CN103922880B - A kind of successive reaction regenerating unit utilizing sulphurized catalyst to carry out dehydrating alkanes - Google Patents
A kind of successive reaction regenerating unit utilizing sulphurized catalyst to carry out dehydrating alkanes Download PDFInfo
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- CN103922880B CN103922880B CN201310014789.1A CN201310014789A CN103922880B CN 103922880 B CN103922880 B CN 103922880B CN 201310014789 A CN201310014789 A CN 201310014789A CN 103922880 B CN103922880 B CN 103922880B
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Abstract
A kind of successive reaction regenerating unit utilizing 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 prevulcanized adopting this regenerating unit can realize dehydrogenation reaction, catalyst regeneration and afterburning and catalyzer is successively carried out, and has increased substantially the production efficiency of 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 utilizing sulphurized catalyst to carry out dehydrating alkanes.
Background technology
Propane, butane dehydrogenation change into the reaction heat of corresponding alkene at about 120kJ/mol, strong endothermic reaction.In addition, in propane, catalytic dehydrogenation of butanes reaction process, catalyzer meeting coking deactivation, some catalyzer dozens of minutes just need coke burning regeneration, within tens hours that have, carry out coke burning regeneration.For such reaction system, adopt fixed-bed reactor, one is that beds heat transfer efficiency is low, is not easy to the timely heat supply of reaction; Two is that catalyzer needs frequent coke burning regeneration, and reaction and the switching of reproduced state, not only will adjust 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 simple, and the such strong heat absorption of propane, butane dehydrogenation, catalyzer are needed to the reaction system of frequent coke burning regeneration, it is very inconvenient to operate, and there is potential safety hazard.
Moving-burden bed reactor is adopted to carry out catalytic dehydrogenation, although achieve reaction and the carrying out continuously of catalyzer coke burning regeneration; But heat transfer character and the fixed bed of moving-burden bed reactor are identical, solid catalyst, except pure metal catalyst, be all the poor conductor of heat, thus, how 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 carry out reaction and catalyzer coke burning regeneration continuously, more rare, and the heat that high temperature regeneration agent can be utilized to carry meets the dehydrogenation reaction of heat absorption to the demand of 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.Wearing and tearing, broken granules of catalyst, to a certain extent little, such as less than 10 μm, cyclonic separator just cannot be reclaimed.Reclaim the particle of not returning from the cyclonic separator of reactive system, will the separation system of gas be entered into; Reclaim the particle of not returning from the cyclonic separator of regeneration system rapidly, will flue gas be entered into.Catalyzer is this runs the existence damaging phenomenon, 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, according to circulating fluidized bed, can not supported Pt catalysts be used, because its expensive, can not with poisonous loading type Cr
2o
3catalyzer, pollutes the environment because run the catalyzer damaged, even if can all reclaim, also there is a difficult problem for harmless treatment aspect.
In order to high efficiency circulating fluid bed reactor being applied in propane, butane dehydrogenation reaction, we successively develop and are suitable for nontoxic, non-noble metal oxide dehydrogenation catalyst that circulating fluid bed reactor uses and nontoxic, non-noble metal sulfided thing catalyzer, and the maintained catalyzer that the present invention be directed to nontoxic, non-noble metal sulfided thing catalyst development is in the circulating fluid bed reaction device of the successive reaction of sulfided state, catalyst regeneration and sulfuration.
Summary of the invention
The object of this invention is to provide a kind of successive reaction regenerating unit utilizing sulphurized catalyst to carry out dehydrating alkanes, this device has the circulating fluid bed reactor technology of prevulcanized function, the prevulcanized that can realize dehydrogenation reaction, catalyst regeneration and afterburning and catalyzer is successively carried out, and has increased substantially the production efficiency of device.
For realizing goal of the invention of the present invention, a kind of successive reaction regenerating unit utilizing 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 of distance 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, due to the position UNICOM with it that its outlet is distance 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 integrated distribution to cause nonselective thermal response in a certain local of dehydrogenation reactor.
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 reducing heat lost by radiation, reduce the energy consumption of device.
In reactor and in catalyst regenerator, all grid distributor is 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-particle two-phase, improves reaction efficiency.
In presulfiding of catalyst device, also grid distributor is set.
The top of reactor is provided with cyclone separator, separation system, equally, in catalyst regenerator, also arranges cyclone separator.
Inclined tube to be generated and regenerator sloped tube are 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 containing 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 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, fuel is sprayed into above catalyzer feed opening, promote medium to enter from lifting transfer lime lower end, carrying catalyzer and fuel enters in catalyst regenerator through promoting transfer lime, under the condition of temperature 550-800 ° of C, coke on catalyzer and full combustion of fuel, make the catalyst regeneration of inactivation;
(3) regenerated catalyst enters in presulfiding of catalyst device through regenerator sloped tube, the import of prevulcanized medium through prevulcanized device lower end enters in prevulcanized device, carry out vulcanization reaction with regenerated catalyst, the axial superficial linear vilocity of prevulcanized medium in prevulcanized device can not more than 3m/s;
(4) catalyzer after prevulcanized enters in reactor from the outlet of presulfiding of catalyst device along with curing medium, then carries out catalysis dehydrating alkanes under the catalytic condition described in step (1), prepares alkene, afterwards repeating step (2), (3) again.
Described alkane refers to the alkane containing 2-6 carbon atom.
Raw material after preheating described in step (1) is fast at 0.02-1m/s with axial average apparent gas.
Preferably, the paraffinic feedstock containing sulfocompound is preheating to 300-550 ° of C through process furnace.
Described sulfocompound comprises H
2s, SO
2deng inorganic sulphide, it also can be 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%, preferably at 0.05wt%-1wt%.Sulphur in the feed can the sulphur that runs off of make-up catalyst surface, keeps the running balance of catalyst surface sulphur, thus ensure that catalyzer has the active and olefine selective of desirable catalytic dehydrogenation.
Preferably, in step (1), in temperature be 500-650 ° of C condition under carry out catalytic dehydrogenation; Preferred, the temperature of propane catalytic dehydrogenation controls at 550-650 ° of C, or the temperature of catalytic dehydrogenation of butanes controls at 500-610 ° of C.
In step (1), reacted gas is isolated after the catalyzer carried through cyclonic separator, then is separated through product separation system.
Fuel described in step (2) can be any liquid fuel, and such as: gasoline, diesel oil, methyl alcohol, CGO, VGO, residual oil or catalytic slurry etc., but from safety and the angle avoiding poisoning of catalyst, it is preferred, and described fuel is diesel oil.
Preferably, under the condition of temperature 600-750 ° of C, the coke on catalyzer and full combustion of fuel.
Promote medium and adopt air.
In step (2), the gas in revivifier is isolated after the catalyzer carried through cyclonic separator, 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 containing hydrogen sulfide that certain embodiments generates is ideal.
Described dry gas refers to the cut of C2 and below the C2 generated in reaction process in oil refining industry, and main component is ethane, ethene, methane and hydrogen, wherein contains 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, also containing a small amount of C3 in dry gas.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 more than 1m/s.
The mean residence time of catalyzer in prevulcanized device can not exceed 1h, is preferably 1-10min.The temperature of prevulcanized need not deliberately control.
Circulating fluidized bed successive reaction regeneration dehydrating alkanes device of the present invention, the catalyzer of employing is 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 with the oxide basis of its maxivalence state, content is in the catalyst 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
5the mixed oxide formed with one or more in MgO or composite oxides, content is between 60 ~ 99.5wt%, and the active constituent on the surface of described dehydrating alkanes sulfide catalyst exists with sulphided form.
Preferably, described active constituent content is in the catalyst between 5 ~ 20wt%.
Preferably, described carrier content is in the catalyst between 80 ~ 95wt%.
Described active constituent is one or more in Fe, Co, Ni, Cu, Zn, Mo, W and Mn element, the quality proportioning of each component, by the oxide basis 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 basis 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 dehydrating alkanes and generates the activity of corresponding alkene, feature that selectivity is high; But the something in common of this catalyzer alkene catalyst corresponding to 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 a certain amount of sulphur will be introduced in the feed, reduce outside the loss of catalyzer sulphur in dehydrogenation reaction process, from revivifier catalyzer out, before generation dehydrogenation reaction, presulfiding of catalyst device in advance through being placed in dehydrogenation reactor catalyst settling section, thus make under reducing atmosphere the metal sulfate on the regenerated catalyst of coming from revivifier or sulphite to be reduced into metallic sulfide, in addition, curing medium also can be utilized the convert metal oxides sulphidisation on regenerated catalyst.
Compared with prior art, advantage of the present invention is: the sulfide type alkane dehydrogenating catalyst adopting high reactivity, high olefin selectivity, and catalyzer is cheap, nontoxic; Adopt the circulating fluid bed reactor technology with prevulcanized function, the prevulcanized that can realize dehydrogenation reaction, catalyst regeneration and afterburning and catalyzer is successively carried out, and has increased substantially the production efficiency of device; Especially prevulcanized device is placed in dehydrogenation reactor settling section, be conducive to reducing 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.
Accompanying drawing explanation
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
By embodiment, technical scheme of the present invention is further described below, the advantage contributed to technical scheme of the present invention, effect are had and further understands, but embodiment does not limit protection scope of the present invention.
As shown in Figure 1, a kind of successive reaction regenerating unit utilizing 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 preheating, enters in reactor 1 by multi-jet endless tube, under the effect of catalyzer, carries out dehydrogenation reaction, 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 controlled by guiding valve to be generated, in catalyzer in reactor 1 needs regeneration, catalyzer promotes transfer lime 12 from the lower end outlet of reactor through inclined tube inflow catalyst to be generated, air 10 upwards passes into from the lower end promoting transfer lime 12 from upper, carry catalyzer to be regenerated and fuel 11 enters catalyst regenerator 13 combustion, the cyclone separator 4 that flue gas 6 is arranged in catalyst regenerator 13 flows out.The catalyzer regenerated is entered in presulfiding of catalyst device 14 by regenerator sloped tube 7 and carries out sulfidizing, the outlet 15 of catalyst vulcanization device is in the position of distance 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.
Two-layer above grid distributor 2 is all set in reactor 1 and in catalyst regenerator 13, more preferably, double-layer separate fabric swatch 2 is all set.Described grid distributor 2 is multihole distributor, or grid grid distributor.In presulfiding of catalyst device, grid distributor 2 is also set.
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 the submit of the applicant that catalyzer uses is the dehydrating alkanes sulfide catalyst described in CN201210536414.7, its median size is 68 μm, altogether 18kg.
Embodiment 1
The inlet amount of propane feed is 5kg/h, and containing hydrogen sulfide in raw material, its content counts 0.5wt% with sulphur, and raw material, after process furnace preheating, enters reactor by the endless tube being provided with multiple nozzle, and arrange double-layer separate fabric swatch in reactor, percentage of open area is 45%.Temperature of reaction is 590 ° of C, and in reactor, under real reaction condition, axial superficial gas velocity is 0.5m/s; Reacted catalyzer enters in revivifier subsequently, and the temperature in revivifier controls 750 ° of C, 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 counts 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, during dehydrogenation reaction, temperature of reaction is 560 ° of C, and in reactor, axial 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, containing hydrogen sulfide in raw material, its content counts 1.0wt% with sulphur, raw material is preheating to 400 ° of C through process furnace, reactor is entered by the endless tube being provided with multiple nozzle, arrange double-layer separate fabric swatch in reactor, percentage of open area is 45%.Temperature of reaction is 650 ° of C, and in reactor, under real reaction condition, axial superficial gas velocity is 0.02m/s; Reacted catalyzer enters in revivifier subsequently, and the temperature in revivifier controls 550 ° of C, 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 counts 0.3wt% with sulphur.
Embodiment 4
The inlet amount of propane (composition in propane feed as in table 1) raw material is 5kg/h, containing hydrogen sulfide in raw material, its content counts 0.05wt% with sulphur, raw material is preheating to 100 ° of C through process furnace, reactor is entered by the endless tube being provided with multiple nozzle, arrange double-layer separate fabric swatch in reactor, percentage of open area is 45%.Temperature of reaction is 550 ° of C, and in reactor, under real reaction condition, axial superficial gas velocity is 1.0m/s; Reacted catalyzer enters in revivifier subsequently, and the temperature in revivifier controls 800 ° of C, 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 counts 0.3wt% with sulphur.
Embodiment 5
The inlet amount of Trimethylmethane (composition in propane feed as in table 1) raw material is 5kg/h, containing SO in raw material
2, hydrogen, its content counts 0.0005wt% with sulphur, and raw material is preheating to 300 ° of C through process furnace, enters reactor by the endless tube being provided with multiple nozzle, and arrange double-layer separate fabric swatch in reactor, percentage of open area is 45%.Temperature of reaction is 610 ° of C, and in reactor, under real reaction condition, axial superficial gas velocity is 0.05m/s; Reacted catalyzer enters in revivifier subsequently, and the temperature in revivifier controls 700 ° of C, 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 counts 0.3wt% with sulphur.
Embodiment 6
The inlet amount of Trimethylmethane (composition in propane feed as in table 1) raw material is 5kg/h, containing SO in raw material
2, hydrogen, its content counts 5wt% with sulphur, and raw material is preheating to 450 ° of C through process furnace, enters reactor by the endless tube being provided with multiple nozzle, and arrange double-layer separate fabric swatch in reactor, percentage of open area is 45%.Temperature of reaction is 500 ° of C, and in reactor, under real reaction condition, axial superficial gas velocity is 0.03m/s; Reacted catalyzer enters in revivifier subsequently, and the temperature in revivifier controls 600 ° of C, 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 counts 0.3wt% with sulphur.
Raw material composition (wt%) of table 1 embodiment 1 ~ 2
Dehydrogenation product distribution (wt%) of table 2 embodiment 1 ~ 2
Claims (18)
1. a dehydrating alkanes reaction, comprises the steps:
(1) paraffinic feedstock containing sulfocompound is preheating to 70-700 DEG 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 carry out catalytic dehydrogenation under the condition of 350-700 DEG C in temperature;
(2) reacted catalyzer enters into catalyzer through inclined tube to be generated and promotes transfer lime, fuel is sprayed into above catalyzer feed opening, promote medium to enter from lifting transfer lime lower end, carrying catalyzer and fuel enters in catalyst regenerator through promoting transfer lime, under the condition of temperature 550-800 DEG C, coke on catalyzer and full combustion of fuel, make the catalyst regeneration of inactivation;
(3) regenerated catalyst enters in presulfiding of catalyst device through regenerator sloped tube, the import of prevulcanized medium through prevulcanized device lower end enters in prevulcanized device, carry out vulcanization reaction with regenerated catalyst, the axial superficial linear vilocity of prevulcanized medium in prevulcanized device can not more than 3m/s;
(4) catalyzer after prevulcanized along with curing medium from presulfiding of catalyst device outlet enter in reactor, catalysis dehydrating alkanes is carried out again under the catalytic condition described in step (1), prepare alkene, afterwards repeating step (2), (3) again.
2. dehydrating alkanes reaction according to claim 1, is characterized in that, the raw material after the preheating described in step (1) is fast at 0.02-1m/s with axial average apparent gas.
3. dehydrating alkanes reaction according to claim 1 and 2, it is characterized in that, sulfocompound accounts for 5 × 10 of total raw material quality in sulphur
-4wt%-5wt%, described raw material comprises sulfocompound and alkane.
4. dehydrating alkanes reaction according to claim 1 and 2, it is characterized in that, in step (1), be carry out catalytic dehydrogenation under the condition of 500-650 DEG C in temperature.
5. dehydrating alkanes reaction according to claim 1, it is characterized in that, in step (3), the axial superficial linear vilocity of prevulcanized medium in prevulcanized device can not more than 1m/s.
6. dehydrating alkanes reaction according to claim 1 or 5, it is characterized in that, in step (3), the mean residence time of catalyzer in prevulcanized device can not exceed 1h.
7. dehydrating alkanes reaction according to claim 1, it is characterized in that, the sulfocompound described in step (1) comprises H
2s, SO
2, mercaptan is or/and thioether; Fuel described in step (2) comprises gasoline, diesel oil, methyl alcohol, CGO, VGO, residual oil or catalytic slurry; In step (3), prevulcanized medium comprises hydrogen, alkane containing element sulphur, or both mixtures, or dry gas.
8. dehydrating alkanes reaction according to claim 1, it is characterized in that, the paraffinic feedstock containing sulfocompound is preheating to 300-550 DEG C through process furnace.
9. dehydrating alkanes reaction according to claim 1, is characterized in that, under the condition of temperature 600-750 DEG C, and the coke on catalyzer and full combustion of fuel.
10. dehydrating alkanes reaction according to claim 3, it is characterized in that, sulfocompound accounts for the 0.05wt%-1wt% of total raw material quality in sulphur.
11. dehydrating alkanes reactions according to claim 4, it is characterized in that, the temperature of propane catalytic dehydrogenation controls at 550-650 DEG C, or the temperature of catalytic dehydrogenation of butanes controls at 500-610 DEG C.
12. dehydrating alkanes reactions according to claim 6, it is characterized in that, in step (3), the mean residence time of catalyzer in prevulcanized device is 1-10min.
13. dehydrating alkanes reactions according to claim 7, it is characterized in that, the sulfocompound described in step (1) comprises hydrogen sulfide; Fuel described in step (2) is diesel oil; In step (3), prevulcanized medium comprises dry gas.
14. 1 kinds of successive reaction regenerating units utilizing sulphurized catalyst to carry out the dehydrating alkanes reaction described in any one of claim 1-13, 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.
15. successive reaction regenerating units according to claim 14, is characterized in that, the outlet of described catalyst vulcanization device is in the position of distance reactor top 1/8-1/4 height for reactor and reactor UNICOM.
16. successive reaction regenerating units according to claim 14, is characterized in that, described presulfiding of catalyst device is arranged in reactor or outside reactor.
17. successive reaction regenerating units according to claim 16, it is characterized in that, presulfiding of catalyst device is arranged in reactor.
18. successive reaction regenerating units according to claim 16, it is characterized in that, presulfiding of catalyst device is arranged in reactor, and is placed in dehydrogenation reactor catalyst settling section, described settling section is positioned at reactor top, accounts for the 1/4-1/2 of whole height for reactor.
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|---|---|---|---|---|
| US9815040B2 (en) * | 2015-06-26 | 2017-11-14 | Dow Global Technologies Llc | Fluid solids contacting device |
| 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 |
| EP3596032A1 (en) * | 2017-03-17 | 2020-01-22 | Haldor Topsøe A/S | A process for the dehydrogenation of alkanes to alkenes and iron-based catalysts for use in the process |
| 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 |
| 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 |
| CN109499486B (en) * | 2017-09-14 | 2022-05-17 | 中国石油大学(华东) | Circulating fluidized bed reaction device for preparing olefin by catalytic dehydrogenation or catalytic cracking of alkane |
| 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 |
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 |
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