CN103071434A - Internal circulation gas-solid fluidized bed reactor - Google Patents
Internal circulation gas-solid fluidized bed reactor Download PDFInfo
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Abstract
The invention provides an internal circulation gas-solid fluidized bed reactor which comprises a reaction zone, a rapid separation zone, a gas-solid separation zone, a steam stripping zone and a catalyst descending zone, wherein the reaction zone provides space for axial motion of a reactant flow along the reactor, the upper part of the reaction zone is the gas-solid separation zone, the lower part of the gas-solid separation zone is communicated with the steam stripping zone, the lower part of the steam stripping zone is communicated with the catalyst descending zone, the catalyst descending zone is parallel to the reaction zone, a splitter plate between the steam stripping zone and the catalyst descending zone is a catalyst distribution plate which is perforated with holes, the reaction zone and the catalyst descending zone are communicated with each other at the lower part of the reactor, the bottom of the reaction zone and the catalyst descending zone is provided with a catalyst collection plate, the edges of the catalyst collection plate are in enclosed connection with the sidewalls of the reactor, and the catalyst collection plate is provided with a slit and is a gas-liquid distributor for feeding at the bottom of the reactor at the same time. The reactor provided by the invention has the advantages of a compact structure, a good gas-solid separation effect and capacity of realizing continuous circulation of a catalyst in the reactor and can be used for preparation of low carbon olefins through catalytic conversion of an oxygen-containing compound.
Description
Technical field
The present invention relates to a kind of catalytic conversion reactor and use the catalysis conversion method of this reactor, more particularly, relate to a kind of interior circulating air solid fluidized bed reactor, and use this reactor by the method for producing low-carbon olefins from oxygen-containing compound.
Background technology
Low-carbon alkene (ethene, propylene, butylene) is the basic material of multiple important chemical products (such as oxirane, polyethylene, polyvinyl chloride, polypropylene and butyl rubber etc.).Development along with World Economics, low-carbon alkene particularly ethene and propylene demand grows with each passing day, because the rapid growth of China's economy, the annual growth of China's ethene and propylene demand are all above world average level, it is significant to increase the low-carbon alkene production capacity.
At present the main steam pyrolysis technology of the lightweight materials such as naphtha that adopts prepares low-carbon alkene, the whole world 90% or more the ethene production capacity and about 70% propylene production capacity by the realization of light petroleum hydrocarbon steam cracking.Because the crude oil heaviness is more and more serious, in the petroleum refining process, the productive rate of light petroleum hydrocarbon feed such as naphtha and straight distillation light diesel oil only is about 1/3 of crude oil gross production rate, and there is the under-supply and lower problem of diesel and gasoline ratio of fuel oil in China, cause the light hydrocarbon situation that there is lack of raw materials even more serious in China, limited the development of steam pyrolysis producing light olefins technique.Therefore particularly ethene, propylene have become the trend of development to develop renewable and alternative materials preparing low-carbon olefins.
Natural gas or coal are the technique that is hopeful to substitute naphtha route alkene processed most via the low-carbon alkenes such as Methanol ethene, propylene (Methanol to Olefin is called for short MTO).Ripe via the technology of synthesising gas systeming carbinol by natural gas or coal, therefore become the key link of this alternative route with the technology of preparing light olefins from methanol (MTO).
Many direct or indirect experimental datas confirm, hydrocarbon pond mechanism is obeyed in the conversion of methyl alcohol on acidic catalyst, described hydrocarbon pond mechanism refers to, methyl alcohol enters in the duct of acidic catalyst, polymerization forms carbon deposit under the acidic site effect, and polysubstituted toluene wherein is active carbon deposit, methyl alcohol can with polysubstituted toluene generation alkylated reaction, alkylate again side chain fracture generates low-carbon alkene, further diffuses out the catalyst duct; And polysubstituted toluene also further polymerization generate active lower polycyclic aromatic hydrocarbon, continue the inertia carbon deposit that polymerization generates HMW and finally cause catalysqt deactivation.Because the oxygen-containing compound conversion to produce olefine process is obeyed hydrocarbon pond mechanism, the active carbon deposit that deposits on the catalyst had both had the function that is total to catalysis MTO process with catalyst, have again and form the effect that the inertia carbon deposit makes catalysqt deactivation, on the catalyst after the regeneration carbonaceous material amount seldom, catalytic performance is relatively poor; One way carbon deposition on the catalyst is less, can't reach the requirement of selectivity of light olefin maximum; But the activated centre on the excessive carbon deposit meeting covering catalyst reduces catalyst activity, and the conversion ratio of oxygenatedchemicals and selectivity of light olefin are reduced; Therefore, suitable carbonaceous material deposition has important function for raising catalytic efficiency, raising selectivity of light olefin on the control catalyst.
In order to improve selectivity of light olefin, adopt lower regeneration temperature or short recovery time in some document, catalyst incomplete regen-eration, the coke content on the control catalyst.Yet, the incomplete regen-eration meeting makes that carbon deposit is more and more heavier, catalyst activity reduces, and too much carbon deposit, can reduce acidity of catalyst, so that the methyl alcohol reaction generates a large amount of dimethyl ether, cause selectivity of light olefin to reduce, therefore need to make in a kind of methanol conversion process catalyst to keep the method for suitable coke content, realize maximum selectivity of light olefin.
Because reactor is generally iron and steel material quality, the materials such as the iron under methyl alcohol and the condition of high temperature, nickel contact, and can generate CO, CO
2, H
2, CH
4Deng accessory substance, and conversion ratio is higher, this is unfavorable for improving selectivity of light olefin, although titanium shows inertia for methanol conversion, but the titanium selling at exorbitant prices can increase equipment investment, therefore greatly, how neither to increase equipment investment, again can the side reaction of establishment methyl alcohol, also requirement has been proposed for selection and the reactor design of equipment.
Stainless key component such as iron, nickel, chromium etc. all have catalytic action to alcohols materials such as methyl alcohol, generate CO, CO
2, CH
4, H
2Deng, in order to suppress these side reactions, need the temperature that reactant and wall etc. contact is controlled at below 400 ℃.Reaction zone methyl alcohol mainly contacts with catalyst, and side reaction is less; And feeding part, owing to there is not catalyst, and temperature is higher, be easy to occur side reaction, therefore, based on to the understanding of methanol oxidation process on the acidic catalyst and some response characteristics of methyl alcohol, must realize that for better methyl alcohol effectively transforms, improve selectivity of light olefin, some patents have proposed unique structure of reactor and form, try hard to reduce side reaction, improve yield of light olefins.
US6166282 discloses technology and the reactor that a kind of oxygenate conversion is low-carbon alkene, adopt fast fluidized bed reactor, gas phase is finished in the lower Mi Xiangfanyingqu reaction of gas speed, after rising to the fast subregion that internal diameter sharply diminishes, adopt special gas-solid separation equipment initial gross separation to go out most entrained catalyst.Because reaction afterproduct gas separates fast with catalyst, has effectively prevented the generation of secondary response.This patent is passed through external warmer, make the partially catalyzed agent direct circulation of not regenerating, another part catalyst is regenerated and is burnt carbon deposit on the catalyst, but this method can cause catalyst mix inhomogeneous, affect reaction effect, and feed distributor gets deeply stuck in beds, and exothermic heat of reaction can make reactant generation side reaction, affects product selectivity and yield.
CN101279873A discloses a kind of method by low-carbon alkenes such as methyl alcohol or dimethyl ether preparing ethylene, propylene.Take the SAPO-34 molecular sieve as catalyst, adopt the dense fluidized bed bioreactor, by the circular regeneration of catalyst, by methyl alcohol or dimethyl ether preparing low-carbon olefins, its methanol conversion can reach 98%, low-carbon alkene selectively can reach 90%.But the reaction mass distributor immerses beds fully in the method, and the methanol feeding excess Temperature causes the generation of side reaction.
US6023005 will contain the part (total reaction volume 2%～3%) of Pd/carbon catalyst and separate and regenerate, then the molecular sieve catalyst that will regenerate and the catalyst mix of not regenerating, make that carbon deposition quantity remains in the OK range on the catalyst, and catalyst evenly mixes, increase methyl alcohol and effectively be converted into the required micropore amount of low-carbon alkene, make selectively being improved of ethene and propylene, but this method guiding valve is more, a plurality of circulations, complicated operation, and the possibility that methyl alcohol contacts with metal material high temperature can occur in the direct charging of methyl alcohol, causes the generation of side reaction.
US6737556 discloses a kind of methanol oxidation and has transformed the method that generates low-carbon alkene, the method adopts new feeding manner, and adopt the less material of methyl alcohol side reaction activity to make reactor, the side reaction activity of also pointing out chromium, aluminium a little less than, titanium is inert substance preferably, but this can increase equipment investment greatly, affects economic benefit.The materials such as pottery also have preferably methyl alcohol reactionlessness, but the impact resistance of pottery is relatively poor, are unfavorable for the stable equilibrium operation of device.
For specific molecular sieve catalyst, if its coke content less than 4 % by weight, selectively the increasing with coke content of ethene, propylene.
Our purpose is the low-carbon alkene that obtains, particularly ethene as much as possible and propylene, and tries one's best and few obtain methane, ethane, propane and greater than C
5Product.For addressing the above problem, the present invention proposes a kind of new reactor types, the regenerating section catalyst, both can keep the required coke content of catalyst, can avoid again the carbon deposit on the catalyst more and more heavier, reach under the substantially constant prerequisite of catalyst activity, and significantly improve the selectivity of light olefin of catalyst.
Summary of the invention
One of technical problem to be solved by this invention is on the basis of existing technology, and a kind of Novel internal circulation gas-solid fluidized bed reactor and reaction-regeneration system are provided.
A kind of interior circulating air solid fluidized bed reactor provided by the present invention, comprise reaction zone, quick Disengagement zone, gas solid separation district, stripping zone and catalyst decline district, reaction zone is positioned at inside reactor, provides the space for reacting logistics along the reactor axially-movable, reaction zone top is for being the gas solid separation district, bottom, gas solid separation district is communicated with stripping zone, the stripping zone bottom descends to distinguishing with catalyst and is communicated with, and catalyst decline district is parallel with reaction zone; The demarcation strip that described stripping zone and catalyst descend between the district is the catalyst distribution plate, have hole or seam on the catalyst distribution plate, reaction zone descends to distinguishing with catalyst and communicates at reactor lower part, reaction zone arranges the catalyst collecting board that the edge is connected with the sidewall of reactor sealing with bottom, catalyst decline district, have the hole seam on the catalyst collecting board, the catalyst collecting board also is the gas-liquid distributor of reactor bottom charging simultaneously.
In the reactor provided by the invention, preferred described reaction zone top is the quick Disengagement zone that cross section constantly dwindles, and top, Disengagement zone is the gas solid separation district fast.
The beneficial effect of interior circulating air solid fluidized bed reactor provided by the invention is:
Interior circulating air solid fluidized bed reactor provided by the invention, oil gas and catalyst mix logistics are after the reaction zone reaction, move to the gas-solid initial gross separation of quick Disengagement zone, again through the further separation oil and gas in gas solid separation district and catalyst, reaction oil gas is drawn reactor, and catalyst is through descending the district to the further reaction of reaction zone bottom through catalyst behind the stripping under Action of Gravity Field.Compact conformation, gas-solid separating effect are good, can realize that catalyst constantly circulates at inside reactor,
A kind of ICFB reaction-regeneration system provided by the invention, it is characterized in that, comprise described interior circulating air solid fluidized bed reactor and catalyst regenerator, the stripping zone of described interior circulating air solid fluidized bed reactor is communicated with catalyst regenerator through reclaimable catalyst inclined tube 11, and described catalyst regenerator is communicated with described circulating fluid bed reactor through regenerated catalyst inclined tube 13.
The beneficial effect of ICFB reaction system provided by the invention is:
ICFB reaction-regeneration system provided by the invention a part of carbon deposited catalyst in the interior circulating air solid fluidized bed reactor is introduced the activity recovery of regenerating in the catalyst regenerator, and it is recycling to return ICFB; The circulation ratio of all right conditioned reaction device inner catalyst, the regeneration cycle amount that also can regulate catalyst.By the catalyst of a part of carbon deposit of regenerating, the catalyst circulation of all the other carbon deposits is returned reaction zone and is continued reaction, the coke content on the catalyst can be controlled in the suitable scope.
Description of drawings
Accompanying drawing is the schematic flow sheet of a kind of embodiment of ICFB reaction-regeneration system provided by the invention;
Wherein: the A-reaction zone; The quick Disengagement zone of B-; C-gas solid separation district; The D-stripping zone; The E-catalyst descends and distinguishes;
1-urceolus (reactor outer wall); The 2-inner core; 3-catalyst distribution plate; The quick Disengagement zone of 4-pipe; The 5-cyclone separator; The outlet of 6-gaseous product; The quick Disengagement zone of 7-truncated cone-shaped baffle plate; The outlet of 8-regenerator flue gas; The 9-cyclone separator; The 10-catalyst regenerator; 11-reclaimable catalyst inclined tube; 12-regeneration gas entrance; 13-regenerated catalyst inclined tube; 14-catalyst collecting board; 15-regenerator catalyst transport standpipe.
The specific embodiment
Described interior circulating air solid fluidized bed reactor provided by the invention and regenerative system are such implementations:
A kind of interior circulating air solid fluidized bed reactor, comprise reaction zone, quick Disengagement zone, gas solid separation district, stripping zone and catalyst decline district, reaction zone is positioned at inside reactor, provides the space for reacting logistics and catalyst along the reactor axially-movable, reaction zone top is the quick Disengagement zone that cross section constantly dwindles, top, Disengagement zone is the gas solid separation district fast, bottom, gas solid separation district is communicated with stripping zone, and the stripping zone bottom descends to distinguishing with catalyst and is communicated with, and catalyst decline district is parallel with reaction zone; The demarcation strip that described stripping zone and catalyst descend between the district is the catalyst distribution plate, have hole or seam on the catalyst distribution plate, reaction zone descends to distinguishing with catalyst and communicates at reactor lower part, reaction zone arranges the catalyst collecting board that the edge is connected with the sidewall of reactor sealing with bottom, catalyst decline district, have the hole seam on the catalyst collecting board, the catalyst collecting board also is the gas-liquid distributor of reactor bottom charging simultaneously.
In the reactor provided by the invention, described interior circulating air solid fluidized bed reactor top is gas solid separation district and stripping zone, and described inner circulation reactor lower catalytic agent collecting board is following to be the raw material feed zone.Under described gas solid separation district, the stripping zone, be parallel reaction zone and catalyst decline district on the catalyst collecting board.Wherein, described reaction zone can be the cylindrical space that is positioned at inside reactor, and described catalyst descends the district for surrounding the annulated column shape space of reaction zone; Also can be that catalyst decline district is positioned at reactor center, the annulated column shape space that described reaction zone descends and distinguishes for surrounding catalyst; Perhaps reaction zone and catalyst decline district is positioned at respectively the both sides of reactor.The present invention is not limited in this respect.
Preferred embodiment be, described reaction zone is to be arranged at the space that the inner core 2 in the reactor surrounds, the space that described quick Disengagement zone surrounds for the up-small and down-big truncated cone-shaped baffle plate 7 that is connected with the inner core top, described catalyst descend and distinguish the annular space that surrounds for reactor outer wall 1 and inner core 2.
The concrete structure of described interior circulating air solid fluidized bed reactor is: inner core 2 is arranged at urceolus 1 (reactor outer wall) inside, preferred structure is urceolus 1 and inner core 2 coaxial settings, the space that inner core 2 surrounds is reaction zone, and described inner core 2 is catalyst decline district with the annular gap that urceolus 1 surrounds; The top of inner core 2 links to each other by catalyst distribution plate 3 with reactor outer wall 1, have hole or seam on the described catalyst distribution plate 3, up-small and down-big truncated cone-shaped baffle plate 7 is equipped with at inner core 2 tops, the space that the truncated cone-shaped baffle plate surrounds is quick Disengagement zone, and truncated cone-shaped baffle plate 7, catalyst distribution plate 3 are stripping zone with the space that the reactor outer wall surrounds; After catalyst by reaction zone and oil gas entered quick Disengagement zone, catalyst and gas mixture rose gradually from the round platform bottom, and circulation area diminishes gradually, gas is accelerated, and solid is because inertia accelerates slower, it is large that the gas-solid speed difference becomes, and can realize the initial gross separation of gas-solid mixture.
Top, Disengagement zone is the gas solid separation district fast, catalyst and reaction oil gas after quick Disengagement zone initial gross separation carry out gas solid separation in the gas solid separation district, the gas solid separation district can arrange cyclone separator or filter, and preferred scheme is the cyclone separator that one or more levels is set.Cyclone separator or filter outside are catalyst settler.Carbon deposited catalyst through cyclone separator separation and sedimentation separation enters stripping zone.
Have hole or seam on the catalyst distribution plate 3 of stripping zone bottom, stripping zone through the catalyst behind the stripping can be on the catalyst baffle plate hole and seam enter catalyst and descend in the district, bottom, catalyst decline district arranges the catalyst collecting board 14 that the edge is connected with the sidewall of reactor sealing, catalyst collecting board 14 and inner core 2 lower limbs leave the space of certain altitude, and the district communicates with reaction zone so that catalyst descends.Collected by catalyst collecting board 14 through described space by the catalyst that catalyst decline district comes, under the lifting of raw material and lifting medium (such as steam, nitrogen etc.), enter reaction zone and recycle.
In the reactor provided by the invention, the diameter of the described inner core 1 that surrounds reaction zone is 1: 1.05～2 with the diameter ratio of reactor.
In the reactor provided by the invention, described quick Disengagement zone is preferably the space that pipe 4 that the up-small and down-big truncated cone-shaped baffle plate 7 that is connected with the inner core top is connected with baffle plate top surrounds.More preferably, on truncated cone-shaped baffle plate top pipe 4 is set, can further improves separating effect.
Preferably, the internal diameter of upper end, described quick Disengagement zone pipe 4 is 0.1-0.9 with the ratio of the internal diameter of reaction zone inner core 2: 1.Preferably, the ratio of height to diameter of top, described quick Disengagement zone pipe 4 is 0.1-20: 1.
In the reactor provided by the invention, the ratio of the internal diameter of the height of described quick Disengagement zone and reaction zone inner core (2) is 0.2-5: 1.
In the reactor provided by the invention, the dividing plate that described stripping zone and catalyst descend between the district is catalyst distribution plate 3, and catalyst distribution plate 3 can be level, perhaps tilt, and can be arc also, the present invention is not limited in this respect.Preferred catalyst distribution grid 3 is fillet with the angle on reactor outer wall top, perhaps is the angle greater than 90 °.Described angle can prevent that greater than 90 ° the catalyst of stripping zone from stockpiling herein.Preferred scheme is described catalyst distribution plate 3 and sidewall of reactor 1 junction, and the tangent line of catalyst distribution plate 3 buses and the angle of sidewall of reactor are 0 °～60 °.
In the reactor provided by the invention, preferred scheme is that described catalyst distribution plate 3 is up big and down small truncated cone-shaped baffle plate, opens trip hole or seam on the baffle plate.More preferably the angle of described truncated cone-shaped baffle plate and horizontal direction is that the catalyst distribution plate of catalyst through tilting in 30 °～60 ° stripping zones enters the catalyst district that descends, and can avoid the partially catalyzed agent to accumulate in angle between catalyst distribution plate and reactor outer wall.
In the reactor provided by the invention, have the hole on the described catalyst collecting board 14, opening diameter is 0.001-0.2 with the ratio of inner diameter of steel flue: 1.Perforate on the preferred described catalyst collecting board covers with metal sintering plate, metal sintering pipe or bubble-cap.Can be so that be entered in the reaction zone by the perforate of raw material oil gas on the catalyst collecting board of reactor bottom charging and to react, prevent simultaneously catalyst on the catalyst collecting board 14 bottom of catalyst collecting board 14 of bleeding.
In the method provided by the invention, preferably be lined with heat-insulating material in the bottom of described catalyst collecting board 14.Can reduce the temperature of reactor bottom, raw material charging place, in the time of in the reaction that is applied to oxygenatedchemicals catalyzed conversion low-carbon alkene, can avoid oxygenatedchemicals under too high temperature, contact consists of the metal such as Fe, the Ni of reactor and feed pipe and side reaction occurs.
In the reactor provided by the invention, arrange in the described reaction zone and improve the inner member that catalyst flows.The inner member of setting example such as barrier can improve the distribution of reaction oil gas in reaction zone so that contact with catalyst more abundant, thereby improve reaction efficiency.
Interior circulating air solid fluidized bed reactor provided by the invention and catalyst regenerator be the anabolic reaction regenerative system together, the stripping zone bottom of described interior circulating air solid fluidized bed reactor communicates with the feed pipe of catalyst regenerator through the reclaimable catalyst inclined tube, and the regenerated catalyst discharging opening of described catalyst regenerator is communicated with the decline district of described circulating fluid bed reactor through the regenerated catalyst inclined tube.
In the ICFB reaction-regeneration system provided by the invention, catalyst in the stripper is divided into two parts, part catalyst returns reaction zone through the district that descends, another part is delivered in the catalyst regenerator through the reclaimable catalyst standpipe, wherein, reclaimable catalyst can directly enter catalyst regenerator or the regeneration gas through introducing regenerator and promotes and enter in the catalyst regenerator.Described regeneration gas is oxygen-containing gas, and preferred air is used for burning the carbon deposit on the catalyst under regeneration temperature.The gas solid separation at regenerator top can adopt cyclone separator, cyclone separator can be one or more levels, after gas solid separation, regenerated flue gas is discharged catalyst regenerator, and catalyst regenerator bottom regenerated catalyst returns in the interior circulating air solid fluidized bed reactor through regenerator sloped tube and recycles.
ICFB reaction provided by the invention and regenerative system can be applied to the technical process that the oxygenatedchemicals catalyzed conversion generates low-carbon alkene, use above-mentioned interior circulating air solid fluidized bed reactor, oxygen-containing compound material is introduced in the interior circulating air solid fluidized bed reactor by the bottom, raw material enters reaction zone after distributing, with the catalyst haptoreaction, the catalyst of reaction oil gas and carbon deposit is after separate the quick Disengagement zone on reaction zone top, enter the gas solid separation district, isolated oil gas further separates through the gaseous phase outlet ejector in gas solid separation district; Catalyst sedimentation after the separation is to stripping zone, stripping zone is introduced stripped vapor further with absorption in the catalyst or the reaction oil gas stripping that is mingled with out, the reaction oil gas that the isolated reaction oil gas in gas solid separation district and stripping go out is drawn reactor through the gaseous phase outlet of reactor head, in subsequent separation system, further separate, stripping enters the district that descends by the catalyst distribution plate and moves downward, and enters the reaction zone bottom cycle through the space of the bottom, district that descends and uses.
Adopt ICFB reaction-regeneration system provided by the invention, can further the partially catalyzed agent in the interior circulating air solid fluidized bed reactor stripping zone be introduced catalyst regenerator through the reclaimable catalyst inclined tube and carry out coke burning regeneration, the decline district that the catalyst after the regeneration returns interior circulating air solid fluidized bed reactor recycles.
Be used for the oxygenatedchemicals catalyzed conversion and prepare low-carbon alkene, the catalyst of regenerating in the described introducing catalyst regenerator is 5～40% of catalyst inventory total in the reactor.
The inventor finds in research process, in the preparing low-carbon olefin from oxygen-containing compounds process of the test, find during the catalyst of regeneration carbon deposit, the coke burning regeneration time in the time of 0～1300 second, CO in the tail gas
2Concentration reduces by increasing afterwards first; The coke burning regeneration time in the time of 1300～1800 seconds, CO
2Concentration almost nil; The coke burning regeneration time in the time of 1800～2100 seconds, tail gas CO
2Concentration is reduced to zero after increasing first again gradually; This shows that the carbon deposit on the catalyst can be divided into two parts according to the complexity of burning, and a part is at catalyst surface, is easy to and the oxygen catalytic combustion; Another part is inner in the duct, because the oxygen diffusion is difficult, needs the long time that catalyst is burnt fully.Therefore, if adopt the method for catalyst incomplete regen-eration, last minute carbon deposit of reservation catalyst, carbon deposit in the molecular sieve pore passage can't active combustion, can make the carbon deposit on the catalyst become gradually heavy, although finally caused controlling the coke content on the catalyst, but the carbon deposit on the catalyst has not been to make oxygenatedchemicals effectively be converted into the needed hydrocarbon of low-carbon alkene pond material, so that catalyst activity and selectivity of light olefin reduce.
The part of the catalyst of the carbon deposit of described stripping zone is introduced holomorphosis activity recovery in the catalyst regenerator, and the catalyst after the regeneration not only carbon deposit on the catalyst surface is burnt and is removed, and the difficult carbon deposit that removes is also burnt in the catalyst duct.Can avoid the catalyst incomplete regen-eration to reduce the defective of catalyst activity.
Regenerated catalyst is in the catalyst decline district of regenerator sloped tube Returning reactor, burn carbon deposit, active higher regenerated catalyst evenly mixes with catalyst without the carbon deposit of regenerating, jointly descending, two kinds of catalyst mix in descending process, the high temperature migration can occur at catalyst surface in the carbon deposit material, acid site and the acid site in the hole of holomorphosis catalyst surface are coated, regulate acid strength and the sour density of catalyst surface, make the holomorphosis catalyst also have preferably selectivity of light olefin, it is selective to reduce carbon deposit, and the method for this partially catalyzed agent holomorphosis, can avoid on the catalyst carbon deposit more and more heavy, can make again catalyst keep suitable coke content, reach the purpose that improves selectivity of light olefin.
The reaction temperature of described reaction zone is 380～680 ℃, and preferable range is 440～520 ℃; The weight (hourly) space velocity (WHSV) of oxygen-containing compound material is 1～50 hour
-1, preferable range is 1～30 hour
-1, more preferably scope is 1.5～20 hours
-1Gas superficial velocity is 0.1～10 meter per second in the reaction zone, preferable range 0.1～2 meter per second.
Described oxygen-containing compound material is selected from one or more the mixture in methyl alcohol, ethanol, dimethyl ether and the animal and plant fat.The % water that preferably also contains 2～50 weight in the described oxygen-containing compound material.
Described catalyst is solid acid catalyst, active component is molecular sieve and/or the SAPO molecular sieve with MFI structure, wherein, the preferred ZSM-5 of described MFI molecular sieve and/or ZRP molecular sieve, the preferred SAPO-34 molecular sieve of described SAPO molecular sieve, the carrier of catalyst are artificial synthetic inorganic oxide and natural clay (such as kaolin).
Below in conjunction with accompanying drawing, specify interior circulating air solid fluidized bed reactor provided by the invention, and the application in the producing low-carbon olefins from oxygen-containing compound method, but the present invention is not therefore subject to any restriction.
Accompanying drawing is the schematic flow sheet of ICFB reaction-regeneration system provided by the invention, as shown in the figure, interior circulating air solid fluidized bed reactor (urceolus) the 1 interior inner core 2 that arranges, and urceolus 1 and inner core 2 are coaxial, the space of inner core 2 inside is reaction zone A, and urceolus 1 is catalyst decline district E with the annular space that inner core 2 surrounds.The top of inner core 2 links to each other by catalyst distribution plate 3 with the reactor outer wall, has hole or seam on the catalyst distribution plate 3, and described catalyst distribution plate 3 is preferably up big and down small truncated cone-shaped baffle plate.Catalyst can enter catalyst decline district E by these holes on the catalyst distribution plate 3 or seam.Up-small and down-big truncated cone-shaped baffle plate 7 is equipped with at inner core 2 tops, and preferred structure is that truncated cone-shaped baffle plate 7 tops also are connected with the pipe 4 with the footpath.This truncated cone-shaped baffle plate 7 and the space that pipe 4 surrounds on it are quick Disengagement zone B, gas-solid mixture in the reaction zone A rises gradually from this round platform bottom, circulation area diminishes gradually, gas is accelerated, and solid is because inertia, accelerate slowlyer, it is large that the gas-solid speed difference becomes, and can realize the initial gross separation of gas-solid mixture.
Space between reactor outer wall 1, catalyst distribution plate 3 and the quick Disengagement zone B is stripping zone D, the catalyst of carbon deposit is deposited to stripping zone D behind the reaction zone A internal reaction after gas solid separation, can introduce stripped vapor, the reaction oil gas that stripping goes out carbon deposited catalyst absorption and carries secretly.Stripping zone D upper space is gas solid separation district C, and gas solid separation district C can arrange gas-solid separation equipment, and for example cyclone separator 5, and the two stage cyclone separator preferably is set, and cyclone separator 5 outsides are the decanting zone.From the catalyst of the carbon deposit of reaction zone A and reaction oil gas at quick Disengagement zone B after initial gross separation, further separate through cyclone separator 5 again, enter stripping zone D through cyclone separator 5 isolated catalyst granules, cyclone separator 5 isolated oil gas export 6 ejectors through gaseous product, enter subsequent separation system and further separate.
The catalyst of stripping zone D is divided into two parts, a part enters catalyst decline district E, the reclaimable catalyst inclined tube 11 of another part through guiding valve is housed enters the bottom of catalyst transport standpipe 15, regeneration gas is introduced catalyst transport standpipe 15 by bottom inlet 12, promoting reclaimable catalyst enters in the catalyst regenerator 10 together, described regeneration gas is oxygen-containing gas, is used at high temperature burning the carbon deposit on the catalyst, makes the catalyst activity recovery.Catalyst regenerator 10 is fluidized-bed reactor, and top is provided with cyclone separator 9 separating catalysts and regenerated flue gas, and isolated regenerated flue gas leaves regenerator through pipeline 8.
The regenerator sloped tube 13 of the regenerated catalyst of catalyst regenerator 10 bottoms through guiding valve is housed enters catalyst decline district E, with contain Pd/carbon catalyst and mix and jointly descending, two kinds of catalyst mix are even in descending process, the carbon deposit material moves at catalyst surface generation high temperature, acid site and the acid site in the hole of holomorphosis catalyst surface are coated, regulate acid strength and the sour density of catalyst surface, make the holomorphosis catalyst also have preferably selectivity of light olefin, it is selective to reduce carbon deposit, and the method for this partially catalyzed agent holomorphosis, can avoid on the catalyst carbon deposit more and more heavy, can make again catalyst keep suitable coke content, reach the purpose that improves selectivity of light olefin.
The internal circulation fluidized bed reactor bottom arranges catalyst collecting board 14, the space that certain altitude is arranged between inner core 2 lower edge and the catalyst collecting board 14, catalyst with suitable coke content is descending in the district E that descends, enter reaction zone A bottom through the space of inner core 1 lower limb, and under the lifting of the raw material oil gas that reactor bottom is introduced, enter reaction zone A, the simultaneously reaction of fcc raw material oil gas.
Evenly have hole or bar seam on the catalyst collecting board 14, catalyst collecting board 14 also as the distributor of raw material oil gas, is evenly introduced among the reaction zone A after the perforate distribution of raw material oil gas on catalyst collecting board 14 by the reactor bottom introducing simultaneously.
The present invention will be further described by the following examples, but not thereby limiting the invention.
Embodiment
Embodiment 1 explanation interior circulating air solid fluidized bed reactor provided by the invention is used the effect with low carbon olefin preparation by using oxygenated chemical.
Flow chart as shown in Figure 1, take methyl alcohol as raw material, catalyst is the SAPO-34 molecular sieve of spray drying forming, 480 ℃ of reaction temperatures, gauge pressure 50KPa, air speed 7.0h
-1Inner core linear speed 1m/s, agent alcohol mass ratio 7.5, regulate the heat transferring medium flow, control methanol feeding temperature is not higher than 350 ℃, and regenerating tube adopts riser, lift gas is air, 600 ℃ of regeneration temperatures, the gas superficial velocity of regulating slide valve aperture and spent agent feed-line is adjusted the regeneration ratio of catalyst, and the average coke content on the control catalyst is 3.1%.When bringing into operation, at first close again guiding valve, circulation is only moved in recirculating fluidized bed, the sample tap of regenerative agent and spent agent lays respectively on the pipeline.After the carbon deposit on the catalyst reaches certain value, open again guiding valve, catalyst is carried out partial regeneration, the internal circulating load of catalyst is remained on a rational value, so that system run all right, control is convenient.Experimental result sees Table 1.
Table 1 preparing light olefins from methanol product distributes
Claims (15)
1. circulating air solid fluidized bed reactor in a kind, it is characterized in that, comprise reaction zone, quick Disengagement zone, gas solid separation district, stripping zone and catalyst decline district, reaction zone is positioned at inside reactor, provides the space for reacting logistics along the reactor axially-movable, reaction zone top is the gas solid separation district, bottom, gas solid separation district is communicated with stripping zone, and the stripping zone bottom descends to distinguishing with catalyst and is communicated with, and catalyst decline district is parallel with reaction zone; The demarcation strip that described stripping zone and catalyst descend between the district is the catalyst distribution plate, have hole or seam on the catalyst distribution plate, reaction zone descends to distinguishing with catalyst and communicates at reactor lower part, reaction zone arranges the catalyst collecting board that the edge is connected with the sidewall of reactor sealing with bottom, catalyst decline district, have the hole seam on the catalyst collecting board, the catalyst collecting board also is the gas-liquid distributor of reactor bottom charging simultaneously.
2. according to the reactor of claim 1, described reaction zone top is the quick Disengagement zone that cross section constantly dwindles, and top, Disengagement zone is the gas solid separation district fast.
3. according to the reactor of claim 2, it is characterized in that, described reaction zone (A) is for being arranged at the space that the inner core (2) in the reactor surrounds, the space that described quick Disengagement zone (B) surrounds for the up-small and down-big truncated cone-shaped baffle plate (7) that is connected with the inner core top, described catalyst descend and distinguish the annulated column shape space that (E) surrounds for reactor outer wall (1) and inner core (2).
4. according to reactor arbitrary in the claim 3, it is characterized in that the diameter of the described inner core (1) that surrounds reaction zone (A) is 1 with the diameter ratio of reactor: 1.05-2.
5. according to the reactor of claim 3, it is characterized in that the space that described quick Disengagement zone (B) surrounds for the pipe (4) on the up-small and down-big truncated cone-shaped baffle plate (7) that is connected with the inner core top and baffle plate top.
6. according to the reactor of claim 5, it is characterized in that the ratio of the internal diameter of described quick Disengagement zone (B) upper end pipe (4) and the internal diameter of reaction zone inner core (2) is 0.1-0.9: 1.
7. according to the reactor of claim 5, it is characterized in that the ratio of height to diameter of described quick Disengagement zone top pipe (4) is 0.1-20: 1.
8. according to reactor arbitrary among the claim 3-7, it is characterized in that, described catalyst distribution plate (3) and sidewall of reactor (1) junction, the tangent line of catalyst distribution plate bus and the sidewall of reactor angle at the contact point place is 0 °～60 °.
9. according to reactor arbitrary among the claim 3-7, it is characterized in that the ratio of the internal diameter of the height of described quick Disengagement zone (B) and reaction zone inner core (2) is 0.2-5: 1.
10. according to reactor arbitrary among the claim 1-7, it is characterized in that, have the hole on the described catalyst collecting board (14), opening diameter is 0.001-0.2 with the ratio of inner diameter of steel flue: 1.
11. the reactor according to claim 9 is characterized in that, the perforate on the described catalyst collecting board covers with metal sintering plate, metal sintering pipe or bubble-cap.
12. the reactor according to arbitrary among the claim 1-7 is characterized in that, the bottom of described catalyst collecting board (14) is lined with heat-insulating material.
13. the reactor according to arbitrary among the claim 1-7 is characterized in that, arranges in the described reaction zone to improve the inner member that catalyst flows.
14. ICFB reaction-regeneration system, it is characterized in that, comprise interior circulating air solid fluidized bed reactor arbitrary among the claim 1-13, and catalyst regenerator, the stripping zone bottom of described interior circulating air solid fluidized bed reactor is communicated with catalyst regenerator through reclaimable catalyst inclined tube (11), and described catalyst regenerator is communicated with described interior circulating air solid fluidized bed reactor through regenerated catalyst inclined tube (13).
15. ICFB reaction-regeneration system, it is characterized in that, the stripping zone bottom of described interior circulating air solid fluidized bed reactor is through the catalyst charge standpipe of reclaimable catalyst inclined tube (11) connection catalyst regenerator bottom, and the regenerated catalyst discharging opening of described catalyst regenerator is communicated with the catalyst decline district of described interior circulating air solid fluidized bed reactor through regenerated catalyst inclined tube (13).
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103420359A (en) * | 2013-08-08 | 2013-12-04 | 山东大展纳米材料有限公司 | Method for preparing carbon nanotube under catalysis of red mud, reaction device and application |
| CN105170038A (en) * | 2015-06-12 | 2015-12-23 | 四川省明信投资有限公司 | Melt collecting tank used for continuous fluidized bed reactor |
| CN106943965A (en) * | 2017-03-25 | 2017-07-14 | 青岛京润石化设计研究院有限公司 | A kind of gas-solid fluidized bed reactor gas-solid separating method |
| CN109651037A (en) * | 2017-10-10 | 2019-04-19 | 中国石油化工股份有限公司 | A method of using double-reaction area by preparing low-carbon olefin |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4541921A (en) * | 1982-02-12 | 1985-09-17 | Mobil Oil Corporation | Method and apparatus for regenerating cracking catalyst |
-
2011
- 2011-10-25 CN CN201110326819.3A patent/CN103071434B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4541921A (en) * | 1982-02-12 | 1985-09-17 | Mobil Oil Corporation | Method and apparatus for regenerating cracking catalyst |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103420359A (en) * | 2013-08-08 | 2013-12-04 | 山东大展纳米材料有限公司 | Method for preparing carbon nanotube under catalysis of red mud, reaction device and application |
| CN103420359B (en) * | 2013-08-08 | 2016-04-06 | 山东大展纳米材料有限公司 | The method of carbon nanotube, reaction unit and application are prepared in red mud catalysis |
| CN105170038A (en) * | 2015-06-12 | 2015-12-23 | 四川省明信投资有限公司 | Melt collecting tank used for continuous fluidized bed reactor |
| CN105170038B (en) * | 2015-06-12 | 2017-06-30 | 四川省明信投资有限公司 | A kind of fused mass collecting tank for continuous fluidized bed reactor |
| CN106943965A (en) * | 2017-03-25 | 2017-07-14 | 青岛京润石化设计研究院有限公司 | A kind of gas-solid fluidized bed reactor gas-solid separating method |
| CN109651037A (en) * | 2017-10-10 | 2019-04-19 | 中国石油化工股份有限公司 | A method of using double-reaction area by preparing low-carbon olefin |
| CN109651037B (en) * | 2017-10-10 | 2021-06-11 | 中国石油化工股份有限公司 | Method for preparing low-carbon olefin from synthesis gas by adopting double reaction zones |
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