CN203355710U - Rapid fluidized bed reactor for producing butadiene by butylene oxydehydrogenation - Google Patents
Rapid fluidized bed reactor for producing butadiene by butylene oxydehydrogenation Download PDFInfo
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- CN203355710U CN203355710U CN 201320420329 CN201320420329U CN203355710U CN 203355710 U CN203355710 U CN 203355710U CN 201320420329 CN201320420329 CN 201320420329 CN 201320420329 U CN201320420329 U CN 201320420329U CN 203355710 U CN203355710 U CN 203355710U
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Abstract
The utility model discloses a rapid fluidized bed reactor for producing butadiene by butylene oxydehydrogenation. A discharge port (1a) is formed at the bottom end of a lifting section (6) of the reactor; an upper heat exchanger (3b) and a lower heat exchanger (3a) are arranged in the middle part and the lower part of the lifting section (6); lower air inlet nozzles (2a) are arranged below the lower heat exchanger (3a); middle air inlet nozzles (2b) are arranged between the upper heat exchanger (3b) and the lower heat exchanger (3a); upper air inlet nozzles (2c) are arranged above the upper heat exchanger (3b); the lifting section (6) is connected with a cyclone separator (9); a solid outlet of the cyclone separator (9) is connected with an auxiliary bed (12) through a return pipe (10); a feed port (11) is formed in the return pipe (10); a discharge port (1b) is formed at the bottom end of the auxiliary bed (12); a gas distributor (16) and a fluidized gas inlet (17) are arranged and formed in the lower part of the auxiliary bed (12); and the lifting section (6) is connected with the auxiliary bed (12) through a connecting section (19). The reactor has the advantages of high butylene conversion rate, high butadiene yield and simple structure.
Description
Technical field
The utility model relates to a kind of fluidized-bed reactor, especially a kind of fluidized-bed reactor of realizing butylene efficient oxidation dehydrogenation generation butadiene.
Background technology
Butadiene is the simplest conjugated diene, and its structural formula is: CH
2=CH-CH=CH
2, belonging to organic compound, it is the intermediate of many petroleum chemicals.Butadiene is a kind of important petrochemicals, is the important monomer of producing synthetic rubber and other high molecular synthetic materials, aspect engineering plastics and Organic chemical products synthetic, also is widely used.Utilize butadiene and styrene copolymerized resin that can the production various uses, make butadiene also occupy gradually critical role in production of resins.In addition, butadiene is also for the production of adiponitrile, oxolane etc., thereby is also important basic chemical industry raw material.Butadiene also has a lot of use in fine chemicals production, and the butadiene of take can make the fine chemicals such as THPA, cyclobufene sultone as raw material.
At present, the production method of butadiene mainly contains C-4-fraction partition method and synthetic method (comprising catalytic dehydrogenation and oxidative dehydrogenation).
Take naphtha or diesel oil when cracking stock is produced ethene, and in the C-4-fraction of by-product, butadiene content is up to 50%, and the industrial extraction rectifying method that all adopts separates butadiene wherein.This method once provided the butadiene supply more than 90%, but its defect also clearly: cost is higher, and energy consumption is excessive, is not the independent process of producing butadiene.Along with the swift and violent increase of butadiene demand, partition method can not be satisfied the demand, therefore needs the special independent process of producing butadiene of development.
The catalytic dehydrogenation method is a kind of independent process of producing butadiene, but there are problems in this method: reaction conversion ratio is lower, and energy consumption is high, and steam consumption is large, and high temperature causes cracking, secondary response and catalyst carbon deposit problem serious.So this method is not suitable for commercially producing of butadiene.
The oxidative dehydrogenation method is also a kind of independent process of producing butadiene, and it utilizes oxygen to capture two hydrogen atoms in butylene, generates butadiene and water.Compare oxidative dehydrogenation method with the obvious advantage with the catalytic dehydrogenation method: owing to having generated stable water, in oxidative dehydrogenation, the equilibrium conversion of butylene approaches 100% in theory, and this has significantly and improve than catalytic dehydrogenation; Oxidative dehydrogenation is exothermic reaction, and the heat supply without extra, reduced energy consumption; Oxidative dehydrogenation can obtain higher butadiene productive rate at lower temperature, and low temperature and oxygen can effectively suppress the deposition of cracking reaction and catalyst surface coke; Oxidative dehydrogenation has also generated water, has reduced the consumption of this technique to water resource.The method is the effective independent process of advanced person for preparing butadiene, and it just replaces the catalytic dehydrogenation method after coming out gradually, becomes the important technology route that commercialization prepares butadiene.
The reactor of Oxidative Dehydrogenation of Butene into Butadiene is main two kinds of bed types, i.e. fixed bed and the shelf fluidized bed of adopting at present.
Fixed-bed structure is relatively simple, and its distinct issues are: be prone to the localized hyperthermia district and cause catalyst carbon deposit serious, conversion ratio and yield are low, and production cost is too high, the operating condition harshness, and difficulty is amplified in industry.
The shelf fluidized bed reactor operates in bubbling or turbulence fluidized state, with fixed bed, compares and it is advantageous that: gas-particle heat transfer in reactor, mass transfer rate are high, uniformity of temperature profile; In bed, the heat exchanger tube heat-transfer effect is fine, is easy to control bed temperature in optimal reaction temperature; Industry amplification performance excellence, be suitable for large-scale operation; The handling of catalyst supplement more convenient.These advantages make the shelf fluidized bed reactor be specially adapted to the process system of oxidative dehydrogenation method, so shelf fluidized bed oxidative dehydrogenation butadiene technology processed obtained generally application, are the mainstream technologys that current industry prepares butadiene.The baffle plate arranged in the shelf fluidized bed reactor can suppress air bubble growth, broken air pocket, improve fluidization quality, and this has improved contacting of gas and catalyst, has suppressed the axial backmixing of gas, is conducive to improve conversion ratio and selective.But still there are some problems in shelf fluidized bed oxidative dehydrogenation method: baffle plate is limited to the inhibitory action of bubble, still there is bubble in the baffle plate bed, cause butene conversion (～69%) and butadiene yield (～62%) in the baffle plate bed bioreactor still relatively low; The existence of baffle plate has limited the axial mixing of catalyst granules, and then causes reactor axial temperature skewness, to reacting unfavorable; Baffle plate is set and makes structure of reactor very complicated, device fabrication and maintenance difficulty, first cost is high.
Summary of the invention
The purpose of this utility model is butene conversion and the low problem of butadiene yield existed in existing shelf fluidized bed Oxidative Dehydrogenation of Butene into Butadiene technology, and a kind of fluidized-bed reactor that butene conversion is high, the butadiene yield is high, simple in structure that has is provided.
In order to reach the purpose of this utility model, the technical scheme of employing is as follows:
Fluidized-bed reactor of the present utility model, it is by raising section, cyclone separator, companion's bed and linkage section form, the bottom, raising section is provided with discharge port, be set up heat exchanger and lower heat exchanger in middle part, raising section and bottom, be provided with lower nozzle of air supply below lower heat exchanger, be provided with middle nozzle of air supply between upper heat exchanger and lower heat exchanger, be provided with the upper air nozzle above upper heat exchanger, the outlet of top, raising section is connected with the import of cyclone separator, the solid outlet of cyclone separator is connected with companion's bed by the feed back pipe, be provided with charging aperture on the feed back pipe, companion's bed bottom is provided with discharge port, the built-in gas distributor in companion bed bottom, external heat exchanger is arranged on gas distributor, be provided with the fluidized gas entrance below the gas distributor of companion's bed, the raising section that is positioned at lower nozzle of air supply top is connected with the companion's bed that is positioned at the gas distributor top by linkage section.
Described lower nozzle of air supply, middle nozzle of air supply and upper air nozzle all adopt the spiral-flow type mounting means, and they have played the effect of gas distributor jointly.Each group nozzle of air supply is installed on same cross section, same cross section can be along circumferentially being evenly arranged 4-8 root nozzle of air supply, during installation, the every acclivitous angle [alpha] of nozzle is 5-25 °, the angle beta of every nozzle Off-Radial is 10-40 °, and many nozzles inclinations are installed and can be produced the air-flow rotated up.When air velocity reaches the fast bed condition, in raising section, tiny catalyst granules will be rotated air-flow upwards and carry motion secretly, in fast fluidized condition.
Described upper heat exchanger and lower heat exchanger adopt sleeve pipe or single hose heat exchanger structure, can to the adverse effect of raising section fluidization quality, be down to minimum by heat exchanger like this.According to size and the temperature controlled requirement of raising section heat exchange amount, upper heat exchanger and lower heat exchanger have also played the effect of vertical inner member.
Described cyclone separator is arranged in outside raising section, has played the effect of gas solid separation, can one or more levels layout according to the requirement of gas solid separation.
Can also heat exchanger be set according to the requirement of heat exchange amount and the size of solid cycle quantity in companion's bed.Because the fluidization quality to companion's bed is less demanding, when being set, external heat exchanger can adopt coiled pipe, U-shaped pipe or bundled tube structure.According to the size of companion's bed heat exchange amount, external heat exchanger can one or more levels layout.
For realizing the fast fluidization operation in raising section, the catalyst granules average grain diameter adopted during described Oxidative Dehydrogenation of Butene into Butadiene fast fluidized bed reactor operation is 20-200 μ m.
Linkage section as above is provided with material returning valve.
The utility model has the advantage of:
Butene feedstock gas and small catalyst particles in raising section in fast fluidized condition.Now the relative velocity of gas and particle is large, is conducive to overcome the alternate diffusional resistance of gas-solid, to promoting reaction very favourable; There do not is bubble in fast bed, fundamentally overcome the inefficient problem of gas-solid contact caused due to bubble in shelf fluidized bed, be conducive to improve conversion ratio; There is hardly gas backmixing in the Oxidative Dehydrogenation of Butene into Butadiene fast fluidized bed reactor, well suppressed the generation of side reaction.With current shelf fluidized bed technology, compare, the fast fluidized bed Oxidative Dehydrogenation of Butene into Butadiene method that the utility model provides can improve butene conversion and the about 15-20% of butadiene yield in maintenance high selectivity and low fluff pulp, and this processes all highly beneficial to reducing energy consumption, raising output and pollutant.
2. owing to there not being bubble in fast bed, thus in the utility model fast bed without baffle plate is set, this is the simplified apparatus structure greatly, reduces initial cost, has facilitated maintenance and has installed.
3. the raising section gas distributor adopts the swirl jet structure, has so just eliminated the potential safety hazard that the pre-distribution air chamber that adopts distribution grid hourglass material to cause may react and even explode.
The accompanying drawing explanation:
Fig. 1 is structural representation of the present utility model.
Fig. 2 is the A-A cutaway view of the utility model embodiment 1.
Fig. 3 is the A-A cutaway view of the utility model embodiment 2.
Fig. 4 is the A-A cutaway view of the utility model embodiment 3.
In figure: 1a is discharge port, and 1b is discharge port; 2a is lower nozzle of air supply, and 2b is middle nozzle of air supply, and 2c is the upper air nozzle; 3a is lower heat exchanger, and 3b is upper heat exchanger; 4 is the heat transferring medium entrance; 5 is the heat transferring medium outlet; 6 is raising section; 7 is the raising section outlet; 8 is product gas outlet; 9 is cyclone separator; 10 is cyclone separator feed back pipe; 11 is charging aperture; 12 is companion's bed; 13 is the external heat exchanger media outlet; 14 is external heat exchanger; 15 is the external heat exchanger medium inlet; 16 is gas distributor; 17 is the fluidized gas entrance; 18 is material returning valve; 19 is linkage section.
Below in conjunction with accompanying drawing, the utility model is elaborated.Be only below preferred embodiment of the present utility model, can not limit scope of the present utility model with this.Be that every equalization of doing according to the utility model claim changes and modifies, within all should belonging to the scope that the utility model patent contains.
The specific embodiment
Embodiment 1
A kind of fluidized-bed reactor of Oxidative Dehydrogenation of Butene into Butadiene, it is by raising section 6, cyclone separator 9, companion's bed 12 and linkage section 19 form, 6 bottoms, raising section are provided with discharge port 1a, establish heat exchanger 3b and lower heat exchanger 3a in middle part, raising section and bottom, below lower heat exchanger 3a on same cross section, along circumferentially being evenly arranged and being provided with 4 lower nozzle of air supply 2a, the every acclivitous angle [alpha] of lower nozzle of air supply is 20 °, the angle beta of Off-Radial is 30 °, on same cross section between upper heat exchanger 3b and lower heat exchanger 3a, along circumferentially being evenly arranged 5 middle nozzle of air supply 2b, the every acclivitous angle [alpha] of middle nozzle of air supply is 15 °, the angle beta of Off-Radial is 25 °, on same cross section above upper heat exchanger 3b, along circumferentially being evenly arranged 4 upper air nozzle 2c, the every acclivitous angle [alpha] of upper air nozzle is 10 °, the angle beta of Off-Radial is 20 °, top, raising section outlet 7 is connected with the import of cyclone separator 9, the solid outlet of cyclone separator 9 is connected with companion's bed 12 by feed back pipe 10, be provided with charging aperture 11 on feed back pipe 10, companion's bed 12 bottoms are provided with discharge port 1b, companion's bed 12 built-in gas distributors 16 in bottom, external heat exchanger 14 is arranged on gas distributor 16, be provided with fluidized gas entrance 17 below the gas distributor 16 of companion's bed 12, the raising section 6 that is positioned at lower nozzle of air supply 2a top is connected with the companion's bed 12 that is positioned at gas distributor 16 tops by linkage section 19, be provided with material returning valve 18 on linkage section 19.
As shown in Figure 1, first open the medium circulation in heat exchanger 3a and 3b during driving, the unstripped gas that then will be preheated to 320-400 ℃ is sent into raising section 6 bottoms formation rotations air-flow upwards through lower nozzle of air supply 2a, as nozzle 2b while needing subsection-inlet, 2c also opens, the temperature to be hoisted section 6 outlet 7 places and the medium temperature at heat exchanger exit 5a and 5b place are opened entrance 17 to accompanying bed 12 to send into fluidizing gas after all reaching stable state, add catalyst granules from charging aperture 11 to companion's bed 12 afterwards, after reaching the stabilization fluid state, the gas-solid in companion's bed 12 opens material returning valve 18 6 bottom feedings to raising section, tiny catalyst granules enters behind 6 bottoms, raising section and contacts with the high temperature unstripped gas and catalytic reaction occurs, overwhelming majority catalyst granules are rotated that updraft carries and, in fast fluidized condition, the small part particle falls discharges raising section 6 by discharge port 1a, carry air-flow upwards motion in raising section 6 of a large amount of particles, after bottom concentrated phase section, middle part changeover portion and top dilute phase section, finally by raising section 6 top exits 7, flow out into cyclone separator 9, after cyclone separator 9 gas solid separation, catalyst granules falls into separator feed back pipe 10, and the gas product after separation is drawn by product gas outlet 8, the recycling catalyst particle separated all enters in the fluidized-bed layer of companion's bed 12 through feed back pipe 10 with the fresh catalyst particle from charging aperture 11, catalyst granules in companion's bed bed reenters the bottom participation reaction of raising section 6 under the control action of material returning valve 18 through linkage section 19, whole process loops.The butylene oxidation-dehydrogenation reaction can discharge very large heat, by being arranged on heat exchanger 3a and the 3b in raising section 6 and being aided with heat exchanger 14, can shift out rapidly unnecessary heat, and the assurance dehydrogenation reaction is carried out under best temperature conditions; Wherein the medium in heat exchanger 3a and 3b enters from bottom entrance 4a and 4b respectively, after heat absorption, by top outlet 5a and 5b, discharged respectively, medium in heat exchanger 14 enters from bottom entrance 15, after heat absorption, by top outlet 13, discharged, the endless form of medium adopts Natural Circulation or forced circulation all can as required.
Adopt the fluidized-bed reactor shown in Fig. 1, the spherical iron series catalysts particle that the average grain diameter of take is 70-110 μ m is solid material, and the mixture of butylene, steam, air of take is unstripped gas, at 370 ℃ of reaction temperatures, air speed 325h
-1, oxygen alkene is than 0.9, and water alkene is than under 7.8 condition, and butene conversion is 90%, and the butadiene yield is 81%.
Embodiment 2
Adopt the fluidized-bed reactor shown in Fig. 1, be provided with 6 lower nozzle of air supply 2a below lower heat exchanger 3a, the every acclivitous angle [alpha] of lower nozzle of air supply is 15 °, the angle beta of Off-Radial is 25 °, be provided with 4 middle nozzle of air supply 2b between upper heat exchanger 3b and lower heat exchanger 3a, the every acclivitous angle [alpha] of middle nozzle of air supply is 10 °, the angle beta of Off-Radial is 20 °, be provided with 5 upper air nozzle 2c above upper heat exchanger 3b, the every acclivitous angle [alpha] of upper air nozzle is 5 °, the angle beta of Off-Radial is 20 °, the spherical iron series catalysts particle that the average grain diameter of take is 20-60 μ m is solid material, with butylene, steam, the mixture of air is unstripped gas, 360 ℃ of reaction temperatures, air speed 280h
-1, oxygen alkene is than 0.75, and water alkene is than under 7 condition, and butene conversion is 86%, and the butadiene yield is 76%.Remainder is identical with embodiment 1.
Embodiment 3
Adopt the fluidized-bed reactor shown in Fig. 1, be provided with 5 lower nozzle of air supply 2a below lower heat exchanger 3a, the every acclivitous angle [alpha] of lower nozzle of air supply is 20 °, the angle beta of Off-Radial is 30 °, be provided with 6 middle nozzle of air supply 2b between upper heat exchanger 3b and lower heat exchanger 3a, the every acclivitous angle [alpha] of middle nozzle of air supply is 15 °, the angle beta of Off-Radial is 20 °, be provided with 4 upper air nozzle 2c above upper heat exchanger 3b, the every acclivitous angle [alpha] of upper air nozzle is 10 °, the angle beta of Off-Radial is 20 °, the spherical iron series catalysts particle that the average grain diameter of take is 160-200 μ m is solid material, with butylene, steam, the mixture of air is unstripped gas, 375 ℃ of reaction temperatures, air speed 380h
-1, oxygen alkene is than 0.8, and water alkene is than under 10.0 condition, and butene conversion is 88%, and the butadiene yield is 78%.Remainder is identical with embodiment 1.
Claims (8)
1. an Oxidative Dehydrogenation of Butene into Butadiene fast fluidized bed reactor, it is by raising section (6), cyclone separator (9), companion's bed (12) and linkage section (19) form, it is characterized in that bottom, raising section (6) is provided with discharge port (1a), be set up heat exchanger (3b) and lower heat exchanger (3a) in raising section (6) middle part and bottom, be provided with lower nozzle of air supply (2a) in lower heat exchanger (3a) below, be provided with middle nozzle of air supply (2b) between upper heat exchanger (3b) and lower heat exchanger (3a), be provided with upper air nozzle (2c) in upper heat exchanger (3b) top, top, raising section (6) outlet (7) is connected with the import of cyclone separator (9), the solid outlet of cyclone separator (9) is connected with companion's bed (12) by feed back pipe (10), be provided with charging aperture (11) on feed back pipe (10), companion's bed (12) bottom is provided with discharge port (1b), companion's bed built-in gas distributor in (12) bottom (16), external heat exchanger (14) is arranged on gas distributor (16), gas distributor (16) below at companion's bed (12) is provided with fluidized gas entrance (17), the raising section (6) that is positioned at lower nozzle of air supply (2a) top is connected with the companion's bed (12) that is positioned at gas distributor (16) top by linkage section (19).
2. a kind of Oxidative Dehydrogenation of Butene into Butadiene fast fluidized bed reactor as claimed in claim 1, is characterized in that described lower nozzle of air supply (2a), middle nozzle of air supply (2b) and upper air nozzle (2c) all adopt the spiral-flow type mounting means.
3. a kind of Oxidative Dehydrogenation of Butene into Butadiene fast fluidized bed reactor as claimed in claim 2, it is characterized in that described spiral-flow type mounting means is each group nozzle of air supply of nozzle of air supply (2a), middle nozzle of air supply (2b) or upper air nozzle (2c) at present to be installed be installed on same cross section, same cross section is along circumferentially being evenly arranged 4-8 root nozzle of air supply, the every acclivitous angle [alpha] of nozzle is 5-25 °, and the angle beta of every nozzle Off-Radial is 10-40 °.
4. a kind of Oxidative Dehydrogenation of Butene into Butadiene fast fluidized bed reactor as claimed in claim 1, is characterized in that described lower nozzle of air supply (2a), middle nozzle of air supply (2b) or upper air nozzle (2c) adopt sleeve pipe or single hose heat exchanger structure.
5. a kind of Oxidative Dehydrogenation of Butene into Butadiene fast fluidized bed reactor as claimed in claim 1, is characterized in that described cyclone separator (9) is for one or more levels.
6. a kind of Oxidative Dehydrogenation of Butene into Butadiene fast fluidized bed reactor as claimed in claim 1, is characterized in that described external heat exchanger (14) adopts coiled pipe, U-shaped pipe or bundled tube structure.
7. a kind of Oxidative Dehydrogenation of Butene into Butadiene fast fluidized bed reactor as claimed in claim 1, is characterized in that described external heat exchanger (14) is for one or more levels.
8. a kind of Oxidative Dehydrogenation of Butene into Butadiene fast fluidized bed reactor as claimed in claim 1, is characterized in that described linkage section (19) is provided with material returning valve (18).
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201320420329 CN203355710U (en) | 2013-07-16 | 2013-07-16 | Rapid fluidized bed reactor for producing butadiene by butylene oxydehydrogenation |
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| Application Number | Priority Date | Filing Date | Title |
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| CN 201320420329 CN203355710U (en) | 2013-07-16 | 2013-07-16 | Rapid fluidized bed reactor for producing butadiene by butylene oxydehydrogenation |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103341341A (en) * | 2013-07-16 | 2013-10-09 | 中国科学院山西煤炭化学研究所 | Fluidized bed reactor for preparing butadiene |
| CN105013412A (en) * | 2014-04-17 | 2015-11-04 | 上海碧科清洁能源技术有限公司 | Fluidized-bed reaction system and application method of system |
| CN110227394A (en) * | 2019-04-24 | 2019-09-13 | 中国科学院山西煤炭化学研究所 | A kind of fluidized-bed reactor for Catalyst for Oxidative Coupling of Methane |
| CN112384294A (en) * | 2018-07-02 | 2021-02-19 | 奥图泰(芬兰)公司 | Apparatus and method for cooling fine particle solids |
| WO2024039872A1 (en) * | 2022-08-18 | 2024-02-22 | Czero, Inc. | Processes and methods for producing hydrogen and carbon from hydrocarbons |
-
2013
- 2013-07-16 CN CN 201320420329 patent/CN203355710U/en not_active Expired - Lifetime
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103341341A (en) * | 2013-07-16 | 2013-10-09 | 中国科学院山西煤炭化学研究所 | Fluidized bed reactor for preparing butadiene |
| CN103341341B (en) * | 2013-07-16 | 2016-01-27 | 中国科学院山西煤炭化学研究所 | One prepares butadiene fluidized-bed reactor |
| CN105013412A (en) * | 2014-04-17 | 2015-11-04 | 上海碧科清洁能源技术有限公司 | Fluidized-bed reaction system and application method of system |
| CN105013412B (en) * | 2014-04-17 | 2017-07-04 | 上海碧科清洁能源技术有限公司 | Fluidized bed reaction system and the method using the system |
| CN112384294A (en) * | 2018-07-02 | 2021-02-19 | 奥图泰(芬兰)公司 | Apparatus and method for cooling fine particle solids |
| US11697100B2 (en) | 2018-07-02 | 2023-07-11 | Metso Outotec Finland Oy | Device and method for cooling or heating a fine-grained solid |
| CN110227394A (en) * | 2019-04-24 | 2019-09-13 | 中国科学院山西煤炭化学研究所 | A kind of fluidized-bed reactor for Catalyst for Oxidative Coupling of Methane |
| WO2024039872A1 (en) * | 2022-08-18 | 2024-02-22 | Czero, Inc. | Processes and methods for producing hydrogen and carbon from hydrocarbons |
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