CN103922880A - Continuous reaction regeneration device utilizing vulcanization catalyst to perform alkane dehydrogenation - Google Patents
Continuous reaction regeneration device utilizing vulcanization catalyst to perform alkane dehydrogenation Download PDFInfo
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- CN103922880A CN103922880A CN201310014789.1A CN201310014789A CN103922880A CN 103922880 A CN103922880 A CN 103922880A CN 201310014789 A CN201310014789 A CN 201310014789A CN 103922880 A CN103922880 A CN 103922880A
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Abstract
The invention relates to a continuous reaction regeneration device utilizing a vulcanization catalyst to perform alkane dehydrogenation. The continuous reaction regeneration device comprises a reactor, a catalyst regenerator and a catalyst pre-vulcanizer. The reactor and the catalyst regenerator are connected by a catalyst generation inclined tube and a catalyst lifting conveying pipe, and the catalyst regenerator and the catalyst pre-vulcanizer are connected through a regeneration inclined pipe. The catalyst pre-vulcanizer consists of an inlet and an outlet, and the outlet is directly communicated with the reactor. The regeneration device can realize a successive process of dehydrogenation reaction, catalyst regeneration and afterburning as well as catalyst prevulcanization, thus greatly improving the production efficiency of the device.
Description
Technical field
The present invention relates to a kind of successive reaction regenerating unit of dehydrating alkanes, concrete, relate to a kind of successive reaction regenerating unit that utilizes sulphurized catalyst to carry out dehydrating alkanes.
Background technology
Propane, butane dehydrogenation change into the reaction heat of corresponding alkene at 120kJ/mol left and right, strong endothermic reaction.In addition, in propane, catalytic dehydrogenation of butanes reaction process, catalyzer can coking deactivation, and some catalyzer dozens of minutes just need coke burning regeneration, and what have carries out coke burning regeneration for tens hours.For such reaction system, adopt fixed-bed reactor, the one, beds heat transfer efficiency is low, is not easy to the timely heat supply of reaction; The 2nd, catalyzer needs frequent coke burning regeneration, and the switching of reaction and reproduced state not only will be adjusted the temperature of bed, and between reaction and regeneration air switch, must purge bed with inert medias such as steam.Obviously, fixed-bed reactor seem simply, and to the so strong heat absorption of propane, butane dehydrogenation, the reaction system that catalyzer needs frequent coke burning regeneration, it is very inconvenient to operate, and has potential safety hazard.
Adopt moving-burden bed reactor to carry out catalytic dehydrogenation, although realized carrying out continuously of reaction and catalyzer coke burning regeneration; But the heat transfer character of moving-burden bed reactor is identical with fixed bed, solid catalyst, except pure metal catalyzer, is all hot poor conductor, thereby, how to give the efficient heat supply of reaction bed, remain a difficult problem.
From the reaction characteristics of propane, the corresponding alkene of catalytic dehydrogenation of butanes system, optimal should be circulating fluid bed reactor.Circulating fluid bed reactor not only heat transfer efficiency is high, and can react continuously and catalyzer coke burning regeneration, more rare, and the heat that can utilize high temperature regeneration agent to carry meets the demand of the dehydrogenation reaction of absorbing heat to heat.The FBD-4 technology of Muscovite Snamprogetti company, employing be exactly circulating fluid bed reactor.
The maximum shortcoming of circulating fluidized bed is exactly that catalyzer exists wearing and tearing, Fragmentation Phenomena.The granules of catalyst of wearing and tearing, fragmentation, to a certain extent little, below 10 μ m, cyclonic separator just cannot be reclaimed.Reclaim the particle of not returning from the cyclonic separator of reactive system, will enter into the separation system of gas; Reclaim the particle of not returning from the cyclonic separator of regeneration system rapidly, will enter into flue gas.The existence of phenomenon is damaged in this race of catalyzer, defines circulating fluid bed reactor and can not use too expensive catalyzer, can not use poisonous catalyzer.Catalyzer is too expensive, causes process not have economy to say; Catalyzer is poisonous, can bring the disaster of environment.
Therefore, for the reaction system of propane, the corresponding alkene of butane dehydrogenation system, if adopt circulating fluidized bed, can not use supported Pt catalysts, because its expensive, can not be with poisonous loading type Cr
2o
3catalyzer, pollutes the environment because run the catalyzer damaging, even if can all reclaim, also has a difficult problem for harmless treatment aspect.
For high efficiency circulating fluid bed reactor being applied in propane, butane dehydrogenation reaction, we have successively developed and have been suitable for nontoxic, non-noble metal oxide dehydrogenation catalyst and nontoxic, the base metal sulfide catalyst that circulating fluid bed reactor uses, the circulating fluid bed reaction device of successive reaction, catalyst regeneration and the sulfuration of the maintained catalyzer that the present invention be directed to nontoxic, base metal sulfide catalyst exploitation in sulfided state.
Summary of the invention
The object of this invention is to provide a kind of successive reaction regenerating unit that utilizes sulphurized catalyst to carry out dehydrating alkanes, this device has the circulating fluid bed reactor technology of prevulcanized function, can realize the prevulcanized of dehydrogenation reaction, catalyst regeneration and afterburning and catalyzer and successively carry out, increase substantially the production efficiency of device.
For realizing goal of the invention of the present invention, a kind of successive reaction regenerating unit that utilizes sulphurized catalyst to carry out dehydrating alkanes, comprise reactor, catalyst regenerator and presulfiding of catalyst device, reactor promotes transfer lime with catalyst regenerator by catalyzer inclined tube to be generated, catalyzer and is connected, catalyst regenerator is connected by regenerator sloped tube with presulfiding of catalyst device, presulfiding of catalyst device comprises import, outlet, and it exports directly and reactor UNICOM.
The outlet of described catalyst vulcanization device is in the position apart from reactor top 1/8-1/4 height for reactor and reactor UNICOM.
Catalyzer is after the sulfuration of prevulcanized device, enter in reactor from the outlet of prevulcanized device, because its outlet is the position UNICOM with it apart from reactor top 1/8-1/4 height for reactor, catalyzer directly enters reactor settling section, be conducive to high temperature catalyst being uniformly distributed in dehydrogenation reactor, avoid high temperature catalyst to concentrate a certain part that is distributed in dehydrogenation reactor to cause nonselective thermal response.
Described presulfiding of catalyst device is arranged in reactor or outside reactor; It is preferred, and presulfiding of catalyst device is arranged in reactor; More preferably, presulfiding of catalyst device is arranged in reactor, and is placed in dehydrogenation reactor catalyst settling section; Settling section is positioned at reactor top, accounts for the 1/4-1/2 of whole height for reactor.So, be conducive to reduce heat lost by radiation, reduce the energy consumption of device.
In reactor and in catalyst regenerator, grid distributor is all set; Preferably, two-layer above grid distributor is all set; More preferably, double-layer separate fabric swatch is all set.
Described grid distributor is multihole distributor, or grid grid distributor.Multihole distributor or grid are set in reactor, can bubble crushing, the contact of strengthening gas-solid two-phase, improves reaction efficiency.
Grid distributor is also set in presulfiding of catalyst device.
The top of reactor is provided with cyclone separator, separation system, same, and cyclone separator is also set in catalyst regenerator.
On inclined tube to be generated and regenerator sloped tube, be equipped with variable valve.
Described successive reaction regenerating unit also comprises raw materials furnace and heating.
Utilize the successive reaction regenerating unit of above-mentioned dehydrating alkanes to carry out dehydrating alkanes reaction, comprise the steps:
(1) paraffinic feedstock that contains sulfocompound is preheating to 70-700 ° of C through process furnace, and then, the speed that the raw material after preheating is not more than 3m/s with axial average apparent gas speed enters in reactor, is to carry out catalytic dehydrogenation under the condition of 350-700 ° of C in temperature;
(2) reacted catalyzer enters into catalyzer through inclined tube to be generated and promotes transfer lime, above catalyzer feed opening, spray into fuel, promoting medium enters from promoting transfer lime lower end, carrying catalyzer and fuel enters in catalyst regenerator through promoting transfer lime, under the condition of temperature 550-800 ° C, coke on catalyzer and full combustion of fuel, make the catalyst regeneration of inactivation;
(3) regenerated catalyst is in regenerator sloped tube enters presulfiding of catalyst device, prevulcanized medium enters in prevulcanized device through the import of prevulcanized device lower end, carry out vulcanization reaction with regenerated catalyst, the axial superficial linear vilocity of prevulcanized medium in prevulcanized device can not exceed 3m/s;
(4) catalyzer after prevulcanized is along with curing medium enters in reactor from presulfiding of catalyst device outlet, then carries out catalysis dehydrating alkanes under catalytic condition step (1) Suo Shu, prepares alkene, afterwards repeating step (2), (3) again.
Described alkane refers to the alkane containing 2-6 carbon atom.
Raw material after the described preheating of step (1) with axial average apparent gas speed at 0.02-1m/s.
Preferably, the paraffinic feedstock that contains sulfocompound is preheating to 300-550 ° of C through process furnace.
Described sulfocompound comprises H
2s, SO
2deng inorganic sulphide, it can be also the organic sulfide such as mercaptan, thioether; It is preferred, hydrogen sulfide.Sulfocompound (in sulphur) accounts for 5 × 10 of total raw material (comprising sulfocompound and alkane) quality
-4wt%-5wt%, is preferably in 0.05wt%-1wt%.Sulphur in raw material can make-up catalyst the sulphur that runs off of surface, keep the running balance of catalyst surface sulphur, thereby ensure that catalyzer has desirable catalytic dehydrogenation activity and olefine selective.
Preferably, in step (1), be to carry out catalytic dehydrogenation under the condition of 500-650 ° of C in temperature; Preferred, the temperature of propane catalytic dehydrogenation is controlled at 550-650 ° of C, or the temperature of catalytic dehydrogenation of butanes is controlled at 500-610 ° of C.
In step (1), reacted gas, after cyclonic separator is isolated the catalyzer carrying, then separates through product separation system.
Fuel described in step (2) can be any liquid fuel, for example: and gasoline, diesel oil, methyl alcohol, CGO, VGO, residual oil or catalytic slurry etc., but from safety and the angle of avoiding poisoning of catalyst, it is preferred, and described fuel is diesel oil.
Preferably, under the condition of temperature 600-750 ° C, the coke on catalyzer and full combustion of fuel.
Promote medium and adopt air.
In step (2), the gas in revivifier, after cyclonic separator is isolated the catalyzer carrying, enters follow-up smoke energy recovering system.
In step (3), prevulcanized medium comprises hydrogen, the alkane of sulfur-bearing, or both mixtures, or dry gas.From the angle of economy and convenience, the dry gas that contains hydrogen sulfide that certain embodiments generates is ideal.
Described dry gas refers to the C2 that generates in reaction process and the cut below C2 in oil refining industry, and main component is ethane, ethene, methane and hydrogen, is wherein comprising a small amount of hydrogen sulfide, carbon monoxide, carbonic acid gas and a large amount of nitrogen., in addition, due to the problem of separation system separation accuracy, in dry gas, also contain a small amount of C3.All can produce dry gas at catalytic cracking, catalytic pyrolysis, catalytic reforming, delayed coking and hydrocracking process, certainly, certain embodiments also has a small amount of dry gas and generates.In the present invention, pre-vulcanization process uses the dry gas that this dehydrating alkanes generates.
Preferably, the axial superficial linear vilocity of prevulcanized medium in prevulcanized device can not exceed 1m/s.
The mean residence time of catalyzer in prevulcanized device can not exceed 1h, is preferably 1-10min.The temperature of prevulcanized needn't deliberately be controlled.
Circulating fluidized bed successive reaction regeneration dehydrating alkanes device of the present invention, the catalyzer of employing is that application number is the load type metal sulfide catalyst that CN201210536414.7 announces.This catalyzer comprises active constituent, carrier, one or more in described active constituent Fe, Co, Ni, Cu, Zn, Mo, W and Mn element, and in the oxide compound of its maxivalence state, the content in catalyzer is at 0.5～40wt%, and described carrier is SiO
2, Al
2o
3, ZrO
2, La
2o
3, CeO
2, CaO, P
2o
5, Nb
2o
5with mixed oxide or the composite oxides of one or more formation in MgO, content is between 60～99.5wt%, and the surperficial active constituent of described dehydrating alkanes sulfide catalyst exists with sulphided form.
Preferably, the content of described active constituent in catalyzer is between 5～20wt%.
Preferably, the content of described carrier in catalyzer is between 80～95wt%.
Described active constituent is one or more in Fe, Co, Ni, Cu, Zn, Mo, W and Mn element, and the quality proportioning of each component, by the oxide compound of the maxivalence state of each metal, is Fe
2o
3: Co
2o
3: Ni
2o
3: CuO:ZnO:MoO
3: WO
3: MnO
2=(0 ~ 5): (0 ~ 15): (0 ~ 25): (0 ~ 5): (0 ~ 20): (0 ~ 25): (0 ~ 28): (0 ~ 3), preferred, described active constituent is one or more in Fe, Co, Ni, Zn, Mo and W, the quality proportioning of each component, by the oxide compound of the maxivalence state of each metal, be Fe
2o
3: Co
2o
3: Ni
2o
3: ZnO:MoO
3: WO
3for (0 ~ 3): (0 ~ 8): (0 ~ 15): (0 ~ 13): (0 ~ 15): (0 ~ 10).
This catalyzer has the high feature of activity, selectivity that dehydrating alkanes generates corresponding alkene; But the something in common of this catalyzer and the corresponding alkene catalyst of other dehydrating alkanes system is the easy coking and deactivation of catalyzer.In addition, except coking and deactivation, in the dehydrogenation reaction atmosphere of low sulfur content, can there is the loss of sulphur on catalyzer in this sulfide catalyst, and in the coke burning regeneration process of coked catalyst, metallic sulfide can change into metal sulfate or sulphite unavoidably.Therefore, dehydrogenation unit of the present invention, except will introduce a certain amount of sulphur in raw material, reduce outside the loss of catalyzer sulphur in dehydrogenation reaction process, from revivifier catalyzer out, before there is dehydrogenation reaction, in advance through being placed in the presulfiding of catalyst device in dehydrogenation reactor catalyst settling section, thereby make, under reducing atmosphere, metal sulfuric acid or sulphite the regenerated catalyst of coming from revivifier are reduced into metallic sulfide, in addition, also can utilize curing medium that the metal oxide on regenerated catalyst is changed into sulfide.
Compared with prior art, advantage of the present invention is: adopt high reactivity, optionally sulfide type alkane dehydrogenating catalyst of high olefin, catalyzer cheapness, nontoxic; Employing has the circulating fluid bed reactor technology of prevulcanized function, can realize the prevulcanized of dehydrogenation reaction, catalyst regeneration and afterburning and catalyzer and successively carry out, and has increased substantially the production efficiency of device; Especially prevulcanized device is placed in dehydrogenation reactor settling section, be conducive to reduce heat lost by radiation, and the high temperature catalyst after prevulcanized sprays from prevulcanized device top with prevulcanized medium, be conducive to high temperature catalyst being uniformly distributed in dehydrogenation reactor, avoid localized hyperthermia and affect the selectivity of object product.
Brief description of the drawings
The circulating fluidized bed continuous dehydrogenation reaction regeneration device schematic diagram of Fig. 1 embodiment of the present invention 1
1. reactor; 2. grid distributor; 3. raw materials furnace and heating; 4. cyclone separator; 5. reacted mixed gas; 6. flue gas;
7. regenerator sloped tube; 8. inclined tube to be generated; 9. raw material; 10. air; 11. fuel; 12. catalyzer promote transfer lime;
13. catalyst regenerators; 14. presulfiding of catalyst devices; 15. imports; 16. outlets
Embodiment
With embodiment, technical scheme of the present invention is further described below, will contribute to advantage, effect to technical scheme of the present invention to have further understanding, but embodiment does not limit protection scope of the present invention.
As shown in Figure 1, a kind of successive reaction regenerating unit that utilizes sulphurized catalyst to carry out dehydrating alkanes of the present invention, comprise reactor 1, catalyst regenerator 13 and presulfiding of catalyst device 14, reactor 1 promotes transfer lime 12 with catalyst regenerator 13 by catalyzer inclined tube 8 to be generated, catalyzer and is connected, catalyst regenerator 13 is connected by regenerator sloped tube 7 with presulfiding of catalyst device 14, presulfiding of catalyst device 14 comprises import 15, outlet 16, and it exports directly and reactor 1 UNICOM.
Raw material 9, after process furnace 3 preheatings, enters in reactor 1 by multi-jet endless tube, carries out dehydrogenation reaction under the effect of catalyzer, and the cyclone separator 4 that reacted mixed gas is provided with through the top of reactor 1 flows out.It is Y-tube that catalyzer promotes transfer lime 12, inclined tube 8 to be generated is by guiding valve control to be generated, in catalyzer in reactor 1 need to be regenerated, catalyzer promotes transfer lime 12 from the lower end outlet of reactor through inclined tube inflow catalyst to be generated, air 10 from promote transfer lime 12 lower end from upwards pass into, carrying and treating that regenerated catalyst and fuel 11 enter the interior burning of catalyst regenerator 13, flue gas 6 flows out through the cyclone separator 4 of catalyst regenerator 13 interior settings.The catalyzer of having regenerated is entered and in presulfiding of catalyst device 14, is carried out sulfidizing by regenerator sloped tube 7, the outlet 15 of catalyst vulcanization device is in the position apart from reactor top 1/8-1/4 height for reactor and reactor 1 UNICOM, presulfiding of catalyst device 14 is arranged in reactor or outside reactor, this example, presulfiding of catalyst device 14 is arranged in reactor, and is placed in dehydrogenation reactor catalyst settling section.Catalyzer after sulfuration exports 16 through prevulcanized device 14 and enters in reactor 1, again plays catalytic dehydrogenation.So recycle, carry out dehydrating alkanes reaction.
In reactor 1 and catalyst regenerator 13 is interior that two-layer above grid distributor 2 is all set, more preferably, double-layer separate fabric swatch 2 is all set.Described grid distributor 2 is multihole distributor, or grid grid distributor.Grid distributor 2 is also set in presulfiding of catalyst device.
Following examples all adopt the circulating fluidized bed successive reaction regenerating unit shown in Fig. 1 to carry out dehydrating alkanes catalyzed reaction, the application number of submitting to before the applicant that catalyzer uses is the dehydrating alkanes sulfide catalyst described in CN201210536414.7, its median size is 68 μ m, altogether 18kg.
Embodiment 1
The inlet amount of propane feed is 5kg/h, contains hydrogen sulfide in raw material, and its content is counted 0.5wt% with sulphur, and raw material, after process furnace preheating, enters reactor by the endless tube that is provided with multiple nozzles, and double-layer separate fabric swatch is set in reactor, and percentage of open area is 45%.Temperature of reaction is 590 ° of C, and in reactor, under real reaction condition, axially superficial gas velocity is 0.5m/s; Reacted catalyzer enters in revivifier subsequently, the 750 ° of C of temperature control in revivifier, and the postcombustion of catalyzer is diesel oil, and the temperature of revivifier is controlled by the amount of diesel oil, and the mean residence time of catalyzer in revivifier is 9min.Regenerated catalyst is entered in the built-in prevulcanized device of reactor by regenerator sloped tube subsequently, and mean residence time is 5min, and prevulcanized medium adopts hydrogen sulfide and hydrogen, and the content of hydrogen sulfide is counted 0.3wt% with sulphur.
Composition in propane feed is as in table 1, and the products distribution after catalytic dehydrogenation is as in table 2, and conversion of propane is 47.50wt%, and Propylene Selectivity is 81.54wt%.
Embodiment 2
The raw material of the present embodiment is containing Trimethylmethane, and it forms as in table 1, when dehydrogenation reaction, temperature of reaction is 560 ° of C, and in reactor, axially superficial gas velocity is 0.35m/s, and except above-mentioned difference, other technical process and processing parameter are as being shown in embodiment 1.Products distribution after catalytic dehydrogenation is as in table 2, and Trimethylmethane transformation efficiency is 65.59wt%, and the selectivity of iso-butylene is 84.51wt%.
Embodiment 3
The inlet amount of propane (composition in propane feed as in table 1) raw material is 5kg/h, in raw material, contain hydrogen sulfide, its content is counted 1.0wt% with sulphur, raw material is preheating to 400 ° of C through process furnace, enter reactor by the endless tube that is provided with multiple nozzles, double-layer separate fabric swatch is set in reactor, and percentage of open area is 45%.Temperature of reaction is 650 ° of C, and in reactor, under real reaction condition, axially superficial gas velocity is 0.02m/s; Reacted catalyzer enters in revivifier subsequently, the 550 ° of C of temperature control in revivifier, and the postcombustion of catalyzer is diesel oil, and the temperature of revivifier is controlled by the amount of diesel oil, and the mean residence time of catalyzer in revivifier is 9min.Regenerated catalyst is entered in the built-in prevulcanized device of reactor by regenerator sloped tube subsequently, and its axial superficial linear vilocity is 0.02m/s, and mean residence time is 10min, and prevulcanized medium adopts hydrogen sulfide and hydrogen, and the content of hydrogen sulfide is counted 0.3wt% with sulphur.
Embodiment 4
The inlet amount of propane (composition in propane feed as in table 1) raw material is 5kg/h, in raw material, contain hydrogen sulfide, its content is counted 0.05wt% with sulphur, raw material is preheating to 100 ° of C through process furnace, enter reactor by the endless tube that is provided with multiple nozzles, double-layer separate fabric swatch is set in reactor, and percentage of open area is 45%.Temperature of reaction is 550 ° of C, and in reactor, under real reaction condition, axially superficial gas velocity is 1.0m/s; Reacted catalyzer enters in revivifier subsequently, the 800 ° of C of temperature control in revivifier, and the postcombustion of catalyzer is diesel oil, and the temperature of revivifier is controlled by the amount of diesel oil, and the mean residence time of catalyzer in revivifier is 6min.Regenerated catalyst is entered in the built-in prevulcanized device of reactor by regenerator sloped tube subsequently, and its axial superficial linear vilocity is 0.02m/s, and mean residence time is 20min, and prevulcanized medium adopts hydrogen sulfide and hydrogen, and the content of hydrogen sulfide is counted 0.3wt% with sulphur.
Embodiment 5
The inlet amount of Trimethylmethane (composition in propane feed as in table 1) raw material is 5kg/h, contains SO in raw material
2, hydrogen, its content is counted 0.0005wt% with sulphur, raw material is preheating to 300 ° of C through process furnace, enters reactor by the endless tube that is provided with multiple nozzles, and double-layer separate fabric swatch is set in reactor, percentage of open area is 45%.Temperature of reaction is 610 ° of C, and in reactor, under real reaction condition, axially superficial gas velocity is 0.05m/s; Reacted catalyzer enters in revivifier subsequently, the 700 ° of C of temperature control in revivifier, and the postcombustion of catalyzer is methyl alcohol, and the temperature of revivifier is controlled by the amount of diesel oil, and the mean residence time of catalyzer in revivifier is 6min.Regenerated catalyst is entered in the built-in prevulcanized device of reactor by regenerator sloped tube subsequently, and its axial superficial linear vilocity is 0.02m/s, and mean residence time is 60min, and prevulcanized medium adopts hydrogen sulfide and hydrogen, and the content of hydrogen sulfide is counted 0.3wt% with sulphur.
Embodiment 6
The inlet amount of Trimethylmethane (composition in propane feed as in table 1) raw material is 5kg/h, contains SO in raw material
2, hydrogen, its content is counted 5wt% with sulphur, raw material is preheating to 450 ° of C through process furnace, enters reactor by the endless tube that is provided with multiple nozzles, and double-layer separate fabric swatch is set in reactor, percentage of open area is 45%.Temperature of reaction is 500 ° of C, and in reactor, under real reaction condition, axially superficial gas velocity is 0.03m/s; Reacted catalyzer enters in revivifier subsequently, the 600 ° of C of temperature control in revivifier, and the postcombustion of catalyzer is methyl alcohol, and the temperature of revivifier is controlled by the amount of diesel oil, and the mean residence time of catalyzer in revivifier is 6min.Regenerated catalyst is entered in the built-in prevulcanized device of reactor by regenerator sloped tube subsequently, and its axial superficial linear vilocity is 0.02m/s, and mean residence time is 1min, and prevulcanized medium adopts hydrogen sulfide and hydrogen, and the content of hydrogen sulfide is counted 0.3wt% with sulphur.
The raw material composition (wt%) of table 1 embodiment 1～2
The dehydrogenation product distribution (wt%) of table 2 embodiment 1～2
Claims (10)
1. a successive reaction regenerating unit that utilizes sulphurized catalyst to carry out dehydrating alkanes, comprise reactor, catalyst regenerator and presulfiding of catalyst device, reactor promotes transfer lime with catalyst regenerator by catalyzer inclined tube to be generated, catalyzer and is connected, catalyst regenerator is connected by regenerator sloped tube with presulfiding of catalyst device, presulfiding of catalyst device comprises import, outlet, and it exports directly and reactor UNICOM.
2. successive reaction regenerating unit according to claim 1, is characterized in that, the outlet of described catalyst vulcanization device is in the position apart from reactor top 1/8-1/4 height for reactor and reactor UNICOM.
3. successive reaction regenerating unit according to claim 1, is characterized in that, described presulfiding of catalyst device is arranged in reactor or outside reactor; It is preferred, and presulfiding of catalyst device is arranged in reactor; More preferably, agent prevulcanized device is arranged in reactor, and is placed in dehydrogenation reactor catalyst settling section, and described settling section is positioned at reactor top, accounts for the 1/4-1/2 of whole height for reactor.
4. utilize the successive reaction regenerating unit of the dehydrating alkanes described in claim 1-3 any one to carry out a dehydrating alkanes reaction, comprise the steps:
(1) paraffinic feedstock that contains sulfocompound is preheating to 70-700 ° of C through process furnace, preferably 300-550 ° of C, then, the speed that the raw material after preheating is not more than 3m/s with axial average apparent gas speed enters in reactor, is to carry out catalytic dehydrogenation under the condition of 350-700 ° of C in temperature;
(2) reacted catalyzer enters into catalyzer through inclined tube to be generated and promotes transfer lime, above catalyzer feed opening, spray into fuel, promoting medium enters from promoting transfer lime lower end, carrying catalyzer and fuel enters in catalyst regenerator through promoting transfer lime, under the condition of temperature 550-800 ° C, coke on catalyzer and full combustion of fuel, make the catalyst regeneration of inactivation; It is preferred, under the condition of temperature 600-750 ° C, and the coke on catalyzer and full combustion of fuel;
(3) regenerated catalyst is in regenerator sloped tube enters presulfiding of catalyst device, prevulcanized medium enters in prevulcanized device through the import of prevulcanized device lower end, carry out vulcanization reaction with regenerated catalyst, the axial superficial linear vilocity of prevulcanized medium in prevulcanized device can not exceed 3m/s;
(4) catalyzer after prevulcanized is along with curing medium enters in reactor from presulfiding of catalyst device outlet, then carries out catalysis dehydrating alkanes under catalytic condition step (1) Suo Shu, prepares alkene, afterwards repeating step (2), (3) again.
5. dehydrating alkanes according to claim 4 reaction, is characterized in that, the raw material after the described preheating of step (1) with axial average apparent gas speed at 0.02-1m/s.
6. according to the dehydrating alkanes reaction described in claim 4 or 5, it is characterized in that, sulfocompound accounts for 5 × 10 of total raw material quality in sulphur
-4wt%-5wt%, is preferably in 0.05wt%-1wt%, and described raw material comprises sulfocompound and alkane.
7. according to the dehydrating alkanes reaction described in claim 4-6 any one, it is characterized in that, in step (1), is to carry out catalytic dehydrogenation under the condition of 500-650 ° of C in temperature; Preferably, the temperature of propane catalytic dehydrogenation is controlled at 550-650 ° of C, or the temperature of catalytic dehydrogenation of butanes is controlled at 500-610 ° of C.
8. dehydrating alkanes reaction according to claim 4, is characterized in that, in step (3), the axial superficial linear vilocity of prevulcanized medium in prevulcanized device can not exceed 1m/s.
9. dehydrating alkanes reaction according to claim 4, is characterized in that, in step (3), the mean residence time of catalyzer in prevulcanized device can not exceed 1h, and it is preferred, is 1-10min.
10. dehydrating alkanes reaction according to claim 4, is characterized in that, the described sulfocompound of step (1) comprises H
2s, SO
2, mercaptan is or/and thioether, it is preferred, hydrogen sulfide; Fuel described in step (2) comprises gasoline, diesel oil, methyl alcohol, CGO, VGO, residual oil or catalytic slurry, and it is preferred, and described fuel is diesel oil; In step (3), prevulcanized medium comprises hydrogen, the alkane containing element sulphur, or both mixtures, or dry gas, its preferred dry gas.
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| CN109107615A (en) * | 2017-06-23 | 2019-01-01 | 中国石油大学(华东) | A kind of alkane dehydrogenating catalyst regeneration method and regenerating unit |
| CN109499486A (en) * | 2017-09-14 | 2019-03-22 | 中国石油大学(华东) | A kind of alkane catalytic dehydrogenation or producing olefin hydrocarbon by catalytic pyrolysis circulating fluid bed reaction device |
| CN109499485A (en) * | 2017-09-14 | 2019-03-22 | 中国石油大学(华东) | A kind of dehydrating alkanes-cracking olefin recycle fluidized bed reaction |
| CN110234432A (en) * | 2016-12-20 | 2019-09-13 | 环球油品有限责任公司 | Method for managing the sulphur on catalyst in light paraffins certain embodiments |
| CN110382449A (en) * | 2017-03-17 | 2019-10-25 | 托普索公司 | Dehydrating alkanes at the method for alkene and are used for the catalyst based on iron of this method |
| CN110614120A (en) * | 2018-06-20 | 2019-12-27 | 中国石油化工股份有限公司 | Non-noble metal isobutane dehydrogenation catalyst, preparation method thereof and method for preparing isobutene through isobutane dehydrogenation |
| EP3705466A3 (en) * | 2015-06-26 | 2020-10-14 | Dow Global Technologies Llc | A fluid solids contacting device |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1160603A (en) * | 1996-01-17 | 1997-10-01 | 欧洲催化剂加工公司 | Process for incorporating sulfur into pores of hydrocarbon treatment catalyst |
| WO2001044146A1 (en) * | 1999-12-17 | 2001-06-21 | Dow Global Technologies Inc. | Dehydrogenation of an alkyl aromatic compound and catalyst regeneration in a fluidized bed reactor |
| US20100234660A1 (en) * | 2007-08-03 | 2010-09-16 | Uhde Gmbh | Regeneration of catalysts for dehydrating alkanes |
| CN102451677A (en) * | 2011-05-13 | 2012-05-16 | 中国石油大学(华东) | Catalyst for alkane dehydrogenation and device |
-
2013
- 2013-01-15 CN CN201310014789.1A patent/CN103922880B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1160603A (en) * | 1996-01-17 | 1997-10-01 | 欧洲催化剂加工公司 | Process for incorporating sulfur into pores of hydrocarbon treatment catalyst |
| WO2001044146A1 (en) * | 1999-12-17 | 2001-06-21 | Dow Global Technologies Inc. | Dehydrogenation of an alkyl aromatic compound and catalyst regeneration in a fluidized bed reactor |
| US20100234660A1 (en) * | 2007-08-03 | 2010-09-16 | Uhde Gmbh | Regeneration of catalysts for dehydrating alkanes |
| CN102451677A (en) * | 2011-05-13 | 2012-05-16 | 中国石油大学(华东) | Catalyst for alkane dehydrogenation and device |
Cited By (10)
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|---|---|---|---|---|
| EP3705466A3 (en) * | 2015-06-26 | 2020-10-14 | Dow Global Technologies Llc | A fluid solids contacting device |
| EP3848343A1 (en) * | 2015-06-26 | 2021-07-14 | Dow Global Technologies LLC | Process for heating and conditioning a deactivated catalyst |
| CN110234432A (en) * | 2016-12-20 | 2019-09-13 | 环球油品有限责任公司 | Method for managing the sulphur on catalyst in light paraffins certain embodiments |
| CN110382449A (en) * | 2017-03-17 | 2019-10-25 | 托普索公司 | Dehydrating alkanes at the method for alkene and are used for the catalyst based on iron of this method |
| CN109107615A (en) * | 2017-06-23 | 2019-01-01 | 中国石油大学(华东) | A kind of alkane dehydrogenating catalyst regeneration method and regenerating unit |
| CN109107615B (en) * | 2017-06-23 | 2021-07-09 | 中国石油大学(华东) | Regeneration method and regeneration device for alkane dehydrogenation catalyst |
| CN109499486A (en) * | 2017-09-14 | 2019-03-22 | 中国石油大学(华东) | A kind of alkane catalytic dehydrogenation or producing olefin hydrocarbon by catalytic pyrolysis circulating fluid bed reaction device |
| CN109499485A (en) * | 2017-09-14 | 2019-03-22 | 中国石油大学(华东) | A kind of dehydrating alkanes-cracking olefin recycle fluidized bed reaction |
| CN109499485B (en) * | 2017-09-14 | 2021-11-23 | 中国石油大学(华东) | Circulating fluidized bed reaction device for preparing olefin by alkane dehydrogenation-cracking |
| CN110614120A (en) * | 2018-06-20 | 2019-12-27 | 中国石油化工股份有限公司 | Non-noble metal isobutane dehydrogenation catalyst, preparation method thereof and method for preparing isobutene through isobutane dehydrogenation |
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