CN106552577B - A kind of multilayer guide shell bubbling reactor and its application method - Google Patents
A kind of multilayer guide shell bubbling reactor and its application method Download PDFInfo
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Abstract
The invention discloses a kind of multilayer guide shell bubbling reactor and its application methods, multilayer guide shell is arranged in reactor shell, the diameter of each guide shell is different, it will be separated into multi-stage annular region in reactor enclosure body, and the height of guide shell reduces step by step outward along center, centrally located guide shell connection inlet, and air inlet is connected in the guide shell at every grade of annular region and center, outermost annular region is connected to liquid outlet, and gas outlet is equipped at the top of reactor shell.In the reactor of the present invention, the hexamethylene successively overflow of liquid phase, and the air by improving the mole content of oxygen being passed through step by step carries out oxidation reaction, can fully ensure that the mass transfer rate of oxygen matches with reaction rate, so that oxidation reaction is stablized, efficiently carry out.Present invention improves the flow conditions in reactor, improve the selectivity of process, and cyclohexane oxidation selectivity 1.0%~2.5% can be improved compared with the prior art.
Description
Technical field
The present invention relates to a kind of multilayer guide shell bubbling reactor and its application methods.
Background technology
Cyclohexanol and cyclohexanone are prepared, the gas oxidizing ethyle alkyl of molecule-containing keto is typically used, firstly generates containing cyclohexyl
The oxidation mixture (cyclohexane oxide solution) of hydroperoxides, cyclohexanol and cyclohexanone, then handles this oxidation mixture, makes
Cyclohexyl hydroperoxide therein decomposes generation cyclohexanol and cyclohexanone, reaction product obtain cyclohexanol and ring through multiple rectifying
Hexanone, hexamethylene then recycle.
Cyclohexane oxidation device is generally bubble tower, the inner members such as guide shell can be added in tower to improve mass transfer, also may be used
Install stirring additional.In bubble tower, liquid phase need not be generally vigorously stirred, gas phase is highly dispersible in the liquid phase, have compared with
Big liquid holdup and phase boundary contact surface, mass transfer and heat transfer efficiency are higher, are suitable for slowly chemical reaction and strongly exothermic situation, instead
Answer device simple in structure, stable operation, investment and maintenance cost low.Between bubbling reactor energy speed up gas and liquid two-phase with stirring
Mass transfer and heat transfer, it is easier to manipulate.
Because intermediate product cyclohexyl hydroperoxide, cyclohexanol and cyclohexanone that oxygen-containing gas oxidizing ethyle alkyl generates etc. are all
It is easier to aoxidize than hexamethylene, and these intermediate products are required purpose products, with single stirring bubbling reactor
When reaction, backmixing of liquid phase is serious, and after using multi-floating bodies instead, the flowing of liquid phase, can compared with complete mixed mode close to laminar flow
It is further oxided with reducing intermediate product, to improve the yield of purpose product.The number of tandem reactor is more, and liquid phase is mixed
The flowing of object is closed just closer to laminar flow, the yield of reaction product is also higher.But considers practical operation and cost, be typically chosen
The number of tandem reactor is 3~8, more selects 5~6.But concatenated reactor quantity it is more when number of devices
Huge thus initial investment is high, and actual effect and piston flow reactor gap are larger when concatenated reactor negligible amounts so that
The selectivity of final purpose product is still relatively low.
In order to improve the selectivity of purpose product, oxidation process generally uses multi-floating bodies, and hexamethylene is followed by each anti-
Device is answered, the cyclohexanol and cyclohexanone in cyclohexane oxide solution maintain in a lower concentration, and the conversion ratio of hexamethylene is general
Control is between 3%~5%.Currently, the domestic first step for producing cyclohexanone by cyclohexane oxidation --- use air oxidation hexamethylene
The commercial plant that alkane prepares cyclohexane oxide solution is reacted by multiple (general 3~8) stirring bubbling reactors or Airlift circulating
Device is composed in series, such as Chinese patent ZL200610031689.X, ZL200610031809.6, ZL201120157789.3 and
CN103804161A。
ZL200510130561.4 discloses a kind of supergravity reactor for cyclohexane oxidation preparing cyclohexanone --- rotation
Turn packed bed, the oxidation process of hexamethylene can be strengthened.Supergravity reactor can greatly improve mass transfer and heat transfer rate, but for
Cyclohexane oxidation preparing cyclohexanone chemically reacts the long response time process of step in order to control in this way, improves mass transfer rate to reaction result
It influences limited.
ZL200710098839.3 discloses a kind of microchannel for cyclohexane oxidation preparing cyclohexanone or micro-pipe reactor,
Compared with bubbling reactor, microchannel or micro-pipe reactor are more complicated, and initial stage input is larger, and there has been no the models of industrialized production
Example.
CN1834078A discloses a kind of cyclohexane liquid phase oxidation technique --- and liquid phase hexamethylene is led in a manner of laminar flow
Bubbling reactor is crossed, the yield of cyclohexane oxidation can be improved.However, removing the residence time of non-liquid hexamethylene in the reactor
Speed that is very short, making the speed that hexamethylene flows up increase close to bubble, the bubble otherwise risen can cause the disturbance of liquid,
The liquid form of liquid can be far from laminar flow, and closer to complete mixing flow in bubble tower.On existing commercial plant, hexamethylene
The total residence time of liquid material is generally 20~80 minutes when oxidation, and conversion also has 4~16 minutes in per stage reactor, and
Bubble rises to tower top only from tower reactor and needs several seconds in reactor.Therefore, it is in laminar flow that liquid is made in the bubble tower being relatively large in diameter
State is difficult to realize.
Polish Zaklady Azotowe W TarnowieMoscicach, Spolka Akcyjna discloses an a kind of kettle multicell level stream oxidation reaction in CN1172098
Baffle is arranged in device in reactor, and material is separated into multiple regions, reaches the effect that multi-floating bodies are realized in first-stage reactor
Fruit.But the patent does not refer to the shape of reactor, does not refer to corresponding structure size yet.
ZL200410000231.9 discloses a kind of cyclohexane oxidation device, and shell is vertical straight cylindrical structure, gas
Direct tube section is divided into multiple regions by distributor, and the internal component that voidage and large specific surface area are provided in straight tube reaction zone is filled out
The bed of material, when react carry out when, liquid material is with plug flow mode by reaction zone, and oxygen-containing gas is by way of bubblings and liquid phase ring
Hexane uniformly mixes, and passes through reaction zone with liquid phase hexamethylene cocurrent.But this reactor is divided into multistage air inlet, when using air oxygen
When change, because containing a large amount of nitrogen in gas, the gas holdup of direct tube section top material can be made to be substantially increased, to make in reactor
Flow regime deteriorate；The gas that gas distributor positioned at reactor direct tube section top comes out will be from by the shorter time
It is escaped in liquid phase, the oxygen content in tail gas may exceed safety margins because the residence time is too short.
CN103055792A discloses one kind and being used for oscillation tube type reactor for liquid phase oxidization of cyclohexane and its application method,
Conversion zone is connected in series by several chambers, and a tubular reactor is equivalent to the series connection of several continuous stir reactor reactors so that
The type of flow of entire reacting fluid is closer to laminar flow, the selective higher of intermediate oxidation product KA oil.However, the reactor
Also multistage air inlet is used, when using air oxidation, because containing a large amount of nitrogen in gas, the gas of direct tube section top material can be made
It is substantially increased containing rate, to make the flow regime in reactor deteriorate；Gas distributor positioned at reactor direct tube section top goes out
The gas come will be escaped by the shorter time from liquid phase, and the oxygen content in tail gas may be too short and super because of the residence time
Go out safety margins.
Invention content
Present invention solves the technical problem that being：Shortcoming in being produced for existing oxidation reaction provides a kind of novel
Multilayer guide shell bubbling reactor and its application method, improve the efficiency of cyclohexane oxidation.
The present invention adopts the following technical scheme that realization：
A kind of multilayer guide shell bubbling reactor, coaxial sleeve sets multilayer guide shell, each guide shell in reactor enclosure body
Diameter it is different, and the bottom of guide shell is connect with reactor shell sealed bottom, will be separated into multistage in reactor enclosure body
Annular region, and the height of guide shell reduces step by step outward along center, and inlet is arranged in centrally located guide shell bottom,
The guide shell bottom at every grade of annular region and center is connected to air inlet, and outermost annular region is connected to liquid outlet, described
Gas outlet is equipped at the top of reactor shell.
Specifically, the number of plies of the reactor inner draft tube is 1~9.
Specifically, the difference in height of adjacent guide cylinder is 0.01~1 meter, outer layer guide shell internal diameter and internal layer guide shell outer diameter it
Between diameter difference be 0.2~2 meter.
Scheme is further expanded as the present invention, it is coaxial by fixing muscle respectively in the inner and outer wall of the guide shell
It is fixed with the interior circulation baffle and outside circulation baffle of tubular, between the interior circulation baffle and guide shell, outside circulation baffle and is led
The interior circulating-area to circulate up and down and outside circulation area are respectively formed between flow cartridge.
Further, interior circulation baffle is coaxially fixed with again by fixing muscle on the inner wall of the reactor shell.
Further, the top of the interior circulation baffle is inwardly bent into the positive conical surface, the top of the outside circulation baffle to
It is bent into inverted cone surface outside, the interior circulation baffle and outside circulation baffle rest part are straight-tube shape.
Specifically, the interior circulation baffle highest point is 0.01~1 meter lower than guide shell highest point, interior circulation baffle lowest point
0.01~1 meter higher than guide shell lowest point, interior circulation baffle straight drum part diameter is 0.01~0.4 meter smaller than draft tube diameter, interior
Diameter at circulation baffle reverse taper portion minimum is 0.04~0.8 meter smaller than draft tube diameter；
The outside circulation baffle highest point is 0.02~1 meter lower than guide shell highest point, and water conservancy diversion is compared in outside circulation baffle lowest point
Cylinder lowest point is 0.02~1 meter high, and outside circulation baffle straight drum part diameter is 0.01~0.4 meter bigger than draft tube diameter, outside circulation gear
The diameter of plate conical section maximum is 0.04~0.8 meter bigger than draft tube diameter.
In the present invention, the guide shell bottom at the annular region in the reactor enclosure body and center is respectively equipped with gas
Distributor is connect with air inlet, is conducive to oxygen-containing gas and is uniformly distributed in reactor.
In the present invention, multiple reactors are connected in series with, wherein the reactor liquid outlet of previous stage and reacting for rear stage
Device inlet connects.
Specifically, the concatenated number of reactor is 2~9.
The application method of multilayer guide shell bubbling reactor in the present invention, in the reactor of plural serial stage, liquid phase ring
Hexane successively from the successively overflow from inside to outside of the central draft tube of the first stage reactor, from outermost layer guide shell and reactor wall it
Between outermost layer annular region overflow draw, from the first stage reactor draw cyclohexane oxide solution lead to the second stage reactor
In central draft tube, then successively overflow to outermost layer annular region overflow is drawn outward, so by kettle successively until from last
The outermost layer annular region of stage reactor is drawn；In every first-stage reactor, the gas of molecule-containing keto is respectively from every stage reactor
Central draft tube in and each layer guide shell between annular region introduce, the hexamethylene alcoxyl that will flow sequentially through in reactor
Change, generate the cyclohexane oxide solution containing cyclohexyl hydroperoxide, cyclohexanol and cyclohexanone, cyclohexane oxide solution is annular from outermost layer
Region is drawn, and the tail gas of each annular region per stage reactor is drawn after reactor head mixing.
Further, in every stage reactor, what the annular region between central draft tube and each layer guide shell introduced
Oxygen content is 5%~70% in the gas of molecule-containing keto, and is improved step by step along the overflow direction of cyclohexane oxide solution.
Further, the liquid phase hexamethylene introduced from the central draft tube of the first stage reactor is previously heated to 100~200
DEG C, and the reaction temperature in every stage reactor is maintained at 100~200 DEG C.
Further, the reaction pressure in every stage reactor is 0.2~2MPa.
According to the present invention, multilayer guide shell is set in every stage reactor, by liquid separation in bubbling reactor at multiple
Annular region, inside centrally located guide shell and each annular region is equivalent to a continuous stir reactor, liquid cyclohexane from
The overflow step by step outward of the guide shell at center, first-stage reactor is equivalent to multiple continuous stir reactor series connection, concatenated according to bubbling reactor
Quantity and the interior guide shell number of plies being arranged per stage reactor, can simulate series more more than existing commercial plant so that whole
The type of flow of a reaction mass is closer to laminar flow, the selective higher of intermediate oxidation product KA oil.
Expansion scheme according to the invention, each annular region in reactor, gas from the center of annular region to
Upper bubbling, in the gas-liquid separation of reactor top, tail gas is drawn from reactor head, and it is bicyclic that most of liquid material falls into last layer
Outside circulation area and this floor double loop guide shell main body between conductance flow cartridge main body and its outside circulation baffle are kept off with its interior circulation
Interior circulating-area between plate, since the two annular spaces are on the periphery of gas distributor, internal liquid material bubbles are seldom,
Circulation, the liquid in inside and outside circulating-area are formed because of density contrast with the liquid rich in bubble at the annular region center of the circulation cylinder
Body flows downward, and material flows up in central annular region, improves the mixing intensity of liquid in annular region, makes single ring
The flowing of liquid is closer to complete mixing flow in shape region.
According to the present invention, when bubbling reactor diameter is smaller, the less guide shell number of plies is set, it is straight in bubbling reactor
When diameter is larger, the more guide shell number of plies is set, the number of plies of setting is more, and the flowing of entire reaction mass is closer to flat-pushing
Stream.
According to the present invention, the height of guide shell reduces successively outward from center, to prevent the liquid in outer annular region
Material cause because pouring in down a chimney it is at different levels between back-mixing, larger difference in height can will be at different levels between back-mixing minimize.
According to the present invention, the diameter difference between outboard diversion cylinder internal diameter and inside guide shell outer diameter is 0.2~2 meter, too small
Diameter difference the most of liquid gone out from internal layer guide shell overflow can be made to be directed across this layer of annular region and enter outer annular
Region, excessive diameter difference can reduce the quantity of same diameter reactor inner draft tube, keep series connection series on the low side and deviate flat-pushing
Stream.
According to the present invention, annular region between central draft tube and each layer guide shell introduces respectively molecule-containing keto
The content of oxygen is 5%~70% in gas.The present inventor discloses a kind of cyclohexane oxidation in ZL200610031809.6
The method of preparing cyclohexanone, cyclohexanol, it is characterised in that the oxygen concentration in the gas of the molecule-containing keto used in oxidation process is with oxygen
The conversion ratio of change process increases and increases, which can be applied in the present invention.For example, from the center of the first stage reactor
Guide shell rises, until the outermost layer annular region of afterbody reactor, oxygen content in used oxygen-containing gas from 5% by
Grade is improved to 70%.
Due to using multilayer guide shell in concatenated every stage reactor, total series connection series is increased, liquids are made
The flowing of material is closer to laminar flow, while the oxygen-containing gas for having used oxygen content different in oxidation process, makes each annular
The ventilatory capacity in region, which maintains one, can make in each annular region in the normal range (NR) of Liquid Flow in order, to make in reactor
Existing enough gas liquid film products, and have enough partials pressure of oxygen, fully ensure that the mass transfer rate and reaction rate phase of oxygen
Match, so that oxidation reaction is stablized, efficiently carry out.
From the above mentioned, present invention improves the flow conditions in reactor, improve the selectivity of process, with the prior art
Than cyclohexane oxidation selectivity 1.0%~2.5% can be improved, the present invention is equally also applicable in the production of other oxidation reactions
Processing.
Below in conjunction with the drawings and specific embodiments, the invention will be further described.
Description of the drawings
Fig. 1 is the multilayer guide shell bubbling reactor schematic internal view in embodiment 1.
Fig. 2 is the guide shell schematic diagram inside the multilayer guide shell bubbling reactor in embodiment 2.
Fig. 3 is the flow schematic diagram inside the multilayer guide shell bubbling reactor in embodiment 2.
Fig. 4 is series connection bubbling reactor process flow diagram.
Figure label：1- reactor shells, the second guide shells of 2-, the first guide shells of 3-, 4- annular regions, 5- inlets,
6- air inlets, the gas outlets 7-, 8- gas distributors, 9- liquid outlets.
G11, G12 and G13 in Fig. 2 are the air inlet pipe of the central draft tube and two annular regions of the first stage reactor
Road, G21, G22 and G23 be the second stage reactor central draft tube and two annular regions air inlet pipeline, G31, G32 and
G33 is the air inlet pipeline of the central draft tube and two annular regions of third stage reactor, and W1, W2 and W3 are the first, second and
The offgas outlet of third stage reactor, L11 are first order liquid reactor import, and L33 is the liquid outlet of third stage reactor.
Specific implementation mode
Embodiment 1
Referring to Fig. 1, it is arranged multilayer guide shell in the reactor shell 1 of multilayer guide shell bubbling reactor, in the present embodiment
Be two layers of guide shell, including centrally located first guide shell 3 and the second guide shell 2 positioned at outside, two guide shells with
Reactor shell 1 is coaxially disposed, and diameter is different, and three-level annular region 4, and water conservancy diversion will be separated into reactor shell 1
The height of cylinder reduces step by step outward along center, and the bottom of the first guide shell 3 and the second guide shell 2 is and reactor shell
1 bottom is welded and fixed, and ensures to seal, and such three-level annular region can only carry out overflow step by step by top and connect, in being located at
It is connected to air inlet 6 in first guide shell 3 at the first guide shell 3 connection inlet 5 of the heart, every grade of annular region 3 and center,
Inlet 5 and air inlet 6 are respectively positioned on reactor bottom, can introduce connection, reactor from reactor head or bottom by pipeline
3 bottom of the first guide shell of annular region 4 and center in shell is respectively equipped with gas distributor and connects with each layer air inlet 6
It connects.Outermost annular region is connected to liquid outlet 9, and liquid outlet 9 is installed in reactor shell 1, and 1 top of reactor shell is equipped with
Gas outlet 7,4 bottom of annular region in reactor shell 1 are equipped with gas distributor 8.
In production application, according to production requirement and the size and quantity of guide shell, reactor can be reset
The number of plies of inner draft tube is that can be arranged 1~9, and the difference in height of adjacent guide cylinder is 0.01~1 meter, outer layer guide shell internal diameter and internal layer
Diameter difference between guide shell outer diameter is 0.2~2 meter.In the present embodiment, reactor shell 1, the second guide shell 2 and first are led
Flow cartridge 3 is smooth cylinder, and the internal diameter 800mm of reactor shell 1, the 3 internal diameter 400mm of the first guide shell at center, second leads
Flow cartridge 2 internal diameter 600mm, the high 3000mm of reactor shell, the 3 high 2600mm of the first guide shell at center, the second guide shell 2 are high
2400mm, the high 2200mm of outermost layer discharge port.
In practical applications, 2~9 stage reactors can be connected in series with, forms train, wherein the reaction of previous stage
The reactor inlet of device liquid outlet and rear stage connects, and referring to Fig. 4, the reactor in three Fig. 1 is connected in series with, below in conjunction with
Fig. 1 and Fig. 4 illustrates the method for the multilayer guide shell bubbling reactor oxidizing ethyle alkyl using embodiment.
Hexamethylene is introduced into from the center feed inlet L11 of first order bubbling reactor in the first stage reactor, is waited for full of the
Start overflow after one guide shell 3 to the annular region between the first guide shell 3 and the second guide shell 2, waits for the first guide shell 3 and the
Annular region between two guide shells 2 starts overflow to the annulus between the second guide shell 2 and water conservancy diversion cylinder shell 1 after being full of
Domain, until being expelled to the first guide shell of center of second level bubbling reactor from liquid outlet overflow, successively overflow is anti-to the second level
Answer the first guide shell of center for being expelled to third stage reactor after outermost one layer of annular region of device from liquid outlet, then successively overflow
To outermost one layer of annular region of third stage reactor, finally decomposing system is led to from L33 overflows.According to every stage reactor
Residence time of the volume of reaction zone and hexamethylene is adjusted between central draft tube reaction zone and each guide shell annular region
The inlet amount of hexamethylene makes liquid product with certain speed overflow step by step, enters lower step process after multistage series winding oxidation.
The liquid phase hexamethylene introduced from the central draft tube of the first stage reactor is previously heated to 100~200 DEG C, and will be every
Reaction temperature in stage reactor is maintained at 100~200 DEG C, and it is 0.2~2MPa to keep the reaction pressure in per stage reactor.
In every grade of bubbling reactor, what the annular region between central draft tube and each layer guide shell introduced contains molecule
Oxygen content is 5%~70% in the gas of oxygen, and is improved step by step along the overflow direction of cyclohexane oxide solution.Specifically it can be used
Pure oxygen made from separation by deep refrigeration, or with pressure swing adsorption method be made oxygen content be 70% or so oxygen-enriched air, then with air
The oxygen-enriched air that oxygen content is 21%~70% is made in mixing；The purity nitrogen made from separation by deep refrigeration, or with rich in nitrogen
Oxidized tail gas, then mixed with air, the oxygen denuded air that oxygen content is 5%~21% is made；Pass through each layer water conservancy diversion of bubbling reactor
The gas distributor of air inlet pipe G11~G33 connections of the first guide shell bottom connection of annular region and center between cylinder
Into carrying out oxidation reaction in liquid phase hexamethylene, while reaction temperature, air inflow and air inlet oxygen concentration are adjusted, makes central draft tube
Oxygen content is below 5% in the tail gas of annular region between each guide shell, and tail gas recycles profit after handling and recycling hexamethylene
With.
During practical oxidation in the present embodiment, lead to step by step in the two layers of guide shell bubbling reactor contacted at three
Enter oxygen-containing gas, adjust the ventilatory capacity and oxygen concentration of each kettle, adjusts reaction temperature, the oxygen content (butt) in each kettle tail gas is made to control
For system 2% or so, it is 45min or so to adjust the hexamethylene residence time.Reaction temperature is 165~170 DEG C after system stable operation,
Reaction pressure 1.2MPa, sampling analysis, analysis result tend towards stability after liquid phase material in contain cyclohexyl hydroperoxide 3.46%,
Containing cyclohexanol 0.62%, contain cyclohexanone 0.28%, it is 3.41% that cyclohexane conversion, which is calculated, the selectivity of useful products
(including cyclohexanone, cyclohexanol and cyclohexyl hydroperoxide) is 95.84%.
Embodiment 2
In conjunction with referring to Fig. 2 and Fig. 3, the structure of reactor in the present embodiment is same as Example 1, unlike, this implementation
Guide shell in example is double loop guide shell, specifically as shown in Fig. 2, to the knot of double loop guide shell by taking the second guide shell 2 as an example
Structure illustrates, and the inner and outer wall of the second guide shell 2 is coaxially fixed with the interior circulation baffle 21 and outside circulation baffle of tubular
22, two circulation baffles are fixed on the inside of the second guide shell 2 by interior circulation fixing muscle 23 and outside circulation fixing muscle 24 respectively
And outside, it is respectively formed between 21 and second guide shell 2 of interior circulation baffle, between outside circulation baffle 22 and the second guide shell 2
The interior circulating-area 26 of lower circulation and outside circulation area 25, it is same again by interior circulation fixing muscle 23 on the inner wall of reactor shell 1
Axis is equipped with interior circulation baffle 21.Each circulation baffle consists of two parts, wherein being placed in the top of the interior circulation baffle 21 of inside
For up-small and down-big positive cone, lower part is cylinder straight tube shape, and the top for being placed in the outside circulation baffle 22 in outside is up big and down small
Back taper, lower part are cylinder straight tube shape.
Specifically, interior 21 highest point of circulation baffle is 0.01~1 meter lower than the highest point of 2 ontology of the second guide shell, interior circulation
21 lowest point of baffle is 0.01~1 meter higher than the lowest point of 2 ontology of the second guide shell, and 21 straight drum part diameter of interior circulation baffle is than
The diameter of two guide shells, 2 ontology is 0.01~0.4 meter small, and the diameter at 21 reverse taper portion minimum of interior circulation baffle is than the second water conservancy diversion
The diameter of 2 ontologies of cylinder is 0.04~0.8 meter small.22 highest point of outside circulation baffle is lower by 0.02 than the highest point of 2 ontology of the second guide shell
~1 meter, 22 lowest point of outside circulation baffle is 0.02~1 meter higher than the lowest point of 2 ontology of the second guide shell, 22 straight tube of outside circulation baffle
Section diameter is 0.01~0.4 meter bigger than the diameter of 2 ontology of the second guide shell, the diameter of 22 conical section maximum of outside circulation baffle
It is 0.04~0.8 meter bigger than 2 ontology diameter of the second guide shell.
In production application, according to production requirement and the size and quantity of guide shell, reactor can be reset
The number of plies of inner draft tube may be configured as 1~9, and the difference in height of adjacent guide cylinder is 0.01~1 meter, outer layer guide shell internal diameter and internal layer
Diameter difference between guide shell outer diameter is 0.2~2 meter.In the present embodiment, two layers of guide shell bubbling reactor housing inner diameter
800mm, high 3000mm；First guide shell internal diameter 400mm, the high 2600mm at center, interior circulation baffle straight drum part diameter
350mm, diameter 200mm at back taper horn mouth minimum, baffle highest point is lower 200mm than the second guide shell highest point, and baffle is most
Lower is higher 30mm than the second guide shell lowest point, outside circulation baffle straight drum part diameter 440mm, and conical horn mouth maximum is straight
Diameter 480mm, baffle highest point are lower 400mm than the first guide shell highest point, and baffle lowest point is higher than the first guide shell lowest point
40mm；Second guide shell internal diameter 600mm, high 2400mm, interior circulation baffle straight drum part diameter 560mm, back taper horn mouth
Diameter 520mm at minimum, baffle highest point is lower 200mm than the second guide shell highest point, and baffle lowest point is most than the second guide shell
The high 25mm of lower, outside circulation baffle straight drum part diameter 640mm, conical horn mouth maximum diameter 680mm, baffle highest point
Lower 200mm than the second guide shell highest point, baffle lowest point is higher 25mm than the second guide shell lowest point；Outermost reactor enclosure
The high 2200mm of discharge port on body.
Likewise, the present embodiment is in practical applications, 2~9 stage reactors can be connected in series with, form train,
In, the reactor inlet of the reactor liquid outlet of previous stage and rear stage connects, referring to Fig. 4, the reactor string in three Fig. 3
Connection connection illustrates the multilayer double loop guide shell bubbling reactor oxidizing ethyle alkyl for using embodiment below in conjunction with Fig. 3 and Fig. 4
Method.
Hexamethylene is introduced into from the center feed inlet L11 of first order bubbling reactor in the first stage reactor, the present embodiment
In inlet introduce liquid from the bottom of the first guide shell 3, after full of starting overflow after the first guide shell 3 to the first guide shell
3 and the second annular region between guide shell 2, it is opened after the annular region between the first guide shell 3 and the second guide shell 2 is full of
Beginning overflow is roused to the annular region between the second guide shell 2 and reactor shell 1 until being expelled to the second level from liquid outlet overflow
The first guide shell of center of reactor is steeped, is arranged from liquid outlet after outermost one layer of annular region of successively overflow to the second stage reactor
Go out to the first guide shell of center of third stage reactor, then successively overflow is to outermost one layer of annular region of third stage reactor,
Finally decomposing system is led to from L33 overflows.Central draft tube reaction zone according to every stage reactor and each guide shell annulus
The residence time of the volume of reaction zone and hexamethylene adjusts the inlet amount of hexamethylene between domain, makes the liquid product with a constant speed
Overflow step by step is spent, enters lower step process after multistage series winding oxidation.
Unlike embodiment 1, interior circulating-area and outside circulation area, portion are increased inside and outside the guide shell in the present embodiment
Point liquid material falls into the outside circulation area between last layer double loop guide shell main body and its outside circulation baffle and this floor is bicyclic
Interior circulating-area between conductance flow cartridge main body and its interior circulation baffle, interior circulating-area 26 and outside circulation area 25 are in gas distributor
Periphery, internal liquid material bubbles are seldom, and the liquid rich in bubble with the annular region center of the circulation cylinder is because close
Degree is poor and forms circulation, the downward liquid flow in inside and outside circulating-area, and material flows up in central annular region, improves
The mixing intensity of liquid in annular region makes the flowing of liquid in single annular region closer to complete mixing flow.
The liquid phase hexamethylene introduced from the central bicyclic conductance flow cartridge of the first stage reactor is previously heated to 100~200 DEG C,
And the reaction temperature in every stage reactor is maintained at 100~200 DEG C, and it is 0.2 to keep the reaction pressure in per stage reactor
~2MPa.
In every grade of bubbling reactor, the annular region between center double loop guide shell and each layer double loop guide shell
Oxygen content is 5%~70% in the gas for the molecule-containing keto being introduced into, and is carried step by step along the overflow direction of cyclohexane oxide solution
It is high.It is specific to can be used pure oxygen made from separation by deep refrigeration, or with pressure swing adsorption method be made oxygen content be 70% or so it is oxygen-enriched
Air, then mixed with air, the oxygen-enriched air that oxygen content is 21%~70% is made；The purity nitrogen made from separation by deep refrigeration, or
Person uses the oxidized tail gas rich in nitrogen, then is mixed with air, and the oxygen denuded air that oxygen content is 5%~21% is made；Pass through center
The first guide shell and each layer double loop guide shell of bubbling reactor between annular region bottom connection air inlet pipe G11~
The gas distributor of G33 connections, which enters, carries out oxidation reaction in liquid phase hexamethylene, while adjusting reaction temperature, air inflow and air inlet
Oxygen concentration, makes between central bicyclic conductance flow cartridge and each double loop guide shell that oxygen content is below 5% in the tail gas of annular region,
Tail gas recycles after handling and recycling hexamethylene.
During practical oxidation in the present embodiment, lead to step by step in the two layers of guide shell bubbling reactor contacted at three
Enter oxygen-containing gas, adjust the ventilatory capacity and oxygen concentration of each kettle, adjusts reaction temperature, the oxygen content (butt) in each kettle tail gas is made to control
For system 2% or so, it is 50min or so to adjust the hexamethylene residence time.Reaction temperature is 164~168 DEG C after system stable operation,
Reaction pressure 1.2MPa, sampling analysis, analysis result tend towards stability after liquid phase material in contain cyclohexyl hydroperoxide 3.38%,
Containing cyclohexanol 0.58%, contain cyclohexanone 0.24%, it is 3.28% that cyclohexane conversion, which is calculated, the selectivity of useful products
(including cyclohexanone, cyclohexanol and cyclohexyl hydroperoxide) is 96.00%.
Above example is the description of the invention, not limitation of the invention, and the technical staff of the industry should
Solution, the present invention is not limited to the above embodiments, and the above embodiments and description only describe the specific of the present invention
Operation principle, without departing from the spirit and scope of the present invention, various changes and improvements may be made to the invention, these variations
It all fall within the protetion scope of the claimed invention with improvement, the claimed scope of the invention is by appended claims and its waits
Effect object defines.
Claims (14)
1. a kind of multilayer guide shell bubbling reactor, it is characterised in that：Coaxial sleeve sets multilayer guide shell in reactor enclosure body, often
The diameter of a guide shell is different, and the bottom of guide shell is connect with reactor shell sealed bottom, by reactor enclosure body points
It is divided into multi-stage annular region, and the height of guide shell reduces step by step outward along center, centrally located guide shell bottom is set
Set inlet, the guide shell bottom at every grade of annular region and center is connected to air inlet, and outermost annular region is connected to out
Liquid mouth, the reactor shell top are equipped with gas outlet.
2. the number of plies of a kind of multilayer guide shell bubbling reactor according to claim 1, the reactor inner draft tube is 2
~9.
3. the difference in height of a kind of multilayer guide shell bubbling reactor according to claim 2, adjacent guide cylinder is 0.01~1
Rice, the diameter difference between outer layer guide shell internal diameter and internal layer guide shell outer diameter are 0.2~2 meter.
4. a kind of multilayer guide shell bubbling reactor according to claim 3, the inner and outer wall difference of the guide shell
The interior circulation baffle and outside circulation baffle of tubular are coaxially fixed with by fixing muscle, between the interior circulation baffle and guide shell,
The interior circulating-area to circulate up and down and outside circulation area are respectively formed between outside circulation baffle and guide shell.
5. a kind of multilayer guide shell bubbling reactor according to claim 4, pass through on the inner wall of the reactor shell
Fixing muscle is coaxially fixed with interior circulation baffle.
6. a kind of multilayer guide shell bubbling reactor according to claim 5, the top of the interior circulation baffle is to infolding
Curve the positive conical surface, the top of the outside circulation baffle is bent into inverted cone surface outward, the interior circulation baffle and outside circulation baffle its
Remaining part point is straight-tube shape.
7. a kind of multilayer guide shell bubbling reactor according to claim 6, the interior circulation baffle highest point compares water conservancy diversion
Cylinder highest point is 0.01~1 meter low, and interior circulation baffle lowest point is 0.01~1 meter higher than guide shell lowest point, interior circulation baffle straight tube
Section diameter is 0.01~0.4 meter smaller than draft tube diameter, and the diameter at interior circulation baffle reverse taper portion minimum is more straight than guide shell
Diameter is 0.04~0.8 meter small；
The outside circulation baffle highest point is 0.02~1 meter lower than guide shell highest point, and outside circulation baffle lowest point is most than guide shell
Lower is 0.02~1 meter high, and outside circulation baffle straight drum part diameter is 0.01~0.4 meter bigger than draft tube diameter, outside circulation baffle cone
The diameter of shape part maximum is 0.04~0.8 meter bigger than draft tube diameter.
8. a kind of multilayer guide shell bubbling reactor according to claim 1, the annular region in the reactor enclosure body
And the guide shell bottom at center is respectively equipped with gas distributor and is connect with air inlet.
9. a kind of multilayer guide shell bubbling reactor according to any one of claim 1-8, multiple reactor series connection connect
It connects, wherein the reactor liquid outlet of previous stage and the reactor inlet of rear stage connect.
10. a kind of multilayer guide shell bubbling reactor according to claim 9, the concatenated number of reactor is 2~
9。
11. the application method of the multilayer guide shell bubbling reactor described in a kind of any one of claim 1-10, feature exist
In：In the reactor of plural serial stage, liquid phase hexamethylene successively overflows from the central draft tube of the first stage reactor from inside to outside successively
Stream is drawn from the outermost layer annular region overflow between outermost layer guide shell and reactor wall, is drawn from the first stage reactor
Cyclohexane oxide solution lead in the central draft tube of the second stage reactor, then outward successively overflow to outermost layer annular region overflow
Stream is drawn, so by kettle successively until being drawn from the outermost layer annular region of afterbody reactor；In every first-stage reactor,
The annular region out of every stage reactor central draft tube and between each layer guide shell introduces the gas of molecule-containing keto respectively,
The cyclohexane oxidation that will flow sequentially through in reactor generates the hexamethylene containing cyclohexyl hydroperoxide, cyclohexanol and cyclohexanone
Oxidation solution, cyclohexane oxide solution are drawn from outermost layer annular region, and the tail gas of each annular region per stage reactor is in reactor
It is drawn after the mixing of top.
12. according to the application method of the multilayer guide shell bubbling reactor described in claim 11, in every stage reactor, from
In the gas for the molecule-containing keto that annular region between central draft tube and each layer guide shell is introduced into oxygen content be 5%~
70%, and improved step by step along the overflow direction of cyclohexane oxide solution.
13. according to the application method of the multilayer guide shell bubbling reactor described in claim 12, from the first stage reactor
The liquid phase hexamethylene that central draft tube introduces is previously heated to 100~200 DEG C, and the reaction temperature in every stage reactor is kept
At 100~200 DEG C.
14. anti-in every stage reactor according to the application method of the multilayer guide shell bubbling reactor described in claim 13
It is 0.2~2MPa to answer pressure.
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