CN106348996A - Process and device for preparing propylene by dehydrogenating propane or propane-enriched light hydrocarbon - Google Patents
Process and device for preparing propylene by dehydrogenating propane or propane-enriched light hydrocarbon Download PDFInfo
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- CN106348996A CN106348996A CN201610767052.0A CN201610767052A CN106348996A CN 106348996 A CN106348996 A CN 106348996A CN 201610767052 A CN201610767052 A CN 201610767052A CN 106348996 A CN106348996 A CN 106348996A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
- C07C5/333—Catalytic processes
- C07C5/3335—Catalytic processes with metals
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
- C07C5/333—Catalytic processes
- C07C5/3335—Catalytic processes with metals
- C07C5/3337—Catalytic processes with metals of the platinum group
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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
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention discloses a process and a device for preparing propylene by dehydrogenating propane or propane-enriched light hydrocarbon. The device comprises a lifting pipe reaction system, a catalyst cyclic regeneration system and a heat carrier circulation system, wherein after propane is subjected to upward reaction in a lifting pipe for a period of time, the temperature of the lifting pipe is lowered and the dehydrogenation reaction speed is reduced; at the moment, a high-temperature small-particle heat carrier enters a low-temperature part in the lifting pipe to increase the temperature of oil gas and a catalyst so as to enable the dehydrogenation reaction to be conducted continuously; the heat carrier supplements heat for the lifting pipe for 2 to 6 times in the way, so that the dehydrogenation reaction is close to an equilibrium conversion rate; the heat carrier separated by a cyclone separator enters a second regenerator and contacts with high-temperature flue gas generated by dry gas combustion, so that the high-temperature heat carrier is obtained again and is circulated to each part of the lifting pipe; a large-particle microsphere catalyst which enters from the upper part of the lifting pipe settles down the lower part of the lifting pipe by virtue of gravity to be discharged and is lifted and conveyed to a first regenerator, and then the catalyst is regenerated under the conditions of low temperature, low oxygen and the like and is circulated and fed into the inlet of the upper part of the lifting pipe, so that catalyst circulation is realized.
Description
Technical field:
The present invention relates to a kind of dehydrogenating technology of low-carbon alkanes, relate more specifically to a kind of propane or be rich in propane lower carbon number hydrocarbons
Dehydrogenation producing propylene technique and its device.
Background technology:
Trends In Preparation of Propene By Catalytic Dehydrogenation of Propane technique has high income, the features such as dehydrogenation gained hydrogen is high value added product, is
The current main method producing propylene.The method of the Trends In Preparation of Propene By Catalytic Dehydrogenation of Propane disclosed in prior art is a lot, such as
Cn100460371c discloses a kind of device of preparing propylene by dehydrogenating propane under hydrogen plasma, due to its needs wait from
Under conditions of son, laboratory test state can only be rested at present it is difficult to carry out plant-scale enforcement.usp4418237、
Usp4435607, usp4788371, usp4886928, cn1179930c etc. disclose a kind of by removing hydrogen in course of reaction
The method of dehydrogenating of hydrocarbon raw material.Cn1268589c then discloses a kind of improved fixed bed low-carbon (LC) hydrocarbon dehydrogenation method, by circulation
Portion of product gas enters reaction zone and improves conversion ratio and improve catalyst life.The caltalyst of preparing propylene by dehydrogenating propane
Owner will have oxidative dehydrogenation type catalyst, chromium-based catalysts and platinum group catalyst etc..Existing change in terms of catalyst
The dehydrogenating low-carbon alkane technology entered is a lot, the cr/al catalyst of the employing infusion process preparation as disclosed in gb2177317a,
The heterogeneously catalyzed partial by improved noble metal catalyst fixed bed hydrocarbon disclosed in cn101384525, cn101460433 takes off
Hydrogen methods, and in the method for dehydrogenating disclosed in cn1220659c, the acidity of catalyst has been carried out adjusting and burn and generated
Hydrogen is thus improve the space-time yield of dehydrogenation reaction, but the hydrogen burning preciousness can affect economy.
A kind of typical fixed bed dehydrogenating propane method houdrycatofin method is disclosed by usp2419997, adopts
The dehydrogenating propane technique of fixed bed reactors, typically adopts multiple reactor parallel operations, part reaction wherein in conversion zone
Device produces, simultaneously a part of reactor regeneration, and the regeneration period of catalyst is generally several hours.Dehydrogenating propane reaction is molecule
The increased endothermic reaction, therefore high temperature and low pressure are conducive to the carrying out reacting.Cn101252989a is changed on this basis
Enter, the inert material such as alpha-oxidation aluminium ball adding 30～50% in beds is used for accumulation of heat thus improve the conversion of bed
Efficiency.
Cn1037765c then disclose by stainless steel reactor formed stannide protective layer modified technique device and
Method, can improve reaction conversion temperature, thus improve transformation efficiency.
Gas chemicals company of the U.S. industrialization catofin dehydrogenating propane technique and complexes, graig r
G, delaney tj, duffaloj m.catalytic dehydrogenation performance of catofin
Process petrocheical review.houston.dewitt.1990, ep192059, gb2162082, insulation fix bed
Reactor, using cr2o3/al2o3 catalyst, is the chromium that activated aluminum bead soaks 18～20wt%.At tiny structure (49kpa), newly
Fresh propane is operated at a temperature of being preheated to 550～750 DEG C (preferably 620～670 DEG C) with recycled propane after being mixed.Temperature of reactor and
Pressure all can have influence on the yield of propylene, and propane conversion per pass is 55～60mol%, and density of propylene is 52% about.This work
The several reactor of skill is in parallel, and including a reaction, reactor switching, catalyst regeneration cycle, the catalyst in reactor steams
Vapour regenerates, when the coking generation on catalyst is burnt, the heat that the energy being discharged can be absorbed as dehydrogenation reaction, and capable of circulation
Carry out forming continuous production process.Whole technique propene yield is 83%.
The star technique of Philips Petroleum Co. of U.S. exploitation is also a kind of fixed-bed intermittent regeneration technology and process unit,
Dunn ro, et al.the phillips steam active re2forming (star) processc3, c1 and c5
Paraffin for the dehydrogenation.petrochemical review.houstondewitt, 1992,
Usp4167532, usp4902849, usp4926005, usp4996387, usp5389342, Petroleum (≤c5) dehydrogenating technology is adopted
With isothermal operation, after vapoury raw material preheating, enter one group of heterogeneous fixed bed reactor, each reactor has many root catalysis
Agent filling pipe.Reactor operation is circulation, as changeable in each reactor after go to carry out catalyst regeneration, holding certain embodiments
It is carried out continuously.Steam is mainly used in diluting, and keeps gross pressure in reactor constant, reduces the partial pressure of hydrocarbon and hydrogen, reaction can be made to put down
Weighing apparatus trends towards increasing the conversion ratio of c5.Reactor online production switched after 7 hours, and decaying catalyst was through combustive regeneration 1 hour
After can activate completely.It is reported that 1 to 2 years entire lives of catalyst.This technique propylene is 80% to propane recovering rate.Side reaction produces
Co2 must remove from reactant when separating.
The poh fixed-bed intermittent regenerative response technique of German Linde Co and process unit are also anti-using fixed bed tubular type
Answer device, peter elsle.ullman ' s encyclopedia of industrial chemistry.vol a22
Barbara elvers hansjugen 2,1993.211～222, its key problem in technology is that reaction temperature is low, reactor is non-etc.
Warm heat-insulating, being operated under conditions of isothermal reaction, with reduce the thermal cracking of propane with coking.With chromium oxide for urging
Agent has the relatively long circulating cycle of 9 hours, and the difference with other techniques is that raw material propane does not need hydrogen or Steam dilution.Cause
This has 91% relatively high selectivity, can obtain polymerization-grade propylene after product is separated.Process avoids catofin technique
The problems such as negative-pressure operation and oleflex technique are diluted with h2, low cost, pollution less, power consumption low and investment less make its with
Similar technique is compared has stronger competitiveness, is carrying out industrialization design.
At present, the outstanding problem using the dehydrogenating propane technique presence of fixed bed reactors is catalyst heap than big, bed
It is available for reactant or space that product passes through is little and resistance is big, reaction pressure drop is larger, and reaction velocity is relatively low, and mass-and heat-transfer is easy slowly
Cause the even product of reaction bed temperature skewness further side reaction to occur, so that reaction selectivity is deteriorated, and with anti-
The carrying out answering, makes catalyst bed Rotating fields change because catalytic mechanical intensity changes, what impact was reacted is normally carried out.
Uop company of the U.S. exploitation oleflex technique adopt moving bed continuous regenerative reaction process device, be by
Pacol technological development, pujado, p.r, vora, b.v.hydrocarbon process, 1990,69 (3): 65,
Usp3584060, usp3878131, usp4438238, usp4595673, usp4716143, usp4786265, usp4827072,
Nineteen ninety realizes industrialized production.Oleflex and catofin both preparing propylene by dehydrogenating propane technique is substantially the same, and institute is different
Simply dehydrogenation and catalyst regenerating section, oleflex technique uses pt/al2o3 moving-bed of catalyst reactor, be one absolutely
Hot continuous processing, reaction institute calorific requirement is by the temperature difference reacted between each step heated rear offer again.This technique is carried out under pressure-fired
Operation, with palladium as catalyst, the selectivity to propylene is 89～91%.Dehydrogenation can be recycled through regeneration, that is, inactivate
Catalyst separates in a regenerator, burns, and removes the coking of catalyst surface, dehydrogenation reactor sent back to by the catalyst of regeneration.Will
Gained propylene, through continuous dethanizer, depropanizing tower, can obtain polymerization-grade propylene.The advantage of oleflex technique is that operation connects
Continuous, load is uniform, space-time yield is constant, and the catalysis activity in reactor cross section is constant, and catalyst regeneration is carried out under isothermal.Should
Technique propene yield is 86.4%, and hydrogen yield is 3.5%.
The disadvantage of oleflex technique is the concurrent heating mode between multistage reactor.Need institute in upper level reactor
There is material (including reaction raw materials and product) to draw reactor, enter after heating furnace supplementary heating heats up and return to next order reaction
Device continues reaction, and this makes the reaction raw materials and product time of staying at high temperature considerably beyond the originally required reaction of dehydrogenation
Time, the side reaction such as the cracking at high temperature of such reaction raw materials and product, condensation, coking is all significantly increased, and reduces reaction and produces
While product Propylene Selectivity, separating energy consumption is made to be significantly increased.
Cn1082018 discloses a kind of noble metal catalyst that can be used for fluidized-bed reactor and c2～c5 light chain alkane is taken off
The manufacturing technology of hydrogen catalyst, but full mixed bed is difficult to ensure that the conversion ratio of propane.
Cn2009102048269 is asked using the cyclic regeneration that riser Circulating Fluidized Bed Process then can solve catalyst
Topic.But for highly endothermic dehydrogenating propane reaction, how in riser heat supply it is ensured that reaction temperature problem does not solve, and
And adopt high temperature regeneration, realize thermally equilibrated simultaneously, propane dehydrogenation catalyst be easy to inactivate.
Cn100453161 discloses a kind of multistage mixing of greatly different particles, heat exchange, reaction, the method that is harmonious of classification.Its base
Present principles are different using of different sizes, the heap density of granule, and under certain gas speed, fluidized state is different and realize size
The separation of grain.This patent adopts multistage gas-solid fluidized bed series connection, and large and small granule is large and small from the gas-solid fluidized bed body of one-level respectively
Article inlet pipe enters fluidized bed body, makes fluidizing gas from entering trachea by gas distribution grid entrance fluidized bed body, with granule
Dense bed and dilute-phase leanphase fluidized bed that the bottom-up formation that interacts is thoroughly mixed, control the superficial gas velocity of air-flow, make little particle from little
Particle outlet pipe is less easily entrained by and leaves fluidized bed body, and bulky grain is then discharged from bulky grain outlet, realizes intergranular classification.
But the heat-carrying function of large and small granule is developed, and large and small granule is shared a regenerator, be unfavorable for that catalyst is lived
The protection of property.
Content of the invention:
A first aspect of the present invention purpose is to provide the low propane of a kind of high conversion rate, energy consumption or be rich in propane lower carbon number hydrocarbons
Dehydrogenation producing propylene device, produces high value added product fine propylene and hydrogen.
The technical scheme that the present invention takes is as follows:
A kind of propane or the dehydrogenation producing propylene device rich in propane lower carbon number hydrocarbons, follow including riser response system, catalyst
Ring regenerative system, heat carrier recirculation system, wherein:
Riser response system includes riser reactor, and the bottom of riser reactor is material inlet, and riser is anti-
The top answering device is catalyst inlet, and riser reactor sets gradually as some conversion zones from lower to upper, in each conversion zone
It is correspondingly arranged on the heat carrier delivery pipe that reaction is carried out with concurrent heating；Reacting-settler is arranged at the top of riser reactor, instead
Answer and in settler, be provided with oil gas cyclone separator；
Catalyst cyclic regeneration system includes the first regenerator for catalyst regeneration, and first regenerator one end is to be generated
Catalyst input, strips inclined tube by reclaimable catalyst, reclaimable catalyst delivery pipe is connected with the bottom of riser reactor,
The first regenerator other end is regenerated catalyst outfan, by the top phase of regenerated catalyst inclined tube and riser reactor
Even；
Heat carrier recirculation system includes the Second reactivator being regenerated for heat carrier, and one end of Second reactivator is to treat
Heat carrier input, receives, by heat carrier inclined tube to be generated, the heat carrier to be generated that oil gas cyclone separator is isolated, second again
The other end of raw device is regeneration heat carrier outfan, by regenerating each conversion zone phase of heat carrier inclined tube and riser reactor
Even, for exporting the high-temperature heat carrier of regeneration to each conversion zone of riser reactor.
Described regeneration heat carrier inclined tube, according to the reaction hop count of riser reactor design, arranges some delivery pipes.
A second aspect of the present invention is to provide a kind of propane or the dehydrogenation producing propylene technique rich in propane lower carbon number hydrocarbons, its feature
It is, comprise the following steps:
(1) catalytic dehydrogenation:
Raw material after preheated is introduced into the first conversion zone of riser reactor bottom, in reaction temperature 530 DEG C～680
DEG C, under the conditions of pressure 0.03mpa～0.4mpa, contact with the downflowing catalyst entering from riser top and carry out dehydrogenation reaction；
After propane up reaction a period of time in riser reactor, temperature drop in riser reactor, dehydrogenation reaction speed drops
Low；Now from Second reactivator, high-temperature heat carrier out enters the low temperature position riser reactor, improves oil gas and urges
The temperature of agent, lower temperature oil gas is continued with the second conversion zone entering riser reactor after high-temperature heat carrier mixing concurrent heating
Dehydrogenation reaction, so repeats, until dehydrogenation reaction is close to balance；
(2) heat carrier circulation:
Enter Second reactivator, the second regeneration through the heat carrier that oil gas cyclone separator is isolated along heat carrier inclined tube to be generated
Obtaining high-temperature flue gas by burning in device is heat carrier heat supply to be generated, becomes high-temperature heat carrier, and high-temperature heat carrier passes through regenerated heat
Each conversion zone that carrier inclined tube enters riser reactor recycles；
(3) catalyst circulation:
Enter the catalyst on riser reactor top under gravity, be deposited to the lower part of riser reactor
Go out, in the presence of lift gas, be delivered to the first regenerator through reclaimable catalyst stripping inclined tube, reclaimable catalyst delivery pipe,
Top after catalyst being regenerated under the conditions of low temperature, hypoxia etc., through regenerated catalyst inclined tube recycled back riser reactor
Entrance, realizes catalyst circulation.
The present invention carries out concurrent heating using high-temperature heat carrier to riser reactor, makes dehydrogenation reaction close to equilibrium conversion；
Hereafter oil gas leaves riser reactor together with heat carrier, isolates oil gas product through oil gas cyclone separator, oil gas is pressed
Conventional entrance cooling, aerostatic press compression section, finally enter knockout tower, tower top separates fine propylene and goes out device, bottom of towe as product
Alkane product Returning reacting system is further reacted.
In riser reactor, raw material under 550 DEG C～630 DEG C of reaction temperature, pressure 0.03mpa～0.15mpa, with
Various dehydrogenations carry out dehydrogenation conversion reaction, and conversion per pass is 10～90%.
Riser reactor is divided into some sections, and in each section, propane carries out dehydrogenation reaction, thing after contacting with catalyst
Material temperature degree reduces, and dehydrogenation speed declines, and introduces high-temperature heat carrier at each section of rear portion, after high-temperature heat carrier is contacted with material,
Make material and catalyst temperature return to 530 DEG C～680 DEG C, so that dehydrogenation reaction is quickly carried out again, so repeatedly, until oil gas with
Heat carrier leaves riser reactor together, enters cyclone separator, separates product oil gas and enters cooling, compression section, under sedimentation
The heat carrier coming is recycled to Second reactivator, and contacting acquisition heat with the high-temperature flue gas of burning becomes high-temperature heat carrier again.
By controlling the air velocity in riser reactor, control less than 0.9 times in catalyst carrying velocity, heat carries
More than 2 times of body carrying velocity, thus realize catalyst in riser separate with heat carrier.
Described heat carrier is stable and inert inorganic compound in 500-750 DEG C, and heat carrier is particle diameter in 10-100 μ
The microsphere particle of m, < 1.0g/ml, because the grain diameter of heat carrier is less, carrying velocity is less, easy and oil gas for apparent bulk density
Together, form piston flow and enter cyclone separator separation.Preferably, the grain diameter of described heat carrier is 30-80 μm, apparent heap
Density < 0.9g/ml.
Do not taken out of by high speed oil gas in riser to realize catalyst, catalyst granules adopts heap density higher, grain
The larger particle in footpath, catalyst granules controls at 200-2000 μm, and apparent bulk density is 0.8-1.8g/ml, preferred catalyst
Grain controls at 400-1500 μm, and apparent bulk density is 1.0-1.5g/ml.
Propane from the above mentioned or be rich in propane lower carbon number hydrocarbons dehydrogenation producing propylene process, described raw material propane or be rich in third
The lower carbon number hydrocarbons of alkane, including propane, casing-head gas, condensate, liquefied petroleum gas, refinery gas and natural gas dampness, preferably propane
And liquefied petroleum gas.
Propane from the above mentioned or the Second reactivator rich in propane lower carbon number hydrocarbons dehydrogenation producing propylene process unit, are system thermal
The afterburning medium of amount includes dry gas, liquefied gas, light diesel fuel and fuel oil.
Beneficial effects of the present invention are as follows:
1st, the present invention adopts riser response system and catalyst cyclic regeneration system, heat carrier recirculation system, catalyst
Using bulky grain microspherical catalyst, catalyst granules controls at 200-2000 μm, and apparent bulk density answers 0.8-1.8g/ml, catalysis
Agent due to, particle diameter larger particle, it is possible to achieve catalyst in riser by high speed oil gas do not taken higher using heap density,
Complete regeneration and the circulation of catalyst；Heat carrier select high temperature little particle heat carrier, heat carrier particle diameter at 10-100 μm, apparent heap
Density should < 1.0g/ml, because the particle diameter of heat carrier granule is less, carrying velocity be less, easily together with oil gas, forms piston flow
Enter cyclone separator to separate.
So, bulky grain microspherical catalyst cooperation catalyst cyclic regeneration system is it is achieved that the circulation of catalyst and regeneration,
High temperature little particle heat carrier coordinates heat carrier recirculation system, realize to the lasting concurrent heating of riser response system it is achieved that efficiently,
Environmental protection, the dehydrogenation producing propylene technique of energy-conservation.
2nd, because Trends In Preparation of Propene By Catalytic Dehydrogenation of Propane technique is a strong endothermic reaction process, provided using fixed bed reactors
Heat is more difficult, and the technological reaction regeneration period is short, switching is frequent, react, regeneration is interrupted switching, poor stability, heat utilization efficiency
Low.And the moving bed reaction system in prior art, need multi-floating bodies, before each kettle, all react preheating furnace, make oil gas at high temperature
The time of staying is significantly increased, and the side reaction such as the cracking at high temperature of reaction raw materials and product, condensation, coking is all significantly increased, fall
Low reaction product Propylene Selectivity；The other pre- heat utilization efficiency of preheating furnace is low, high energy consumption, and operating cost and labor intensity are high.Although
It is also successive reaction and regeneration, but investment and occupation of land are larger.Catalyst unit price is higher and reduction with catalyst activity, needs not
, to maintain the conversion ratio of requirement, product slates are unstable for the disconnected operating condition that changes.The high-temperature position heat utilization rate burning generation is low, temperature
Degree constantly declines, and have impact on conversion ratio.The noble metal catalyst of matched high cost also can affect the economy of process unit
Property.
Compared with the prior art, propane provided by the present invention or rich in propane lower carbon number hydrocarbons dehydrogenation producing propylene process unit and
The advantage of method is embodied in, due to lifting tube reaction-catalyst cyclic regeneration system-heat carrier recirculation system using fluid bed.
Catalyst carries out dehydrogenation (concurrent heating) reaction in recirculating fluidized bed riser reactor, is conducive to mass transfer and the carrying out of heat transfer, makes
Reaction can be carried out continuously, and the high-temperature residence time of oil gas is short, and the conversion ratio of reaction and selectivity are higher.Heat carrier can be continuously de-
Hydrogen reaction provides heat, and energy consumption is low.The independent loops system of catalyst, can effective control catalyst regeneration condition it is ensured that
Catalyst activity.Smooth operation product quality is stable, and present invention process device can be made to carry out continuous-stable long period at full capacity
Safety in production, and invest and take up an area all less.
Below by embodiment and the present invention is further elucidated with reference to the figures, but not thereby limiting the invention.
Brief description:
Fig. 1 is the system structure diagram of the present invention；
In figure label: 01, riser reactor, 02, reacting-settler, 03, regenerated catalyst inclined tube, 04, catalysis to be generated
Agent inclined tube, 05, reclaimable catalyst delivery pipe, the 06, first regenerator, 07, heat carrier inclined tube to be generated, 08, Second reactivator, 09,
Regeneration heat carrier inclined tube, 10, oil gas cyclone separator, 11, flue gas cyclone separator, 12, flue gas cyclone separator, 13, raw material,
14th, the first conversion zone, the 15, second conversion zone, the 16, the 3rd conversion zone, the 17, the 4th conversion zone, 18, exhanst gas outlet, 19, oil gas goes out
Mouthful, 20, stripping vapour, 21, air, 22, lifting gas, 23, fuel gas.
Specific embodiment:
Embodiment 1:
As shown in figure 1, a kind of propane of the present invention or the dehydrogenation producing propylene device rich in propane lower carbon number hydrocarbons, including riser
Response system, catalyst cyclic regeneration system, heat carrier recirculation system, wherein:
Riser response system includes riser reactor 01, and the bottom of riser reactor 01 is material inlet, lifting
The top of pipe reactor 01 is catalyst inlet, and riser reactor 01 sets gradually as some conversion zones from lower to upper, every
Individual conversion zone is correspondingly arranged on the heat carrier delivery pipe that reaction is carried out with concurrent heating；Reacting-settler 02 is arranged at riser reactor
01 top, is provided with oil gas cyclone separator 10 in reacting-settler 02；
Catalyst cyclic regeneration system includes the first regenerator 06 for catalyst regeneration, and the first regenerator 06 one end is
Reclaimable catalyst input, strips inclined tube 04, reclaimable catalyst delivery pipe 05 and riser reactor 01 by reclaimable catalyst
Bottom be connected, the first regenerator 06 other end be regenerated catalyst outfan, by regenerated catalyst inclined tube 03 and riser
The top of reactor 01 is connected；
Heat carrier recirculation system includes the Second reactivator 08 being regenerated for heat carrier, one end of Second reactivator 08
For heat carrier input to be generated, treat that heat carries by what heat carrier inclined tube 07 to be generated reception oil gas cyclone separator 10 was isolated
Body, the other end of Second reactivator 08 is regeneration heat carrier outfan, by regenerating heat carrier inclined tube 09 and riser reactor
01 each conversion zone is connected, for exporting the high-temperature heat carrier of regeneration to each conversion zone of riser reactor 01, regenerated heat
Carrier inclined tube 09 can arrange some delivery pipes according to the reaction hop count of riser reactor 01, such as in the embodiment of Fig. 1,
The reaction hop count of riser reactor 01 is set to four sections, then be provided with 3 delivery pipes (9-1,9-2,9-3).
It is respectively arranged with flue gas cyclone separator 11, flue gas cyclonic separation in the first regenerator 06, Second reactivator 08
Device 12.
As shown in figure 1, a kind of propane of the present invention or the dehydrogenation producing propylene technique rich in propane lower carbon number hydrocarbons, walk including following
Rapid:
(1) catalytic dehydrogenation:
Raw material 13 after preheated is introduced into the first conversion zone 14 of riser reactor 01 bottom, and from riser top
The downflowing catalyst contact entering carries out dehydrogenation reaction；After propane up reaction a period of time in riser reactor 01, carry
Temperature drop in riser reactors 01, dehydrogenation reaction speed reduces；Now the high-temperature heat carrier from the first delivery pipe 9-1 conveying enters
(i.e. the end of the first conversion zone, the present embodiment adopts four concurrent heatings, positioned at lifting to enter low temperature position in riser reactor 01
1/4 position of pipe reactor), improve the temperature of oil gas and catalyst, lower temperature oil gas with after high-temperature heat carrier mixing concurrent heating
The second conversion zone 15 entering riser reactor 01 continues dehydrogenation reaction, after the completion of the second conversion zone 15 reaction, lower temperature
With after the high-temperature heat carrier mixing concurrent heating of the second delivery pipe 9-2, the 3rd conversion zone 16 entering riser reactor 01 continues oil gas
Continuous dehydrogenation reaction, after the completion of the 3rd conversion zone 16 reaction, lower temperature oil gas is mixed with the high-temperature heat carrier of the 3rd delivery pipe 9-3
After concurrent heating, the 4th conversion zone 17 entering riser reactor 01 continues dehydrogenation reaction, and now, dehydrogenation reaction is close to balance.
The present embodiment carries out concurrent heating 01 4 times using high-temperature heat carrier to riser reactor, makes dehydrogenation reaction close to balance
Conversion ratio；Hereafter oil gas leaves riser reactor 01 together with heat carrier, isolates oil gas product through cyclone separator 10,
Oil gas routinely enters the operations such as cooling, aerostatic press compression, finally enters knockout tower, and tower top separates fine propylene and goes out dress as product
Put, bottom of towe alkane product Returning reacting system is further reacted.
(2) heat carrier circulation:
Enter Second reactivator 08 through the heat carrier that oil gas cyclone separator 10 is isolated along heat carrier inclined tube 07 to be generated, the
In two regeneratoies 08, natural gas burns under high temperature and excess oxygen and obtains high-temperature flue gas for heat carrier heat supply, becomes high warm and carries
Body, high-temperature heat carrier passes through to regenerate each conversion zone recycling that heat carrier inclined tube 09 enters riser reactor 01.Second again
Raw device 08 must continuously be passed through natural gas/combustion oil come the heat balance to improve regeneration temperature and maintain reaction-regeneration system.
(3) catalyst circulation:
Enter the catalyst on riser reactor 01 top under gravity, be deposited under riser reactor 01
Part goes out, and in the presence of lift gas, strips inclined tube 04 through reclaimable catalyst, reclaimable catalyst delivery pipe 05 is delivered to first
Regenerator 06, after catalyst being regenerated under the conditions of low temperature, hypoxia etc., anti-through regenerated catalyst inclined tube 03 recycled back riser
Answer the upper entrance of device 01, realize catalyst circulation.
The catalyst of embodiment 1, heat carrier and technological parameter select as shown in table 1.
Embodiment 2:
With embodiment 1, difference is process equipment, and catalyst, heat carrier, technological parameter are as shown in table 2.
Effect detection:
By the technique of the embodiment of the present invention 1,2 and device, contrasted with prior art, comparative example selects
The technique of usp9051230, catalyst is prepared according to usp4827072 and gb2162082, and reaction result is shown in Table 1.
Table 1, the comparison of dehydrogenating propane reaction result
As can be seen from Table 1: the present invention compared with prior art: the selectivity of propylene improves, and total propene yield rises, tool
There is more preferable economic benefit.
Claims (11)
1. a kind of propane or the dehydrogenation producing propylene device rich in propane lower carbon number hydrocarbons, including riser response system, catalyst circulation
Regenerative system, heat carrier recirculation system, wherein:
Riser response system includes riser reactor, and the bottom of riser reactor is material inlet, riser reactor
Top be catalyst inlet, riser reactor sets gradually from lower to upper as some conversion zones, corresponds in each conversion zone
It is provided with the heat carrier delivery pipe that reaction is carried out with concurrent heating；Reacting-settler is arranged at the top of riser reactor, and reaction is heavy
It is provided with oil gas cyclone separator in fall device；
Catalyst cyclic regeneration system includes the first regenerator for catalyst regeneration, and first regenerator one end is catalysis to be generated
Agent input, strips inclined tube by reclaimable catalyst, reclaimable catalyst delivery pipe is connected with the bottom of riser reactor, and first
The regenerator other end is regenerated catalyst outfan, is connected with the top of riser reactor by regenerated catalyst inclined tube；
Heat carrier recirculation system includes the Second reactivator being regenerated for heat carrier, and one end of Second reactivator is to treat heat
Carrier input, receives the heat carrier to be generated that oil gas cyclone separator is isolated, Second reactivator by heat carrier inclined tube to be generated
The other end be regeneration heat carrier outfan, by regenerate heat carrier inclined tube be connected with each conversion zone of riser reactor, use
In the high-temperature heat carrier of regeneration is exported to each conversion zone of riser reactor.
2. a kind of propane according to claim 1 or rich in propane lower carbon number hydrocarbons dehydrogenation producing propylene device it is characterised in that:
Regeneration heat carrier inclined tube, according to the reaction hop count of riser reactor, arranges some delivery pipes.
3. a kind of propane or the dehydrogenation producing propylene technique rich in propane lower carbon number hydrocarbons are it is characterised in that comprise the following steps:
(1) catalytic dehydrogenation:
Raw material after preheated is introduced into the first conversion zone of riser reactor bottom, 530 DEG C～680 DEG C of reaction temperature,
Under the conditions of pressure 0.03mpa～0.4mpa, contact with the downflowing catalyst entering from riser top and carry out dehydrogenation reaction；Propane
After up reaction a period of time in riser reactor, temperature drop in riser reactor, dehydrogenation reaction speed reduces；This
When enter low temperature position riser reactor from Second reactivator high-temperature heat carrier out, improve oil gas and catalyst
Temperature, lower temperature oil gas is anti-with the second conversion zone continuation dehydrogenation entering riser reactor after high-temperature heat carrier mixing concurrent heating
Should, so repeat, until dehydrogenation reaction is close to balance；
(2) heat carrier circulation:
Enter Second reactivator through the heat carrier that oil gas cyclone separator is isolated along heat carrier inclined tube to be generated, in Second reactivator
Obtaining high-temperature flue gas by burning is heat carrier heat supply to be generated, becomes high-temperature heat carrier, and high-temperature heat carrier passes through to regenerate heat carrier
Each conversion zone that inclined tube enters riser reactor recycles；
(3) catalyst circulation:
Enter the catalyst on riser reactor top under gravity, the bottom being deposited to riser reactor separates,
In the presence of lift gas, it is delivered to the first regenerator through reclaimable catalyst stripping inclined tube, reclaimable catalyst delivery pipe, low
After catalyst being regenerated under the conditions of temperature, hypoxia etc., upper entrance through regenerated catalyst inclined tube recycled back riser reactor,
Realize catalyst circulation.
4. a kind of propane according to claim 3 or rich in propane lower carbon number hydrocarbons dehydrogenation producing propylene technique it is characterised in that:
Concurrent heating is carried out to riser reactor using high-temperature heat carrier, makes dehydrogenation reaction close to equilibrium conversion；Hereafter oil gas and heat carry
Body leaves riser reactor together, isolates oil gas product through oil gas cyclone separator, and oil gas routinely enters cooling, gas
Press compression operation, finally enters knockout tower, and tower top separates fine propylene and goes out device as product, and bottom of towe alkane product returns reaction
System is further reacted.
5. a kind of propane according to claim 3 or rich in propane lower carbon number hydrocarbons dehydrogenation producing propylene technique it is characterised in that:
In riser reactor, raw material under 550 DEG C～630 DEG C of reaction temperature, pressure 0.03mpa～0.15mpa, with various dehydrogenations
Catalyst carries out dehydrogenation conversion reaction, and conversion per pass is 10～90%.
6. a kind of propane according to claim 3 or rich in propane lower carbon number hydrocarbons dehydrogenation producing propylene technique it is characterised in that:
Riser reactor is divided into some sections, and in each section, propane carries out dehydrogenation reaction with catalyst after contacting, and temperature of charge drops
Low, dehydrogenation speed decline, each section rear portion introduce high-temperature heat carrier, after high-temperature heat carrier contacts with material, make material with
Catalyst temperature returns to 530 DEG C～680 DEG C, so that dehydrogenation reaction is quickly carried out again, so repeatedly, until oil gas and heat carrier one
Rise and leave riser reactor, enter cyclone separator, separate product oil gas and enter cooling, compression section, the heat load settling down
To Second reactivator, contact acquisition heat with the high-temperature flue gas of burning become high-temperature heat carrier to body circulation again.
7. a kind of propane according to claim 3 or rich in propane lower carbon number hydrocarbons dehydrogenation producing propylene technique it is characterised in that:
Air velocity in riser reactor, controls less than 0.9 times in catalyst carrying velocity, 2 times of heat carrier carrying velocity
More than, thus realize catalyst in riser separating with heat carrier.
8. a kind of propane according to claim 7 or rich in propane lower carbon number hydrocarbons dehydrogenation producing propylene technique it is characterised in that:
Described heat carrier is stable and inert inorganic compound in 500-750 DEG C, and heat carrier is particle diameter in 10-100 μm of microsphere
Granule, and apparent bulk density < 1.0g/ml, because the grain diameter of heat carrier is less, carrying velocity is less, easily together with oil gas, shape
Become piston flow to enter cyclone separator to separate.
9. a kind of propane according to claim 8 or rich in propane lower carbon number hydrocarbons dehydrogenation producing propylene technique it is characterised in that:
The grain diameter of described heat carrier is 30-80 μm, apparent bulk density < 0.9g/ml.
10. a kind of propane according to claim 7 or the dehydrogenation producing propylene technique rich in propane lower carbon number hydrocarbons, its feature exists
In: do not taken out of by high speed oil gas in riser to realize catalyst, catalyst granules is higher using heap density, and particle diameter is larger
Particle, catalyst granules controls at 200-2000 μm, and apparent bulk density answers 0.8-1.8g/ml.
A kind of 11. propane according to claim 10 or the dehydrogenation producing propylene technique rich in propane lower carbon number hydrocarbons, its feature exists
In: catalyst granules controls at 400-1500 μm, and apparent bulk density should be 1.0-1.5g/ml.
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| CN115282885A (en) * | 2022-07-07 | 2022-11-04 | 濮阳市远东科技有限公司 | Propane dehydrogenation product separator |
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|---|---|---|---|---|
| DE3439176A1 (en) * | 1984-10-25 | 1986-04-30 | Linde Ag, 6200 Wiesbaden | Process and reactor for carrying out an endothermic reaction |
| CN101723778A (en) * | 2009-11-27 | 2010-06-09 | 清华大学 | Coupling process method for preparing alkene with alcohol or ether and dehydrogenating alkane |
| CN102040445A (en) * | 2009-10-14 | 2011-05-04 | 青岛石大卓越投资有限公司 | Technology device and method for preparing propylene by dehydrogenating propane or propane-enriched low carbon hydrocarbon |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3439176A1 (en) * | 1984-10-25 | 1986-04-30 | Linde Ag, 6200 Wiesbaden | Process and reactor for carrying out an endothermic reaction |
| CN102040445A (en) * | 2009-10-14 | 2011-05-04 | 青岛石大卓越投资有限公司 | Technology device and method for preparing propylene by dehydrogenating propane or propane-enriched low carbon hydrocarbon |
| CN101723778A (en) * | 2009-11-27 | 2010-06-09 | 清华大学 | Coupling process method for preparing alkene with alcohol or ether and dehydrogenating alkane |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115282885A (en) * | 2022-07-07 | 2022-11-04 | 濮阳市远东科技有限公司 | Propane dehydrogenation product separator |
| CN115282885B (en) * | 2022-07-07 | 2024-04-30 | 濮阳市远东科技有限公司 | Propane dehydrogenation product separator |
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