CN1879956A - Method and device for solid alkylation reaction - Google Patents
Method and device for solid alkylation reaction Download PDFInfo
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- CN1879956A CN1879956A CN 200610078559 CN200610078559A CN1879956A CN 1879956 A CN1879956 A CN 1879956A CN 200610078559 CN200610078559 CN 200610078559 CN 200610078559 A CN200610078559 A CN 200610078559A CN 1879956 A CN1879956 A CN 1879956A
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Abstract
The invention relates to a solid alkyl reaction regenerator, which comprises a liquid distributor, a lifter tube reactor, a fluid bed reactor, a circulate bed regenerator and a movable bed regenerator, wherein the liquid distributor is connected to the bottom of lifter tube reactor whose top is connected to the bottom of fluid bed reactor; the lower part of fluid bed reactor via valve tube is connected to the circulate bed regenerator and the movable bed regenerator; the lower part of circulate bed regenerator via the valve tube is connected to the top of movable bed; the lower part of circulate bed regenerator and the bottom of movable bed regenerator via valve tubes are connected to the liquid distributor, to form the cycle loop. The invention also provides a relative method, based on different catalysts, react liquids, and regenerate liquid, to select the reaction- regeneration loop, to meet the application of different solid acid catalyst particles.
Description
Technical field
The present invention relates to a kind of reaction regeneration method and device, particularly a kind of solid acid alkylating reaction regeneration method and device belong to petrochemical industry.
Background technology
The alkylate oil that alkylation process utilizes isoparaffin and low-molecular olefine to carry out alkylated reaction production has that octane number height, steam force down, combustion heat value height, the characteristics of sulfur-bearing nitrogen non-hydrocarbon component not, is desirable gasoline blend component.
Traditional alkylation process starts from the forties, and it makes catalyst with liquid acid sulfuric acid or hydrofluoric acid, is characterized in that selectivity is good, price is low, recyclable and continuous maintenance active.But hydrofluoric acid toxicity is big, the serious harm health; Sulfuric acid corrosion equipment, a large amount of acid sludge contaminated environment of generation.Therefore, along with the enhancing day by day of social enviroment protection consciousness, the development of making the alkylation process of catalyst with sulfuric acid or hydrofluoric acid has been subjected to considerable restraint.
Solid acid alkylation processes is the environment-friendly type technique process of the alternative liquid acid technology developed in recent years, both at home and abroad to the existing history more than 20 years of its research.The maximum characteristics of this technology are environmental friendliness, do not produce problem of environmental pollution.
Research for solid acid alkylation processes at present mainly concentrates on two aspects: one, and the research of solid acid catalyst; Two, the research of solid acid alkylating reactor and technology.In recent years, the research of solid acid catalyst has obtained major progress, and various types of solid acid catalysts continue to bring out, as zeolite molecular sieve, halogen-containing cationic ion-exchange resins such as HX, HY, ZSM-5, USY and REHY, halogen-containing solid super-strong acid, SO
4 -/ M
XO
YThe type solid super-strong acid, SO
4 -/ compound oxide type solid super-strong acid etc.But, the good but easy shortcoming of inactivation of these catalyst ubiquity initial activities, i.e. the polymerization of alkene causes catalyst surface the carbon deposit coking to occur and then causes catalyst activity to descend rapidly.For this reason, the scientific research personnel adopts continuous reproduction process to guarantee carrying out smoothly continuously of alkylated reaction from the Chemical Engineering angle again when updating catalyst performance.Alkylation reactor commonly used at present has paste state bed reactor, fixed bed reactors, moving-burden bed reactor, fluidized-bed reactor and recirculating fluidized bed etc.Paste state bed reactor is kept activity of such catalysts by discharging dead catalyst and adding fresh catalyst, but exists undercompounding, not easy to operate, technology to be difficult to problems such as amplification.In fixed bed reactors, because catalyst can finally lose activity and need regenerate, therefore need to adopt a plurality of reactors to switch keeping continuous production in producing, so this technology also exist the equipment investment height, switch shortcoming frequent, that be difficult to operate.In the moving-burden bed reactor, two laminar flows that are close flow full contact, reaction efficiency height; Shortcoming is treating capacity when big, and pressure drop is bigger.In the fluidized-bed reactor, particle is the same with fluid to be flowed freely, and therefore has higher mass-and heat-transfer characteristic.The exploitation Alkylene of American UOP company solid acid alkylation processes core apparatus is exactly the riser fluidized-bed reactor, participating in reacted decaying catalyst separates by separator, send into the regeneration of carrying out catalyst in the regenerator then, by the continued operation of reactor and regenerator, can keep activity of such catalysts and high selectivity.This reaction process of its shortcoming is more than fixed bed reaction technology complexity, and the two-stage regeneration of catalyst all will be faced the hydrogen operation, does not better solve the regeneration problem.
In recent years, circulating fluid bed reactor is big because of its particle disposal amount, integrated level is high, can realize the advantage of multi-functional simultaneously operating, obtains primary study and application in the solid acid alkylating field.Alkylation process and liquid-solid circulating fluidized bed device that the alkylating aromatic hydrocarbon of the common exploitation of China Petrochemical Corporation and Tsing-Hua University and used liquid-solid circulating fluidized bed (number of patent application 94105710.0) thereof relate to a kind of solid acid catalyst catalyzing aromatic hydrocarbon or derivatives thereof.This device is mainly by liquid-solid and flow up reactor, reclaimable catalyst sedimentation back scrubber, liquid-solid and flow up regenerator and four capital equipments of regeneration rear catalyst sedimentation back scrubber are formed, realized carrying out continuously of reaction-regeneration, guaranteed that catalyst turns round all the time under high activity.The shortcoming of this structure is that reactor types is single, and operating flexibility is limited, and reaction and regenerative process are not taken in respectively.
Korea Spro of Tsing-Hua University Framinghams etc. are very fast at solid acid catalyst deactivation rate in the detergent alkylate production process, shortcomings such as production process is discontinuous, developed the circulated moving bed reactor of manifold type (CCMB), and this reactor has been used for the new technology (seeing CN 1087647C) of synthetic linear alkylbenzene (LAB).This technology is formed closed circuit by moving-burden bed reactor, liquid-solid riser and moving bed regenerator, will react and regenerative process be coupled together, realized catalyst reaction and regeneration carry out continuously.This structural disadvantages is that liquid-solid separation problem is outstanding, and it is serious to scurry the liquid phenomenon.
In sum, existing solid acid alkylating process and device are difficult to realize catalyst running continuously under high activity.
Summary of the invention
The objective of the invention is to solve the problem that the reaction regeneration process can not be carried out continuously in the existing solid acid alkylation processes, realize catalyst running continuously under high activity.
To achieve these goals, the invention provides a kind of solid acid alkylating reaction regeneration method, this method comprises:
Well-mixed catalyst granules and the reactant liquor bottom from a riser reactor is infeeded, alkylated reaction takes place in the process that moves upward of liquid-solid two-phase in described riser reactor, reactant mixture enters a fluidized-bed reactor through a distributor subsequently, proceeds alkylated reaction in described fluidized-bed reactor; In described fluidized-bed reactor, liquid-solid two-phase takes place owing to the liquid prompt drop is low to be separated, treat that regenerated catalyst is deposited in the bottom of described fluidized-bed reactor, the described reactant liquor of liquid product and part leaves described fluidized-bed reactor from the top of described fluidized-bed reactor;
The described combination regeneration device for the treatment of that regenerated catalyst is selected to enter a circulation bed regenerator respectively, enters a moving bed regenerator or entered a circulation bed according to the needs of its recovery time and a moving bed constitutes, in described regenerator, contact and carry out regenerative response with regenerated liquid, catalyst after the regeneration mixes with reactant liquor again, and the reaction of catalyst and regenerative process are carried out continuously.
Operation liquid speed in the wherein said riser reactor is the 0.1-3 meter per second, and bed voidage is 3-50%; Operation liquid speed in the described fluidized-bed reactor is 0.26-7.68 * 10
-2Meter per second, bed voidage are 0.48-8%; Operation liquid speed is 0.2-3 * 10 in the described moving bed regenerator
-2Meter per second.
Wherein the reaction time of the selection of catalyst regeneration route and catalyst granules is closely related with the recovery time.In the combined reactor of riser reactor and fluidized-bed reactor formation, according to the requirement in catalyst granules reaction time, by regulating the time of staying that controlling level comes the flexible modulation catalyst granules in riser reactor liquid speed and the fluidized-bed reactor.When recovery time of catalyst granules at several seconds between tens seconds the time, select the circulation regenerator comparatively suitable, and have liquid-solid full contact, reaction efficiency advantages of higher, therefore select riser-fluid bed-circulation bed-riser loop to finish the reaction regeneration process; When the recovery time of catalyst granules is tens seconds between dozens of minutes the time, selects the moving bed regenerator comparatively suitable, has advantages such as liquid-solid time of contact of length, full contact, so selects riser-fluid bed-moving bed-riser loop; Circulation bed-moving bed combination regeneration device has not only further prolonged the time of staying of particle, and combine the characteristics that the circulation bed reacts efficient and moving bed full contact, so riser-fluid bed-circulation bed-moving bed-riser loop also is a selection preferably of finishing the reaction regeneration process.
Solid acid alkylating reaction regeneration method provided by the invention, based on riser, fluid bed, circulation bed, the different time of staying distribution characteristics of moving bed, at different rerum natura catalyst granules, reactant liquor, regenerated liquid rerum natura, different requirements according to reaction time and recovery time, select suitable reactor, regenerator compound mode flexibly, make catalyst granules react i.e. regeneration in short-term, reaction regeneration carries out continuously, reach and prolong catalyst service life, keep the purpose of high activity of catalyst and high selectivity, catalyst is turned round under high activity all the time.
The present invention also provides a kind of solid acid alkylating reaction regeneration device, it comprises liquid distribution trough, riser reactor, fluidized-bed reactor, circulation bed regenerator and moving bed regenerator, wherein said liquid distribution trough is connected with the bottom of described riser reactor, the top of described riser reactor is connected with the bottom of described fluidized-bed reactor, described fluidized-bed reactor bottom is connected with the moving bed regenerator with described circulation bed regenerator respectively by the band valve pipe, described circulation bed regenerator bottom is connected with described moving bed top by the band valve pipe, described circulation bed regenerator bottom also is connected with described liquid distribution trough by the band valve pipe respectively with the moving bed regenerator bottoms, to constitute closed circuit.
Wherein above-mentioned liquid distribution trough is made of pipe distributor and sleeve pipe, described sleeve pipe is provided with reducer, be provided with the particle pipeloop in described reducer side direction, described particle pipeloop adopts V-shaped valve with being connected of described sleeve pipe, be provided with loosening nozzle for liquid in the bottom of described V-shaped valve, between the primary first-order equation liquid inlet of described reducer and described sleeve pipe, be provided with secondary response liquid inlet.The outlet gross area of this pipe distributor is the 5-30% of described riser reactor sectional area, and the reducer diameter is 1.2-1.5 a times of riser reactor diameter, and the reducer height is the 30-55% of sleeve pipe height, and the angle of V-shaped valve is the 40-100 degree.Liquid distribution trough of the present invention is compared with existing distributor, has not only reduced pressure oscillation, has also improved the particle intensity of circulation greatly, has obviously improved the bias current phenomenon that the unidirectional charging of particle causes.
Above-mentioned fluidized-bed reactor bottom is provided with the shower-head type distributor, and this shower-head type distributor is made of inverted cone segment and straight length, and straight length communicates with the top exit of riser reactor; The surface of inverted cone segment is provided with perforate, and opening diameter is 6-30mm, and percent opening is 5-20%.
The bottom of above-mentioned moving bed regenerator is provided with discharge cone, described discharge cone by a plurality of discharge lists awl and up and down each fixed head constitute, described fixed head is provided with perforate in the junction, inner passage with described discharge list awl, and internal diameter is identical up and down with the inner passage respectively in the perforate of last bottom plate.Have a plurality of bar-shaped troughs in each described discharge list cone flank side, the area of always slotting is the 30-70% of lateral area; The band valve pipe of described moving bed regenerator bottoms communicates with the inner passage of described discharge cone, and the bottom of described moving bed regenerator is provided with the regenerated liquid inlet, and described regenerated liquid inlet communicates with the space outerpace of described discharge cone.By the setting of this discharge cone, realized reverse the contact and reaction of continous-stable of catalyst granules and regenerated liquid in the moving bed regenerator.
The middle part of above-mentioned circulation bed regenerator is provided with catalyst inlet and communicates with the band valve pipe that is connected fluidized-bed reactor and circulation bed regenerator; The catalyst inlet below is provided with sieve plate, and the hypotenuse of sieve plate and the angle of vertical direction are the 20-60 degree, and percent opening is 5-30%; The sieve plate below links to each other with tremie pipe, is provided with the circulation tube under sieve plate, and the length that tremie pipe stretches into the circulation tube is the 60-90% of circulation tube length overall; The circulation tube highly is a 0.7-1.5 rice, and diameter is the 60-90% of circulation bed regenerator internal diameter.
Adopt solid acid alkylating reaction regeneration device provided by the invention, can in the scope of broad, regulate the time of staying, at utmost satisfy the application of different performance solid acid catalyst by selecting compound mode flexibly.
Description of drawings
Fig. 1 is a solid acid alkylating reaction regeneration device schematic diagram of the present invention.
Fig. 2 is the pipe distributor structural representation of liquid distribution trough of the present invention.
Fig. 3 is the structural representation of one of sleeve pipe of liquid distribution trough of the present invention.
Fig. 4 is two a structural representation of the sleeve pipe of liquid distribution trough of the present invention.
Fig. 5 is the structural representation of the discharge list awl of discharge cone of the present invention.
Fig. 6 is the vertical view of discharge cone of the present invention.
Fig. 7 is the upward view of discharge cone of the present invention.
Fig. 8 is the schematic flow sheet of solid acid alkylating reaction regeneration method embodiment one of the present invention.
Fig. 9 is the schematic flow sheet of solid acid alkylating reaction regeneration method embodiment two of the present invention.
Figure 10 is the schematic flow sheet of solid acid alkylating reaction regeneration method embodiment three of the present invention.
The specific embodiment
Below in conjunction with accompanying drawing solid acid alkylating reaction regeneration method and apparatus of the present invention is done and to be explained.
Solid acid alkylating reaction regeneration device provided by the invention as shown in Figure 1, it mainly is made of five parts: liquid distribution trough 1, riser reactor 2, fluidized-bed reactor 3, circulation bed regenerator 4 and moving bed regenerator 5.Riser reactor 2 bottoms are provided with liquid distribution trough 1; Riser reactor 2 tops communicate with fluidized-bed reactor 3 bottoms; Fluidized-bed reactor 3 can be selected flexibly and circulation bed regenerator 4,5 independent linking to each other of moving bed regenerator constitute closed circuit, or constitute closed circuit with connecting of they; Riser reactor 2 and fluidized-bed reactor 3 are formed combined reactor; Circulation bed regenerator 4 can be formed the combination regeneration device with moving bed regenerator 5.
Referring to Fig. 1, riser reactor 2 of the present invention adopts liquid-solid and flows up bed.In fluidized-bed reactor 3 bottoms shower-head type distributor 8 is set, distributor 8 is made up of top inverted cone segment and bottom straight length, and distributor bottom straight length links to each other with riser reactor 2 outlets; Distributor 8 inverted cone segment upper surface perforates, opening diameter is 6-30mm, percent opening is 5-20%; Fluidized-bed reactor 3 bottoms are back taper, under be provided with reactant liquor inlet 17 and export with riser reactor 2 and communicate, conical section is provided with catalyst outlet 18 and communicates with circulation regenerator 4 or moving bed regenerator 5; Fluidized-bed reactor 3 tops are provided with liquid product outlet 19.
Be provided with catalyst inlet 21 communicates with fluidized-bed reactor 3 bottom catalyst outlets 18 pipelines at circulation bed regenerator 4 middle parts; Catalyst inlet 21 belows are provided with tilting sieve plate 9, and sieve plate 9 hypotenuses and vertical direction angle are not all 20-60 ° according to particle rerum natura and discharge requirement, and sieve plate 9 percent openings are 5-30%; Sieve plate 9 belows link to each other with tremie pipe 10, are provided with circulation tube 11 under the sieve plate 9, and it is h/H=60-90% that tremie pipe stretches into circulation tube position, and wherein h is the distance that tremie pipe stretches into the circulation bucket, and H is a circulation bucket height; The circulation bucket highly is a 0.7-1.5 rice, and diameter circulation bed regenerator diameter compares d/D=60-90%; Circulation bed regenerator 4 bottoms are provided with shower-head type regenerated liquid distributor 12, form by top inverted cone segment and bottom straight length, and the perforate of distributor inverted cone segment upper surface, opening diameter is 10-30mm, percent opening is 5-20%; Distributor bottom straight length communicates with regenerated liquid inlet 23; Circulation bed regenerator 4 bottoms are back taper, and awl is provided with regenerated liquid inlet 23 at the end; Becoming 60-120 ° of direction to be provided with catalyst outlet 22 with the conical section hypotenuse communicates with moving bed regenerator 5 or particle pipeloop 33; Circulation bed top is provided with regenerated liquid outlet 20.
Be provided with discharge cone 13 in moving bed regenerator 5 inside, see Fig. 5-7, discharge cone 13 by a plurality of discharge lists awl 60 and up and down respectively a fixed head 61,63 constitute, discharge list cone flank side has a plurality of bar-shaped troughs 62, always slot area and lateral area percentage are 30-70%; Each discharge list is bored 60 outer side covers stainless steel filtering net (not shown)s; Moving bed regenerator 5 bottoms are provided with catalyst outlet 27, communicate with discharge cone 13 inner spaces; Moving bed regenerator 5 bottoms become 90 ° of directions to be provided with regenerated liquid inlet 26 with cylindrical shell, communicate with the discharge cone space outerpace; Moving bed regenerator 5 tops are respectively equipped with regenerated liquid outlet 24 and catalyst inlet pipeline 25, and catalyst inlet pipeline 25 inserts moving bed regenerator 5 inner length to be decided on controlling level, is generally the 1/3-1/2 of moving bed height.
Among the present invention, each reaction, reclaim equiment can be according to the requirements of the reaction and the regenerative process time of staying, flexible modulation is formed three different circuits, is respectively: riser-fluid bed-circulation bed-riser loop, riser-fluid bed-moving bed-riser loop, riser-fluid bed-circulation bed-moving bed-riser loop.
Referring to Fig. 1, solid acid alkylating reaction regeneration method provided by the invention will be described below.The reactant liquor that mixes by reaction ratio divides two-way to be pumped into by measuring pump by primary first-order equation liquid inlet 14 and secondary response liquid inlet 15 respectively, the reactant liquor stream that is entered by primary first-order equation liquid inlet makes catalyst granules be in the circulation fluidized bed state, thereby then is used for changing the internal circulating load that the resistance of catalyst inlet end is regulated catalyst by the reactant liquor stream that secondary response liquid inlet enters.Catalyst granules enters riser reactor 2 bottoms and alkylated reaction takes place in the process of moving upward on the liquid-solid two-phase and the flow direction after liquid distribution trough 1 neutralization reaction liquid fully mixes.In the riser reactor 2, operation liquid speed is the 0.1-3 meter per second, bed voidage is controlled at 3-50%, catalyst is doubly bottom-up motion in reactor under the carrier band of the reactant of catalyst granules terminal sinking speed and product of 1-15 in liquid speed, leave riser reactor 2 at last, enter fluidized-bed reactor 2 through shower-head type distributor 8.In the fluidized-bed reactor, the liquid speed control is built in 0.26-7.68 * 10
-2M/s, bed voidage is controlled at 0.48-8%.Reaction logistics and catalyst granules continue to take place alkylated reaction after distributor 8 perforates ejection, because the increase liquid of reactor diameter speed reduces rapidly, while is owing to the reason of density contrast, liquid-solid two-phase separates, the catalyst granules reactor bottom that falls back behind the segment distance that moves upward is piled up, piling height is by fluid bed outlet at bottom valve 29 or 28 controls, and the liquid product of separation and partial reaction liquid continue to move upward and exports 19 separating devices from reactor head.So far, course of reaction is finished.
After catalyst granules leaves fluidized-bed reactor, can select to enter circulation bed regenerator 3 or moving bed regenerator 4 separately according to the needs of catalyst granules recovery time, also can connect enters circulation bed+moving bed combination regeneration device.When the catalyst granules recovery time was several seconds-tens seconds, catalyst granules can select to enter separately circulation bed regenerator 3.After catalyst entered circulation bed regenerator, catalyst granules entered circulation tube 11 centers through tremie pipe 10 after carrying out regenerative response with bottom-up regenerated liquid short-time contact from the sieve aperture process on the tilting sieve plate 9.At the bottom of by the circulation bed under the drag force effect of the fresh regenerated liquid of shower-head type distributor 12 ejections, particle is reproduced liquid and drags band and rise to circulation bucket top, under the effect of inner and outer ring density contrast, enter the annular space space then, the whereabouts particle passes the winding fluidized bed bottom that falls behind the annular space space, and wherein the part particle reenters circulation bucket inside and circulates.Regenerated liquid is upwards left by circulation bed regenerator top exit 20.Bed end catalyst granules leaves from circulation bed outlet at bottom 22, gets back to liquid distribution trough 1 through the particle pipeloop.Help catalyst granules to enter the liquid distribution trough center from the loosening liquid of loosening nozzle for liquid 16 ejections, thereby finish catalyst granules circulating in reactor and regenerator.
When the catalyst granules recovery time was tens seconds-dozens of minutes, catalyst granules can select to enter separately moving bed regenerator 5.Liquid speed is 0.2～3cm/s in the moving bed regenerator 5.After catalyst granules enters moving bed, contact with the up fresh regenerated liquid of adverse current and to carry out regenerative response.Particle continues slowly to move down after falling to bed, passes discharge cone 13 central passages until arriving reactor bottom, piles up in the moving bed bottom.Regenerated liquid enters from moving bed bottom inlet 26, passes the discharge cone outside and cracks and enter the discharge cone central passage, and contact with the catalyst granules adverse current and to carry out regenerative response.Regeneration back liquid leaves from moving bed top exit 24, and moving bed bottom particle leaves from outlet at bottom 27, gets back to liquid distribution trough 1 through particle pipeloop 33.The loosening liquid of loosening nozzle for liquid 16 ejections helps catalyst granules to enter the liquid distribution trough center, thereby finishes catalyst granules circulating in reactor and regenerator.
Catalyst granules also can select to enter circulation bed+moving bed combination regeneration device.Catalyst granules enters circulation regenerator 4 successively and moving bed regenerator 5 carries out two-stage regeneration, and regeneration back particle is got back to liquid distribution trough 1 through particle pipeloop particle pipeloop 33.The loosening liquid of loosening nozzle for liquid 16 ejections helps catalyst granules to enter the liquid distribution trough center, thereby finishes catalyst granules circulating in reactor and regenerator.
Solid acid alkylating device provided by the invention has been realized carrying out continuously of solid acid catalyst reaction-regenerative process, owing to reaction-regenerative process is carried out under the circulating fluidization state, thereby can guarantee that catalyst turns round all the time under high activity.In this device, because reactant liquor and regenerated liquid all have separately independently loop in-out apparatus, therefore can control total inventory and catalyst concentration in reactor and the regenerator and then the conversion ratio of control reaction and the regeneration efficiency of reclaimable catalyst by the inlet amount ratio of regulating the two-way material.In addition, fluidized-bed reactor, circulation bed regenerator and moving bed regenerator all are provided with by-pass valve control at catalyst outlet, can control each catalyst reactor controlling level, thereby can control the time of staying of catalyst granules in each reactor effectively.
This device be a little each reaction, reclaim equiment can flexible combination become a plurality of loops, can be according to different catalysts particle, reactant liquor, the flexible choice reaction-regenerative circuit of regenerated liquid rerum natura, thereby adjust the time of staying of catalyst granules in reactor and regenerator flexibly, at utmost satisfy the application of different rerum natura solid acid catalyst particles, guarantee that product quality meets the requirements.Simultaneously, liquid distribution trough of the present invention is compared with the liquid distribution trough of existing riser, has removed the porous sieve plate distributor, has increased reducer, can guarantee the uniformity of distribution of particles when increasing substantially the particle intensity of circulation.
Below by specific embodiment method and apparatus of the present invention is described in further detail:
Embodiment one
Referring to Fig. 8, the loop that the solid acid alkylating reaction regeneration method of present embodiment mainly utilizes liquid distribution trough 1, riser reactor 2, fluidized-bed reactor 3 and circulation bed regenerator 4 to constitute, by opening control valve 29 and control valve 31 among Fig. 8, closed control valve 28, control valve 30 and control valve 32 (referring to Fig. 1) can be made as apparatus of the present invention this loop operation.Idiographic flow is, the reactant liquor that mixes by reaction ratio divides two-way to enter the mouth 15 by measuring pump pumping liquid distributor 1 by primary first-order equation liquid inlet 14 and secondary response liquid respectively, the reactant liquor stream that is entered by primary first-order equation liquid inlet makes catalyst granules be in the circulation fluidized bed state, thereby then is used for changing the internal circulating load that the resistance of catalyst inlet end is regulated catalyst by the reactant liquor stream that secondary response liquid inlet enters.Catalyst granules enters riser reactor 2 bottoms on the liquid-solid two-phase and the flow direction, and alkylated reaction takes place in the process of moving upward after liquid distribution trough 1 neutralization reaction liquid fully mixes.In the riser reactor, operation liquid speed is the 0.1-3 meter per second, and bed voidage is 3-50%, and catalyst doubly drags bottom-up motion in reactor under the band to the reactant liquor of catalyst granules terminal sinking speed in liquid speed for 1-15.Catalyst granules and reactant liquor rise to the riser reactor outlet, enter fluidized-bed reactor 3 by fluid bed bottom inlet 17 through shower-head type distributor 8.In the fluidized-bed reactor 3, the liquid speed control is built in 0.26-7.68cm/s, and bed voidage is controlled at 0.48-8%, and reactant liquor stream and catalyst granules continue to take place alkylated reaction after distributor perforate ejection.Because the increase liquid of reactor diameter speed reduces rapidly, while is owing to the reason of density contrast, catalyst granules separates with reactant liquor, catalyst granules slows down behind the segment distance that moves upward to be zero and to begin to move downward under the gravity effect, the reactor bottom that falls is back gradually piled up, piling height is by 29 controls of fluid bed outlet at bottom valve, and the liquid product of separation and partial reaction liquid continue to move upward and exports 19 separating devices from reactor head.So far, the solid acid catalyst course of reaction is finished.
In the regenerative process, the catalyst granules that pile up fluidized-bed reactor 3 bottoms is left by fluidized-bed reactor 3 outlet at bottoms 18 under the gravity effect, enters circulation bed regenerator 4 through control valve 29 from circulation bed regenerator 3 centre entrances 21.After entering circulation bed regenerator 4, catalyst granules enters circulation tube 11 centers through tremie pipe 10 after carrying out regenerative response with bottom-up regenerated liquid short-time contact from the sieve aperture process on the tilting sieve plate 9.Under the effect of the fresh regenerated liquid that sprays by circulation bed regenerator 4 bottom distributors 12, particle is reproduced the liquid suspension and rises to circulation bucket 1 top, under the effect of inner and outer ring density contrast, enter the annular space space then, the whereabouts particle passes winding fluidized bed regenerator 4 bottoms that fall behind the annular space space, and wherein the part particle reenters circulation bucket inside and circulates.Regenerated liquid is upwards left by circulation bed regenerator 4 top exits 20.Catalyst granules after the regeneration leaves from circulation bed regenerator 4 outlet at bottoms 22, gets back to liquid distribution trough 1 through particle pipeloop 33 under the control of control valve 31.The loosening liquid of loosening nozzle for liquid 16 ejections helps catalyst granules to enter the liquid distribution trough center, thereby finishes catalyst granules circulating in reactor and regenerator.
Embodiment two
Referring to Fig. 9, the solid acid alkylating reaction regeneration method of present embodiment is mainly utilized the loop that is made of liquid distribution trough 1, riser reactor 2, fluidized-bed reactor 3 and moving bed regenerator 5, by opening control valve 28 and the control valve 32 among Fig. 9, closed control valve 29, control valve 30 and control valve 31 (referring to Fig. 1) can be made as apparatus of the present invention this loop operation.In the idiographic flow, catalyst granules carries out alkylated reaction in riser reactor 2 and fluidized-bed reactor 3 part is identical with embodiment one.Different is that catalyst granules enters moving bed regenerator 5 inner catalyst beds through control valve 28 by connecting line after flowing out from fluid bed outlet at bottom 18.It should be noted that catalyst granules suction line 25 inserts the moving bed inner length and looks the needs of controlling level and be controlled at moving bed total height 1/3-1/2.It is in order to guarantee the steady blanking of catalyst granules that control catalyst inlet pipeline inserts controlling level, and the particle that prevents from just to enter regenerator is kicked up by upstream regenerated liquid and taken moving bed out of.Liquid speed is 0.2-3cm/s in the moving bed regenerator 5.Catalyst granules slowly moves down with mobile bed, and in the inner passage of moving bed bottom by discharge cone 13.Fresh regenerated liquid enters discharge cone 13 space outerpaces and enters moving bed regenerator 5 inside to cracking by discharge list cone flank through moving bed regenerator 5 bottom side entrance 26, contacts with bed catalyst granules adverse current and carries out regenerative response.Regenerated liquid after the regeneration is through moving bed regenerator 5 top exits 24 separating devices.Catalyst granules after the regeneration leaves from moving bed outlet at bottom 27, gets back to liquid distribution trough 1 through particle pipeloop 33 under the control of control valve 32.The loosening liquid of loosening nozzle for liquid 16 ejections helps catalyst granules to enter the liquid distribution trough center, thereby finishes catalyst granules circulating in reactor and regenerator.
Embodiment three
Referring to Figure 10, the loop that the solid acid alkylating reaction regeneration method of present embodiment mainly utilizes liquid distribution trough 1, riser reactor 2, fluidized-bed reactor 3, circulation bed regenerator 4 and moving bed regenerator 5 to constitute.By opening control valve 29, control valve 30 and the control valve 32 among Figure 10, closed control valve 28 and control valve 31 (referring to Fig. 1) can be made as apparatus of the present invention this loop operation.In the idiographic flow, catalyst granules carries out alkylated reaction in riser reactor 2 and fluidized-bed reactor 3 reactive moieties is identical with embodiment one.In the regenerative process, fluidized-bed reactor 3 bottom reclaimable catalyst particles leave from fluid bed outlet at bottom 18, enter circulation bed regenerator 4 through control valve 29 from circulation bed regenerator 4 centre entrances 21.Circulation regenerator 4 catalyst particles regenerative processes are identical with embodiment one regeneration process.Circulation regenerator bottoms catalyst granules leaves from circulation bed outlet at bottom 22, enters moving bed regenerator 5 inside through control valve 30 from moving bed top suction line 25.Moving bed moving bed regenerator 5 internal accelerator granules regeneration processes are identical with embodiment two.Catalyst granules after the regeneration leaves from moving bed outlet at bottom 27, gets back to liquid distribution trough 1 through particle pipeloop 33 under control valve 32 controls.The loosening liquid of loosening nozzle for liquid 16 ejections helps catalyst granules to enter the liquid distribution trough center, thereby finishes catalyst granules circulating in reactor and regenerator.
It should be noted that at last: above embodiment only in order to the explanation the present invention and and unrestricted technical scheme described in the invention; Therefore, although this specification has been described in detail the present invention with reference to each above-mentioned embodiment,, those of ordinary skill in the art should be appreciated that still and can make amendment or be equal to replacement the present invention; And all do not break away from the technical scheme and the improvement thereof of the spirit and scope of the present invention, and it all should be encompassed in protection scope of the present invention.
Claims (10)
1, a kind of solid alkylation reaction regeneration method comprises:
Well-mixed catalyst granules and the reactant liquor bottom from a riser reactor is infeeded, alkylated reaction takes place in the process that moves upward of liquid-solid two-phase in described riser reactor, reactant mixture enters a fluidized-bed reactor through a distributor subsequently, proceeds alkylated reaction in described fluidized-bed reactor; In described fluidized-bed reactor, liquid-solid two-phase takes place owing to the liquid prompt drop is low to be separated, treat that regenerated catalyst is deposited in the bottom of described fluidized-bed reactor, liquid product leaves described fluidized-bed reactor from the top of described fluidized-bed reactor;
The described combination regeneration device for the treatment of that regenerated catalyst is selected to enter a circulation bed regenerator respectively, enters a moving bed regenerator or entered a circulation bed according to the needs of its recovery time and a moving bed constitutes, in described regenerator, contact and carry out regenerative response with regenerated liquid, catalyst after the regeneration mixes with reactant liquor again, and the reaction of catalyst and regenerative process are carried out continuously.
2, solid alkylation reaction regeneration method according to claim 1, the operation liquid speed in the wherein said riser reactor is the 0.1-3 meter per second, bed voidage is 3-50%.
3, solid alkylation reaction regeneration method according to claim 1, the operation liquid speed in the wherein said fluidized-bed reactor is 0.26-7.68 * 10
-2Meter per second, bed voidage are 0.48-8%.
4, operation liquid speed is 0.2-3 * 10-2 meter per second in the solid alkylation reaction regeneration method according to claim 1, wherein said moving bed regenerator.
5, a kind of solid alkylation reaction regeneration device, comprise liquid distribution trough, riser reactor, fluidized-bed reactor, circulation bed regenerator and moving bed regenerator, wherein said liquid distribution trough is connected with the bottom of described riser reactor, the top of described riser reactor is connected with the bottom of described fluidized-bed reactor, described fluidized-bed reactor bottom is connected with the moving bed regenerator with described circulation bed regenerator respectively by the band valve pipe, described circulation bed regenerator bottom is connected with described moving bed top by the band valve pipe, described circulation bed regenerator bottom also is connected with described liquid distribution trough by the band valve pipe respectively with the moving bed regenerator bottoms, to constitute closed circuit.
6, solid alkylation reaction regeneration device according to claim 5, wherein said liquid distribution trough is made of pipe distributor and sleeve pipe, described sleeve pipe is provided with reducer, be provided with the particle pipeloop in described reducer side direction, described particle pipeloop adopts V-shaped valve with being connected of described sleeve pipe, be provided with loosening nozzle for liquid in the bottom of described V-shaped valve, between the primary first-order equation liquid inlet of described reducer and described sleeve bottom, be provided with secondary response liquid inlet.
7, solid alkylation reaction regeneration device according to claim 6, the outlet gross area of wherein said pipe distributor is the 5-30% of described riser reactor sectional area, the 1.2-1.5 that described reducer diameter is described riser reactor diameter doubly, described reducer height is the 30-55% of described sleeve pipe height, and the angle of described V-shaped valve is the 40-100 degree.
8, solid alkylation reaction regeneration device according to claim 5, wherein said fluidized-bed reactor bottom is provided with the shower-head type distributor, described shower-head type distributor is made of inverted cone segment and straight length, and described straight length communicates with the top exit of described riser reactor; The surface of described inverted cone segment is provided with perforate, and opening diameter is 6-30mm, and percent opening is 5-20%.
9, solid alkylation reaction regeneration device according to claim 5, the bottom of wherein said moving bed regenerator is provided with discharge cone, described discharge cone by a plurality of discharge lists awl and up and down each fixed head constitute, described fixed head is provided with perforate in the junction, inner passage with described discharge list awl, have a plurality of bar-shaped troughs in each described discharge list cone flank side, the area of always slotting is the 30-70% of lateral area; The band valve pipe of described moving bed regenerator bottoms communicates with the inner passage of described discharge cone, and the bottom of described moving bed regenerator is provided with the regenerated liquid inlet, and described regenerated liquid inlet communicates with the space outerpace of described discharge cone.
10, solid alkylation reaction regeneration device according to claim 5, the middle part of wherein said circulation bed regenerator are provided with catalyst inlet and communicate with the band valve pipe that is connected described fluidized-bed reactor and circulation bed regenerator; Described catalyst inlet below is provided with sieve plate, and the hypotenuse of described sieve plate and the angle of vertical direction are the 20-60 degree, and percent opening is 5-30%; Described sieve plate below links to each other with tremie pipe, is provided with the circulation tube under the described sieve plate, and the length that described tremie pipe stretches into described circulation tube is the 60-90% of described circulation tube length overall; Described circulation tube highly is a 0.7-1.5 rice, and diameter is the 60-90% of described circulation bed regenerator internal diameter.
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| CNB2006100785591A CN100345622C (en) | 2006-05-10 | 2006-05-10 | Method and device for solid alkylation reaction |
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| CN105396517A (en) * | 2014-09-05 | 2016-03-16 | 中国石油化工股份有限公司 | Fluidized bed reaction and regeneration apparatus and method for alkylating solid acid |
| CN105441116A (en) * | 2014-09-05 | 2016-03-30 | 中国石油化工股份有限公司 | Solid-acid alkylation reaction method |
| CN105457566A (en) * | 2014-09-05 | 2016-04-06 | 中国石油化工股份有限公司 | Fluidized bed reaction and regeneration device and solid acid alkylation method |
| CN105457567A (en) * | 2014-09-05 | 2016-04-06 | 中国石油化工股份有限公司 | Fluidized bed solid acid alkylation reaction and regeneration device and application method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1009659B (en) * | 1985-06-24 | 1990-09-19 | 法国石油公司 | Process and equipment for fluidized bed catalytic cracking |
| US5462717A (en) * | 1989-09-13 | 1995-10-31 | Pfeiffer; Robert W. | Processes using fluidized solids and apparatus for carrying out such processes |
| CN1113689C (en) * | 2000-02-15 | 2003-07-09 | 清华大学 | Gas and solid parallel-flow folding type quick fluidizied-bed reactor |
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| CN111068590A (en) * | 2018-10-22 | 2020-04-28 | 中国石油化工股份有限公司 | Solid acid alkylation method |
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