CN106279078B - Prepare the method and low pressure drop radial direction isothermal reactor of cis-butenedioic anhydride - Google Patents
Prepare the method and low pressure drop radial direction isothermal reactor of cis-butenedioic anhydride Download PDFInfo
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- CN106279078B CN106279078B CN201510369479.0A CN201510369479A CN106279078B CN 106279078 B CN106279078 B CN 106279078B CN 201510369479 A CN201510369479 A CN 201510369479A CN 106279078 B CN106279078 B CN 106279078B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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Abstract
The invention discloses a kind of method preparing cis-butenedioic anhydride and low pressure drop radial direction isothermal reactor, the method is realized in a kind of low pressure drop radial direction isothermal reactor equipped with bushing type fused salt heat exchanging pipe with the center gas-distributing pipe for being provided with point stomata；Unstripped gas normal butane or benzene enter reactor with air by air inlet, and the material after reaction is discharged from gas outlet；Reaction temperature is 380~420 DEG C, and reaction pressure is 0.05~0.15MPa, and the residence time is 1.0~3.0 seconds, and catalyst is V-P-O systems5Or V-Mo-O systems.Reactor scale of the present invention is easy to amplify, and can be used for 0.2~100,000 tons/year of maleic anhydride production scales, device pressure drop is answered to be greatly reduced, only 5~20kPa, catalyst is filled on the outside of heat exchanger tube, is easy to ensure the uniformity of catalyst filling, substantially reduces the possibility that regional area reaction deteriorates green coke.
Description
Technical field
The invention belongs to a kind of low pressure drop radial direction isothermal for normal butane method cis-butenedioic anhydride and benzene method maleic anhydride process units is anti-
Answer device.
Background technology
Maleic anhydride abbreviation cis-butenedioic anhydride also known as maleic anhydride are a kind of important Organic Chemicals, are to be only second to benzene
The big organic acid anhydride in the third place in the world of acid anhydride and aceticanhydride, is widely used in the industries such as petrochemical industry, food processing, medicine, building materials.
Currently, pressing raw material route, the production method of cis-butenedioic anhydride can be divided into benzene oxidatoin method, n butane oxidation method.Wherein, normal butane
Oxidizing process is occupied an leading position in maleic anhydride production, and production capacity accounts for about the 80% of world's cis-butenedioic anhydride total productive capacity.It is suitable in the world
Acid anhydride mainly uses n butane oxidation method to produce, and the cis-butenedioic anhydride in China then mainly uses benzene oxidatoin method to produce, but since normal butane method has
The advantages that standby raw material is inexpensive, and pollution is relatively light, carbon atom utilization rate height and maleic anhydride production at low cost, normal butane method is suitable in recent years
The production capacity of acid anhydride is continuously increased, and has the tendency that gradually substituted benzene oxidizing process.
Currently, the research in maleic anhydride process field concentrates on catalyst and aftertreatment technology substantially, for reactor
Almost all is studied based on axial calandria type fixed bed reactor.Such as the patent CN103071433A of Zhejiang University is proposed
A kind of fixed bed reactors for preparing cis-anhydride by n-butane oxidation gas pre-distributor, the distributor by horizontal flow deflector,
Diversion pipe, tapered cap composition, it is possible to reduce the area in low gas velocity region, and improve the shadow to distribution grid local assault unevenness
It rings, improves the stability of operation.The patent CN102423666A of Tianjin Chemical Design Inst. proposes a kind of normal butane method cis-butenedioic anhydride
Fixed bed oxidizing reaction temperature control set for adjusting and method：It is provided with guiding valve between reactor and molten salt cooler, passes through
The open degree of guiding valve is accurately controlled, the stabilization of reactor shell side temperature of molten salt is realized, solves and reaction temperature is overcome to fluctuate, make oxygen
Change reaction cis-butenedioic anhydride weight yield and improve 0.5~1.0%, reduces the by-product in reaction product.China LanXing Harbin stone
The patent CN202983655U for changing Co., Ltd proposes a kind of maleic anhydride unit oxidation reactor fused salt return duct structure, using this
Structure can increase the reflowing result of cis-butenedioic anhydride benzene oxidatoin reactor fused salt, extend the service life of cis-butenedioic anhydride benzene oxidatoin reactor.
Although axial calandria type fixed bed reactor is applied for many years in benzene method maleic anhydride device and normal butane method maleic anhydride unit,
Technology maturation, but cis-butenedioic anhydride oxidator still has many problems using axial calandria type fixed bed reactor, such as：
1. can not also preferably solve super-large diameter shell and tube reactor (6~10m of diameter) shell-side heat transport fluid at present
It is uniformly distributed problem, for the reactor of super-large diameter, fused salt cannot still be controlled 2~3 in the temperature difference of reactor radial direction
Within DEG C, this makes the shifting hot property of each pipe in reactor differ greatly, and directly affects the control of reaction temperature, cis-butenedioic anhydride is caused to receive
The consequences such as rate decline, reaction tube coking and blocking or even temperature control, thus, the axial direction of domestic production at present is calandria type fixed bed
For reactor maximum gauge still in 6m or so, this directly limits the production scale of cis-butenedioic anhydride reactor, for producing on a large scale only
It can be solved in such a way that multiple small-scale reaction systems are in parallel；
2. due to the limitation of reactor maximum gauge, fluid is also restrained by the circulation area of reactor, thus urges
The bed height of agent is limited, and the cis-butenedioic anhydride catalyst in reactor bed ratio of height to diameter for causing present industrial is big, reaction stream
Pressure drop when body flows through catalyst bed is larger, and higher outlet pressure must be used by resulting in wind turbine so that the power consumption of wind turbine
It is substantially increased, becomes the energy consumption rich and influential family of entire maleic anhydride production device；
3. the tubulation in axial calandria type fixed bed reactor is more, such as 2.5 ten thousand tons/year of normal butane method maleic anhydride units
There are about 24000 pipes in oxidator, this makes the filling of the catalyst in entire oxidator tube array uniformity be difficult to be guaranteed,
Each pipe catalyst filling amount has difference so that air speed when operation in each pipe is different, this will lead to the reaction in some pipes
Conversion ratio, which does not reach, to be required, and the side reaction in some pipes is more, generates more coking material, finally blocks reaction tube；
4. there are temperature gradients on direction for tube inner diameter, the temperature for reacting tube hub is higher than reaction tube surrounding always,
This causes the reaction temperature for reacting tube hub higher, and side reaction is more, and then influences the W-response selectivity of cis-butenedioic anhydride.
In order to improve and solve the above problems, researchers have done some effort, document chemical engineering March the 37th in 2009
Roll up the 3rd phase P20-22,26《In shell-and-tube reactor in circle distributor uniform fluid distribution discussion》To shell and tube reactor in one text
The equation of momentum of fluid flowing in interior circle distributor is corrected, it is intended to more accurately be described fluid and be reacted in tubulation
The flow behavior of device shell-side.Document East China University of Science master thesis in 2012《The simulation of calandria type fixed bed reactor
With design》A small pool model of two dimension about shell and tube reactor shell side is proposed in one text, and by the model for difference
The simulation and design of shell side structure (segmental baffle and disc and doughnut baffle) calandria type fixed bed reactor.These grind
The purpose studied carefully is to understand the fused salt flow behavior of axial calandria type fixed bed reactor shell-side, designs better fused salt distributor
And collector, using baffle plate preferably, to reduce radial temperature difference, so that the reactor of manufacture larger diameter is become can
Energy.And for reducing cis-butenedioic anhydride reactor pressure decrease, the pack uniformity for improving catalyst, the reaction yield aspect for improving cis-butenedioic anhydride and grinding
Study carefully also fewer.
Invention content
It is existing to overcome the object of the present invention is to provide a kind of method preparing cis-butenedioic anhydride and low pressure drop radial direction isothermal reactor
Defect existing for technology.
The method that the present invention prepares cis-butenedioic anhydride is divided with the center for being provided with point stomata equipped with bushing type fused salt heat exchanging pipe a kind of
It is realized in the low pressure drop radial direction isothermal reactor of tracheae；
Unstripped gas normal butane or benzene enter reactor with air by air inlet, and the material after reaction is discharged from gas outlet；
Reaction temperature is 380~420 DEG C, and reaction pressure is 0.05~0.15MPa, and the residence time is 1.0~3.0 seconds, is urged
Agent is V-P-O systems5Or V-Mo-O systems.
Preferably：
When using normal butane as raw material, the conversion ratio of normal butane is 80~85%, and the selectivity of cis-butenedioic anhydride is 66~73%, with benzene
For raw material when, the conversion ratio of benzene is 98~99%, and the selectivity of cis-butenedioic anhydride is 70~78%；
When using normal butane as raw material, reaction temperature is 380~420 DEG C, and reaction pressure is 0.08~0.15MPa, normal butane
Residence time be 1.8~2.25 seconds, catalyst be V-P-O systems, main component V2O5-P2O5；
When using benzene as raw material, reaction temperature is 350~400 DEG C, and reaction pressure is 0.06~0.15MPa, and normal butane stops
It is 1.4~1.8 seconds to stay the time, and catalyst is V-Mo-O systems, main component V2O5-MoO3；
When using normal butane as raw material, unstripped gas normal butane：Air=1：54.5~61.5vol；
When using benzene as raw material, unstripped gas benzene：Air=1：65.7~83vol；
Above-mentioned catalyst is the prior art, such as 2012《Contemporary chemical industry》The phase of volume 41 the 7th, " maleic anhydride production was urged with VPO
The catalyst reported in the progress of an agent " text.
The method of the present invention, advantageous effect are：
Reactor scale is easy to amplify, and can be used for 0.2~100,000 tons/year of maleic anhydride production scales；
Reactor pressure decrease is greatly reduced, only 5~20kPa；
Catalyst is filled on the outside of heat exchanger tube, is easy to ensure the uniformity of catalyst filling, big to reduce regional area reaction
Deteriorate the possibility of green coke；
Description of the drawings
Fig. 1 is the low pressure drop radial direction isothermal reactor structural schematic diagram for strong exothermal reaction.
Fig. 2 a are stringing schematic diagram；
Fig. 2 b are to flow to schematic diagram when reaction mass flows between the pipe of invention；
Fig. 3 is the sectional structure chart of fused salt heat exchanging pipe.
Cooperation figures of the Fig. 4 between gas distributor outer wall and bottom edge.
Specific implementation mode
The method that the present invention prepares cis-butenedioic anhydride is at a kind of center for being equipped with bushing type fused salt heat exchanging pipe 22 and being provided with point stomata
It is realized in the low pressure drop radial direction isothermal reactor of gas-distributing pipe 8；
Unstripped gas normal butane or benzene enter reactor with air by air inlet 15, and material after reaction is from 5 row of gas outlet
Go out,
Reaction temperature is 380~420 DEG C, and reaction pressure is 0.05~0.15MPa, and the residence time is 1.0~3.0 seconds, is urged
Agent is V-P-O systems5Or V-Mo-O systems.
When wherein using normal butane as raw material, the conversion ratio of normal butane is 80~85%, and the selectivity of cis-butenedioic anhydride is 66~73%,
When using benzene as raw material, the conversion ratio of benzene is 98~99%, and the selectivity of cis-butenedioic anhydride is 70~78%；
When using normal butane as raw material, reaction temperature is 380~420 DEG C, and reaction pressure is 0.08~0.15MPa, normal butane
Residence time be 1.8~2.25 seconds, catalyst be V-P-O systems, main component V2O5-P2O5；
When using benzene as raw material, reaction temperature is 350~400 DEG C, and reaction pressure is 0.06~0.15MPa, and normal butane stops
It is 1.4~1.8 seconds to stay the time, and catalyst is V-Mo-O systems, main component V2O5-MoO3；
When using normal butane as raw material, unstripped gas normal butane：Air=1：54.5~61.5vol；
When using benzene as raw material, unstripped gas benzene：Air=1：65.7~83vol；
Referring to Fig. 1~Fig. 4, the radial direction isothermal reactor include vertical outer barrel 11, upper perforated plate 17, lower perforated plate 16,
Fixed plate 18, lateral wall are provided with the radial reaction basket 12 of venthole, are provided with the center gas-distributing pipe 13 and bushing type fused salt of point stomata
Heat exchanger tube 22；
The lower perforated plate 16 is built in the lower part of the outer barrel 11, and the upper perforated plate 17 is arranged under described
The top of tube sheet 16, the fixed plate 18 set the top of the outer barrel 11 described in inherence, the upper perforated plate 17 and lower perforated plate
16 both ends are fixedly connected with the inner wall of the outer barrel 11, for into fused salt chamber 2 between 11 bottom of lower perforated plate 16 and outer barrel,
Be fused salt chamber 4 between upper perforated plate 17 and lower perforated plate 16, it is described go out fused salt chamber 4 at outer barrel 11 be equipped with fused salt export 3, it is excellent
Choosing, if there are two symmetrically arranged fused salts to export 3, the bottom of outer barrel 11 is equipped with fused salt import 1；
The described radial reaction basket 12 is coaxial with outer barrel 11, and lower end is fixed on the upper perforated plate 17, upper end and
The both ends of the fixed plate 18 are connected, and the radial annular space reacted between basket 12 and outer barrel 11 is air collecting chamber 6；
The center gas-distributing pipe 13 is arranged in radially 12 middle part of reaction basket, upper end and the air inlet being arranged at the top of outer barrel 11
Mouth 15 connects, and lower end is connect with upper perforated plate 17, and gas distributor 8, center gas-distributing pipe 13 and gas are equipped in the gas-distributing pipe 13
It is to divide air cavity 7 between distributor 8；
Gas outlet 5 is arranged in the lower part of the outer barrel 11, and reacting basket 12 with radial direction is connected；
Preferably, the gas distributor 8 is up-small and down-big laddertron, is coaxially disposed with the outer barrel 11,
Lower end is fixed on upper perforated plate 17；
Preferably, the angle α between 8 outer wall of gas distributor and bottom edge is 85~89 °；
Preferably, the aperture of stomata is divided to be 2~25mm on 13 outer wall of center gas-distributing pipe, percent opening is 20~40%；
Preferably, the outer barrel 11 and radial reaction basket 12 are cylinder；
The ratio of height to diameter of the described radial reaction basket 12 is 2~6, the radial aperture for reacting the venthole on basket 12 is 2~
25mm, percent opening are 20~40%；
22 centrally disposed gas-distributing pipe 13 of described sleeve pipe formula fused salt heat exchanging pipe with it is radial react 12 outer wall of basket between, one end and
Go out the connection of fused salt chamber 4, the other end is connected into fused salt chamber 2；
Preferably, described sleeve pipe formula fused salt heat exchanging pipe 22 is made of outer tube 9 and inner tube 10, the outer tube 9 with it is described
There are annular space, 9 upper end closed of outer tube between inner tube 10, and be fixed in the fixed plate 18, lower end connects with fused salt chamber 4 is gone out
Logical, 10 open upper end of inner tube, lower end is connected into fused salt chamber 2；
Preferably, 22 arrangement mode of fused salt heat exchanging pipe is concentric circles, triangle or square；
Preferably, the top of the outer barrel 11 is equipped with the head cover 14 by flanged joint, and the setting of air inlet 15 is being pushed up
On lid 14；
Preferably, the head cover 14 is equipped with catalyst loading and unloading mouth 19 and the nitrogen mouth 20 for deadband eliminating；
By above-mentioned structure as it can be seen that since the fused salt of the radial isothermal reactor of the present invention is flowed in pipe side, point of fused salt
Cloth problem becomes the limitation of reactor diameter no longer as axial shell-and-tube reactor shell-side, produces the reaction of 6~10m diameters
Device is possibly realized, and the generation scale of reactor also increases as；
Due to the circulation area many bigger than axial flow reactor when gas flows through catalytic bed in radial reactor, thus urge
Agent bed flow direction height and fluid flow rate, which compare axial bed, significant decrease, thus the pressure drop of catalytic bed is also obviously dropped
It is low, even as low as 5~10kPa.This can significantly reduce the outlet pressure of air compressor, and the equipment for not only reducing air compressor machine is thrown
Money, also significantly reduces the operating cost of air compressor machine, improves the capacity usage ratio of device.
Catalyst filling is an entirety in reaction basket on the outside of heat exchanger tube, and filling uniformity is easier to be guaranteed,
Compared to the single tube of axial shell and tube reactor, and it is in extensive area property, this will filling even if being filled with uneven situation
Non-uniform influence is substantially average so that reaction gas is consistent substantially in the air speed of catalyst bed, avoids axial row
The excessive problem of side reaction in certain pipes in pipe reactor.
As shown in Figure 2 b, when reaction gas flows in catalyst bed, present heating ----cooling cycle, i.e., with urge
Agent bed reacts when contacting, and generating reaction heat makes reaction gas heat up, and when flowing to heat exchanger tube, heat is into heat exchanger tube
It transmits, reaction gas cooling.Due to the presence of the cycle, reaction gas is in catalyst bed without apparent, not amendatory
High-temperature region, this can reduce CO, CO2、H2The byproducts such as O；
Due to the circulation area many bigger than axial flow reactor when gas flows through catalytic bed in radial reactor, thus urge
Agent bed flows to thickness has significant decrease compared to axially-located bed, thus the pressure drop of catalytic bed is significantly reduced, for
The embodiment of the present invention 1, only 10kPa.This can significantly reduce the outlet pressure of air compressor, not only reduce air compressor machine
Equipment investment also significantly reduces the power consumption of air compressor machine, reduces the energy consumption of maleic anhydride unit.Another is worth the problem of discussing
It is that radial isothermal cis-butenedioic anhydride reactor of the invention, if fused salt pressure drop is excessively high, causes catalyst bed pressure drop in practical operation
Reduce and the electric energy saved is less than and when the increased electric energy of the high institute of fused salt side pressure falling-rising, low drop-out nature of the invention will become
It is nonsensical, thus for the radial isothermal cis-butenedioic anhydride reactor of the present invention, the pressure drop of salt melting system is also one and necessarily investigates
Factor.In the embodiment of the present invention 1, the salt melting system pressure drop of 2.5 ten thousand tons/year of normal butane method cis-butenedioic anhydride radial direction isothermal reactors is
113.1kPa is less than the axial shell and tube reactor of traditional same maleic anhydride production scale, and this reduces the energy consumptions of device；It urges
Agent is filled on the outside of heat exchanger tube, is an entirety in reaction basket, filling uniformity is easier to be guaranteed, even if objectively
It is unable to reach absolute uniform, compared to the single tube of axial shell and tube reactor, the inhomogeneities of radial catalyst bed is in a wide range of
Region property, this will fill non-uniform influence and substantially equalize so that reaction gas is protected substantially in the air speed of catalyst bed
It holds unanimously, avoids in axial shell-and-tube reactor the problem of side reaction is excessive in certain reaction tubes, is easy to green coke blocks, reaction gas
When normal butane or benzene flow in catalyst bed, presents and " react and --- heat up and --- contacted with heat exchanger tube --- cooling ---
React again " cycle, i.e., react when being contacted with catalyst bed, generate reaction heat so that reaction gas is heated up, and flow to change
When heat pipe, heat is transmitted into heat exchanger tube, reaction gas cooling.Due to the presence of the cycle, reaction gas is in catalyst bed
Without apparent, not amendatory high-temperature region, this can reduce CO, CO2、H2The generation of the byproducts such as O improves the receipts of cis-butenedioic anhydride product
Rate.
Embodiment 1
Using the reactor of Fig. 1~Fig. 4,2.5 ten thousand tons/year of normal butane method cis-butenedioic anhydrides.
Structure of reactor parameter：
Angle α between 8 outer wall 801 of gas distributor and bottom edge is 87.5 °；
The aperture of stomata is divided to be 25mm, percent opening 30% on 13 outer wall 1301 of center gas-distributing pipe；
Outer barrel 11 and radial reaction basket 12 are cylinder；
The ratio of height to diameter of radial reaction basket 12 is 3, and the radial aperture for reacting the venthole on basket 12 is 25mm, and percent opening is
30%；
22 arrangement mode of fused salt heat exchanging pipe is concentric circles；
Unstripped gas is that normal butane enters reactor with air by air inlet 15, and the material after reaction is discharged from gas outlet 5,
The conversion ratio of middle normal butane is 83.5%, and the selectivity of cis-butenedioic anhydride is 69.5%；
Reaction temperature is 420 DEG C, and reaction inlet pressure is 0.1MPa；The residence time of normal butane is 2 seconds, and catalyst is
V2O5-P2O5System Catalyst；
Pressure drop of the unstripped gas in reactor is 10kPa.
Unstripped gas normal butane: air=1: 54.5vol；
Radial direction of embodiment of the present invention isothermal reactor is being respectively used to 2.5 ten thousand tons/year just with conventional axial shell and tube reactor
Performance after butane method maleic anhydride device is relatively shown in Table 1.
1 embodiment reactor of table is compared with conventional axial shell and tube reactor performance
| Project | Conventional axial shell and tube reactor | Reactor of the present invention |
| Bed pressure drop Δ P, kPa | 60~90 | 10 |
| Fused salt pressure drop Δ P, kPa | ~190 | 113.1 |
| Air compressor machine power consumption, kWh/h | ~3500 | ~2200 |
| Yield of maleic anhydride, wt% | 95~101% | 98~101% |
Embodiment 2
Using the reactor of Fig. 1~Fig. 4,2.5 ten thousand tons/year of benzene method maleic anhydrides.
Structure of reactor parameter：
Angle α between 8 outer wall 801 of gas distributor and bottom edge is 87.8 °；
The aperture of stomata is divided to be 20mm, percent opening 35% on 13 outer wall 1301 of center gas-distributing pipe；
Outer barrel 11 and radial reaction basket 12 are cylinder；
The ratio of height to diameter of radial reaction basket 12 is 3.3, and the radial aperture for reacting the venthole on basket 12 is 20mm, percent opening
It is 35%；
22 arrangement mode of fused salt heat exchanging pipe is equilateral triangle；
Unstripped gas is that benzene enters reactor with air by air inlet 15, and the material after reaction is discharged from gas outlet 5, wherein benzene
Conversion ratio be 98.6%, the selectivity of cis-butenedioic anhydride is 75%；
Reaction temperature is 370 DEG C, reaction pressure 0.09MPa；The residence time of benzene is 1.5 seconds, catalyst V2O5-
MoO3System Catalyst；
Pressure drop of the unstripped gas in reactor is 8kPa.
Unstripped gas benzene: air=1: 70.5vol.
Claims (14)
1. the method for preparing cis-butenedioic anhydride, which is characterized in that be to be equipped with bushing type fused salt heat exchanging pipe a kind of and be provided in point stomata
It is realized in the low pressure drop radial direction isothermal reactor of heart gas-distributing pipe；
Unstripped gas normal butane or benzene enter reactor with air by air inlet, and the material after reaction is discharged from gas outlet；
Reaction temperature is 380~420 DEG C, and reaction pressure is 0.05~0.15MPa, and the residence time is 1.0~3.0 seconds, catalyst
For V-P-O systems or V-Mo-O systems；
The low pressure drop radial direction isothermal reactor, including it is vertical outer barrel (11), upper perforated plate (17), lower perforated plate (16), solid
Fixed board (18), lateral wall are provided with the radial reaction basket (12) of venthole, are provided with the center gas-distributing pipe (13) and bushing type of point stomata
Fused salt heat exchanging pipe (22)；
The lower perforated plate is built in the lower part of the outer barrel, and the upper perforated plate is arranged in the upper of the lower perforated plate
Side, the fixed plate are located at the top of the outer barrel, the both ends and the outer barrel of the upper perforated plate and lower perforated plate
The inner wall of body is fixedly connected, into fused salt chamber, between upper perforated plate and lower perforated plate to be fused salt between lower perforated plate and outer barrel bottom
Chamber, it is described go out fused salt chamber at outer barrel be equipped with fused salt and export (3), the bottom of outer barrel is equipped with fused salt import (1)；
Described radial reaction basket (12) lower end is fixed on the upper perforated plate, the both ends phase of upper end and the fixed plate
Connection, the radial annular space reacted between basket and outer barrel are air collecting chamber (6)；
The center gas-distributing pipe is arranged in the middle part of the radial reaction basket, upper end and the air inlet being arranged at the top of outer barrel
(15) it connects, lower end is connect with upper perforated plate, and gas distributor (8), center gas-distributing pipe and gas are equipped in the gas-distributing pipe (13)
It is to divide air cavity (7) between distributor；
Gas outlet (5) is arranged in the lower part of the outer barrel, and reacting basket with radial direction is connected；
Described sleeve pipe formula fused salt heat exchanging pipe (22) centrally disposed gas-distributing pipe with it is radial react basket outer wall between, one end with go out fused salt
Chamber (4) is connected to, and the other end is connected into fused salt chamber (2)；
The gas distributor is up-small and down-big laddertron, is coaxially disposed with the outer barrel, lower end is fixed on upper tube
On plate.
2. according to the method described in claim 1, it is characterized in that, when using normal butane as raw material, reaction temperature is 380~420
DEG C, reaction pressure is 0.08~0.15MPa, and the residence time of normal butane is 1.8~2.25 seconds, and catalyst is V-P-O systems；
When using benzene as raw material, reaction temperature is 350~400 DEG C, and reaction pressure is 0.06~0.15MPa, when the stop of normal butane
Between be 1.4~1.8 seconds, catalyst be V-Mo-O systems.
3. according to the method described in claim 2, it is characterized in that, when using normal butane as raw material, unstripped gas normal butane：Air=
1：54.5~61.5vol；When using benzene as raw material, unstripped gas benzene：Air=1：65.7~83vol.
4. according to the method described in claim 1, it is characterized in that, symmetrically arranged fused salt exports (3) there are two setting.
5. according to the method described in claim 1, it is characterized in that, the radial reaction basket and outer barrel are coaxial.
6. according to the method described in claim 1, it is characterized in that, angle between the gas distributor outer wall and bottom edge
α is 85~89 °.
7. according to the method described in claim 1, it is characterized in that, the aperture of stomata of dividing on center gas-distributing pipe (13) outer wall is
2~25mm, percent opening are 20~40%, and the ratio of height to diameter of the radial reaction basket is 2~6, the radial venthole reacted on basket
Aperture be 2~25mm, percent opening be 20~40%.
8. according to the method described in claim 1, it is characterized in that, described sleeve pipe formula fused salt heat exchanging pipe (22) is by outer tube (9)
It is constituted with inner tube (10), has annular space, outer sleeve upper closing between the outer tube and said inner tube, and be fixed on described consolidate
On fixed board, lower end is connected to fused salt chamber is gone out, and inner tube (10) open upper end, lower end is connected into fused salt chamber.
9. according to the method described in claim 8, it is characterized in that, the fused salt heat exchanging pipe arrangement mode is concentric circles, three
It is angular or square.
10. according to the method described in claim 1, it is characterized in that, the top of the outer barrel, which is equipped with, passes through flanged joint
Head cover (14), air inlet be arranged on head cover, the head cover be equipped with catalyst loading and unloading mouth (19) and be used for deadband eliminating
Nitrogen mouth.
11. low pressure drop radial direction isothermal reactor, which is characterized in that including vertical outer barrel (11), upper perforated plate (17), lower perforated plate
(16), fixed plate (18), lateral wall be provided with the radial reaction basket (12) of venthole, be provided with point stomata center gas-distributing pipe (13) and
Bushing type fused salt heat exchanging pipe (22)；
The lower perforated plate is built in the lower part of the outer barrel, and the upper perforated plate is arranged in the upper of the lower perforated plate
Side, the fixed plate are located at the top of the outer barrel, the both ends and the outer barrel of the upper perforated plate and lower perforated plate
The inner wall of body is fixedly connected, into fused salt chamber, between upper perforated plate and lower perforated plate to be fused salt between lower perforated plate and outer barrel bottom
Chamber, it is described go out fused salt chamber at outer barrel be equipped with fused salt and export (3), the bottom of outer barrel is equipped with fused salt import (1)；
Described radial reaction basket (12) lower end is fixed on the upper perforated plate, the both ends phase of upper end and the fixed plate
Connection, the radial annular space reacted between basket and outer barrel are air collecting chamber (6)；
The center gas-distributing pipe is arranged in the middle part of the radial reaction basket, upper end and the air inlet being arranged at the top of outer barrel
(15) it connects, lower end is connect with upper perforated plate, and gas distributor (8), center gas-distributing pipe and gas are equipped in the gas-distributing pipe (13)
It is to divide air cavity (7) between distributor；
Gas outlet (5) is arranged in the lower part of the outer barrel, and reacting basket with radial direction is connected；
Described sleeve pipe formula fused salt heat exchanging pipe (22) centrally disposed gas-distributing pipe with it is radial react basket outer wall between, one end with go out fused salt
Chamber (4) is connected to, and the other end is connected into fused salt chamber (2)；
The gas distributor is up-small and down-big laddertron, is coaxially disposed with the outer barrel, lower end is fixed on upper tube
On plate.
12. low pressure drop radial direction isothermal reactor according to claim 11, which is characterized in that outside the gas distributor
Angle α between wall and bottom edge is 85~89 °.
13. low pressure drop radial direction isothermal reactor according to claim 11, which is characterized in that center gas-distributing pipe (13) outer wall
On divide the aperture of stomata to be 2~25mm, percent opening is 20~40%, and the ratio of height to diameter of the described radial reaction basket is 2~6, diameter
The aperture of venthole on reaction basket is 2~25mm, and percent opening is 20~40%.
14. according to claim 11~13 any one of them low pressure drop radial direction isothermal reactor, which is characterized in that described sleeve pipe
Formula fused salt heat exchanging pipe (22) is made of outer tube (9) and inner tube (10), there is annular space, housing between the outer tube and said inner tube
Pipe upper end closed, and being fixed in the fixed plate, lower end is connected to fused salt chamber is gone out, inner tube (10) open upper end, lower end and
It is connected into fused salt chamber.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101898103A (en) * | 2010-02-24 | 2010-12-01 | 南京钟腾化工有限公司 | Molten salt internal circulating reactor with annual output of maleic anhydride up to 20,000t and reaction process thereof |
| CN203944358U (en) * | 2014-07-14 | 2014-11-19 | 南京博扬化工科技有限公司 | A kind of saturated hot-water moves the isothermal radial shift-converter of the full self-unloading of heat |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101898103A (en) * | 2010-02-24 | 2010-12-01 | 南京钟腾化工有限公司 | Molten salt internal circulating reactor with annual output of maleic anhydride up to 20,000t and reaction process thereof |
| CN203944358U (en) * | 2014-07-14 | 2014-11-19 | 南京博扬化工科技有限公司 | A kind of saturated hot-water moves the isothermal radial shift-converter of the full self-unloading of heat |
Non-Patent Citations (2)
| Title |
|---|
| 正丁烷法顺酐生产工艺现状;畅志坚;《天津化工》;20110930;第25卷(第5期);11-13 * |
| 顺酐生产工艺与反应器研究进展;王斌;《兰州石化职业技术学院学报》;20130630;第13卷(第2期);4-6 * |
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