil gas and reclaimable catalyst are separated, the oil gas after separation is sent into production
Product separation and recovery system, reclaimable catalyst is continuously drawn from reactor；The reclaimable catalyst drawn from reactor is conveyed
Reclaimable catalyst head tank is delivered to reclaimable catalyst receiver, then by locking hopper, is then entered from reclaimable catalyst
Batch can is delivered to fluid bed regenerator, and carries out coke burning regeneration under an oxygen-containing atmosphere in a regenerator, obtains regenerated catalyst；Will
After regenerated catalyst is continuously drawn out to regenerated catalyst receiver from regenerator, then regeneration catalyzing is delivered to by locking hopper
Agent head tank, and continuously returned in the reactor from regenerated catalyst head tank.
It will be appreciated by persons skilled in the art that although reclaimable catalyst may be deposited after the coke burning regeneration of regenerator
The situation that active component wherein is partially oxidized, but because dehydrating alkanes reaction can produce hydrogen, the regeneration after burning
Even if catalyst, without reduction treatment, it is returned to after reactor still can be to carry out dehydrogenation reaction when being reduced.But it is
Preferably improve the activity of catalyst, it is preferred that method of the invention also includes：The regeneration catalyzing that will be drawn from regenerator
After agent is delivered to regenerated catalyst head tank by locking hopper, reduction treatment is carried out under reducing atmosphere, obtains reduction catalystses
Agent, then the reducing catalyst is continuously returned in the reactor.
According to the present invention, the low-carbon alkanes can be C2~C5 alkane either their mixture, such as can be
In ethane, propane, iso-butane, normal butane and isopentane one or more or selected from natural gas condensate, day
At least one of right gas-liquid, catalytic cracking liquefied gas, casing-head gas condensed liquid and shale gas condensed liquid, can also be other sources
Industrial or natural low-carbon alkanes monomer or mixture.
According to the present invention, described fluidized-bed reactor is known to those skilled in the art, can be bubbling
Fluidized-bed reactor or turbulent fluidized bed reactor, or other streams industrially commonly used such as fluidizing fluid-bed reactor
Fluidized bed reactor.Described fluidized-bed reactor is preferably bubbling fluidized bed reactor or turbulent fluidized bed reactor, more
Preferably bubbling fluidized bed reactor.
According to a kind of embodiment of the present invention, the interior of layered arrangement can be set inside the fluidized-bed reactor
Baffle plate is put, for preventing the uneven mixed flow of oil gas and/or catalyst, makes oil gas and/or catalyst with a kind of horizontal sliding streaming
State reacted by reactor, to improve the selectivity of the conversion ratio of low-carbon alkanes and required low-carbon alkene；In described
It can be board-like grid to put baffle plate, board-like grid can every 20~150cm install one layer, preferably 50~100cm installs one layer, from most
The bottom surface of board-like grid to the distance between top surface of board-like grid topmost can be reactor inner space total height below
5%~80%, preferably 20%~70%, more preferably 30%~50%；The material of described board-like grid may be selected from
Catalytic cracking regenerator gas distributor or wide bore distribution plate use material, and grille-like can be the shapes such as waveform, lattice
There are the aperture or macropore that pass through for catalyst and gas rule being evenly arranged on grid.
In order that caused oil gas and reclaimable catalyst are separated after being reacted in reactor, traditional whirlwind can be used
Separator, this is well-known to those skilled in the art, and the present invention is to this without being described in detail.
, can also be by using metal sintered filter to make according to a kind of preferred embodiment of the present invention
State oil gas and reclaimable catalyst is separated；The metal sintered filter is a kind of known porous material, can be effectively
Solid particle or powder are separated with gas component, and it is sturdy and durable.The present invention is to the metal sintered filter
Species and structure have no particular limits, as long as it effectively can be separated the oil gas with reclaimable catalyst,
Thus without repeating.It by using metal sintered filter, can reduce investment outlay, simplify operation, and separating effect is compared
Cyclone separator is more preferable.
According to the present invention, described dehydrogenation can use the conventional alkane known to those skilled in the art
Hydrocarbon dehydrogenation, the present invention have no particular limits to it.In order to meet the operation requirement of fluidized-bed reactor and regenerator,
The shape of the dehydrogenation is generally microspheroidal.The dehydrogenation typically contains active component and carrier.According to this
A kind of embodiment of invention, for example, the active component can be metal platinum or chromium oxide, the carrier can be
Aluminum oxide；The aluminum oxide is preferably γ-Al2O3With θ-Al2O3Or the mixture of the two；On the basis of the gross weight of catalyst,
The content of the metal platinum can be the 0.01 heavy % in weight %~1.0, the preferably 0.05 heavy % in weight %~0.2, or work as activearm
The content for being divided into chromium oxide during chromium oxide can be the 1.0 heavy % in weight %~30, the preferably 8.0 heavy % in weight %~20, described
The content of carrier is aequum (i.e. gross weight is 100%).According to a kind of embodiment of the present invention, the catalysis dehydrogenation
Agent can be with or without iron oxide and/or tin oxide, and can be with or without alkali metal oxide or alkaline earth oxide；
On the basis of the gross weight of catalyst, the content of iron oxide and/or tin oxide can be the 0 heavy % in weight %~5.0, preferably 0.2
The heavy % in weight %~2；The content of alkali metal oxide or alkaline earth oxide can be the 0 heavy % in weight %~5.0, preferably 0.5
The heavy % in weight %~2, the alkali metal oxide for example can be potassium oxide, and the alkaline earth oxide for example can be oxidation
Magnesium.
According to the present invention, the process conditions of the dehydrogenation reaction are the present invention known to those skilled in the art
It is had no particular limits.For example, the condition of the dehydrogenation reaction can be：500~700 DEG C of reaction temperature, reaction pressure
0.1~3MPa, low-carbon alkanes volume space velocity 100~2000 hours-1, catalyst residence times 1~30 minute；Preferable dehydrogenation is anti-
The condition answered can be：530~600 DEG C, 0.4~2.0MPa of reaction pressure of reaction temperature, low-carbon alkanes volume space velocity 200~
500 hours-1, catalyst residence times 3~8 minutes.
According to the present invention, the condition of the coke burning regeneration is well-known to those skilled in the art, and the present invention does not have to it
Special limitation.For example, the condition of the coke burning regeneration can be：550~750 DEG C of temperature, pressure are 0.1~0.5MPa, are urged
The agent residence time is 5~60 minutes；Described oxygen-containing atmosphere can be with air, the air or oxygen-enriched with nitrogen dilution
For gas as fluidizing agent, preferable regenerator fluidizing agent is air or the air diluted with nitrogen, it may be necessary to is mended
Fuel gas such as oil refinery dry gas is filled to improve the temperature of beds in regenerator.
As previously described, it is preferred that method of the invention can also include：The regenerated catalyst drawn from regenerator is led to
Cross locking hopper and be delivered to regenerated catalyst head tank, carry out reduction treatment under reducing atmosphere, obtain reducing catalyst, so that
The high-valence state metal oxide being oxidized in catalyst is reduced to the active dehydrogenation component of lower valency, then by the reduction catalystses
Agent is continuously returned in the reactor.The condition of the reduction treatment can be according to the situation of used catalyst come really
Fixed, this is well known to those skilled in the art and understood that this need not be described in detail the present invention.For example, the reduction
The condition of processing can be：Temperature is 500~600 DEG C, and pressure is 0.4~2.0MPa, and catalyst residence times are 1~10 point
Clock；Described reducing atmosphere can be used as fluidizing agent using the reduction logistics of hydrogen；The reduction logistics can be substantially free of
Oxygen and containing 50~100 volume % hydrogen, and can the refinery dry gas containing 0~50 volume %.In addition, working as makes
During to catalyst that platinum is active component, reacted catalyst may need chlorination more after regeneration is burnt for a long time
New process, to redistribute platinum activated centre, now the regenerated catalyst head tank can be used as chlorination processor to make
With.
In the fluidized-bed process method by low-carbon alkanes preparing low-carbon olefins, when only using a reactor, and instead
When answering the device to be operated at atmospheric or low pressure as regenerator, to reach and fixed bed or moving bed process identical are handled
Amount, it is necessary to increase the size of reactor, this can equally increase investment and cost.To solve this problem, the solution that the present invention uses
Certainly method is：The operating pressure of the reactor is improved so as to improve the treating capacity of device.Due to the present invention in reactor and again
Locking hopper is provided with catalyst stream passage between raw device so that controls the operating pressure of reactor higher than regenerator
Operating pressure becomes possibility.
Therefore, according to a kind of preferred embodiment of the present invention, produced according to provided by the invention by low-carbon alkanes
In the method for low-carbon alkene, control the reaction pressure in reactor at least higher 0.3MPa than the regeneration pressure in regenerator.
According to the present invention, described locking hopper can make catalyst from the high pressure hydrocarbon of reactor or hydrogen environment to regenerator
Low pressure oxygen environment, and shifted from high pressure hydrocarbon from the low pressure oxygen environment of regenerator to reactor or hydrogen Environmental security and effectively.
That is, by using locking hopper, reactor and the regeneration catalyzing for regenerated catalyst reduction on the one hand can be made
The oxygen-containing atmosphere of the reducing atmosphere (hydrogen atmosphere) and the coke burning regeneration of regenerator of agent head tank is well isolated from, it is ensured that the present invention
It the security of process, on the other hand can neatly regulate and control the operating pressure of reactor and regenerator, not carry especially
The operating pressure of reactor can be improved in the case of high regenerator operation pressure so as to improve the treating capacity of device.
Locking hopper of the present invention is a kind of to make same material flow in different atmosphere (such as oxidizing atmosphere and also
Primordial Qi atmosphere) between and/or different pressure environment (otherwise such as from high pressure to low pressure, or) between the device that switches over,
Its structure is known to correlative technology field those of skill in the art.Catalyst granules is completed from high pressure hydrocarbon ring by locking hopper
The step of transfer of the border to low pressure oxygen environment, can include：1st, oxygen remaining in the locking hopper emptied is blown using hot nitrogen
Sweep in regenerator；2nd, nitrogen is purged away from locking hopper using hydrogen；3rd, using hydrogen to the locking hopper that has emptied
Pressurization；4th, the reclaimable catalyst from reclaimable catalyst receiver is filled into the locking hopper emptied；5th, discharge is passed through
The hydrogen to pressurize in locking hopper, the locking hopper of filling is depressurized；6th, hydrogen is blown from the locking hopper of filling with hot nitrogen
Scan out；7th, by reclaimable catalyst from the lockhopper of filling to reclaimable catalyst head tank.Completed by locking hopper
The step of transfer of the catalyst granules from low pressure oxygen environment to high pressure hydrocarbon environment, can include：1st, using hot nitrogen by oxygen from filling
The locking hopper of regenerated catalyst is purged in regenerator；2nd, nitrogen is purged away from locking hopper using hydrogen；3rd, use
Hydrogen pressurizes to the locking hopper of filling；4th, regenerated catalyst is fed from the lockhopper of filling to regenerated catalyst
Tank；5th, by discharging the hydrogen in pressurization locking hopper, the locking hopper emptied is depressurized；6th, with hot nitrogen by hydrogen from
The locking hopper of emptying purges away；The 7th, regenerated catalyst is filled into the locking hopper emptied from Regenerator receiver.
According to a kind of embodiment of the present invention, the locking hopper can only use one, i.e. reclaimable catalyst
Conveyed, can also be entered respectively using different locking hoppers as needed using same locking hopper with regenerated catalyst
The conveying of the row reclaimable catalyst and the regenerated catalyst, such change belong to protection scope of the present invention.
According to a kind of embodiment of the present invention, by setting reclaimable catalyst receiver, regenerated catalyst to receive
Device, reclaimable catalyst head tank and regenerated catalyst head tank, the reclaimable catalyst drawn from reactor can continuously be conveyed
Reclaimable catalyst head tank is delivered to by locking hopper again after to reclaimable catalyst receiver, then fed from reclaimable catalyst
Tank is continuously delivered to regenerator, and the regenerated catalyst drawn from regenerator can be continuously delivered into regenerated catalyst and connect
Regenerated catalyst head tank is delivered to by locking hopper again after receiving device, is then continuously delivered to from regenerated catalyst head tank
Reactor, so as to realize being carried out continuously for course of reaction and regenerative process；Regenerated catalyst head tank therein both can be when charging
Tank uses, and the reductor that can also work as regenerated catalyst uses.In reclaimable catalyst receiver, available hydrogen is by reclaimable catalyst
Oil gas contained by logistics is stripped in the reactor to avoid the loss of material；In regenerated catalyst receiver, nitrogen can be used
On the one hand gas or other non-oxidising gas make catalyst in receiver keep fluidisation, on the other hand by contained by regenerated catalyst logistics
Oxygen is stripped in the regenerator；Similarly, in reclaimable catalyst head tank, can be urged by the use of air or nitrogen as lifting
The lifting gas of agent, to keep catalyst in head tank to be in fluidized state.
In the present invention, the heat needed for dehydrogenation reaction is carried out mainly to be provided by the regenerated catalyst of high temperature, if it is desired,
Also can set in addition for the raw material and/or the heater of catalyst into reactor.
Below in conjunction with accompanying drawing, the embodiment of the present invention is further described.
The flow of the method for the low-carbon alkanes preparing low-carbon olefins that Fig. 1 is provided is as follows：
As shown in figure 1, the raw material after preheating enters fluidized-bed reactor 1 by feed distributor through pipeline 7, and from pipe
1 top of fluidized-bed reactor is delivered to after regenerated catalyst contact, gasification and the reaction of the activity recovery of line 28.In fluid bed
The top of reactor 1, reaction oil gas and a small amount of catalyst granules separate through gas-solid separation equipment, and catalyst granules returns to fluid bed
Reactor bed, the dehydrogenation product after separation enter subsequent separation system through pipeline 8 and carry out product separation.On fluidized-bed reactor
The reclaimable catalyst of the carbon distribution in portion enters reclaimable catalyst receiver 3 through pipeline 21.Catalyst in reclaimable catalyst receiver 3
After the hydrogen stripped from pipeline 11 goes out the reaction oil gas of carrying, locking hopper is flowed into by pipeline 22 and control valve 15 successively
4, the oil gas being stripped off is sent into fluidized-bed reactor 1 through pipeline 31.
After reclaimable catalyst undergoes a series of processes such as purgings, boosting, filling and decompression in locking hopper 4, pass through successively
Pipeline 23 and control valve 18 flow into reclaimable catalyst head tank 5, then successively through pipeline 24 and control valve 19 with coming from pipeline 12
Air mixing after, the middle and upper part of fluid bed regenerator 2 is promoted to through pipeline 25.Reclaimable catalyst is in fluid bed regenerator 2
The burnt reaction of concurrent raw burn is contacted with the oxygen-containing gas from pipeline 9, to recover catalyst activity.Regenerated flue gas is through pipeline 10 by again
The discharge of the raw top of device 2 is simultaneously vented after heat exchange and catalyst powder dust recovery system.Regenerated catalyst is through control valve 20 with coming from pipe
After the nitrogen mixing of line 13, regenerated catalyst receiver 6 is promoted to through pipeline 26, the catalyst in regenerated catalyst receiver 6
After the nitrogen from pipeline 14 fluidizes and the oxygen of catalyst carrying is stripped off, flow into close through pipeline 27 and control valve 17 successively
Lock hopper 4.
After regenerated catalyst undergoes a series of processes such as purgings, decompression, filling and boosting in locking hopper 4, pass through successively
Control valve 16 and pipeline 28 first flow into regenerated catalyst head tank 40, then are flowed into by pipeline 42 in fluidized-bed reactor 1, with coming
From the raw material contact and reaction of pipeline 7.
Fig. 2 is a kind of further embodiment of the present invention, and its flow is the regeneration catalyzing on the basis of Fig. 1
After agent is discharged by locking hopper 4, regenerated catalyst head tank 40 is first flowed into through control valve 16 and pipeline 28 successively, by from pipeline
After 41 hydrogen-containing gas reduction, then flowed into fluidized-bed reactor 1 by pipeline 42 and contacted with raw material.Raw material and catalyst are in cloth
It is equipped with the fluidized-bed reactor 1 of board-like grid 50 and contacts and react.
Following embodiment will illustrate with reference to accompanying drawing to the embodiment of invention.
Device used in embodiment is pressurised fluidized bed device, has the embodiment party similar to accompanying drawing described device
Formula, to reach similar reaction and regeneration effect.
The raw materials used source of the gas for purchase of embodiment, respectively propane (purity more than 99.5%), iso-butane (purity
More than 99.5%), propane and iso-butane mixture (mass ratio 1:1).
Embodiment used catalyst for prepare catalyst, respectively Cr-Fe-K/Al2O3Catalyst and Pt-Sn-K/
Al2O3Catalyst.
Cr-Fe-K/Al2O3Catalyst (hereinafter referred to as chromium-based catalysts) preparation process is as follows：First, by 780g chromic nitrates
(analysis is pure), 100g ferric nitrates (analysis is pure), 80g potassium nitrate (analysis is pure) solid are dosed into and fill the vertical of 3000g distilled water
In agitator tank, 1h is stirred；Then, the 2000g γ-Al that will be pre-dried2O3It is dosed into above-mentioned vertical mixing tank, fully stirs
Mix and stir dipping 2h；Slurries in agitator tank are transferred in filtering tank and filter out unnecessary bright water, catalyst is then placed into 200
DEG C drying box in dry, this process need at least 2h；Dried catalyst is placed into 520 DEG C of Muffle kiln roasting
6h, the Cr-Fe-K/Al of activation is made2O3Dehydrogenation, it is put into standby in drier.
Pt-Sn-K/Al2O3Catalyst (hereinafter referred to as platinum group catalyst) preparation process is as follows：First, by 20g chloroplatinic acids
(analysis is pure), 120g nitric acid tin (analysis is pure), 90g potassium nitrate (analysis is pure) solid are dosed into and fill the vertical of 2400g distilled water
In agitator tank, 1h is stirred；Then, the 2000g γ-Al that will be pre-dried2O3It is dosed into above-mentioned vertical mixing tank, fully stirs
Mix and stir dipping 2h；Slurries in agitator tank are transferred in filtering tank and filter out unnecessary bright water, catalyst is then placed into 180
Dried in DEG C drying box, this process needs at least 2h；Dried catalyst is placed into 500 DEG C of Muffle kiln roasting 4h,
The Pt-Sn-K/Al of activation is made2O3Dehydrogenation, it is put into standby in drier.
Embodiment 1
Technique is carried out embodiment 1 as shown in Figure 1, and raw materials used is propane, respectively using the chromium-based catalysts and platinum prepared
Series catalysts.Experiment condition, feed stock conversion and product selectivity data are listed in table 1.
Embodiment 2
Embodiment 2 as shown in Figure 2 technique carry out, raw materials used be iso-butane, respectively using prepare chromium-based catalysts with
Platinum group catalyst.Experiment condition, feed stock conversion and product selectivity data are listed in table 2.
Embodiment 3
Technique is carried out embodiment 3 as shown in Figure 2, and raw materials used is propane and iso-butane mixture, respectively using preparation
Chromium-based catalysts and platinum group catalyst.Experiment condition, feed stock conversion and product selectivity data are listed in table 3.
From table 1, table 2 and table 3 as can be seen that using fluidized-bed reaction-regenerative system of the invention, in reaction temperature and again
Under conditions of raw temperature is relatively low, the yield of feed stock conversion and target alkene can reach the level of existing commercial dehydrogenation technique,
And because the pressure of reaction system is higher than existing commercial plant, therefore under other operating condition same cases, present invention reaction
The feed throughput of system is higher than existing commercial plant.
Table 1
Table 2
Table 3
Claims (15)
1. a kind of method by low-carbon alkanes preparing low-carbon olefins, this method includes：
Continuously the low-carbon alkanes after preheating are contacted with dehydrogenation in a fluidized bed reactor and issued in dehydrogenation condition
Raw dehydrogenation reaction, produce the reclaimable catalyst of oil gas and carbon distribution rich in low-carbon alkene；The low-carbon alkanes are C2~C5 alkane
Either their mixture；
Separate oil gas and reclaimable catalyst, the oil gas after separation be sent into product separation and recovery system, by reclaimable catalyst from
Reactor is continuously drawn；
After the reclaimable catalyst drawn from reactor is delivered into reclaimable catalyst receiver, then it is delivered to and is treated by locking hopper
Raw catalyst feed tank, is then delivered to fluid bed regenerator from reclaimable catalyst head tank, and in a regenerator oxygenous
Coke burning regeneration is carried out under atmosphere, obtains regenerated catalyst；
After regenerated catalyst is continuously drawn out into regenerated catalyst receiver from regenerator, then it is delivered to again by locking hopper
Raw catalyst feed tank, and continuously returned in the reactor from regenerated catalyst head tank；Control anti-in reactor
Answer at least high 0.3MPa of the regeneration pressure in pressure ratio regenerator.
2. method according to claim 1, this method also include：The regenerated catalyst in regenerated catalyst head tank will be delivered to
Reduction treatment is carried out under reducing atmosphere, obtains reducing catalyst, is then continuously returned to the reducing catalyst described anti-
Answer in device.
3. according to the method for claim 1, wherein the low-carbon alkanes be selected from ethane, propane, iso-butane, normal butane,
One or more in pentane and isopentane.
4. method according to claim 1, wherein the low-carbon alkanes are to be split selected from natural gas condensate, natural gas liquid, catalysis
Change at least one of liquefied gas, casing-head gas condensed liquid and shale gas condensed liquid.
5. method according to claim 1, wherein the fluidized-bed reactor is bubbling fluidized bed reactor or turbulent fluidised
Bed reactor.
6. method according to claim 1, wherein the fluidized-bed reactor has the internal baffle of layered arrangement.
7. according to the method for claim 6, wherein the internal baffle is board-like grid, the board-like every 20~150cm of grid
One layer of installing, it is empty for inside reactor from the bottom surface of bottom board-like grid to the distance between top surface of board-like grid topmost
Between total height 20%~70%.
8. method according to claim 1, wherein separating oil gas and reclaimable catalyst by metal sintered filter.
9. method according to claim 1, wherein the dehydrogenation contains active component and carrier；The active component is
Metal platinum or chromium oxide, the carrier are aluminum oxide；On the basis of the gross weight of catalyst, the content of the metal platinum is
The 0.01 heavy % in weight %~1.0, or the content of the chromium oxide is the 1.0 heavy % in weight %~30, the content of the carrier is balance
Amount.
10. method according to claim 1, wherein the condition of the dehydrogenation reaction is：500~700 DEG C of reaction temperature, reaction pressure
0.1~3MPa of power, low-carbon alkanes volume space velocity 100~2000 hours-1, catalyst residence times 1~30 minute.
11. method according to claim 10, wherein the condition of the dehydrogenation reaction is：530~600 DEG C of reaction temperature, reaction
0.4~2.0MPa of pressure, low-carbon alkanes volume space velocity 200~500 hours-1, catalyst residence times 3~8 minutes.
12. method according to claim 1, wherein the condition of the coke burning regeneration is：Temperature is 550~750 DEG C, and pressure is
0.1~0.5MPa, catalyst residence times are 5~60 minutes；Described oxygen-containing atmosphere is with air, the sky diluted with nitrogen
Gas or oxygen rich gas are as fluidizing agent.
13. method according to claim 2, wherein the condition of the reduction treatment is：Temperature is 500~600 DEG C, and pressure is
0.4~2.0MPa, catalyst residence times are 1~10 minute；Described reducing atmosphere is to be used as stream using hydrogeneous reduction logistics
Change medium；The reduction logistics contains 0~50 volume % refining without oxygen and containing 50~100 volume % hydrogen
Oily factory's dry gas.
14. method according to claim 1, wherein the oil gas contained by by the reclaimable catalyst logistics in reclaimable catalyst receiver
With hydrogen stripped to the reactor.
15. method according to claim 1, this method also include：Will be isolated not through the product separation and recovery system
The low-carbon alkanes of reaction are back in the reactor as raw material.
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| CN201410557715.7A CN105585400B (en) | 2014-10-20 | 2014-10-20 | A kind of method by low-carbon alkanes preparing low-carbon olefins |
| CN201580011667.4A CN106068253B (en) | 2014-10-20 | 2015-10-20 | A kind of manufacturing method of low-carbon alkene |
| JP2017521190A JP6693952B2 (en) | 2014-10-20 | 2015-10-20 | Light olefin production method |
| PCT/CN2015/000704 WO2016061905A1 (en) | 2014-10-20 | 2015-10-20 | Low-carbon olefin production method |
| US15/520,721 US10144680B2 (en) | 2014-10-20 | 2015-10-20 | Process for producing light olefins |
| SG11201703275TA SG11201703275TA (en) | 2014-10-20 | 2015-10-20 | A process for producing light olefins |
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| RU2638934C1 (en) * | 2017-04-26 | 2017-12-19 | Акционерное общество "Специальное конструкторско-технологическое бюро "Катализатор" | Installation of dehydration of paraffin hydrocarbons c3-c5 |
| US10301233B2 (en) * | 2017-07-03 | 2019-05-28 | Chevron U.S.A. Inc. | Natural gas liquid upgrading by ionic liquid catalyzed alkylation |
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| CN1952060A (en) * | 2005-10-19 | 2007-04-25 | 中国石油化工股份有限公司 | Production process of producing cleaning gasoline |
| CN101481289A (en) * | 2008-01-11 | 2009-07-15 | 山东科技大学 | Process for preparing propylene by propane riser circulating fluid bed catalysis |
| CN101658799A (en) * | 2009-09-14 | 2010-03-03 | 洛阳瑞泽石化工程有限公司 | Continuous catalyst regeneration method and device thereof |
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