CN106552577A - A kind of multilamellar guide shell bubbling reactor and its using method - Google Patents
A kind of multilamellar guide shell bubbling reactor and its using method Download PDFInfo
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- CN106552577A CN106552577A CN201510639482.XA CN201510639482A CN106552577A CN 106552577 A CN106552577 A CN 106552577A CN 201510639482 A CN201510639482 A CN 201510639482A CN 106552577 A CN106552577 A CN 106552577A
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Abstract
The invention discloses a kind of multilamellar guide shell bubbling reactor and its using method, multilamellar guide shell is arranged in reactor shell, the diameter of each guide shell is different, multi-stage annular region will be separated in reactor enclosure body, and the height of guide shell is reduced laterally step by step along center, air inlet is connected in the guide shell at the guide shell connection inlet at center, every grade of annular region and center, outermost annular region connects liquid outlet, and gas outlet is provided with the top of reactor shell.In the reactor of the present invention, the hexamethylene successively overflow of liquid phase, and oxidation reaction is carried out by improving the air of the mole content of oxygen being passed through step by step, the mass transfer rate and reaction rate that can fully ensure that oxygen matches, and oxidation reaction is stablized, efficiently carries out.Present invention improves the flow condition in reactor, improves the selectivity of process, 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 multilamellar guide shell bubbling reactor and its using method.
Background technology
Hexalin and Ketohexamethylene are prepared, typically with the gas oxidizing ethyle alkyl of molecule-containing keto, is firstly generated and is contained
The oxidation mixture (cyclohexane oxide solution) of cyclohexyl hydroperoxide, Hexalin and Ketohexamethylene, then locates
Manage this oxidation mixture so as in cyclohexyl hydroperoxide decompose and generate Hexalin and Ketohexamethylene, instead
Many rectification of product Jing is answered to obtain Hexalin and Ketohexamethylene, hexamethylene is then recycled.
Cyclohexane oxidation device is generally bubble tower, can add the inner members such as guide shell to improve mass transfer in tower,
Stirring can also be installed additional.In bubble tower, typically liquid phase need not be stirred vigorously, gas phase highly can be divided
Dissipate in the liquid phase, have larger liquid holdup and phase boundary contact surface, mass transfer and heat transfer efficiency are higher, it is adaptable to
Slow chemical reaction and strongly exothermic situation, structure of reactor is simple, stable operation, investment and maintenance cost it is low.
Mass transfer and heat transfer between bubbling reactor energy speed up gas and liquid with stirring is biphase, it is easier to manipulate.
Because the intermediate product cyclohexyl hydroperoxide that oxygen-containing gas oxidizing ethyle alkyl is generated, Hexalin and hexamethylene
Ketone etc. is all easily aoxidized than hexamethylene, and these intermediate products are required purpose products, with single
Stirring bubbling reactor reaction when, backmixing of liquid phase is serious, and after using multi-floating bodies instead, the flowing of liquid phase
Laminar flow is close to, intermediate product can be reduced compared with complete mixed mode and be further oxided, so as to improve purpose
The yield of product.The number of tandem reactor is more, the flowing of liquid phase mixture just closer to laminar flow, instead
Answer the yield of product also higher.But consider practical operation and cost, the number of the tandem reactor being typically chosen
For 3～8, more 5～6 are selected.But, when the reactor quantity of series connection is more, number of devices is huge
Thus initial investment is high, during the reactor negligible amounts of series connection, actual effect is larger with piston flow reactor gap,
So that the selectivity of final purpose product is still low.
In order to improve the selectivity of purpose product, oxidizing process typically adopts multi-floating bodies, hexamethylene to flow successively
The each reactors of Jing, the Hexalin and Ketohexamethylene in cyclohexane oxide solution are maintained in a relatively low concentration, ring
The conversion ratio general control of hexane is between 3%～5%.At present, it is domestic that Ketohexamethylene is produced by cyclohexane oxidation
The first step --- the commercial plant of cyclohexane oxide solution is prepared by multiple (general 3～8 with air oxidation of cyclohexane
It is individual) stirring bubbling reactor or Airlift circulating reactor be composed in series, such as Chinese patent
ZL200610031689.X, ZL200610031809.6, ZL201120157789.3 and CN103804161A.
ZL200510130561.4 disclose a kind of supergravity reactor for cyclohexane oxidation preparing cyclohexanone-
- RPB, can strengthen the oxidizing process of hexamethylene.Supergravity reactor can greatly improve mass transfer and
Heat transfer rate, but for the such chemical reaction of cyclohexane oxidation preparing cyclohexanone is the long response time process of rate-determining steps,
Improve impact of the mass transfer rate to reaction result limited.
ZL200710098839.3 discloses a kind of microchannel for cyclohexane oxidation preparing cyclohexanone or micro-pipe is anti-
Device is answered, compared with bubbling reactor, microchannel or micro-pipe reactor are more complicated, initial stage input is larger, still
There is not the example of industrialized production.
CN1834078A discloses a kind of cyclohexane liquid phase oxidation technique --- and liquid phase hexamethylene is with the side of laminar flow
Formula can improve the yield of cyclohexane oxidation by bubbling reactor.However, except non-liquid hexamethylene is anti-
Answer the time of staying in device very short, make the speed that hexamethylene is flowed up be close to the speed of bubble rising, otherwise
The bubble of rising can cause the disturbance of liquid, and in bubble tower, the liquid form of liquid can be away from laminar flow, and more
Close to complete mixing flow.On existing commercial plant, the total residence time one of liquid material during cyclohexane oxidation
As be 20～80 minutes, conversion also has 4～16 minutes to interior per stage reactor, and bubble is from tower reactor in reactor
Rising to tower top only needs several seconds.Therefore, in the bubble tower being relatively large in diameter liquid is made to be difficult in horizontal sliding stream mode
With what is realized.
Polish Zaklady Azotowe W TarnowieMoscicach, Spolka Akcyjna discloses a kind of kettle multicell level stream oxidation in CN1172098
Reactor, arranges baffle plate in reactor, material is separated into multiple regions, is reached in A reactor
Realize the effect of multi-floating bodies.But the patent does not refer to the shape of reactor, corresponding structure chi is not referred to yet
It is very little.
ZL200410000231.9 discloses a kind of cyclohexane oxidation device, and housing is vertical straight cylindrical structure,
Direct tube section is divided into multiple regions by gas distributor, and voidage and specific surface area are provided with straight tube reaction zone
Big internals packing layer, when reaction is carried out, liquid material, is contained by reaction zone with plug flow mode
Carrier of oxygen is uniformly mixed with liquid phase hexamethylene by bubbling mode, passes through reaction zone with liquid phase hexamethylene cocurrent.
But this reactor is divided into multistage air inlet, when using air oxidation, because containing substantial amounts of nitrogen in gas,
It is substantially increased can the gas holdup of direct tube section top material, so that the flow regime in reactor deteriorates；Position
Gas distributor gas out in reactor direct tube section top will escape from liquid phase through the shorter time
Go out, the oxygen content in tail gas may exceed safety marginses because the time of staying is too short.
CN103055792A discloses one kind for oscillation tube type reactor for liquid phase oxidization of cyclohexane and its use
Method, conversion zone are in series by several chambers, and a tubular reactor is anti-equivalent to several continuous stir reactors
Answer the series connection of device so that, closer to laminar flow, intermediate oxidation product KA is oily for the type of flow of whole reacting fluid
Selectivity it is higher.However, the reactor is also adopted by multistage air inlet, when using air oxidation, because of gas
In contain substantial amounts of nitrogen, be substantially increased can the gas holdup of direct tube section top material, so that in reactor
Flow regime deteriorate；Gas distributor gas out positioned at reactor direct tube section top is through shorter
Time will be escaped from liquid phase, and the oxygen content in tail gas may exceed safe pole because the time of staying is too short
Limit.
The content of the invention
Present invention solves the technical problem that being：For the weak point in the production of existing oxidation reaction, there is provided one
New multilamellar guide shell bubbling reactor and its using method are planted, the efficiency of cyclohexane oxidation is improved.
The present invention adopts the following technical scheme that realization：
A kind of multilamellar guide shell bubbling reactor, coaxial sleeve sets multilamellar guide shell in the reactor enclosure body, each
The diameter of guide shell is different, and the bottom of guide shell is connected with reactor shell sealed bottom, by reactor
Multi-stage annular region is separated in housing, and the height of guide shell is reduced laterally step by step along center, is located at
The guide shell bottom at center arrange the guide shell bottom at inlet, every grade of annular region and center connect into
QI KOU, outermost annular region connect liquid outlet, are provided with gas outlet at the top of the 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
Diameter difference between external diameter is 0.2～2 meter.
Scheme is further expanded as of the invention, passes through respectively to fix in the inner and outer wall of the guide shell
Muscle is coaxially fixed with the interior circulation baffle plate and outside circulation baffle plate of tubular, between the interior circulation baffle plate and guide shell,
Form the interior circulating-area and outside circulation area for circulating up and down between outside circulation baffle plate and guide shell respectively.
Further, interior circulation is coaxially fixed with again by fixing muscle on the inwall of the reactor shell
Baffle plate.
Further, the top of the interior circulation baffle plate is inwardly bent into the positive conical surface, the outside circulation baffle plate
Top is outwards bent into inverted cone surface, and the interior circulation baffle plate and outside circulation baffle plate remainder are straight-tube shape.
Specifically, the interior circulation baffle plate highest point is lower than guide shell highest point 0.01～1 meter, interior circulation baffle plate
Lowest point is higher than guide shell lowest point 0.01～1 meter, and interior circulation baffle plate straight drum part diameter is less than draft tube diameter
0.01～0.4 meter, the diameter at interior circulation baffle plate reverse taper portion minimum is less than draft tube diameter by 0.04～0.8
Rice；
The outside circulation baffle plate highest point is lower than guide shell highest point 0.02～1 meter, outside circulation baffle plate lowest point ratio
Guide shell lowest point is high 0.02～1 meter, and outside circulation baffle plate straight drum part diameter is bigger than draft tube diameter by 0.01～
0.4 meter, the diameter of outside circulation baffle plate conical section maximum is bigger than draft tube diameter 0.04～0.8 meter.
In the present invention, in the reactor enclosure body annular region and the guide shell bottom at center is set respectively
There is gas distributor to be connected with air inlet, be conducive to oxygen-containing gas to be uniformly distributed in reactor.
In the present invention, multiple reactors in series connection, wherein, the reactor liquid outlet of previous stage with it is latter
The reactor inlet connection of level.
Specifically, the number of the reactors in series is 2～9.
The using method of the multilamellar guide shell bubbling reactor in the present invention, in the reactor of plural serial stage,
Liquid phase hexamethylene successively from the central draft tube successively overflow from inside to outside of the first stage reactor, from outermost layer water conservancy diversion
Outermost layer annular region overflow between cylinder and reactor wall is drawn, from the hexamethylene that the first stage reactor is drawn
Alkoxide liquid is caused in the central draft tube of the second stage reactor, then outside successively overflow is to outermost layer annuluses
Domain overflow is drawn, so by kettle successively until drawing from the outermost layer annular region of afterbody reactor；
Per in A reactor, the gas of molecule-containing keto is respectively from the central draft tube of every stage reactor and each layer
Annular region between guide shell is introduced, the cyclohexane oxidation that will flow sequentially through in reactor, is generated containing ring
The cyclohexane oxide solution of hexyl hydrogen peroxide, Hexalin and Ketohexamethylene, cyclohexane oxide solution is from outermost layer annular
Region is drawn, and the tail gas of each annular region per stage reactor is drawn after reactor head mixing.
Further, the annular region in every stage reactor, between central draft tube and each layer guide shell
In the gas of the molecule-containing keto being introduced into, oxygen content is 5%～70%, and along the overflow direction of cyclohexane oxide solution
Improve step by step.
Further, the liquid phase hexamethylene for introducing 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 into 100～200 DEG C.
Further, the reaction pressure in every stage reactor is 0.2～2MPa.
According to the present invention, multilamellar guide shell is set in every stage reactor, by liquid separation in bubbling reactor
Into multiple annular regions, inside the guide shell at center and each annular region is complete mixed equivalent to one
Kettle, guide shell outwards step by step overflow of the liquid cyclohexane from center, A reactor is equivalent to multiple continuous stir reactors
Series connection, according to the guide shell number of plies arranged in the quantity and every stage reactor of bubbling reactor series connection, can be with mould
Draw up than the more series of existing commercial plant so that the type of flow of whole reaction mass is closer to horizontal sliding
Stream, the selectivity of intermediate oxidation product KA oil are higher.
According to the expansion scheme of the present invention, each annular region in the reactor, gas is from annular region
Center bubbling upwards, in the gas-liquid separation of reactor top, tail gas is drawn from reactor head, most of liquid
The outside circulation area and this layer that material is fallen between last layer double loop guide shell main body and its outside circulation baffle plate is double
Circulation guide shell main body and the interior circulating-area in which between circulation baffle plate, as the two annular spaces are distributed in gas
The periphery of device, its internal liquid material bubbles are little, with being rich in for the annular region center of the circulation cylinder
The liquid of bubble forms circulation, the downward liquid flow in inside and outside circulating-area, center annular because of density contrast
In region, material is flowed up, and improves the mixing intensity of liquid in annular region, is made in single annular region
The flowing of liquid is closer to complete mixing flow.
According to the present invention, when bubbling reactor diameter is less, the less guide shell number of plies is set, in bubbling
When reactor diameter is larger, the more guide shell number of plies is set, the number of plies of setting is more, whole reaction mass
Flowing be closer to laminar flow.
According to the present invention, the height of guide shell is outwards reduced successively from center, to prevent in outer annular region
Liquid 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 return
It is mixed to be down to minimum.
According to the present invention, the diameter difference between outboard diversion cylinder internal diameter and inner side guide shell external diameter is 0.2～2 meter,
Too small diameter difference can make from internal layer guide shell overflow the most of liquid for going out be directed across this layer of annular region and
Into outer annular region, excessive diameter difference can reduce the quantity of same diameter reactor inner draft tube, make
Series connection series it is on the low side and deviate laminar flow.
According to the present invention, respectively the annular region between central draft tube and each layer guide shell introduce containing point
In the gas of sub- oxygen, the content of oxygen is 5%～70%.The present inventor discloses one in ZL200610031809.6
Kind of cyclohexane oxidation preparing cyclohexanone, the method for Hexalin, it is characterised in that adopt in oxidizing process containing molecule
Oxygen concentration in the gas of oxygen increases with the conversion ratio of oxidizing process and increases, and the patented technology can be applicable to this
In invention.For example, from the central draft tube of the first stage reactor, until the outermost of afterbody reactor
Layer annular region, the oxygen content in the oxygen-containing gas for being adopted are improved to 70% step by step from 5%.
Due to multilamellar guide shell being employed in every stage reactor of series connection, increased total series connection series, make
The flowing of liquid material is closer to laminar flow, while different oxygen-containing of the oxygen content used in oxidizing process
Gas, making the ventilation of each annular region maintain one can make Liquid Flow situation in each annular region good
In good normal range, existing enough gas liquid film products in reactor are made, there are enough partial pressure of oxygens again,
The mass transfer rate and reaction rate for having fully ensured that oxygen matches, and oxidation reaction is stablized, efficiently carries out.
From the above mentioned, present invention improves flow condition in reactor, improves the selectivity of process, with
Prior art ratio can improve cyclohexane oxidation selectivity 1.0%～2.5%, and the present invention is equally also applicable in which
The production and processing of his oxidation reaction.
Below in conjunction with the drawings and specific embodiments, the invention will be further described.
Description of the drawings
Fig. 1 is the multilamellar guide shell bubbling reactor schematic internal view in embodiment 1.
Fig. 2 is the guide shell schematic diagram inside the multilamellar guide shell bubbling reactor in embodiment 2.
Fig. 3 is the flow schematic diagram inside the multilamellar guide shell bubbling reactor in embodiment 2.
Fig. 4 is series connection bubbling reactor process flow diagram.
Label in figure：1- reactor shells, the second guide shells of 2-, the first guide shells of 3-, 4- annular regions,
5- inlets, 6- air inlets, 7- gas outlets, 8- gas distributors, 9- liquid outlets.
G11, G12 and G13 in Fig. 2 is entering for the central draft tube of the first stage reactor and two annular regions
Air pipe, G21, G22 and G23 are the air inlet pipe of the central draft tube of the second stage reactor and two annular regions
Road, the air inlet pipeline of G31, G32 and G33 for the central draft tube and two annular regions of third level reactor,
W1, W2 and W3 are the offgas outlet of first, second, and third stage reactor, and L11 is first order liquid reactor
Import, liquid outlets of the L33 for third level reactor.
Specific embodiment
Embodiment 1
Referring to Fig. 1, in the reactor shell 1 of multilamellar guide shell bubbling reactor, multilamellar guide shell, this reality are arranged
Apply in example for two-layer guide shell, including the first guide shell 3 and the second guide shell positioned at outside positioned at center
2, two guide shells are coaxially disposed with reactor shell 1, and diameter is different, will be separated in reactor shell 1
Reduced step by step into three-level annular region 4, and the height of guide shell laterally along center, and the first guide shell
3 and second the bottom of guide shell 2 fix with 1 bottom welding of reactor shell, and ensure sealing, such three-level
Annular region can only carry out the series connection of overflow step by step by top, positioned at the connection inlet of the first guide shell 3 at center
5, air inlet 6, inlet 5 and air inlet are connected in first guide shell 3 at every grade of annular region 3 and center
6 are respectively positioned on reactor bottom, can introduce connection from reactor head or bottom by pipeline, in reactor enclosure body
Annular region 4 and 3 bottom of the first guide shell at center be respectively equipped with gas distributor with each layer air inlet 6
Connection.Outermost annular region connects liquid outlet 9, and liquid outlet 9 is installed in reactor shell 1, reactor
Gas outlet 7 is provided with the top of housing 1,4 bottom of annular region in reactor shell 1 is provided with gas distributor 8.
In production application, according to production requirement and the size and quantity of guide shell can be reset,
To arrange 1～9, the difference in height of adjacent guide cylinder is 0.01～1 meter to the number of plies of reactor inner draft tube, outer layer
Diameter difference between guide shell internal diameter and internal layer guide shell external diameter is 0.2～2 meter.In the present embodiment, react
Device housing 1, the second guide shell 2 and the first guide shell 3 are smooth cylinder, the internal diameter of reactor shell 1
800mm, the 3 internal diameter 400mm of the first guide shell at center, 2 internal diameter 600mm of the second guide shell, reactor shell are high
3000mm, the 3 high 2600mm of the first guide shell at center, 2 high 2400mm of the second guide shell, outermost layer discharging opening
High 2200mm.
In actual applications, 2～9 stage reactors can be connected in series, forms train, wherein, it is previous
The reactor liquid outlet of level is connected with the reactor inlet of rear stage, referring to Fig. 4, the reaction in three Fig. 1
Device is connected in series, and is aoxidized using the multilamellar guide shell bubbling reactor of embodiment below in conjunction with Fig. 1 and Fig. 4 explanations
The method of hexamethylene.
Hexamethylene is introduced in the first stage reactor from the center feed inlet L11 of first order bubbling reactor, waits to fill
Start overflow after full first guide shell 3 to the annular region between the first guide shell 3 and the second guide shell 2, treat the
Annular region between one guide shell 3 and the second guide shell 2 is full of rear beginning overflow is to the second guide shell 2 and leads
Annular region between flow cartridge housing 1, until the center of second level bubbling reactor is expelled to from liquid outlet overflow
First guide shell, is expelled to from liquid outlet after one layer of annular region of outermost of successively overflow to the second stage reactor
First guide shell of center of third level reactor, then one layer of the outermost of successively overflow to third level reactor is annular
Region, finally leads to decomposing system from L33 overflows.According to every stage reactor central draft tube reaction zone and
Between each guide shell annular region, the volume of reaction zone and the time of staying of hexamethylene are adjusting entering for hexamethylene
Doses, makes liquid product with certain speed overflow step by step, enters lower step operation Jing 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 the reaction temperature in every stage reactor is maintained at into 100～200 DEG C, and keep the reaction in per stage reactor
Pressure is 0.2～2MPa.
In every grade of bubbling reactor, what the annular region between central draft tube and each layer guide shell was introduced
In the gas of molecule-containing keto, oxygen content is 5%～70%, and is carried along the overflow direction of cyclohexane oxide solution step by step
It is high.Pure oxygen obtained in separation by deep refrigeration can be specifically adopted, or oxygen content is obtained for 70% with pressure swing adsorption method
The oxygen-enriched air of left and right, then mix with air, prepared oxygen content is 21%～70% oxygen-enriched air；With depth
Purity nitrogen obtained in cold partition method, or with the oxidized tail gas rich in nitrogen, then mix with air, prepared oxygen contains
Measure the oxygen denuded air for 5%～21%；By the annular region between each layer guide shell of bubbling reactor and in
The gas distributor of air inlet pipe G11 of the first guide shell bottom connection of the heart～G33 connections enters liquid phase hexamethylene
In carry out oxidation reaction, while adjust reaction temperature, air inflow and air inlet oxygen concentration, make central draft tube and
Between each guide shell, in the tail gas of annular region, oxygen content is below 5%, and tail gas is Jing after processing and reclaim hexamethylene
Recycle.
During actual oxidation in the present embodiment, in two layers of guide shell bubbling reactor of three series windings
Oxygen-containing gas is passed through step by step, is adjusted the ventilation and oxygen concentration of each kettle, is adjusted reaction temperature, make each kettle tail gas
In oxygen content (butt) control 2% or so, it is 45min or so to adjust the hexamethylene time of staying.System is steady
After fixed operation, reaction temperature is 165～170 DEG C, and reaction pressure 1.2MPa, sample analysis, analysis result tend to
Contain cyclohexyl hydroperoxide 3.46% in liquid phase material after stable, containing Hexalin 0.62%, containing Ketohexamethylene 0.28%,
It is 3.41% to calculate cyclohexane conversion, and the selectivity of useful products (includes Ketohexamethylene, Hexalin and ring
Hexyl hydroperoxides) for 95.84%.
Embodiment 2
With reference to referring to Fig. 2 and Fig. 3, the structure of reactor in the present embodiment is same as Example 1, except for the difference that,
Guide shell in the present embodiment is double loop guide shell, concrete as shown in Fig. 2 right by taking the second guide shell 2 as an example
The structure of double loop guide shell is illustrated, and the inner and outer wall of the second guide shell 2 is coaxially fixed with tubular
Interior circulation baffle plate 21 and outside circulation baffle plate 22, two circulation baffle plates are respectively by interior circulation fixing muscle 23 and outer shroud
Stream fixing muscle 24 is fixed on the inner side and outer side of the second guide shell 2, interior circulation baffle plate 21 and the second guide shell 2 it
Between, form interior circulating-area 26 and the outside circulation for circulating up and down between outside circulation baffle plate 22 and the second guide shell 2 respectively
Area 25, is coaxially provided with interior circulation baffle plate again by interior circulation fixing muscle 23 on the inwall of reactor shell 1
21.Each circulation baffle plate is made up of two parts, wherein the top for being placed in the interior circulation baffle plate 21 of inner side is upper little
Big positive taper down, bottom are cylinder straight tube shape, be placed in outside outside circulation baffle plate 22 top for it is upper it is big under
Little inverted cone, bottom are cylinder straight tube shape.
Specifically, interior 21 highest point of circulation baffle plate is lower than the highest point of 2 body of the second guide shell 0.01～1 meter,
Interior 21 lowest point of circulation baffle plate is higher than the lowest point of 2 body of the second guide shell 0.01～1 meter, interior circulation baffle plate 21
Straight drum part diameter is less than the diameter of 2 body of the second guide shell 0.01～0.4 meter, interior 21 inverted cone of circulation baffle plate
Diameter at the minimum of part is less than the diameter of 2 body of the second guide shell 0.04～0.8 meter.Outside circulation baffle plate 22 is most
Eminence is lower than the highest point of 2 body of the second guide shell 0.02～1 meter, and 22 lowest point of outside circulation baffle plate is led than second
The lowest point of 2 body of flow cartridge is high 0.02～1 meter, and 22 straight drum part diameter of outside circulation baffle plate is than the second guide shell 2
The diameter of body is big 0.01～0.4 meter, and the diameter of 22 conical section maximum of outside circulation baffle plate is than the second guide shell 2
Body diameter is big 0.04～0.8 meter.
In production application, according to production requirement and the size and quantity of guide shell can be reset,
The number of plies of reactor 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
Diameter difference between guide shell internal diameter and internal layer guide shell external diameter is 0.2～2 meter.In the present embodiment, two-layer
Guide shell bubbling reactor housing inner diameter 800mm, high 3000mm；The first guide shell internal diameter 400mm at center,
High 2600mm, circulation baffle plate straight drum part diameter 350mm in which, diameter 200mm at inverted cone horn mouth minimum,
Baffle plate highest point 200mm lower than the second guide shell highest point, baffle plate lowest point are higher than the second guide shell lowest point
30mm, its outside circulation baffle plate straight drum part diameter 440mm, conical horn mouth maximum diameter 480mm, gear
Plate highest point 400mm lower than the first guide shell highest point, baffle plate lowest point are higher by 40 than the first guide shell lowest point
mm；Second guide shell internal diameter 600mm, high 2400mm, circulation baffle plate straight drum part diameter 560mm in which,
Diameter 520mm, baffle plate highest point 200mm lower than the second guide shell highest point at inverted cone horn mouth minimum,
Baffle plate lowest point 25mm higher than the second guide shell lowest point, its outside circulation baffle plate straight drum part diameter 640mm,
Conical horn mouth maximum diameter 680mm, baffle plate highest point 200mm lower than the second guide shell highest point, gear
Plate lowest point 25mm higher than the second guide shell lowest point；Discharging opening in outermost reactor shell is high by 2200
mm。
Likewise, the present embodiment is in actual applications, 2～9 stage reactors can be connected in series, form series connection
System, wherein, the reactor liquid outlet of previous stage is connected with the reactor inlet of rear stage, referring to Fig. 4,
Reactors in series connection in three Fig. 3, uses the multilamellar double loop of embodiment below in conjunction with Fig. 3 and Fig. 4 explanations
The method of guide shell bubbling reactor oxidizing ethyle alkyl.
Hexamethylene is introduced in the first stage reactor from the center feed inlet L11 of first order bubbling reactor, this reality
The inlet applied in example introduces liquid from the bottom of the first guide shell 3, starts to overflow after full of the first guide shell 3
The annular region flowing between the first guide shell 3 and the second guide shell 2, treats the first guide shell 3 and the second guide shell
Annular region between 2 is full of rear beginning overflow to the annuluses between the second guide shell 2 and reactor shell 1
Domain, until first guide shell of center of second level bubbling reactor, successively overflow are expelled to from liquid outlet overflow
The center of third level reactor is expelled to one layer of annular region of outermost of the second stage reactor from liquid outlet
One guide shell, then one layer of annular region of the outermost of successively overflow to third level reactor, finally draw from L33 overflows
Go out to decomposing system.According to every stage reactor central draft tube reaction zone and each guide shell annular region between
The time of staying of the volume and hexamethylene of reaction zone adjusts the inlet amount of hexamethylene, makes liquid product with one
Determine stepwise speed overflow, lower step operation is entered Jing after multistage series winding oxidation.
Unlike embodiment 1, interior circulating-area and outside circulation inside and outside the guide shell in the present embodiment, are increased
Area, the outside circulation that partially liq material is fallen between last layer double loop guide shell main body and its outside circulation baffle plate
Area and this floor double loop guide shell main body and the interior circulating-area in which between circulation baffle plate, 26 He of interior circulating-area
Periphery of the outside circulation area 25 in gas distributor, its internal liquid material bubbles are little, with the circulation cylinder
The liquid rich in bubble at annular region center form circulation, the liquid in inside and outside circulating-area because of density contrast
Body flows downward, and in central annular region, material is flowed up, and the mixing that improve liquid in annular region is strong
Degree, 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 into 100～200 DEG C, and keep in per stage reactor
Reaction pressure be 0.2～2MPa.
Ring in every grade of bubbling reactor, between center double loop guide shell and each layer double loop guide shell
In the gas of the molecule-containing keto that shape region is introduced into, oxygen content is 5%～70%, and overflowing along cyclohexane oxide solution
Improve step by step in stream direction.Pure oxygen obtained in separation by deep refrigeration can be specifically adopted, or is obtained with pressure swing adsorption method
Oxygen content is 70% or so oxygen-enriched air, then is mixed with air, and prepared oxygen content is 21%～70% richness
Oxygen air；It is with purity nitrogen obtained in separation by deep refrigeration, or with the oxidized tail gas rich in nitrogen then mixed with air
Close, prepared oxygen content is 5%～21% oxygen denuded air；By first guide shell and blistering reaction at center
The gas point of air inlet pipe G11 of the annular region bottom connection between each layer double loop guide shell of device～G33 connections
Cloth device carries out oxidation reaction in liquid phase hexamethylene, while it is dense to adjust reaction temperature, air inflow and air inlet oxygen
Degree, makes between central bicyclic conductance flow cartridge and each double loop guide shell that oxygen content is low in the tail gas of annular region
In 5%, tail gas Jing is processed and is reclaimed the utilization of hexamethylene Posterior circle.
During actual oxidation in the present embodiment, in two layers of guide shell bubbling reactor of three series windings
Oxygen-containing gas is passed through step by step, is adjusted the ventilation and oxygen concentration of each kettle, is adjusted reaction temperature, make each kettle tail gas
In oxygen content (butt) control 2% or so, it is 50min or so to adjust the hexamethylene time of staying.System is steady
After fixed operation, reaction temperature is 164～168 DEG C, and reaction pressure 1.2MPa, sample analysis, analysis result tend to
Contain cyclohexyl hydroperoxide 3.38% in liquid phase material after stable, containing Hexalin 0.58%, containing Ketohexamethylene 0.24%,
It is 3.28% to calculate cyclohexane conversion, and the selectivity of useful products (includes Ketohexamethylene, Hexalin and ring
Hexyl hydroperoxides) for 96.00%.
Above example is the description of the invention, not limitation of the invention, the technical staff of the industry
It should be appreciated that the present invention is not restricted to the described embodiments, described in above-described embodiment and description simply
The concrete operating principle of the present invention is illustrated, without departing from the spirit and scope of the present invention, the present invention is also
Various changes and modifications are had, these changes and improvements are both fallen within scope of the claimed invention, this
Bright claimed scope is by appending claims and its equivalent thereof.
Claims (14)
1. a kind of multilamellar guide shell bubbling reactor, it is characterised in that：Coaxial sleeve sets multilamellar in the reactor enclosure body
Guide shell, the diameter of each guide shell are different, and the bottom of guide shell is connected with reactor shell sealed bottom
Connect, in reactor enclosure body, will be separated into multi-stage annular region, and the height of guide shell along center laterally by
Level is reduced, and the guide shell bottom positioned at center arranges the guide shell at inlet, every grade of annular region and center
Bottom connects air inlet, and outermost annular region connects liquid outlet, is provided with the top of the reactor shell
Gas outlet.
2. a kind of multilamellar guide shell bubbling reactor according to claim 1, the reactor inner draft tube
The number of plies is 1～9.
3. a kind of multilamellar guide shell bubbling reactor according to claim 3, the difference in height of adjacent guide cylinder is
0.01～1 meter, the diameter difference between outer layer guide shell internal diameter and internal layer guide shell external diameter is 0.2～2 meter.
4. a kind of multilamellar guide shell bubbling reactor according to claim 3, the inwall of the guide shell and outer
Wall is coaxially fixed with the interior circulation baffle plate and outside circulation baffle plate of tubular, the interior circulation gear respectively by fixing muscle
Form the interior circulating-area that circulates up and down and outer between plate and guide shell, between outside circulation baffle plate and guide shell respectively
Circulating-area.
5. a kind of multilamellar guide shell bubbling reactor according to claim 4, the inwall of the reactor shell
It is upper that interior circulation baffle plate is coaxially fixed with by fixing muscle.
6. a kind of multilamellar guide shell bubbling reactor according to claim 5, the top of the interior circulation baffle plate
The positive conical surface is bent into inwardly, the top of the outside circulation baffle plate is outwards bent into inverted cone surface, the interior circulation gear
Plate and outside circulation baffle plate remainder are straight-tube shape.
7. a kind of multilamellar guide shell bubbling reactor according to claim 6, the interior circulation baffle plate highest point
Lower than guide shell highest point 0.01～1 meter, interior circulation baffle plate lowest point is higher than guide shell lowest point 0.01～1 meter,
Interior circulation baffle plate straight drum part diameter is less than draft tube diameter 0.01～0.4 meter, interior circulation baffle plate reverse taper portion
Diameter at minimum is less than draft tube diameter 0.04～0.8 meter；
The outside circulation baffle plate highest point is lower than guide shell highest point 0.02～1 meter, outside circulation baffle plate lowest point ratio
Guide shell lowest point is high 0.02～1 meter, and outside circulation baffle plate straight drum part diameter is bigger than draft tube diameter by 0.01～
0.4 meter, the diameter of outside circulation baffle plate conical section maximum is bigger than draft tube diameter 0.04～0.8 meter.
8. a kind of multilamellar guide shell bubbling reactor according to claim 1, the ring in the reactor enclosure body
The guide shell bottom at shape region and center is respectively equipped with gas distributor and is connected with air inlet.
9. a kind of multilamellar guide shell bubbling reactor according to any one of claim 1-8, multiple reactors
It is connected in series, wherein, the reactor liquid outlet of previous stage is connected with the reactor inlet of rear stage.
10. a kind of multilamellar guide shell bubbling reactor according to claim 9, the number of the reactors in series
For 2～9.
11. a kind of using method of the multilamellar guide shell bubbling reactor described in claim 1-10, its feature exist
In：In the reactor of plural serial stage, liquid phase hexamethylene is successively from the central draft tube of the first stage reactor
Outwards successively overflow, draws from the outermost layer annular region overflow between outermost layer guide shell and reactor wall,
The cyclohexane oxide solution drawn from the first stage reactor is caused in the central draft tube of the second stage reactor, then to
Outer successively overflow is drawn to the overflow of outermost layer annular region, so by kettle successively until from afterbody reactor
Outermost layer annular region draw；In every A reactor, the gas of molecule-containing keto is respectively from every order reaction
Annular region in the central draft tube of device and between each layer guide shell is introduced, and will be flowed successively in reactor
The cyclohexane oxidation crossed, generates the cyclohexane oxide solution containing cyclohexyl hydroperoxide, Hexalin and Ketohexamethylene,
Cyclohexane oxide solution is drawn from outermost layer annular region, and the tail gas of each annular region per stage reactor is in reaction
Draw after mixing at the top of device.
12. according to the using method of the multilamellar guide shell bubbling reactor described in claim 11, in every order reaction
In device, oxygen in the gas of the molecule-containing keto that the annular region between central draft tube and each layer guide shell is introduced into
Gas content is 5%～70%, and is improved along the overflow direction of cyclohexane oxide solution step by step.
13. it is according to the using method of the multilamellar guide shell bubbling reactor described in claim 12, anti-from the first order
The liquid phase hexamethylene that the central draft tube of device is introduced is answered to be previously heated to 100～200 DEG C, and will be per stage reactor
Interior reaction temperature is maintained at 100～200 DEG C.
14. according to the using method of the multilamellar guide shell bubbling reactor described in claim 13, per stage reactor
Interior reaction pressure is 0.2～2MPa.
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| CN107032948A (en) * | 2017-06-17 | 2017-08-11 | 石嘴山市瑞新化工有限公司 | A kind of dichloroethanes pretreating device |
| CN109589880A (en) * | 2019-01-22 | 2019-04-09 | 常州瑞华化工工程技术股份有限公司 | A kind of horizontal efficient plug flow bubbling reactor |
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| CN112237769A (en) * | 2019-07-17 | 2021-01-19 | 杭州特种纸业有限公司 | Needle head type filter |
| CN110586020A (en) * | 2019-09-29 | 2019-12-20 | 沧州旭阳化工有限公司 | Redistribution type reaction device |
| NO20210332A1 (en) * | 2021-03-16 | 2022-09-19 | Minox Tech As | Device with variable volume for treatment of gases and liquids |
| WO2022194700A1 (en) | 2021-03-16 | 2022-09-22 | Minox Technology As | Device with variable volume for treatment of gases and liquids |
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