CN105536654B - A kind of large-scale axial multistage mixed heat transfer formula butylene oxidation-dehydrogenation reactor - Google Patents
A kind of large-scale axial multistage mixed heat transfer formula butylene oxidation-dehydrogenation reactor Download PDFInfo
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- CN105536654B CN105536654B CN201510935008.1A CN201510935008A CN105536654B CN 105536654 B CN105536654 B CN 105536654B CN 201510935008 A CN201510935008 A CN 201510935008A CN 105536654 B CN105536654 B CN 105536654B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/04—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds
- B01J8/0446—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/42—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor
- C07C5/48—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor with oxygen as an acceptor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/00008—Controlling the process
- B01J2208/00017—Controlling the temperature
- B01J2208/00106—Controlling the temperature by indirect heat exchange
- B01J2208/00115—Controlling the temperature by indirect heat exchange with heat exchange elements inside the bed of solid particles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/00008—Controlling the process
- B01J2208/00017—Controlling the temperature
- B01J2208/00327—Controlling the temperature by direct heat exchange
Abstract
The present invention relates to a kind of large-scale axial multistage mixed heat transfer formula butylene oxidation-dehydrogenation reactors, including reactor shell, mixing arrangement is arranged in the reactor shell top, and the reactor enclosure body is interior at least provided with two axial catalyst beds, at least containing there are one direct heat transfer sections；The direct heat transfer section is located between two axial catalyst beds, cold shock stream stock is passed through the direct heat transfer section in reactor enclosure body, it carries out after mixing direct heat transfer to the outlet material after catalyst bed reaction with square shaft thereon, is reacted into axial catalyst bed below.Compared with prior art, the present invention have be easily achieved enlargement, can effectively controlling reaction temperature, bed pressure drop it is low, the advantage that capacity usage ratio is high, production capacity is big.
Description
Technical field
The present invention relates to Chemical Reaction Engineering technical fields, and in particular to a kind of large-scale axial multistage mixed heat transfer formula butylene
Oxidative dehydrogenation reactor.
Background technology
Butadiene is to produce the base stock of styrene butadiene rubber sbr, ABS resin, polybutadiene rubber BR etc., and produce oneself
The key intermediate of the chemicals such as dintrile, chlorobutadiene, sulfolane, vinylcyclohexene, it is widely used.Butylene oxidation-dehydrogenation is
A kind of important method of butadiene is produced, butylene mainly generates butadiene by following main reaction partial oxidation dehydrogenation：
C4H8+0.5O2=C4H6+H2O
Butylene and butadiene are further aoxidized by following side reaction respectively generates by-product CO2：
C4H8+6O2=4CO2+4H2O
C4H6+5.5O2=4CO2+3H2O
Oxidative Dehydrogenation of Butene into Butadiene is in the presence of a large amount of water vapours, and butylene is made with the oxygen in air in catalyst
Dehydrogenation reaction is carried out under, generates butadiene and water.The major influence factors of butylene oxidation-dehydrogenation reaction have reaction temperature, reaction
Pressure, water alkene ratio, oxygen alkene ratio etc..It is that guard catalyst and control are anti-because Oxidative Dehydrogenation of Butene into Butadiene is exothermic reaction
Temperature is answered, needs to introduce a large amount of water vapour in reaction process, energy consumption is slightly higher for single stage adiabatic formula reactor.Butylene oxygen
Fluidized dehydrogenation generates butadiene reaction, and wherein oxygen alkene ratio is crucial, raw material proportioning cannot be made to fall into explosion limit, oxygen content mistake
Height can lead to the increase of by-product carbon dioxide, also be easy to cause temperature runaway, too low seriously to reduce butene conversion, this is anti-in addition
Answering pressure is more sensitive, and lower pressure is conducive to the raising of butene conversion and butadiene selective, therefore how to ensure
Safe and stable operation is most important under appropriate conditions for butylene oxidation-dehydrogenation reactor.
It is in flow manifold and afflux runner that patent CN103721643B, which discloses a kind of Z-type i.e. reacting gas stream flowing mode,
The conical water conservancy diversion of setting in the consistent butylene oxidation-dehydrogenation fixed bed radial reactor in interior flow direction, wherein flow manifold
Body, inside and outside distributing barrel be high opening rate, cylinder itself not to reaction gas implement control, although bed pressure drop is low, merely according to
It can not ensure fluid being uniformly distributed inside radial reactor by conical baffle, and butylene oxidation-dehydrogenation reaction is to fluid
Mixed uniformity requirement is very high, and the stabilization for being not only related to reactor temperature also has safety, and the reactor is in butylene oxygen
The feasibility of fluidized dehydrogenation reaction system need the verification of commercial Application.
Patent CN102442874A discloses a kind of method of constant temperature fixed bed preparing butadiene with butylene oxo-dehydrogenation, uses
Tube-shell type fixed bed reactor, middle pipe is built-in to fill out catalyst, and heat transferring medium is used to move heat between pipe, anti-for butylene oxidation-dehydrogenation
It is out of question for the temperature control answered, but the scale of the reactor can be restricted, and tube-shell type fixed bed reactor
Pressure drop is big, cannot be satisfied the requirement of device enlargement.
Patent CN101367702 discloses a kind of method of preparing butadiene with butylene oxo-dehydrogenation of axially-located bed, stream
Journey is using two sections of axially-located bed reactors, and butene feedstock, water vapour and air segmenting enter, and reactor outlet passes through heating
Water vapour and cool down, reach and enter next section of reactor after next section of reactor inlet temperature, even but using this method
Small-scale production is also required to two reactors, more reactors in parallel is just needed if you need to enhance production capacities, from equipment investment and occupation of land
It is all uneconomical from the aspect of area.
Patent CN102675027A discloses a kind of preparing butadiene with butylene oxo-dehydrogenation technique, using adiabatic radially fixed
By preparing butadiene with butylene oxo-dehydrogenation, radial adiabatic fixed bed is formed bed by three sections, but that reactor is not disclosed is specific for patent
Structure.Patent CN103071429A and CN103071430A, which are disclosed, a kind of to react for butylene oxidation-dehydrogenation to be radial fixed-bed
Device uses radial adiabatic fixed bed reactors, catalyst to be mounted between runner and mass flow pathway.Although using radial fixed-bed
Bed pressure drop can be reduced on reactor theory, however, to ensure that reaction gas being uniformly distributed in reactor, it is necessary to adopt
With the distributor of low percent opening, distributor certainly will be caused to generate prodigious pressure drop, butylene oxidation-dehydrogenation cannot be suitable for well
Reaction system.
Currently, industrial Oxidative Dehydrogenation of Butene into Butadiene device generally uses multiple axial insulation fix bed reactor strings
Connection, although structure of reactor is simple, separate unit production capacity is limited, and Oxidative Dehydrogenation of Butene into Butadiene system uses radial reactor
Carry out industrial production mainly due to uniform fluid distribution the problem of limitation also has not been reported, in order to change using increase reactor number of units come
The present situation of production capacity is solved, the novel reactor for being easy to enlargement of exploitation is very necessary.
Invention content
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide one kind being easily achieved large size
Change, can effectively controlling reaction temperature, reduce bed pressure drop, to obtain the big profile shaft that capacity usage ratio is high, production capacity is big
To multistage mixed heat transfer formula butylene oxidation-dehydrogenation reactor.
The present invention mentality of designing be：By the intrinsic and reaction macrokinetics to Oxidative Dehydrogenation of Butene into Butadiene into
Row is investigated, and the reaction rule of the reaction system is grasped.Based on its response characteristic, a kind of large-scale axial multistage mixed heat transfer formula is designed
Butylene oxidation-dehydrogenation reactor：It is provided in reactor suitable for the inlet gas distributor of major diameter reactor, adiabatic catalytic
Agent bed, cold shock distributor and the catalyst bed containing indirect heat exchange, in adiabatic catalyst bed lower end, setting is sprayed containing cold shock
The distributor pipe of mouth, distributor pipe keep enough distances away from next catalyst bed, and sky is provided for abundant, the uniform mixing of gas
Between.Being relatively large in diameter based on reactor, for ensure fluid it is radial be evenly distributed by with reactor axis to parallel baffle
The cross section of adiabatic catalytic bed is divided into equal-sized square or equilateral triangle, and is arranged in baffle upper edge and sprays
Mouth.Ensure fluid in the reactor uniformly by inlet gas distributor and cold shock distributor, blending space, baffle in this way
Property, the temperature of reactor is controlled, adjusts by being distributed in cold shock nozzle and the indirect heat exchange of catalyst bed lower end,
Reduce water usage amount save energy consumption, so that each section of catalyst bed of reactor is reached optimum response operating mode, can be greatly improved compared with
The separate unit production capacity of the axially-located bed reactor easily amplified.
The purpose of the present invention can be achieved through the following technical solutions：A kind of large-scale axial multistage mixed heat transfer formula butylene
Oxidative dehydrogenation reactor, including reactor shell, which is arranged mixing arrangement, in the reactor enclosure body
At least provided with two axial catalyst beds, at least containing there are one direct heat transfer sections；The direct heat transfer section is located at two axis
To between catalyst bed, cold shock stream stock is passed through the direct heat transfer section in reactor enclosure body, with square shaft thereon to catalyst bed
After outlet material after reaction carries out mixing direct heat transfer, reacted into axial catalyst bed below.
The mixing arrangement includes the straight tube or conically shaped that side wall is equipped with opposed type nozzle arranged in parallel from top to down,
Blending space is formed, raw material enters mixing arrangement by the opposed type nozzle, is sufficiently mixed in blending space；
Import distributor is connected under the mixing arrangement.
Multiple axial catalyst beds parallel arrangement in reactor enclosure body from top to down, the height of each axial catalyst bed
Degree is 30~90cm, a diameter of 750~1200cm, in first segment axial catalyst bed upper ends ceramic ring layer, ceramic ring thickness
Degree is 18~22cm.
The axial catalyst bed includes adiabatic catalytic bed or adiabatic catalytic bed and catalyst containing indirect heat exchange
The combination of bed, the adiabatic catalytic bed height be 30~70cm, the catalyst bed layer height containing indirect heat exchange be 50~
90cm, the direct heat transfer section height are 150~180cm.
The adiabatic catalytic bed includes that supporting screening plate, upper edge baffle and crossbeam, Catalyst packing with nozzle exist
Between supporting screening plate and crossbeam, and the catalyst bed that catalyst is divided by area equation by baffle and is isolated between each other
The cross section of layer, the axial catalyst bed is divided into equal-sized square or equilateral triangle.
The catalyst bed containing indirect heat exchange includes heat exchanger tube, catalyst and heat-exchange system, and heat exchanger tube is urged with axial
Agent bed is arranged with parallel or vertical mode, and cooling medium is led in heat exchanger tube or fills out catalyst, if every heat exchanger tube is equipped with
Dry fin.
The heat exchanger tube is axial heat exchanger tube or radial heat exchanger tube；
When heat exchanger tube is axial heat exchanger tube, Catalyst packing is in heat exchanger tube, and cooling medium flows outside heat exchanger tube, shape
At the heat-exchange system of logical heat transferring medium outside pipe；Setting three pieces fin is mutually 120 ° of settings on the outside of the heat exchanger tube of the axial alignment,
Each fin all points to the central point of positive triangle or concentric arrays, it is ensured that the heat transfer effect of axial flow reactor；
When heat exchanger tube is radial heat exchanger tube, Catalyst packing is between heat exchanger tube, and cooling medium is in heat exchange Bottomhole pressure, shape
At the heat-exchange system for leading to heat transferring medium in pipe, ring fin is set on the outside of the radial direction heat exchanger tube, every is spaced 2~3cm, each
Ring fin is parallel to the cross section of heat exchanger tube, it is ensured that the heat transfer effect of axial flow reactor.
The cooling medium includes one kind in fused salt, desalted water or conduction oil.
The direct heat transfer section include horizontally arranged cold shock material distributor pipe with cold shock nozzle, gas distributor,
The mixed uniformly space of gas, cold shock stream stock are entered after the cold shock material distributor pipe in reactor by cold shock material inlet through cold
The outlet material for swashing nozzle and the axial catalyst bed above direct heat transfer section is distributed by gas distributor, into gas
The mixed uniformly space of body, hot and cold stream stock is in direct contact to be sufficiently mixed and exchange heat in the space, every cold shock material distribution
Cold shock nozzle pitch on pipe is 40~80cm；The cold shock stream stock group of the direct heat transfer section is divided into butylene, air and water
Mixture or butylene and air mixture.
Contain 2~5 axial catalyst beds in the reactor shell.
The axial multistage mixed heat transfer formula butylene oxidation-dehydrogenation reactor of above-mentioned large size, can be used alone with one, in order to
Facilitating catalyst regeneration not influences to produce, can more it is used in parallel, required according to integrated artistic, can be two large-scale axial
Heat exchanger is set between multistage mixed heat transfer formula butylene oxidation-dehydrogenation reactor, optimizes whole energy consumption.
Compared with prior art, the present invention combines the advantages of axial adiabatic reactor and shell-and-tube reactor, has easy
In realize enlargement, can effectively controlling reaction temperature, bed pressure drop it is low, the advantage that capacity usage ratio is high, production capacity is big has
Beneficial effect is embodied in following several respects：
(1) enlarged process units is adapted to, such as produces 100000 tons of butadiene product equipments per year, it is about 7.5m only to need a diameter, high
The axial backmixing heat exchange type reactor of about 5m, and about need 3~5 sets of two-stage series connections anti-using conventional axial fixed bed reactors
Device is answered, 6~10 reactors are taken around.
(2) can effective controlling reaction temperature, can be by changing the thickness of axial catalyst bed, cold shock reaction gas
Temperature and flow, the temperature of heat transferring medium and flow carry out controlling reaction temperature, and general axial direction catalyst bed thickness is 30~
90cm。
(3) pressure drop of reactor entirety is low, and since axial catalyst bed is not thick, reactor diameter is big, and can pass through
Cold shock nozzle slightly makes up part droop loss, can effectively reduce the total bed pressure drop of reactor.
(4) capacity usage ratio is high, since direct heat transfer and indirect heat exchange are combined, on the one hand can effectively control each section and urge
On the other hand agent bed temperature can reduce the consumption of water, save energy consumption.
(5) production capacity is big, using major diameter axial backmixing heat exchange type structure of reactor, can effectively improve reactor sky
Between utilization rate, improve the loadings of catalyst, improve the production capacity of separate unit reactor.
Description of the drawings
Fig. 1 is that there are one the axial multistage mixed heat transfer formula butylene oxidation-dehydrogenation reactors of the large size of direct heat transfer section to show for setting
It is intended to；
Fig. 2 is direct heat transfer section there are one the settings of top, and lower part is provided with catalyst loaded on the indirect heat exchange section in pipe
Large-scale axial direction multistage mixed heat transfer formula butylene oxidation-dehydrogenation reactor schematic diagram；
Fig. 3 is direct heat transfer section there are one the settings of top, and lower part is provided with catalyst loaded on the indirect heat exchange section between pipe
Large-scale axial direction multistage mixed heat transfer formula butylene oxidation-dehydrogenation reactor schematic diagram；
Fig. 4 is direct heat transfer section there are one the settings of top, and middle part is provided with the indirect heat exchange section that catalyst is loaded in pipe, under
The axial multistage mixed heat transfer formula butylene oxidation-dehydrogenation reactor schematic diagram of large size of a direct heat transfer section is arranged in portion again；
Fig. 5 is direct heat transfer section there are one the settings of top, and middle part is provided with the indirect heat exchange section that catalyst is loaded between pipe, under
The axial multistage mixed heat transfer formula butylene oxidation-dehydrogenation reactor schematic diagram of large size of a direct heat transfer section is arranged in portion again；
For Fig. 6 to be set gradually from top to bottom there are one direct heat transfer section, a catalyst is loaded on the indirect heat exchange section between pipe,
One direct heat transfer section, the axial multistage mixed heat transfer formula butylene oxidation of large size of the catalyst loaded on the indirect heat exchange section between pipe
Dehydrogenation reactor schematic diagram；
Wherein, 1 is air intlet, and 2 be opposed type nozzle, and 3 be Reactor inlet gas distributor, and 4 be ceramic ring layer, and 5 are
Catalyst, 6 be cold shock material inlet, and 7 be blending space, and 8 be No.1 manhole, and 9 be baffle, and 10 be supporting screening plate, and 11 be cold shock
Nozzle, 12 be No. two manholes, and 13 be cooling medium inlet, and 14 be No. three manholes, and 15 be reactor outlet, and 16 be cold shock material point
Stringing, 17 be the mixed uniformly space of gas, and 18 be heat exchanger tube, and 19 be No. four manholes.
Specific implementation mode
It elaborates below to the embodiment of the present invention, the present embodiment is carried out lower based on the technical solution of the present invention
Implement, gives detailed embodiment and specific operating process, but protection scope of the present invention is not limited to following implementation
Example.
Embodiment 1
As shown in Figure 1, for there are one the axial multistage mixed heat transfer formula butylene oxidation-dehydrogenation reactions of the large size of direct heat transfer section
Device, which is arranged mixing arrangement, two axial catalyst beds is equipped in reactor enclosure body, containing there are one straight
Connect heat exchanging segment；The direct heat transfer section is located between two axial catalyst beds, and cold shock stream stock is passed through in reactor enclosure body
Outlet material after cold shock material distributor pipe after cold shock nozzle is reacted with top axial catalyst bed passes through gas distributor
It is uniformly distributed, after the blending space of direct heat transfer section carries out mixing direct heat transfer, entrance is axially catalyzed hot and cold stream stock below
Agent bed is reacted, and the concrete structure of the reactor is as follows：
The mixing arrangement includes the straight tube or taper that side wall is equipped with opposed type nozzle 2 arranged in parallel from top to down
Cylinder, forms blending space 7, and reactor head is arranged air intlet, is connected with blending space 7；The bottom connection of blending space 7 is anti-
Device inlet gas distributor 3, air is answered to enter blending space 7 by air intlet 1, water vapour and butylene mixing gained raw material are logical
It crosses opposed type nozzle 2 and sprays into blending space 7, by Reactor inlet gas distributor 3 after the full and uniform mixing of three, into urging
Agent bed.
It is equipped with two sections of axial catalyst beds in reactor enclosure body, is adiabatic catalyst bed.Adiabatic catalyst bed
The baffle 9 and crossbeam of nozzle are carried including supporting screening plate 10, upper edge, catalyst 5 is seated between supporting screening plate 10 and crossbeam, and
The catalyst bed that catalyst 5 is divided into area equation by baffle 9 and is isolated between each other.In addition it is axially urged in first segment
The top of agent bed covers the ceramic ring layer 4 of one layer of 18cm thickness.
One direct heat transfer section is set between two sections of adiabatic catalyst beds, which includes horizontally arranged band
There is a mixed uniformly space 17 of cold shock material distributor pipe 16, gas distributor, gas of cold shock nozzle 11, cold shock stream stock is from cold shock
Material inlet 6 enters in cold shock material distributor pipe 16, is sprayed by cold shock nozzle 11 and comes from first segment axial catalyst bed
Outlet material after reaction enters the mixed uniformly space 17 of gas, the hot and cold stream stock in the space after gas distributor is distributed
Be in direct contact be sufficiently mixed exchanged heat after enter second segment axial catalyst bed, flowed out instead finally by reactor outlet 15
Answer device.
In addition, since the reactor volume is larger, for the ease of maintenance, on the top, middle part, lower part of reactor shell
It She Zhi not 8, No. two manholes 12 of No.1 manhole and No. three manholes 14.
Certain 100,000 tons/year of Oxidative Dehydrogenation of Butene into Butadiene device, reactor use structural shape shown in FIG. 1.Reaction
The a diameter of 7.5m of device, upper and lower adiabatic catalyst bed height are 0.5m, altogether loading catalyst about 44m3, reactor inlet temperature is
320 DEG C, pressure 0.14MPa, the outlet temperature of first segment catalyst bed is about 500 DEG C, and cold shock ensures that second segment is urged later
In the case of the inlet temperature of agent bed is 335 DEG C, the outlet temperature of two sections of catalyst beds is about 510 DEG C, first segment catalysis
Agent bed pressure drop is 0.78kPa, and butylene volume space velocity is 185h-1, two sections of catalyst bed pressure drops are 1.66kPa, butylene volume
Air speed is 225h-1, it is such large size axial backmixing heat exchange type fixed bed reactors can produce 100000 tons of butadiene per year (based on 300 days
Calculate), butene conversion 80%, butadiene selective 94%.
Embodiment 2
As shown in Fig. 2, being arranged there are one direct heat transfer section for top, lower part is provided with catalyst loaded on changing indirectly in pipe
The axial multistage mixed heat transfer formula butylene oxidation-dehydrogenation reactor of large size of hot arc, using structure similar to Example 1, but its
Two sections of axial catalyst beds are the catalyst bed containing indirect heat exchange, catalyst bed containing indirect heat exchange include heat exchanger tube 18,
Catalyst 5 and heat-exchange system, heat exchanger tube 18 are arranged in a vertical manner with axial catalyst bed, and wherein Catalyst packing is exchanging heat
In pipe 18, logical cooling medium outside heat exchanger tube 18 forms the heat-exchange system of the outer logical heat transferring medium of pipe.
Embodiment 3
As shown in figure 3, being arranged there are one direct heat transfer section for top, lower part is provided with catalyst loaded on changing indirectly between pipe
The axial multistage mixed heat transfer formula butylene oxidation-dehydrogenation reactor of large size of hot arc, using structure similar to Example 1, but second
Section axial catalyst bed is the catalyst bed containing indirect heat exchange, and catalyst bed containing indirect heat exchange includes heat exchanger tube 18, urges
Agent 5 and heat-exchange system, heat exchanger tube 18 are arranged in parallel with axial catalyst bed, and wherein Catalyst packing is in heat exchanger tube
Lead to cooling medium between 18, in heat exchanger tube 18, forms the heat-exchange system of logical heat transferring medium in pipe.
Embodiment 4
As shown in figure 4, being arranged there are one direct heat transfer section for top, middle part is provided with catalyst loaded on changing indirectly in pipe
Hot arc, lower part are arranged the axial multistage mixed heat transfer formula butylene oxidation-dehydrogenation reactor of large size of a direct heat transfer section, use again
Air intake 1, mixing arrangement, Reactor inlet gas distributor 3, ceramic ring layer 4 and reactor outlet same as Example 1
15。
It is internally provided with 3 sections of axial catalyst beds, 2 direct heat transfer sections and an indirect heat exchange in the reactor shell
Section, first segment and third section axial catalyst bed are adiabatic catalyst bed, and first direct heat transfer section is arranged in first segment
The bottom of axial catalyst bed, second direct heat transfer section are arranged in the bottom of second segment axial catalyst bed, directly change
Hot arc structure is same as Example 1, and the cold shock nozzle being wherein arranged below second segment axial catalyst bed can be according to reality
Situation chooses whether addition water and adjusts the molar ratio between butylene, empty gas and water；Second segment axial catalyst bed be containing
The catalyst bed of heat exchange is connect, catalyst bed containing indirect heat exchange includes heat exchanger tube 18, catalyst 5 and heat-exchange system, heat exchanger tube
18 arrange in a vertical manner with axial catalyst bed, and wherein Catalyst packing is in heat exchanger tube 18, logical cooling outside heat exchanger tube 18
Medium forms the heat-exchange system of the outer logical heat transferring medium of pipe.
In addition, the height due to reactor shell increases, in order to which the convenience of maintenance is being reacted on the basis of embodiment 1
No. four manholes 19 are arranged in the middle part of device shell again, and No. four manholes 19 are located at No. two 12 lower sections of manhole.
Embodiment 5
As shown in figure 5, being arranged there are one direct heat transfer section for top, middle part is provided with catalyst loaded on changing indirectly between pipe
Hot arc, lower part are arranged the axial multistage mixed heat transfer formula butylene oxidation-dehydrogenation reactor of large size of a direct heat transfer section, use again
Structure similar to Example 4, the lower section setting of first segment axial catalyst bed there are one direct heat transfer section, axially urge by second segment
Agent bed is the catalyst bed containing indirect heat exchange, and catalyst bed containing indirect heat exchange includes heat exchanger tube 18, catalyst 5 and changes
Hot systems, heat exchanger tube 18 are arranged in parallel with axial catalyst bed, and wherein Catalyst packing changes between heat exchanger tube 18
Lead to cooling medium in heat pipe 18, forms the heat-exchange system of logical heat transferring medium in pipe, set again below second segment axial catalyst bed
A direct heat transfer section is set, the cold shock nozzle being wherein arranged below second segment catalyst bed can be according to actual conditions selection
Molar ratio between no addition water and adjusting butylene, empty gas and water.Embodiment 6 uses the reaction of structure same as Example 2
Device, but some of which parameter adjusts, and adjustment is as follows：
(1) the ceramic ring layer of 18cm thickness is equipped in the top of first segment axial catalyst bed (adiabatic catalyst bed),
To stablize the distribution of material mixed gas；
(2) thickness of adiabatic catalyst bed is 30cm, and is being internally provided with reactor axis to parallel baffle, by axis
It is divided into equal-sized equilateral triangle to the cross section of catalyst bed, and nozzle, adiabatic catalytic are set in baffle upper edge
A diameter of 750cm of agent bed；
(3) direct heat transfer section is set below adiabatic catalyst bed, and direct heat transfer section includes cold shock material inlet, cold shock
Material distributor pipe, cold shock nozzle and blending space；Cold shock material distributor pipe is parallel with adiabatic catalyst bed, and is urged positioned at axial
The lower end of agent bed；Cold shock material inlet is located at the both ends of cold shock material distributor pipe, and cold shock nozzle is located at the distribution of cold shock material
Guan Shang, the spacing between two cold shock nozzles are 40cm, axially downwardly spray cold shock material, and blending space is located at the cold shock and sprays
The lower section of mouth comes from the outlet thermal material after the reaction of adiabatic catalyst bed and comes from the cold shock material of cold shock nozzle through gas
Mixing is come into full contact in blending space after the distribution of body distributor, is exchanged heat；The direct heat transfer section height is 150cm；
(4) below above-mentioned direct heat transfer section be arranged second segment axial catalyst bed, the axial catalyst bed be containing
The catalyst bed of indirect heat exchange, height 50cm；
(5) but second segment axial catalyst bed is the catalyst bed containing indirect heat exchange, and indirect heat exchange section is urged with axial
Agent bed is vertical, and wherein Catalyst packing is in heat exchanger tube, logical cooling medium outside heat exchanger tube.
Embodiment 7
Using the reactor of structure same as Example 2, but some of which parameter adjusts, and adjustment is as follows：
(1) the ceramic ring layer of 22cm thickness is equipped in the top of first segment axial catalyst bed (adiabatic catalyst bed),
To stablize the distribution of material mixed gas；
(2) thickness of adiabatic catalyst bed is 70cm, and sets the right side with reactor axis to parallel baffle, by axis in inside
It is divided into equal-sized equilateral triangle to the cross section of catalyst bed, and nozzle, adiabatic catalytic are set in baffle upper edge
A diameter of 1200cm of agent bed；
(3) direct heat transfer section is set below adiabatic catalyst bed, and direct heat transfer section includes cold shock material inlet, cold shock
Material distributor pipe, cold shock nozzle and blending space；Cold shock material distributor pipe is parallel with adiabatic catalyst bed, and is urged positioned at axial
The lower end of agent bed；Cold shock material inlet is located at the both ends of cold shock material distributor pipe, and cold shock nozzle is located at the distribution of cold shock material
Guan Shang, the spacing between two cold shock nozzles are 80cm, axially downwardly spray cold shock material, and blending space is located at the cold shock and sprays
The lower section of mouth comes from the outlet thermal material after the reaction of adiabatic catalyst bed and comes from the cold shock material of cold shock nozzle through gas
Mixing is come into full contact in blending space after the distribution of body distributor, is exchanged heat；The direct heat transfer section height is 180cm；
(4) below above-mentioned direct heat transfer section be arranged second segment axial catalyst bed, the axial catalyst bed be containing
The catalyst bed of indirect heat exchange, height 90cm；
(5) but second segment axial catalyst bed is the catalyst bed containing indirect heat exchange, and indirect heat exchange section is urged with axial
Agent bed is vertical, and wherein Catalyst packing is in heat exchanger tube, logical cooling medium outside heat exchanger tube.
Embodiment 8
As shown in fig. 6, it is respectively provided with 1 adiabatic catalyst bed from top to bottom, 1 catalyst bed containing indirect heat exchange
Layer, 1 adiabatic catalyst bed, 1 catalyst bed containing indirect heat exchange, the totally five axial catalysis of 1 adiabatic catalyst bed
The axial multistage mixed heat transfer formula butylene oxidation-dehydrogenation reactor of large size of agent bed, using structure similar to Example 5, first
There are one direct heat transfer section, second segment axial catalyst bed is urging containing indirect heat exchange for setting below section axial catalyst bed
Agent bed, catalyst bed containing indirect heat exchange include heat exchanger tube 18, heat exchanger tube 20, catalyst 5 and heat-exchange system, heat exchanger tube 18
It arranges in parallel with axial catalyst bed, wherein Catalyst packing leads to cooling between heat exchanger tube 18 in heat exchanger tube 18
Medium forms the heat-exchange system of logical heat transferring medium in pipe, unlike, no longer it is arranged one below second segment axial catalyst bed
A direct heat transfer section, and there are one direct heat transfer section, wherein third section are adiabatic for setting below third section adiabatic catalyst bed
The cold shock nozzle being arranged below catalyst bed addition water can be chosen whether according to actual conditions and adjust butylene, air,
Molar ratio between water.
Claims (7)
1. a kind of large-scale axial multistage mixed heat transfer formula butylene oxidation-dehydrogenation reactor, including reactor shell, the reactor enclosure
Mixing arrangement is arranged in body top, which is characterized in that at least provided with two axial catalyst beds in the reactor enclosure body, until
Few direct heat transfer section containing there are one；The direct heat transfer section is located between two axial catalyst beds, and cold shock stream stock is passed through
Direct heat transfer section in reactor enclosure body mix directly changing with square shaft thereon to the outlet material after catalyst bed reaction
After heat, reacted into axial catalyst bed below；
The mixing arrangement includes the straight tube or conically shaped that side wall is equipped with opposed type nozzle (2) arranged in parallel from top to down,
Blending space (7) is formed, raw material enters mixing arrangement by the opposed type nozzle (2), fully mixed in blending space (7)
It closes；
Reactor inlet distributor (3) is connected under the mixing arrangement；
The parallel arrangement in reactor enclosure body, the height of each axial catalyst bed are multiple axial catalyst beds from top to down
30~90cm, a diameter of 750~1200cm；
The axial catalyst bed includes adiabatic catalytic bed or adiabatic catalytic bed and catalyst bed containing indirect heat exchange
Combination, the adiabatic catalytic bed height be 30~70cm, the catalyst bed layer height containing indirect heat exchange be 50~90cm, institute
It is 150~180cm to state direct heat transfer section height；
The adiabatic catalytic bed includes supporting screening plate (10), upper edge baffle (9) and crossbeam with nozzle, catalyst (5)
Supporting screening plate (10) is seated between crossbeam, and by baffle (9) by catalyst (5) be divided into area equation and between each other
The catalyst bed of isolation.
2. a kind of large-scale axial multistage mixed heat transfer formula butylene oxidation-dehydrogenation reactor according to claim 1, feature
It is, the catalyst bed containing indirect heat exchange includes heat exchanger tube (18), catalyst and heat-exchange system, heat exchanger tube (18) and axis
It is arranged to catalyst bed with parallel or vertical mode, cooling medium is led in heat exchanger tube (18) or fills out catalyst, every heat exchanger tube
(18) several fins are equipped with.
3. a kind of large-scale axial multistage mixed heat transfer formula butylene oxidation-dehydrogenation reactor according to claim 2, feature
It is, the heat exchanger tube is axial heat exchanger tube or radial heat exchanger tube；
When heat exchanger tube (18) is axial heat exchanger tube, Catalyst packing is in heat exchanger tube (18), and cooling medium is in heat exchanger tube (18)
Outer flowing forms the heat-exchange system of the outer logical heat transferring medium of pipe；
When heat exchanger tube (18) is radial heat exchanger tube, Catalyst packing is between heat exchanger tube (18), and cooling medium is in heat exchanger tube (18)
Interior flowing forms the heat-exchange system of logical heat transferring medium in pipe.
4. a kind of large-scale axial multistage mixed heat transfer formula butylene oxidation-dehydrogenation reactor according to claim 2 or 3, special
Sign is that the cooling medium includes one kind in fused salt, desalted water or conduction oil.
5. a kind of large-scale axial multistage mixed heat transfer formula butylene oxidation-dehydrogenation reactor according to claim 1, feature
It is, the direct heat transfer section includes horizontally arranged cold shock material distributor pipe (16), gas point with cold shock nozzle (11)
The mixed uniformly space of cloth device, gas (17), cold shock stream stock enter the cold shock material in reactor by cold shock material inlet (6)
After distributor pipe (16), pass through gas through cold shock nozzle and the outlet material of the axial catalyst bed above direct heat transfer section
Enter the mixed uniformly space of gas (17) after distributor distribution, hot and cold stream stock, which is in direct contact, in the space is sufficiently mixed progress
Heat exchange.
6. a kind of large-scale axial multistage mixed heat transfer formula butylene oxidation-dehydrogenation reactor according to claim 1 or 5, special
Sign is, the cold shock stream stock group of the direct heat transfer section is divided into mixture or butylene and the air mixing of butylene, air and water
Object.
7. a kind of large-scale axial multistage mixed heat transfer formula butylene oxidation-dehydrogenation reactor according to claim 1, feature
It is, 2~5 axial catalyst beds is contained in the reactor shell.
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| WO2018096018A1 (en) * | 2016-11-24 | 2018-05-31 | Haldor Topsøe A/S | Multi bed reactor comprising an adiabatic and a heated catalyst bed |
| CN107513016B (en) * | 2017-06-30 | 2021-01-29 | 惠生工程（中国）有限公司 | Method for preparing methyl acetate |
| CN107185460A (en) * | 2017-07-10 | 2017-09-22 | 山东海丰能源科技有限公司 | A kind of dehydrogenation of isobutane reactor and dehydrogenation of isobutane reaction process |
| CN112705114B (en) * | 2019-10-24 | 2022-11-15 | 中国石油化工股份有限公司 | Heat exchange type multiphase reactor, application method thereof and light gasoline etherification method |
| CN111514826B (en) * | 2020-03-13 | 2022-04-08 | 宁波巨化化工科技有限公司 | Sectional independent control type fixed bed reactor |
| CN115337870B (en) * | 2022-08-30 | 2024-03-01 | 陕西氢易能源科技有限公司 | Conical rotary packed bed dehydrogenation reactor suitable for organic liquid hydrogen storage |
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