CN102675027A - Process for preparing butadiene through oxidative dehydrogenation of butene - Google Patents
Process for preparing butadiene through oxidative dehydrogenation of butene Download PDFInfo
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Abstract
The invention relates to a process for preparing butadiene through the oxidative dehydrogenation of butene on an adiabatic radial fixed bed. The process comprises the step of performing oxidative dehydrogenation reaction of butene, air and water vapor in an adiabatic radial fixed bed reactor to obtain the butadiene. The radial fixed bed reactor is divided into three sections (or three stages); and process equipment sequentially comprises a first-section reactor, a first-section recuperative heat exchanger, a second-section reactor, a second-section recuperative heat exchanger, a third-section reactor, a medium-pressure steam generator, a low-pressure steam generator, a rear heat exchanger and the like. The preparation process is technically characterized in that the yield of the butadiene is high, the selectivity is high, the production device has high production capacity, the unit consumption of steam is low, and the heat energy is reasonably utilized; and the yield of wastewater, the pretreatment capacity of internal wastewater and the discharge amount of sewage can also be effectively reduced.
Description
Technical field
The present invention relates to a kind of preparing butadiene with butylene oxo-dehydrogenation technology, belong to chemical technology field.
Background technology
Divinyl is the main raw material of Chemicals such as viton, like cis-1,4-polybutadiene rubber, paracril, styrene-butadiene rubber(SBR), SBC thermoplastic elastomer, ABS engineering plastics, adiponitrile, hexanediamine, 1, and 4-butyleneglycol etc.
The process method of at present, producing divinyl both at home and abroad mainly contains steam cracking process (ethylene unit) and butylene oxidation-dehydrogenation technology.Recent two decades comes, because of the development of steam cracking process makes the butylene oxidation-dehydrogenation Technology almost be in stagnation.
In recent years; Steam cracking device, refinery catalytic cracking unit and methanol-to-olefins device are much overlapped in domestic construction; By-product a large amount of mixed c 4s, except separated utilizations such as wherein divinyl, iso-butylene, the use that only acts as a fuel of a large amount of butene-1s and butene-2 and butane.The divinyl supply that brings along with external cracker lighting reduces; Domestic divinyl derived product increases; Divinyl is in that supply falls short of demand, and in the coming years, is difficult to change, and utilizes the operational path of butene-1 and butene-2 oxydehydrogenation production divinyl to have great application prospect.
In nineteen sixty-five, american petroleum-Texas chemical company has realized the butylene oxidation-dehydrogenation suitability for industrialized production, adopts the hereynite catalyzer, and Shell and Dow company also succeed in developing new catalyzer and corresponding technology subsequently, and are widely used.China has developed butylene oxidation-dehydrogenation the seventies in last century and has produced butadiene product equipment, but unit scale is generally less than normal.
In China, butylene oxidation-dehydrogenation is produced divinyl technology has two types, and one type is that employing B-02 catalyzer is the insulation fix bed reaction process of representative, and another kind of is that employing H-198 catalyzer is the fluidized-bed reaction technology of representative; Two kinds of butylene catalytic dehydrogenations respectively have characteristics, can be used for industrial production steadily in the long term.
Butylene oxidation-dehydrogenation is a strong exothermal reaction; The insulation fix bed reactor domestic demand feeds a large amount of water vapors; Water vapor is as thinner and thermal barrier; Have conditioned reaction thing and product dividing potential drop, take reaction heat out of, improve the transformation efficiency of butylene and generate the selectivity of divinyl, remove the catalyst surface carbon deposit, consume a large amount of steam and produce great amount of wastewater but also brought to prolong the catalyzer effect in work-ing life.For the insulation fix bed reaction process of B-02 catalyzer, the butylene that industry is adopted: oxygen: water is 1:0.65:16 (mol ratio).Along with the production equipment scale enlarges, the expansion of reactor drum throughput, energy-saving and cost-reducing and reduce waste water and become and need to consider direction.
Radial flow reactor drum and axial-radial flow reactor have advantages such as runner is short, resistance is little, throughput is big, can use catalyst particle, air speed is big, in devices such as synthetic ammonia, methyl alcohol, vinylbenzene, CR, aromatic hydrocarbons isomery and disproportionation, are widely used.
Butylene oxidation-dehydrogenation fluidized-bed reactor technology has catalyzer to be prone to pulverize, to run off and consumes high shortcoming, and simultaneously total steam consumption is big; And existing butylene oxidation-dehydrogenation technology is two sections oxidizing reaction technical process (like Fig. 1), employing be that Adiabatic axle is to fixed-bed reactor.For large-scale butylene oxidation-dehydrogenation system butadiene product equipment; Receive restrictions such as design, manufacturing and installation; Adopt very large diameter Adiabatic axle all to have difficulties to fixed-bed reactor or fluidized-bed reactor, at present, main through increasing reactor drum platform number to solve throughput; Therefore, adopt multistage reactor drum and radial reactor to seem more meaningful.
Summary of the invention
The object of the present invention is to provide a kind of preparing butadiene with butylene oxo-dehydrogenation technology.
Technical scheme of the present invention is: adopt insulation fix bed reactor form and reaction process flow process thereof, it is characterized in that: reactor drum is adiabatic radial fixed-bed reactor; The reaction process flow process is three sections reaction process flow processs; Described three sections reaction process flow processs are: the used water vapor of first stage reactor generates gas heat exchange, intensification with the high temperature that first stage reactor and second stage reactor come out respectively through a sect heat-exchanger, two sect heat-exchangers successively; Reach the first stage reactor temperature in certain proportion butylene, air mixed then, get into first stage reactor and react; One section reaction generates gas after sect heat-exchanger heat exchange cooling, mixes with two section feeding butylene, air, water to reach the second stage reactor temperature in again, gets into second stage reactor and reacts; The high temperature that second stage reactor comes out generates gas after two sect heat-exchanger heat exchange cooling, reaches the second stage reactor temperature in three sections reactor feed butylene, water, air mixed again, gets into three sections reactor drums and reacts.What the first stage reactor charging was adopted is water vapor and gas phase butylene; What second stage reactor and three sections reactor feeds were adopted is liquid phase water and liquid phase butylene, liquid phase water and liquid phase butylene mix with corresponding generation gas afterwards water vapor and gas phase butylene get into respective reaction device (like Fig. 2) again, with save energy.
The first stage reactor temperature in is by controlling through the quantity of steam of sect heat-exchanger heating.The material inlet temperature that gets into second stage reactor and three sections reactor drums is controlled by each section feeding institute amount of water.The first stage reactor butylene is a gas-phase feed, and second stage reactor and three sections reactor drum butylene are liquid phase feeding or gas phase state.The water alkene of first stage reactor is 22～12 (mol ratios) than scope, is preferably 18～14 (mol ratios).Behind three sections reactor drums, be provided with MP steam producer, low pressure steam generator and back interchanger, produce MP steam, LP steam and hot water respectively, with abundant recovery reaction heat.
Each section reactor drum of the present invention can partly or entirely adopt radially, the diameter of axle to or the insulation fix bed reactor of its combination, its preferred complete radially fixed reactor of thermal insulation that adopts.Adiabatic radial fixed-bed reactor comprises radial reactor and axial-radial flow reactor; Radial reactor is made up of reactor shell, two co-axial porous distribution tubes, upper cover, lower cover and catalyzer cover plates; Cylindrical shell and the outer annular space that distributes between the tube form outer flow passage; The internal space of inside distributor forms center flow channels, loads catalyzer between the inside and outside distribution tube; Axial-radial flow reactor is a kind of radial reactor that adopts catalyzer self-sealing structure at the top of radial bed; The catalyst in reactor thickness of bed layer is at 400～600mm.
Each section of the present invention reactor drum adopt thermal insulation radially or the diameter of axle to fixed-bed reactor, have advantages such as runner is short, resistance is little, throughput is big, can use catalyst particle, air speed is big.
The present invention adopts three sections reaction process, and reactor drum adopts adiabatic radial fixed-bed pattern, relatively has following beneficial effect with prior art:
Adopt three sections oxidizing reaction technologies and adiabatic radial fixed-bed reactor, make total water alkene ratio reduce to 6～8, reduced steam consumption, practiced thrift energy by 14～16.Main technique equipment is made up of first stage reactor, a sect heat-exchanger, steam heater, second stage reactor, two sect heat-exchangers, steam heater, three sections reactor drums, MP steam producer, low pressure steam generator and back interchanger successively, is filled with Fe-series catalyst in the reactor drum; The used water vapor of first stage reactor through one, two sect heat-exchangers generate gas with one section reaction respectively and second-stage reaction generate the gas heat exchange, heat up overheated after; Reach the first stage reactor temperature in one section reaction batching butylene, air mixed in proportion again, get into first stage reactor and react; One section generates gas after sect heat-exchanger heat exchange cooling, mixes and reaches the second stage reactor temperature in again with through measuring two section feeding liquid phase butylene, air and liquid phase water respectively, and the entering second stage reactor reacts.Two sections generate gas after two sect heat-exchanger heat exchange cooling, measure three section feeding liquid phase butylene, air and liquid phase water respectively with warp again and mix and reach three sections reactor inlet temperatures, get into three sections reactor drums and react.
Steam or water are to add respectively in three sections reactions, and wherein, steam is adopted in one section reaction, and liquid phase water is adopted in two, three sections reactions, has reduced by one section quantity of steam that reaction is added; Two sections, three sections are adopted water, directly generate gas with the preceding paragraph reaction and mix, evaporate and form gas phase mixture, minimizing steam add-on; Three sections reactor outlet high temperature, no longer with the charging heat exchange, but respectively with low pressure steam generator and MP steam producer in water heat exchange, cooling, and by-product MP steam and LP steam are with the heat energy of efficient recovery.Produce divinyl per ton, total steam consumption of oxidation reaction process is reduced to below 2 tons, and joint steam effect is obvious; In the time of minimizing system steam add-on, wastewater flow rate, Wastewater Pretreatment amount and externally discharged waste water amount that correspondence minimizing system is produced.
By one group of 2 diameter is 3 meters, the axially-located bed second-stage reaction system that forms of high 4.5 meters thermal insulation, and its yearly capacity is about 20,000 tons of divinyl.During 100,000 tons of divinyl of current year's production ability, need 5 groups to compose in parallel the second-stage reaction system, every group is that 3 meters, high about 4.5 meters reactor drums constitute by 2 diameters; When adopting adiabatic radial fixed-bed reactor of the present invention and existing two-stage oxidizing reaction process, only need one group by 2 radially or axial-radial flow reactor, reactor diameter is 3.6 meters, high 8.5 meters, can produce 100000 tons of divinyl per year; When adopting three sections oxidizing reaction technologies of the present invention and adiabatic radial fixed-bed reactor, only need one group by 3 radial reactors, about 3.2 meters of reactor diameter, high 7.5 meters can be produced 100000 tons of divinyl per year.Number obviously reduces and reduces investment greatly, simultaneously because of the minimizing of number, also will reduce the corresponding investment of plant area, civil engineering, instrument and pipe arrangement aspect; Compare to fixed-bed process with original two step process Adiabatic axle, technology of the present invention will be practiced thrift investment about 30%.
Description of drawings
Fig. 1 is the axial insulation fix bed reactor FB(flow block) of two-stage oxidizing dehydrogenation;
Fig. 2 is three sections oxydehydrogenation radial adiabatics of the present invention fixed-bed reactor FB(flow block).
Embodiment
Embodiment 1:
Produce the oxidative dehydrogenation process of 100,000 tons of butadiene product equipments per year, adopt three sections oxidizing reaction technologies of the present invention, insulation fix bed reactor is 1 group 3, and one section adds steam, and two, three sections add entry, and each section reactor drum butylene adds per-cent and is: 40:30:30.
One section adds 0.7MPa.G MP steam amount: 50 tons/hour.
Two sections add the water yield: 0.5 ton/hour.
Three sections add the water yield: 0.5 ton/hour.
Three sections by-product 0.7MPa.G MP steam amounts: 33.7 tons/hour.
Three sections by-product 0.3MPa.G LP steam amounts: 2.3 tons/hour.
Total water alkene ratio: 7.2:1.
MP steam consumption: 16.3 tons/hour (one section adds the MP steam amount and subtracts three sections by-product MP steam amounts).
The ton divinyl consumes the MP steam amount: 1.304 tons of/ton divinyl.
When adopting two sections insulation fix bed reactors, it is configured to 5 groups, second-stage reaction; One section adds steam, and two sections add entry; One section adds 62.5 tons/hour of 0.7MPa.G MP steam amounts, and two sections add 2 tons/hour of the water yields; By-product 0.7MPa.G MP steam amount is 31 tons/hour; By-product 0.3MPa.G LP steam amount is 2.6 tons/hour.
Compare with the steam consumption of two sections insulation fix bed reaction process, adopt oxidizing reaction technology of the present invention to use 12.5 tons/hour of 0.7MPa.G MP steams less; 2.7 tons/hour of this many by-product of technology 0.7MPa.G MP steams, 0.3 ton/hour of few by-product 0.3MPa.G LP steam; Total 15.2 tons/hour of MP steam amounts of practicing thrift.
Compare with two sections insulation fix bed reaction process, the sewage quantity that adopts three sections oxidizing reaction technologies of the present invention to produce is reduced to 51 tons/hour by 64.5 tons/hour.
Embodiment 2:
Produce the oxidative dehydrogenation process of 100,000 tons of butadiene product equipments per year, adopt three sections oxidizing reaction technologies of the present invention, insulation fix bed reactor, one section adds steam, and two sections add entry, three sections and add entry, and each reactor drum butylene adds per-cent: 45:30:25.
One section adds 0.7MPa.G MP steam amount: 54 tons/hour.
Two sections add the water yield: 0.7 ton/hour.
Three sections add the water yield: 0.5 ton/hour.
Three sections by-product 0.7MPa.G MP steam amounts: 33.3 tons/hour.
Three sections by-product 0.3MPa.G LP steam amounts: 2.3 tons/hour.
Total water alkene ratio: 7.5:1.
MP steam consumption: 20.7 tons/hour (one section adds the MP steam amount and subtracts three sections by-product MP steam amounts).
The ton divinyl consumes the MP steam amount: 1.656 tons of/ton divinyl.
When adopting two sections insulation fix bed reactors, it disposes 5 groups, second stage reactor; One section adds steam, and two sections add entry; One section adds 62.5 tons/hour of 0.7MPa.G MP steams, and two sections add 2 tons/hour of the water yields; By-product 0.7MPa.G MP steam amount is 31 tons/hour; By-product 0.3MPa.G LP steam amount is 2.6 tons/hour.
Compare with the steam consumption of two sections insulation fix bed reaction process, adopt oxidizing reaction technology of the present invention to use 8.5 tons/hour of 0.7MPa.G MP steams less; 2.3 tons/hour of this many by-product of technology 0.7MPa.G MP steams, few 0.3 ton/hour of few by-product 0.3MPa.G LP steam amount; Total 10.8 tons/hour of MP steam amounts of practicing thrift.
Compare with two sections insulation fix bed reaction process, the sewage quantity that adopts three sections oxidizing procesies of the present invention to produce is reduced to 55.2 tons/hour by 64.5 tons/hour.
Embodiment 3:
Produce the oxidative dehydrogenation process of 100,000 tons of butadiene product equipments per year, adopt three sections oxidizing reaction technologies of the present invention, insulation fix bed reactor, one section adds steam, and two sections add entry, three sections and add entry, and each reactor drum butylene adds per-cent and is: 45:35:20.
One section adds 0.7MPa.G MP steam amount: 54 tons/hour.
Two sections add the water yield: 0.1 ton/hour.
Three sections add the water yield: 1.2 tons/hour.
Three sections by-product 0.7MPa.G MP steam amounts: 36.1 tons/hour.
Three sections by-product 0.3MPa.G LP steam amounts: 2.3 tons/hour.
Total water alkene ratio: 7.5:1.
MP steam consumption: 17.9 tons/hour (one section adds the MP steam amount and subtracts three sections by-product MP steam amounts).
The ton divinyl consumes the MP steam amount: 1.432 tons of/ton divinyl.
When adopting two sections insulation fix bed reactors, it disposes 5 groups, second stage reactor; One section adds steam, and two sections add entry; One section adds 62.5 tons/hour of 0.7MPa.G MP steams, and two sections add 2 tons/hour of the water yields; By-product 0.7MPa.G MP steam amount is 31 tons/hour; By-product 0.3MPa.G LP steam amount is 2.6 tons/hour.
Compare with the steam consumption of two sections insulation fix bed reaction process, adopt oxidizing reaction technology of the present invention to use 8.5 tons/hour of 0.7MPa.G MP steams less; 5.1 tons/hour of this many by-product of technology 0.7MPa.G MP steams.0.3 ton/hour of few by-product 0.3MPa.G LP steam is always practiced thrift 13.6 tons/hour of MP steam amounts.
Compare with two sections insulation fix bed reaction process, the sewage quantity that adopts three sections oxidizing procesies of the present invention to produce is reduced to 55.3 tons/hour by 64.5 tons/hour.
Claims (6)
1. a preparing butadiene with butylene oxo-dehydrogenation technology adopts insulation fix bed reactor and multistage reaction process flow process, and it is characterized in that: reactor drum is adiabatic radial fixed-bed reactor; The reaction process flow process is three sections reaction process flow processs; Described three sections reaction process flow processs are: one section used water vapor through metering of reaction generates gas heat exchange, intensification and overheated with the high temperature that comes out of first stage reactor and second stage reactor respectively through a sect heat-exchanger, two sect heat-exchangers successively; After mixing by a certain percentage and reach the first stage reactor temperature in one section used butylene, air again, get into first stage reactor and react through metering respectively; One section reaction is given birth to the high temperature that device comes out and is generated gas after sect heat-exchanger heat exchange cooling, again with through second-stage reaction charging butylene, the air of metering respectively, water mixes and reach the second stage reactor temperature in, the entering second stage reactor reacts; The high temperature that second stage reactor comes out generates gas after two sect heat-exchanger heat exchange cooling; Mix with three sections reaction feed butylene, air, water again and reach three sections reactor inlet temperatures through metering; Getting into three sections reactor drums reacts; The high temperature that three sections reactor drums come out generates gas and cools off through MP steam producer, low pressure steam generator and aftercooler heat exchange, and by-product MP steam, LP steam and hot water respectively.
2. preparing butadiene with butylene oxo-dehydrogenation technology according to claim 1 is characterized in that: what the first stage reactor charging was used is water vapor and gas phase butylene; Second stage reactor and three sections used water and butylene of reactor drum are liquid phase states, and first stage reactor water alkene is 22～12 mol ratios than scope, preferred 18～14 mol ratios.
3. preparing butadiene with butylene oxo-dehydrogenation technology according to claim 1 is characterized in that: the butene feed per-cent of first stage reactor, second stage reactor and three sections reactor drums is: 65～40:50～20:40～15.
4. preparing butadiene with butylene oxo-dehydrogenation technology according to claim 1 is characterized in that: the oxygen alkene mol ratio of advancing first stage reactor, second stage reactor and three sections reactor drums is respectively: 0.50～0.65:0.55～0.70:0.60～0.75.
5. preparing butadiene with butylene oxo-dehydrogenation technology according to claim 1 and 2 is characterized in that: each section reactor drum part or all adopt radially, the diameter of axle to or the insulation fix bed reactor of its combination, the preferred complete adiabatic radial fixed-bed reactor that adopts; Radial reactor comprises radial reactor and axial-radial flow reactor; Radial reactor reactor shell, two co-axial porous distribution tubes, upper cover, lower cover and catalyzer cover plates are formed; Cylindrical shell and the outer annular space that distributes between the tube form outer flow passage; The internal space of inside distributor forms center flow channels, loads catalyzer between the inside and outside distribution tube; Axial-radial flow reactor is a kind of radial reactor that adopts catalyzer self-sealing structure at the top of radial bed; The catalyst in reactor thickness of bed layer is at 400～600mm.
6. divinyl preparation technology according to claim 1 is characterized in that: radially or in the axial-radial flow reactor, fluid through catalyst bed, adopts the radial inflow fluid-flow mode with the radial flow mode at each section.
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| CN103086829A (en) * | 2013-01-30 | 2013-05-08 | 中国石油化工股份有限公司 | Recycling method for butylene oxidative dehydrogenation wastewater |
| CN103965001A (en) * | 2013-01-30 | 2014-08-06 | 中国石油化工股份有限公司 | Heat recovery method used for oxidative dehydrogenation reaction of butylene |
| CN103965000A (en) * | 2013-01-30 | 2014-08-06 | 中国石油化工股份有限公司 | Method for producing butadiene through oxidation dehydrogenation of butene |
| CN103965004A (en) * | 2013-01-30 | 2014-08-06 | 中国石油化工股份有限公司 | Butylene oxidation method for producing butadiene |
| CN103964997A (en) * | 2013-01-30 | 2014-08-06 | 中国石油化工股份有限公司 | Treatment method for butylene oxydehydrogenation products |
| CN104418693A (en) * | 2013-09-02 | 2015-03-18 | 中国石化工程建设有限公司 | Energy-saving method of device for preparing butadiene by oxidative dehydrogenation of butene |
| CN104974004A (en) * | 2014-04-03 | 2015-10-14 | 中国石化工程建设有限公司 | Method for reducing steam consumption of device reactor for preparing butadiene by virtue of oxidative dehydrogenation of butene |
| WO2016003215A1 (en) * | 2014-07-02 | 2016-01-07 | 주식회사 엘지화학 | Method for recycling energy in butadiene preparation process |
| CN107986930A (en) * | 2017-12-15 | 2018-05-04 | 常州瑞华化工工程技术股份有限公司 | Using the process of Oxidative Dehydrogenation of Butene Into Butadiene and three sections of insulation fix bed reaction systems |
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| CN103965001B (en) * | 2013-01-30 | 2016-12-28 | 中国石油化工股份有限公司 | Butylene oxidation-dehydrogenation reaction heat recovery method |
| CN103086829A (en) * | 2013-01-30 | 2013-05-08 | 中国石油化工股份有限公司 | Recycling method for butylene oxidative dehydrogenation wastewater |
| CN103965004A (en) * | 2013-01-30 | 2014-08-06 | 中国石油化工股份有限公司 | Butylene oxidation method for producing butadiene |
| CN103964997A (en) * | 2013-01-30 | 2014-08-06 | 中国石油化工股份有限公司 | Treatment method for butylene oxydehydrogenation products |
| CN103964997B (en) * | 2013-01-30 | 2016-04-13 | 中国石油化工股份有限公司 | The treatment process of butylene oxidation-dehydrogenation product |
| CN103965000A (en) * | 2013-01-30 | 2014-08-06 | 中国石油化工股份有限公司 | Method for producing butadiene through oxidation dehydrogenation of butene |
| CN103965001A (en) * | 2013-01-30 | 2014-08-06 | 中国石油化工股份有限公司 | Heat recovery method used for oxidative dehydrogenation reaction of butylene |
| CN103965000B (en) * | 2013-01-30 | 2016-08-03 | 中国石油化工股份有限公司 | The method of Oxidative Dehydrogenation of Butene Into Butadiene |
| CN104418693A (en) * | 2013-09-02 | 2015-03-18 | 中国石化工程建设有限公司 | Energy-saving method of device for preparing butadiene by oxidative dehydrogenation of butene |
| CN104418693B (en) * | 2013-09-02 | 2016-06-15 | 中国石化工程建设有限公司 | A kind of power-economizing method of Oxidative Dehydrogenation of Butene into Butadiene device |
| CN104974004A (en) * | 2014-04-03 | 2015-10-14 | 中国石化工程建设有限公司 | Method for reducing steam consumption of device reactor for preparing butadiene by virtue of oxidative dehydrogenation of butene |
| CN106458790A (en) * | 2014-07-02 | 2017-02-22 | Lg化学株式会社 | Method for recycling energy in butadiene preparation process |
| US10066514B2 (en) | 2014-07-02 | 2018-09-04 | Lg Chem, Ltd. | Method of recycling energy in process of butadiene preparation |
| WO2016003215A1 (en) * | 2014-07-02 | 2016-01-07 | 주식회사 엘지화학 | Method for recycling energy in butadiene preparation process |
| US10526259B2 (en) | 2015-08-29 | 2020-01-07 | Uop Llc | Staged pressure for butadiene reactors to enhance energy recovery |
| CN107986930A (en) * | 2017-12-15 | 2018-05-04 | 常州瑞华化工工程技术股份有限公司 | Using the process of Oxidative Dehydrogenation of Butene Into Butadiene and three sections of insulation fix bed reaction systems |
| CN114459263B (en) * | 2020-10-21 | 2023-08-29 | 中国石油化工股份有限公司 | Heat exchanger, butene oxidative dehydrogenation device and method for preparing butadiene by butene oxidative dehydrogenation |
| CN114459263A (en) * | 2020-10-21 | 2022-05-10 | 中国石油化工股份有限公司 | Heat exchanger, butylene oxidative dehydrogenation device and method for preparing butadiene through butylene oxidative dehydrogenation |
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