CN115350652A - Fluidized bed propane dehydrogenation device using dehydrogenation catalyst and process thereof - Google Patents

Fluidized bed propane dehydrogenation device using dehydrogenation catalyst and process thereof Download PDF

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CN115350652A
CN115350652A CN202210932719.3A CN202210932719A CN115350652A CN 115350652 A CN115350652 A CN 115350652A CN 202210932719 A CN202210932719 A CN 202210932719A CN 115350652 A CN115350652 A CN 115350652A
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reactor
catalyst
dehydrogenation
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regeneration
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CN115350652B (en
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韩伟
潘相米
梁衡
艾珍
李扬
张军
李博
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Southwest Research and Desigin Institute of Chemical Industry
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Abstract

The invention belongs to the technical field of propylene preparation by propane dehydrogenation, and particularly relates to a fluidized bed propane dehydrogenation device using a dehydrogenation catalyst and a process thereof. The catalyst used in the process is environment-friendly high-strength Ga/Al 2 O 3 The microsphere based dehydrogenation catalyst has relatively stable high alkane conversion rate and high propylene selectivity. The fluidized bed process of the invention comprises relatively independent dehydrogenation, regeneration and reduction reactors, and the catalyst flows among the three reactors in sequence to complete the dehydrogenation process cycle of reaction-regeneration-reduction-reaction. The invention adopts a novel catalyst system to be matched with a novel fluidized bed reaction system for propane dehydrogenation, has excellent propane dehydrogenation performance, and has very stable catalyst regeneration performance.

Description

Fluidized bed propane dehydrogenation device using dehydrogenation catalyst and process thereof
Technical Field
The invention belongs to the technical field of propylene preparation by propane dehydrogenation, and particularly relates to a fluidized bed propane dehydrogenation device using a dehydrogenation catalyst and a process thereof.
Background
The current worldwide large-scale industrialized propane hydrocarbon dehydrogenation technologies mainly comprise an Oleflex moving bed process of U.S. UOP and a fixed bed Catofin process of ABB Lummus company, wherein the former adopts Pt-Sn/Al 2 O 3 Catalyst the latter of which is Cr 2 O 3 /Al 2 O 3 A catalyst. The Oleflex technology adopts a mode of connecting a plurality of moving bed reactors in series for production, and has complex technological process and great operation difficulty; in addition, high Pt-Sn/Al content is adopted 2 O 3 The catalyst is expensive, and needs chlorine regeneration treatment when being deactivated for regeneration, thereby improving the equipment investment cost. The Catofin process adopts a plurality of fixed bed reactors, the switching operation is frequent, and Cr series catalysts not onlyHas high toxicity and large dosage, and is not friendly to the environment. In view of the problems related to the catalyst in the production process technology, the propane dehydrogenation catalyst of a non-Cr system and a process system thereof are researched at home and abroad, and important achievements are obtained.
Chinese patents CN 112844445A, CN109289908A and CN109675548A provide a molecular sieve based propane dehydrogenation catalyst; CN 109939688A provides an iron gallium base propane dehydrogenation catalyst; CN109382090A provides a molybdenum-vanadium bimetallic oxide catalyst and a preparation method thereof; CN 102451677, CN104610768 and CN105289622 provide a series of Al 2 O 3 、SiO 2 、ZrO 2 、TiO 2 And an alkane dehydrogenation catalyst with MgO as a carrier and various metals as active components. The catalyst carrier and the active component in the above patent are greatly different, and the dehydrogenation performance of the catalyst is greatly different: the propane conversion rate and the propylene selectivity, the stabilization time and the deactivation rate are different, so that the dehydrogenation processes corresponding to the catalytic systems are different inevitably.
Disclosure of Invention
The invention provides a high-efficiency dehydrogenation catalyst and a fluidized bed propane dehydrogenation device matched with the catalyst in characteristics, when part of the catalyst in a regenerator is insufficiently burned, the incompletely burned catalyst can be input to the bottom of the regenerator again through an internal circulation pipe for burning regeneration; when part of the catalyst in the reducer is insufficiently reduced, the incompletely reduced catalyst can be fed into the bottom of the reducer again through the internal circulation pipe for reduction and regeneration.
It is another object of the present invention to provide a fluid bed propane dehydrogenation process and a compatible high efficiency dehydrogenation catalyst utilizing the above apparatus. In the process, a high-speed circulating fluidized bed dehydrogenation technology is adopted, so that the reaction can be continuously carried out, the equipment investment is low, and the investment cost is 10-20% lower than that of the prior art in the same scale.
In order to achieve the above purpose, the invention adopts the technical scheme that:
a fluidized bed propane dehydrogenation device comprises a dehydrogenation reactor, a regeneration reactor and a reduction reactor; a dehydrogenation reaction zone is arranged in a dehydrogenation reactor, a primary separation device of the dehydrogenation reactor is arranged at the top of a reaction bed layer in the dehydrogenation reactor, and a cyclone separation system of the dehydrogenation reactor is arranged at the top of the dehydrogenation reactor; a charcoal burning reaction zone is arranged in the regeneration reactor, a primary separation device of the regeneration reactor is arranged at the top of a combustion chamber in the regeneration reactor, and a cyclone separation system of the regeneration reactor is arranged at the top of the regeneration reactor; a reduction reaction zone is arranged in the reduction reactor, a primary separation device of the reduction reactor is arranged at the top of the reduction reaction zone, and a cyclone separation system of the reduction reactor is arranged at the top of the reduction reactor;
the dehydrogenation reactor is connected with the bottom of the regeneration reactor through a deactivated catalyst pipeline arranged in the middle of the dehydrogenation reactor; the regeneration reactor is connected with the bottom of the reduction reactor through a regenerated catalyst pipeline arranged in the middle of the regeneration reactor, and the reduction reactor is connected with the bottom of the dehydrogenation reactor through a reduced catalyst pipeline arranged in the middle of the reduction reactor.
Further, a reaction raw material inlet is arranged at the bottom of the dehydrogenation reactor, and a mixed gas outlet is arranged at the top of the dehydrogenation reactor; the reaction raw material enters a dehydrogenation reactor through a raw material gas inlet pipeline, is mixed with a reduction catalyst and then enters a dehydrogenation reaction zone; a stripping zone is arranged between a reaction tube in the dehydrogenation reactor and the inner wall of the reactor, and stripping gas enters the stripping zone through a stripping gas inlet pipeline.
Furthermore, a regeneration air inlet, a fuel inlet and an oxygen-containing gas inlet are respectively arranged at the bottom of the regeneration reactor; the top of the regeneration reactor is provided with a regeneration waste gas outlet.
Furthermore, a reducing gas inlet is arranged at the bottom of the reduction reactor, and a reducing waste gas outlet is arranged at the top of the reduction reactor.
Further, the process for carrying out propane dehydrogenation by using the fluidized bed propane dehydrogenation device comprises the following steps:
the method comprises the following steps of taking a mixed gas of circulating propane and fresh propane as a reaction raw material, preheating the mixed gas at a certain temperature through heat exchange, then entering the bottom of a dehydrogenation reactor through a raw material gas inlet pipeline, contacting with a regenerated and reduced catalyst, carrying out dehydrogenation reaction in a dehydrogenation reaction zone, carrying out primary separation on the reacted gas and the catalyst in a primary separation device of the dehydrogenation reactor arranged at the top of a reaction bed layer, and allowing most of the catalyst to flow downwards to a stripping zone between a reaction pipe and the inner wall of the reactor; carrying part of fine particle catalyst in the reacted mixed gas to perform secondary separation in a cyclone separation system of the dehydrogenation reactor arranged at the top of the dehydrogenation reactor, allowing the fine particles to flow downwards to a stripping zone, allowing the reacted mixed gas as a reaction product to continuously leave from a reaction gas outlet pipeline at the top of the reactor, and allowing the reaction product to enter a separation section;
the deactivated catalyst in the stripping zone is treated with stripping gas delivered via a stripping gas inlet pipe and then delivered to the bottom of the regeneration reactor via a deactivated catalyst pipe. The regenerated air and the regenerated fuel gas are mixed and combusted at the bottom of the regeneration reactor, the mixture is maintained in a certain temperature range after being mixed with the oxygen-containing gas supplemented from the oxygen-containing gas inlet pipeline, the deactivated catalyst is subjected to charcoal burning regeneration in a charcoal burning reaction zone, the regenerated waste gas and the catalyst after carbon deposition removal are subjected to primary separation in a primary separation device of the regeneration reactor, and most of the catalyst flows downwards to a retention zone between a combustion chamber and the regenerator and enters the bottom of the reduction reactor through a regenerated catalyst pipeline; the regenerated waste gas carrying a small amount of catalyst is continuously subjected to secondary separation in a cyclone separation system at the top of the reactor, the regenerated waste gas leaves from a regenerated waste gas outlet pipeline arranged at the top of the regenerator, and fine particles flow downwards and are gathered with the regenerated catalyst to enter a reduction reactor;
the method comprises the following steps that reducing gas is heated to a certain temperature and then enters the bottom of a reduction reactor through a reducing gas inlet pipeline, the reducing gas is in contact with a catalyst regenerated by burning carbon and is subjected to reduction reaction in a reduction reaction zone, the reduced gas and the catalyst are subjected to primary separation in a primary separation device of the reduction reactor at the top of the reduction zone, and most of the catalyst flows downwards to a retention zone between the reduction zone and the reactor and enters the bottom of a dehydrogenation reactor through a reducing catalyst pipeline; and carrying a small amount of catalyst reduction waste gas to continue to carry out secondary separation in a cyclone separation system at the top of the reduction reactor, wherein the reduction waste gas leaves from a reduction waste gas outlet pipeline at the top of the reduction regenerator, and fine particles flow downwards to be gathered with the regenerated catalyst to enter the dehydrogenation reactor.
Further, when part of the catalyst in the regeneration reactor is not fully burnt, the incompletely burnt catalyst is input to the bottom of the regeneration reactor again through the internal circulation pipe of the regeneration reactor for carbon burning regeneration; when part of the catalyst in the reduction reactor is insufficiently reduced, the incompletely reduced catalyst can be fed into the bottom of the reduction reactor again through the circulating pipe in the reduction reactor to be reduced again.
Furthermore, the novel dehydrogenation catalyst matched with the dehydrogenation device and the process flow is environment-friendly high-strength Ga/Al 2 O 3 The microsphere dehydrogenation catalyst is A-type particles, the particle size range is 30-150 mu m, the D50 of the particles is 60-80 mu m, and the pore diameter of the particles is 5-12 nm; the abrasion rate is 0.5-1.5% by adopting the ASTM standard. Ga/Al used 2 O 3 Other active components of the microsphere based dehydrogenation catalyst are respectively one of trace platinum, alkaline earth metal and rare earth metal; wherein the platinum content is 50-1000 ppm, the sum of the contents of alkaline earth metal and rare earth metal oxide is 0.1-10.0%, and the catalyst has stable high alkane conversion rate and high propylene selectivity within-300 s after the reaction starts.
The environment-friendly high-strength Ga/Al 2 O 3 The preparation method of the microsphere dehydrogenation catalyst comprises the following steps:
(1) Preparing 30-150 mu m class A Al according to the prior art 2 O 3 Microspherical particles for later use;
(2) Dissolving gallium nitrate, platinum nitrate, magnesium nitrate (calcium nitrate) and cerium nitrate (lanthanum nitrate) which are weighed according to a certain proportion into a proper amount of deionized water, stirring at room temperature to clarify, and adding the A-type Al prepared in the step (1) 2 O 3 The microsphere particles are impregnated in equal volume, placed for a period of time at room temperature, dried and calcined to obtain the desired catalyst.
The preferred time of placing at room temperature is 2h, and the drying temperature is 120 ℃; the calcining temperature is 500-800 ℃; the calcination time is 2-6h.
In the presence of the catalyst, the catalyst is,in percentage by mass, ga 2 O 3 2 to 9 percent; the content of MgO or CaO is 1-5%; ceO (CeO) 2 Or La 2 O 3 The content of (A) is 1-5%; the balance being Al 2 O 3 。
Further, the catalyst flows among the three reactors in sequence and completes the dehydrogenation process cycle of reaction-regeneration-reduction-reaction; the dehydrogenation reactor is a high-speed fluidized bed, the dehydrogenation temperature is 590-650 ℃, the regeneration temperature is 600-700 ℃, and the reduction temperature is 600-650 ℃.
Furthermore, the fuel gas in the regeneration reactor is one of methane, ethane or dry gas. The oxygen content of the supplemental oxygen-containing gas is 20 to 40%.
Further, the reducing gas in the reduction reactor is H 2 -N 2 Mixed gas, N 2 The content is 0-50%.
Further, when the deactivated catalyst flows to the regeneration reactor, the air and a certain proportion of fuel are subjected to a charcoal burning reaction; the heat generated by fuel combustion can keep the temperature of the regenerated catalyst above 600 ℃, and the air speed is 2000-8000 h -1 To (c) to (d); the carbon burning time of the catalyst is 1-4 times of the reaction time, the carbon content of the catalyst is lower than 0.01 percent after the carbon burning is finished, and the pressure of a regeneration reactor is 30-100 KPa.
Further, after the regenerated catalyst flows into the reduction reactor, H is introduced into the reduction reactor 2 Or H diluted with inert gas 2 (ii) a The air speed of the introduced reducing gas is 2000-8000 h -1 The reduction time is 0.5 to 2 times of the reaction time, and the pressure of the reduction reactor is 30 to 100KPa. When propane is used for feeding, the catalyst-oil ratio of the feeding of the dehydrogenation reactor is between 3 and 30, the adaptability is strong, the dehydrogenation reaction pressure is between 30 and 150KPa, the conversion per pass in the dehydrogenation section is more than or equal to 35 percent, and the propylene selectivity is more than or equal to 86 percent.
Compared with the prior art, the invention has the following beneficial effects:
compared with the existing moving bed or fixed bed industrialization technology, the high-speed circulating fluidized bed dehydrogenation technology is adopted, so that the reaction can be continuously carried out, the equipment investment is low, and the investment cost is 10-20% lower than that of the prior art in the same scale.
The novel process of the invention is matched with a unique dehydrogenation catalyst, the olefin selectivity is high in effective dehydrogenation time, and the unit consumption of the olefin raw material per ton is obviously reduced compared with the prior industrial technology; the main active component of the catalyst system in the process of the invention adopts cheap metal and has low dosage, so the cost of the catalyst has obvious competitive advantage and is very environment-friendly under the condition of high activity.
Drawings
FIG. 1 is a schematic view of the structure of a fluidized-bed propane dehydrogenation apparatus according to the present invention
Wherein R1 is a dehydrogenation reactor; r2: a regeneration reactor; r3: a reduction reactor; d1, a dehydrogenation reaction zone; d2, a charcoal burning reaction zone; d3, a reduction reaction zone; f1: a feed gas inlet conduit; f1, reaction raw materials; f2: a reaction gas outlet conduit; f2, reaction products; f3: a stripping gas inlet line; f3, stripping gas; f4: a regeneration gas inlet conduit; f4, regenerating air; f5: a regeneration exhaust gas outlet conduit; f5, regenerating waste gas; f6: a fuel gas inlet conduit; f6, regenerating fuel gas; f7: an oxygen-containing gas inlet conduit; f7, oxygen-containing gas; f8: a reducing gas inlet conduit; f8, reducing gas; f9: a reducing exhaust gas outlet conduit; f9, reducing the waste gas; f10, reducing the catalyst material flow; t1: an internal circulation pipeline of the dehydrogenation reactor; t2: a deactivated catalyst conduit; t3: a recycle line in the regeneration reactor; t4: a regenerated catalyst conduit; t5: a circulation pipeline in the reduction reactor; t6: a reduction catalyst conduit; x1: a primary separation device of a dehydrogenation reactor; x2: a dehydrogenation reactor cyclone separation system; x3: a regenerative reactor primary separation device; x4: a regenerative reactor cyclone separation system; x5: a primary separation device of the reduction reactor; x6: a reduction reactor cyclone separation system.
Detailed Description
Through repeated experiments and researches, the invention limits the content of the steps and parameters involved in the process and the specific components in the catalyst to a specific value, so that the dehydrogenation function of the catalyst can be better exerted, and simultaneously, reaction process parameters capable of maximally exerting the catalyst performance are matched and adopted in the fluidized bed reactor, so that the whole set of reaction system can better realize the effect of producing more propylene.
A fluidized bed propane dehydrogenation device comprises a dehydrogenation reactor, a regeneration reactor and a reduction reactor; a dehydrogenation reaction zone is arranged in a dehydrogenation reactor, a primary separation device of the dehydrogenation reactor is arranged at the top of a reaction bed layer in the dehydrogenation reactor, and a cyclone separation system of the dehydrogenation reactor is arranged at the top of the dehydrogenation reactor; a charcoal burning reaction zone is arranged in the regeneration reactor, a primary separation device of the regeneration reactor is arranged at the top of a combustion chamber in the regeneration reactor, and a cyclone separation system of the regeneration reactor is arranged at the top of the regeneration reactor; a reduction reaction zone is arranged in the reduction reactor, a primary separation device of the reduction reactor is arranged at the top of the reduction reaction zone, and a cyclone separation system of the reduction reactor is arranged at the top of the reduction reactor;
the dehydrogenation reactor is connected with the bottom of the regeneration reactor through a deactivated catalyst pipeline arranged in the middle of the dehydrogenation reactor; the regeneration reactor is connected with the bottom of the reduction reactor through a regenerated catalyst pipeline arranged in the middle of the regeneration reactor, and the reduction reactor is connected with the bottom of the dehydrogenation reactor through a reduced catalyst pipeline arranged in the middle of the reduction reactor.
Further, a reaction raw material inlet is arranged at the bottom of the dehydrogenation reactor, and a mixed gas outlet is arranged at the top of the dehydrogenation reactor; the reaction raw material enters a dehydrogenation reactor through a raw material gas inlet pipeline, is mixed with a reduction catalyst and then enters a dehydrogenation reaction zone; a stripping zone is arranged between a reaction tube in the dehydrogenation reactor and the inner wall of the reactor, and stripping gas enters the stripping zone through a stripping gas inlet pipeline.
Furthermore, a regeneration air inlet, a fuel inlet and an oxygen-containing gas inlet are respectively arranged at the bottom of the regeneration reactor; the top of the regeneration reactor is provided with a regeneration waste gas outlet.
Furthermore, a reducing gas inlet is arranged at the bottom of the reduction reactor, and a reducing waste gas outlet is arranged at the top of the reduction reactor.
Further, the process for carrying out propane dehydrogenation by using the fluidized bed propane dehydrogenation device comprises the following steps:
the method comprises the following steps of taking a mixed gas of circulating propane and fresh propane as a reaction raw material, preheating the mixed gas at a certain temperature through heat exchange, then entering the bottom of a dehydrogenation reactor through a raw material gas inlet pipeline, contacting with a regenerated and reduced catalyst, and carrying out dehydrogenation reaction in a dehydrogenation reaction zone, wherein the reacted gas and the catalyst are primarily separated in a primary separation device of the dehydrogenation reactor arranged at the top of a reaction bed layer, and most of the catalyst flows downwards to a stripping zone between a reaction tube and the inner wall of the reactor; carrying part of fine particle catalyst in the reacted mixed gas to perform secondary separation in a cyclone separation system of the dehydrogenation reactor arranged at the top of the dehydrogenation reactor, allowing the fine particles to flow downwards to a stripping zone, allowing the reacted mixed gas as a reaction product to continuously leave from a reaction gas outlet pipeline at the top of the reactor, and allowing the reaction product to enter a separation section;
the deactivated catalyst in the stripping zone is treated with stripping gas delivered via a stripping gas inlet pipe and then delivered to the bottom of the regeneration reactor via a deactivated catalyst pipe. The regenerated air and the regenerated fuel gas are mixed and combusted at the bottom of the regeneration reactor, and are mixed with the oxygen-containing gas supplemented from the oxygen-containing gas inlet pipeline and then are maintained in a certain temperature range to carry out coke burning regeneration on the deactivated catalyst in a coke burning reaction zone, the regenerated waste gas and the catalyst after carbon deposition removal are primarily separated in a primary separating device of the regeneration reactor, and most of the catalyst flows downwards to a staying zone between a combustion chamber and the regenerator and enters the bottom of the reduction reactor through a regenerated catalyst pipeline; the regenerated waste gas carrying a small amount of catalyst is continuously subjected to secondary separation in a cyclone separation system at the top of the reactor, the regenerated waste gas leaves from a regenerated waste gas outlet pipeline arranged at the top of the regenerator, and fine particles flow downwards and are gathered with the regenerated catalyst to enter a reduction reactor;
the method comprises the following steps that reducing gas is heated to a certain temperature and then enters the bottom of a reduction reactor through a reducing gas inlet pipeline, the reducing gas is in contact with a catalyst regenerated by burning carbon and is subjected to reduction reaction in a reduction reaction zone, the reduced gas and the catalyst are subjected to primary separation in a primary separation device of the reduction reactor at the top of the reduction zone, and most of the catalyst flows downwards to a retention zone between the reduction zone and the reactor and enters the bottom of a dehydrogenation reactor through a reducing catalyst pipeline; and carrying a small amount of catalyst reduction waste gas to continue to carry out secondary separation in a cyclone separation system at the top of the reduction reactor, wherein the reduction waste gas leaves from a reduction waste gas outlet pipeline at the top of the reduction regenerator, and fine particles flow downwards to be gathered with the regenerated catalyst to enter the dehydrogenation reactor.
Further, when part of the catalyst in the regeneration reactor is not fully burnt, the incompletely burnt catalyst is input to the bottom of the regeneration reactor again through the internal circulation pipe of the regeneration reactor for carbon burning regeneration; when part of the catalyst in the reduction reactor is insufficiently reduced, the incompletely reduced catalyst can be fed into the bottom of the reduction reactor again through the circulating pipe in the reduction reactor for re-reduction.
Furthermore, the novel dehydrogenation catalyst matched with the dehydrogenation device and the process flow is environment-friendly high-strength Ga/Al 2 O 3 The microsphere based dehydrogenation catalyst is an A-type particle, the particle size range is 30-150 mu m, the D50 of the particle is 60-80 mu m, and the pore diameter is 5-12 nm; the abrasion rate is 0.5-1.5% by adopting the ASTM standard. Ga/Al used 2 O 3 Other active components of the microsphere based dehydrogenation catalyst are respectively one of trace platinum, alkaline earth metal and rare earth metal; wherein the platinum content is 50-1000 ppm (specifically 50ppm, 1000ppm, 200ppm, 300ppm, 400ppm, 500ppm, 600ppm, 700ppm, 800ppm, 900ppm, 1000 ppm), the sum of the alkaline earth metal and rare earth metal oxide content is 0.1-10.0% (specifically 0.1%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10.0%), and the catalyst has stable high alkane conversion rate and high propylene selectivity within 300s after the reaction starts.
The environment-friendly high-strength Ga/Al 2 O 3 The preparation method of the microsphere dehydrogenation catalyst comprises the following steps:
(1) 30-150 μm (specifically 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, 100 μm, 110 μm, 120 μm, 130 μm, 140 μm, 150 μm) of A-type Al is prepared according to the prior art 2 O 3 Microspherical particles for later use;
(2) Dissolving one of gallium nitrate, platinum nitrate, magnesium nitrate or calcium nitrate and one of cerium nitrate or lanthanum nitrate which are weighed according to a certain proportion in a proper amount of deionized water, stirring at room temperature to clarify, and adding the A-type Al prepared in the step (1) 2 O 3 The microsphere particles are soaked in the same volume, placed for a period of time at room temperature, dried and calcined to obtain the required catalyst.
The time of placing at room temperature is preferably 2h, and the drying temperature is 120 ℃; the calcination temperature is 500-800 deg.C, specifically 500 deg.C, 550 deg.C, 600 deg.C, 650 deg.C, 700 deg.C, 750 deg.C, 800 deg.C; the calcination time is 2-6h, specifically 2h, 3h, 4h, 5h, 6h.
In the catalyst, ga 2 O 3 2-9% (specifically, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%), 1-5% (specifically, 1%, 2%, 3%, 4%, 5%) MgO or CaO, and CeO 2 Or La 2 O 3 The content is 1-5% (specifically 1%, 2%, 3%, 4%, 5%), and the balance is Al 2 O 3 。
Further, the catalyst flows among the three reactors in sequence and completes the dehydrogenation process cycle of reaction-regeneration-reduction-reaction; the dehydrogenation reactor is a high-speed fluidized bed, the dehydrogenation temperature is 590-650 ℃ (590 ℃, 600 ℃, 610 ℃, 620 ℃, 630 ℃, 640 ℃, 650 ℃), the regeneration temperature is 600-700 ℃, specifically 600 ℃, 610 ℃, 620 ℃, 640 ℃, 650 ℃, 660 ℃, 670 ℃, 680 ℃, 690 ℃, 700 ℃), and the reduction temperature is 600-650 ℃ (specifically 600 ℃, 610 ℃, 620 ℃, 630 ℃, 640 ℃, 650 ℃).
Furthermore, the fuel gas in the regeneration reactor is one of methane, ethane or dry gas. The oxygen-containing gas may further contain 20 to 40% (specifically, 20%, 25%, 30%, 35%, 40%) of oxygen.
Further, the reducing gas in the reduction reactor is H 2 -N 2 Mixed gas, N 2 The content is 0-50% (specifically 0%, 10%, 20%, 30%),40％、50％)。
Further, when the deactivated catalyst flows to the regeneration reactor, the air and a certain proportion of fuel are subjected to a charcoal burning reaction; the heat generated by fuel combustion can keep the temperature of the regenerated catalyst above 600 ℃, and the air speed is 2000-8000 h -1 To (c) to (d); the carbon burning time of the catalyst is 1-4 times of the reaction time, the carbon content of the catalyst is lower than 0.01 percent after the carbon burning is finished, and the pressure of a regeneration reactor is 30-100 KPa.
Further, after the regenerated catalyst flows into the reduction reactor, H2 or H diluted by inert gas is introduced into the reduction reactor 2 (ii) a The air speed of the introduced reducing gas is 2000-8000 h -1 The reduction time is 0.5 to 2 times of the reaction time, and the pressure of the reduction reactor is 30 to 100KPa. When propane is used for feeding, the catalyst-oil ratio of the feeding of the dehydrogenation reactor is between 3 and 30, the adaptability is strong, the dehydrogenation reaction pressure is between 30 and 150KPa, the single-pass conversion rate in the dehydrogenation section is more than or equal to 35 percent, and the propylene selectivity is more than or equal to 86 percent.
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and do not limit the invention.
In the invention, the catalyst-oil ratio is the mass ratio of the circulating amount of the catalyst to the feeding amount in unit time.
Example 1
A fluidized bed propane dehydrogenation device, the structural schematic diagram of which is shown in fig. 1, comprises a dehydrogenation reactor R1, a regeneration reactor R2 and a reduction reactor R3. A dehydrogenation reaction zone D1 is arranged in the dehydrogenation reactor R1, a primary separation device X1 of the dehydrogenation reactor is arranged at the top of a reaction bed layer in the dehydrogenation reactor R1, and a cyclone separation system X2 of the dehydrogenation reactor is arranged at the top of the dehydrogenation reactor R1; a charcoal burning reaction zone D2 is arranged in the regeneration reactor R2, a primary separation device X3 of the regeneration reactor is arranged at the top of a combustion chamber in the regeneration reactor R2, and a cyclone separation system X4 of the regeneration reactor is arranged at the top of the regeneration reactor R2; a reduction reaction zone D3 is arranged in the reduction reactor R3, a primary separation device X5 of the reduction reactor is arranged at the top of the reduction zone in the reduction reactor R3, and a cyclone separation system X6 of the reduction reactor is arranged at the top of the reduction reactor R3;
the dehydrogenation reactor R1 is connected with the bottom of the regeneration reactor R2 through an inactivated catalyst pipeline T2; the regeneration reactor R2 is connected with the bottom of the reduction reactor R3 through a regenerated catalyst pipeline T4, and the reduction reactor R3 is connected with the bottom of the dehydrogenation reactor R1 through a reduced catalyst pipeline T6.
The bottom of the dehydrogenation reactor is provided with a reaction raw material inlet f1, and the top of the dehydrogenation reactor is provided with a mixed gas outlet f2. Feeding the reduced catalyst F10 to a dehydrogenation reactor through a reduction catalyst pipeline T6, feeding the reaction raw material F1 into a dehydrogenation reactor R1 through a raw material gas inlet pipeline F1, mixing the reaction raw material F1 with a reduction catalyst, and feeding the mixture into a dehydrogenation reaction zone D1 in the dehydrogenation reactor R1; a stripping zone is arranged between the reaction tube in the dehydrogenation reactor R1 and the inner wall of the reactor, and stripping gas F3 enters the stripping zone through a stripping gas inlet pipeline F3.
A regeneration air inlet f4, a fuel inlet f6 and an oxygen-containing gas inlet f7 are respectively arranged at the bottom of the regeneration reactor R2; a regeneration off-gas outlet f5 is provided at the top of the regeneration reactor R2.
A reducing gas inlet f8 is provided at the bottom of the reduction reactor R3, and a reducing off-gas outlet f9 is provided at the top.
Example 2
The process for propane dehydrogenation using the fluid bed propane dehydrogenation unit described in example 1, comprising the steps of:
preheating mixed gas of circulating propane and fresh propane to a certain temperature through heat exchange, taking the preheated mixed gas as a reaction raw material F1 to enter the bottom of a dehydrogenation reactor R1 through a raw material gas inlet pipeline F1, contacting with a regenerated and reduced catalyst and generating dehydrogenation reaction in a D1 area, preliminarily separating the reacted gas and the catalyst in a primary separation device X1 of the dehydrogenation reactor arranged on a reaction bed layer, and allowing most of the catalyst to flow downwards to a stripping area between a reaction pipe and the inner wall of the reactor; carrying part of fine particle catalyst in the reacted mixed gas to perform secondary separation in a cyclone separation system X2 of the dehydrogenation reactor at the top of the dehydrogenation reactor, allowing the fine particles to flow downwards to a stripping zone, allowing the reacted mixed gas serving as a reaction product F2 to continuously leave from a reaction gas outlet pipeline F2 at the top of the reactor, and allowing the reacted mixed gas to enter a separation section;
the deactivated catalyst in the stripping zone is treated with stripping gas F3 delivered via stripping gas inlet conduit F3 and then delivered to the bottom of the regeneration reactor R2 via deactivated catalyst conduit T2. The regeneration air F4 and the regeneration fuel gas F6 are mixed and combusted at the bottom of the regenerator reactor R2, the mixture is maintained in a certain temperature range after being mixed with the supplemented oxygen-containing gas to carry out charcoal burning regeneration on the deactivated catalyst in a D2 charcoal burning area, the regeneration exhaust gas F5 and the catalyst after carbon deposition removal are primarily separated in a primary separation device X3 of the regeneration reactor, and most of the catalyst flows downwards to a retention area between a combustion chamber and the regenerator and enters the bottom of the reduction reactor R2 through a regeneration catalyst pipeline T4; carrying a small amount of catalyst regeneration waste gas F5 to continue to carry out secondary separation in a cyclone separation system X4 at the top of the reactor, wherein the regeneration waste gas F5 leaves from a regeneration waste gas outlet pipeline F5 arranged at the top of the regenerator reactor R2, and fine particles flow downwards to be gathered with the regenerated catalyst to enter a reduction reactor R3.
The reducing gas F8 is heated to a certain temperature and then enters the bottom of a reduction reactor R3 through a reducing gas inlet pipeline F8, contacts with the catalyst after the carbon burning regeneration and carries out a reduction reaction in a reduction reaction zone D3, the reduced gas F8 and the catalyst are primarily separated in a primary separation device X5 of the reduction reactor, and most of the catalyst flows downwards to a retention zone between the reduction zone and the reactor and enters the bottom of a dehydrogenation reactor R3 through a reducing catalyst pipeline T6; and continuously carrying out secondary separation on the reduction waste gas F9 carrying a small amount of catalyst in a cyclone separation system X6 of the reduction reactor, wherein the reduction waste gas F9 leaves from a reduction waste gas outlet pipeline F9 at the top of the reduction reactor R3, and fine particles flow downwards to be gathered with the regenerated catalyst to enter a dehydrogenation reactor R1.
When part of the catalyst in the regeneration reactor R2 is not fully burnt, the incompletely burnt catalyst is input to the bottom of the regeneration reactor R2 again through the internal circulation pipe T3 of the regeneration reactor for burning regeneration; when part of the catalyst in the reduction reactor R3 is insufficiently reduced, the incompletely reduced catalyst can be fed into the bottom of the reduction reactor R3 again through the inner circulation pipe T5 of the reduction reactor for re-reduction.
Example 3
Propane dehydrogenation was carried out using the fluid bed propane dehydrogenation unit as described in example 1 and the process steps described in example 2, with the following specific operations:
(1) Dissolving weighed gallium nitrate, platinum nitrate, magnesium nitrate and cerium nitrate into a proper amount of deionized water, stirring at room temperature to clarify, and adding the self-prepared A-type Al with the particle size of 30-150 mu m 2 O 3 Soaking the microsphere particles in the same volume, standing at room temperature for 2h, drying, and calcining at 600 ℃ for 4h to obtain the required catalyst. In the catalyst, ga 2 O 3 4.8% of MgO, 2% of PtO 2 The content was 500ppm 2 The content is 3.5 percent, and the balance is Al 2 O 3 。
(2) The catalyst prepared in the step 1 is subjected to propane dehydrogenation reaction on a fluidized bed device, and the whole process flow is basically consistent with the process flow of the figure 1. Wherein the dehydrogenation reaction temperature is 610 ℃, the reaction pressure is 50KPa, and the agent-oil ratio is 20; the regeneration temperature is 650 ℃, the regeneration pressure is 100KPa, and the air speed is 5000h -1 The carbon content of the catalyst is 50ppm after the carbon burning is finished; the reduction temperature is 620 ℃, and the pure H 2 Reduction is carried out at the reduction pressure of 60KPa and the gas velocity of 4000h -1 . After many cycles of stabilization under the above conditions, the activity is shown in Table 1.
Example 4
The propane dehydrogenation was carried out using the fluidized bed propane dehydrogenation unit as described in example 1, the process for propane dehydrogenation as described in example 2, and the specific operation was as follows:
(1) Dissolving weighed gallium nitrate, platinum nitrate, magnesium nitrate and lanthanum nitrate into a proper amount of deionized water, stirring at room temperature to clarify, and adding the self-prepared A-type Al with the particle size of 30-150 mu m 2 O 3 Soaking the microsphere particles in the same volume, standing at room temperature for 2h, drying, and calcining at 600 ℃ for 4h to obtain the required catalyst. In the catalyst, ga 2 O 3 3.7% of MgO, 0.8% of PtO 2 The content was 300ppm, la 2 O 3 The content is 2.8 percent, and the balance is Al 2 O 3 。
(2) The catalyst prepared in step 1 is subjected to propane dehydrogenation reaction on a fluidized bed device, and the whole process flow is basically consistent with the process flow of the figure 1. Wherein the dehydrogenation reaction temperature is 610 ℃, the reaction pressure is 30KPa, and the agent-oil ratio is 3; the regeneration temperature is 700 ℃, the regeneration pressure is 50KPa, and the air speed is 4000h -1 The carbon content of the catalyst after the carbon burning is finished is 40ppm; reduction temperature 600 ℃ and pure H 2 Reduction is carried out at the pressure of 50KPa and the gas speed of 6000h -1 . After many cycles of stabilization under the above conditions, the activity is shown in Table 1.
Example 5
(1) Dissolving weighed gallium nitrate, platinum nitrate, calcium nitrate and cerium nitrate in proper amount of deionized water, stirring at room temperature for clarification, and adding self-prepared A-type Al of 30-150 mu m 2 O 3 Soaking the microsphere particles in the same volume, standing at room temperature for 2h, drying, and calcining at 600 ℃ for 4h to obtain the required catalyst. In the catalyst, ga 2 O 3 6.0% of CaO, 0.6% of CaO, ptO 2 The content is 700ppm, ceO 2 0.5% of Al and the balance of 2 O 3 。
(2) The catalyst prepared in step 1 is subjected to propane dehydrogenation reaction on a fluidized bed device, and the whole process flow is basically consistent with the process flow of the figure 1. Wherein the dehydrogenation reaction temperature is 615 ℃, the reaction pressure is 60KPa, and the agent-oil ratio is 9; the regeneration temperature is 750 ℃, the regeneration pressure is 100KPa, and the air speed is 5500h -1 The carbon content of the catalyst after carbon burning is 30ppm; reduction temperature 610 ℃ N 2 -H 2 (50%) reduction of mixed gas, the reduction pressure is 30KPa, and the gas speed is 4500h -1 . After many cycles of stabilization under the above conditions, the activity is shown in Table 1.
Example 6
The dehydrogenation of propane was carried out using the fluidized bed propane dehydrogenation unit as described in example 1, the process for the dehydrogenation of propane as described in example 2, with the following specific operations:
(1) The catalyst was identical to step (1) of example 3.
(2) The catalyst prepared in the step 1 is subjected to propane dehydrogenation reaction on a fluidized bed device, and the whole process flow is basically consistent with the process flow of the figure 1. Wherein the dehydrogenation reaction temperature is 625 ℃, the reaction pressure is 30KPa, and the catalyst-oil ratio is 30; the regeneration temperature is 680 ℃, the regeneration pressure is 80KPa, and the air speed is 6000h -1 The carbon content of the catalyst after the carbon burning is finished is 40ppm; reduction temperature 620 ℃ and pure H 2 Reduction is carried out at the pressure of 80KPa and the gas speed of 6000h -1 . After many cycles of stabilization under the above conditions, the activity is shown in Table 1.
Example 7
The propane dehydrogenation was carried out using the fluidized bed propane dehydrogenation unit as described in example 1, the process for propane dehydrogenation as described in example 2, and the specific operation was as follows:
(1) The catalyst was identical to example 5, step (1).
(2) The catalyst prepared in step 1 is subjected to propane dehydrogenation reaction on a fluidized bed device, and the whole process flow is basically consistent with the process flow of the figure 1. Wherein the dehydrogenation reaction temperature is 615 ℃, the reaction pressure is 70KPa, and the agent-oil ratio is 15; the regeneration temperature is 800 ℃, the regeneration pressure is 100KPa, and the air speed is 8000h -1 The carbon content of the catalyst is 15ppm after the carbon burning is finished; reduction temperature 610 ℃ N 2 -H 2 (80%) mixed gas is reduced, the reduction pressure is 60KPa, and the gas speed is 7000h -1 . After many stable cycles under the above conditions, the dehydrogenation activity is shown in Table 1.
Comparative example 1
It is generally consistent with the catalyst sample and process flow prepared in example 6, except that the carbon-deactivated catalyst is regenerated by charring without being recycled to the dehydrogenation reactor. After 50 cycles of stabilization under the above conditions, the dehydrogenation activity was as shown in Table 1.
Comparative example 2
The catalyst prepared in step (1) was the same as the catalyst used in the preparation of example 6, except that the catalyst composition and content were different, and a high platinum alumina formulation was used. In the catalyst, ptO 2 0.3% of SnO 2 Content of 1.0%, K 2 The content of O is 1.2 percent, and the balance is Al 2 O 3 。
Step (2) was identical to the procedure of example 6 with an initial propane conversion per pass of 45.6% and a propylene selectivity of 91.5%. After many cycles, the dehydrogenation activity was as shown in Table 1.
Comparative example 3
Preparation of typical Cr 2 O 3 /Al 2 O 3 A catalyst. Dissolving weighed chromium nitrate and potassium nitrate into proper amount of deionized water, stirring and dissolving at room temperature, and adding self-prepared A-type Al with the particle size of 30-150 mu m 2 O 3 Soaking the microsphere particles in the same volume, stirring for 2 hours at room temperature, heating while stirring until the microsphere particles are filled in a paste, drying in an oven, and calcining for 4 hours at 600 ℃ to obtain the required catalyst. In the catalyst, cr 2 O 3 Content 18%, K 2 The content of O is 1.5 percent, and the balance is Al 2 O 3 。
The catalyst was evaluated and the parameters used in example 3. After many stable cycles under the above conditions, the dehydrogenation activity is shown in Table 1.
Comparative example 4
The catalyst is the same as example 4, but the process scheme is similar to that of figure 1, except that the catalyst enters R2 to be burned after coming out of the dehydrogenation reactor R1, and the burned carbon directly enters R1 without reduction (without entering the reduction reactor R3) after being blown, so that the cyclic regeneration of the catalyst in R1-R2-R1 is realized. After many stable cycles under the above conditions, the dehydrogenation activity is shown in Table 1.
TABLE 1 dehydrogenation activity data for examples and comparative examples
Propane conversionRate/%) Propylene selectivity/%) Number of regenerations
Example 3 39.7 90.4 50
Example 4 35.8 92.6 50
Example 5 38.4 87.5 50
Example 6 43.5 89.6 50
Example 7 41.6 91.8 50
Comparative example 1 34.7 88.9 50
Comparative example 2 37.2 90.4 20
Comparative example 3 29.6 91.7 50
Comparative example 4 16.7 92.3 50
It can be seen from the data of the examples and comparative examples that the optimum dehydrogenation results are not obtained without using the catalyst system of the present invention in the fluidized bed dehydrogenation process of the present invention or by reducing part of the process in the process of the present invention. Therefore, the invention adopts a unique catalyst system to be matched with a novel fluidized bed reaction mode for propane dehydrogenation, has poor dehydrogenation activity and has very stable catalyst regeneration performance.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.

Claims (10)

1. A fluidized bed propane dehydrogenation unit comprising a dehydrogenation reactor (R1), a regeneration reactor (R2) and a reduction reactor (R3), characterized in that: a dehydrogenation reaction zone (D1) is arranged in the dehydrogenation reactor (R1), a primary separation device (X1) of the dehydrogenation reactor is arranged at the top of a reaction bed layer in the dehydrogenation reactor (R1), and a cyclone separation system (X2) of the dehydrogenation reactor is arranged at the top of the dehydrogenation reactor (R1); a charcoal burning reaction zone (D2) is arranged in the regeneration reactor (R2), a primary separation device (X3) of the regeneration reactor is arranged at the top of a combustion chamber in the regeneration reactor (R2), and a cyclone separation system (X4) of the regeneration reactor is arranged at the top of the regeneration reactor (R2); a reduction reaction zone (D3) is arranged in the reduction reactor (R3), a primary separation device (X5) of the reduction reactor is arranged at the top of the reduction reaction zone (D3), and a cyclone separation system (X6) of the reduction reactor is arranged at the top of the reduction reactor (R3);
the dehydrogenation reactor (R1) is connected with the bottom of the regeneration reactor (R2) through an arranged deactivated catalyst pipeline (T2); the regeneration reactor (R2) is connected with the bottom of the reduction reactor (R3) through a regeneration catalyst pipeline (T4), and the reduction reactor (R3) is connected with the bottom of the dehydrogenation reactor (R1) through a reduction catalyst pipeline (T6).
2. The fluid bed propane dehydrogenation apparatus of claim 1, wherein: a reaction raw material inlet (f 1) is arranged at the bottom of the dehydrogenation reactor (R1), and a mixed gas outlet (f 2) is arranged at the top of the dehydrogenation reactor (R1); the reaction raw material (F1) enters a dehydrogenation reactor (R1) through a raw material gas inlet pipeline (F1), is mixed with a reduction catalyst and then enters a dehydrogenation reaction zone (D3); a stripping area is arranged between the reaction tube in the dehydrogenation reactor (R1) and the inner wall of the reactor, and stripping gas (F3) enters the stripping area through a stripping gas inlet pipeline (F3).
3. The fluidized bed propane dehydrogenation apparatus of claim 1, wherein: a regeneration air inlet (f 4), a fuel inlet (f 6) and an oxygen-containing gas inlet (f 7) are respectively arranged at the bottom of the regeneration reactor (R2); a regeneration waste gas outlet (f 5) is arranged at the top of the regeneration reactor (R2).
4. The fluid bed propane dehydrogenation apparatus of claim 1, wherein: the bottom of the reduction reactor (R3) is provided with a reducing gas inlet (f 8), and the top is provided with a reducing waste gas outlet (f 9).
5. Process for the dehydrogenation of propane using a fluidized bed propane dehydrogenation unit according to any of claims 1 to 4, characterized by the following steps:
preheating mixed gas of circulating propane and fresh propane to a certain temperature through heat exchange, taking the mixed gas as a reaction raw material (F1) to enter the bottom of a dehydrogenation reactor (R1) through a raw material gas inlet pipeline (F1), contacting with a regenerated and reduced catalyst and carrying out dehydrogenation reaction in a dehydrogenation reaction zone (D1) area, carrying out primary separation on the reacted gas and the catalyst in a primary separation device (X1) of the dehydrogenation reactor arranged on a reaction bed layer, and enabling most of the catalyst to flow downwards to a stripping zone between a reaction tube and the inner wall of the reactor; carrying part of fine particle catalyst in the reacted mixed gas to perform secondary separation in a cyclone separation system (X2) of the dehydrogenation reactor arranged at the top of the dehydrogenation reactor, allowing the fine particles to flow downwards to a stripping zone, taking the reacted mixed gas as a reaction product (F2), continuously leaving from a reaction gas outlet pipeline (F2) at the top of the reactor, and then entering a separation section;
the deactivated catalyst in the stripping zone is treated by stripping gas (F3) conveyed by a stripping gas inlet pipeline (F3) and then is conveyed to the bottom of a regeneration reactor (R2) by a deactivated catalyst pipeline (T2); the regeneration air (F4) and the regeneration fuel gas (F6) are mixed and combusted in the regenerator reactor (R2), the mixture is mixed with the oxygen-containing gas (F7) supplemented from the oxygen-containing gas inlet pipeline (F7) and then is maintained in a certain temperature range to carry out carbon burning regeneration on the deactivated catalyst in the carbon burning reaction zone (D2), the regeneration exhaust gas (F5) and the catalyst after carbon deposition removal are primarily separated in a primary separation device (X3) of the regeneration reactor, most of the catalyst flows downwards to a retention zone between a combustion chamber and the regenerator and enters the bottom of the reduction reactor (R2) through a regeneration catalyst pipeline (T4); the regeneration waste gas (F5) carrying a small amount of catalyst is continuously subjected to secondary separation in a cyclone separation system (X4) at the top of the reactor, the regeneration waste gas (F5) leaves from a regeneration waste gas outlet pipeline (F5) arranged at the top of the regenerator reactor (R2), and fine particles flow downwards and are gathered with the regenerated catalyst to enter a reduction reactor (R3);
heating reducing gas (F8) to a certain temperature, then entering the bottom of a reduction reactor (R3) through a reducing gas inlet pipeline (F8), contacting with a catalyst regenerated by burning carbon and carrying out reduction reaction in a reduction reaction zone (D3), carrying out primary separation on the reducing gas (F8) and the catalyst in a primary separation device (X5) of the reduction reactor, and enabling most of the catalyst to flow downwards to a retention zone between the reduction zone and the reactor and enter the bottom of a dehydrogenation reactor (R3) through a reducing catalyst pipeline (T6); carrying a small amount of catalyst reduction waste gas (F9) to continue to carry out secondary separation in a reduction reactor cyclone separation system (X6), wherein the reduction waste gas (F9) leaves from a reduction waste gas outlet pipeline (F9) at the top of the reduction reactor (R3), and fine particles flow downwards to be gathered with the regenerated catalyst to enter a dehydrogenation reactor (R1).
6. The process of claim 5, wherein: when part of the catalyst in the regeneration reactor (R2) is not fully burnt, the incompletely burnt catalyst is input into the bottom of the regeneration reactor (R2) again through the internal circulation pipe (T3) of the regeneration reactor to be burnt and regenerated; when the catalyst in the reduction reactor (R3) is not reduced sufficiently, the catalyst which is not reduced sufficiently can be fed again to the bottom (R3) of the reduction reactor through the internal circulation pipe (T5) of the reduction reactor for re-reduction.
7. The process of claim 5, wherein: the catalyst involved in the process is environment-friendly high-strength Ga/Al 2 O 3 The microsphere based dehydrogenation catalyst is an A-type particle, the particle size range is 30-150 mu m, the D50 of the particle is 60-80 mu m, and the pore diameter is 5-12 nm; the abrasion rate is 0.5-1.5% by adopting the ASTM standard.
8. The process of claim 7, wherein: the Ga/Al 2 O 3 Other active components of the microsphere-based dehydrogenation catalyst are respectively one of trace platinum, alkaline earth metal and rare earth metal; wherein the platinum content is 50-1000 ppm, the sum of the contents of alkaline earth metal and rare earth metal oxide is 0.1-10.0%, and the catalyst has stable high alkane conversion rate and high propylene selectivity within-300 s after the reaction starts.
9. The process of claim 5, wherein: the catalyst flows among the dehydrogenation reactor (R1), the regeneration reactor (R2) and the reduction reactor (R3) in sequence and completes the dehydrogenation process cycle of reaction-regeneration-reduction-reaction; the dehydrogenation reactor (R1) is a high-speed fluidized bed,the dehydrogenation temperature is 590-650 ℃, the regeneration temperature is 600-700 ℃, and the reduction temperature is 600-650 ℃; the fuel gas in the regeneration reactor (R2) is one of methane, ethane or dry gas; the oxygen content of the supplementary oxygen-containing gas is 20-40%; the reducing gas in the reduction reactor is H 2 -N 2 Mixed gas, N 2 The content is 0-50%.
10. The process of claim 5, wherein: when the deactivated catalyst flows to the regeneration reactor (R2), air and a proportion of fuel undergo a char-combusting reaction; the heat generated by fuel combustion can keep the temperature of the regenerated catalyst above 600 ℃, and the air speed is 2000-8000 h -1 In the middle of; the carbon burning time of the catalyst is 1 to 4 times of the reaction time, the carbon content of the catalyst is lower than 0.01 percent after the carbon burning is finished, and the pressure of a regeneration reactor (R2) is 30 to 100KPa; after the regenerated catalyst flows into the reduction reactor (R3), H is introduced into the reduction reactor (R3) 2 Or H diluted with inert gas 2 (ii) a The air speed of the reduction gas is between 2000 and 8000h -1 The reduction time is 0.5 to 2 times of the reaction time, and the pressure of the reduction reactor (R3) is 30 to 100KPa; when propane is used for feeding, the catalyst-oil ratio of the feeding of the dehydrogenation reactor (R1) is between 3 and 30, the dehydrogenation reaction pressure is between 30 and 150KPa, the conversion per pass of the dehydrogenation section is more than or equal to 35 percent, and the propylene selectivity is more than or equal to 86 percent.
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