CN108546256A - Selective oxidation of n -butane produces maleic anhydride process and device - Google Patents
Selective oxidation of n -butane produces maleic anhydride process and device Download PDFInfo
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- CN108546256A CN108546256A CN201810550607.5A CN201810550607A CN108546256A CN 108546256 A CN108546256 A CN 108546256A CN 201810550607 A CN201810550607 A CN 201810550607A CN 108546256 A CN108546256 A CN 108546256A
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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
- C07D307/60—Two oxygen atoms, e.g. succinic anhydride
Abstract
The invention belongs to maleic anhydride production fields, and in particular to a kind of selective oxidation of n -butane production maleic anhydride process and device.Normal butane vaporizes successively, overheat after mixed with auxiliary agent, subsequently enter air/normal butane mixer；Air mixes in humidification mixer with humidification steam, is mixed into air/normal butane mixer with normal butane, agent mixture after air heater heats；Mixed material enters reactor reaction, generates gas and is discharged into next unit；More tubulations are equipped in reactor, loading catalyst in tubulation, the shell side outside tubulation is divided into using partition board and multiple not connected up and down takes hot chamber, each it is all connected with by thermal medium inlet pipe by hot chamber import, it each takes the outlet of hot chamber to be all connected with by thermal medium exit tube, each takes hot chamber and by being respectively provided with flow control valve on the pipeline between thermal medium inlet pipe.The present invention can effectively prevent temperature of reactor hot-spot, improves catalyst activity, extends the service life of catalyst.
Description
Technical field
The invention belongs to maleic anhydride production fields, and in particular to a kind of selective oxidation of n -butane production maleic anhydride process and device.
Background technology
Maleic anhydride abbreviation cis-butenedioic anhydride also known as maleic anhydride are a kind of important Organic Chemicals, are widely used in stone
The industries such as oiling work, food processing, medicine, building materials.By raw material route, the production method of cis-butenedioic anhydride can be divided into benzene oxidatoin method, positive fourth
Alkoxide method.It is inexpensive that normal butane method has a raw material, and it is excellent that pollution is relatively light, and carbon atom utilization rate height and maleic anhydride production are at low cost etc.
Point, production capacity accounts for about the 80% of world's cis-butenedioic anhydride total productive capacity, and has the tendency that gradually substituted benzene oxidizing process.
The core of maleic anhydride production technology is that with air gas occurs in the reactor for being filled with vanadium-phosphor oxide catalyst for normal butane
Solid catalysis oxidation reaction.The oxidation reaction have the characteristics that it is strongly exothermic, main reaction generate cis-butenedioic anhydride reaction heat be 1236KJ/
Mol, side reaction generate CO2, CO reaction heat be respectively 2656KJ/mol and 1521KJ/mol, and the presence for reacting hot spot can be to urging
Agent performance has an adverse effect, and the hot spot height of concretely catalyst bed directly affects conversion ratio, the cis-butenedioic anhydride of normal butane
Selectivity, the yield of product cis-butenedioic anhydride and the stability of catalyst.Therefore reduce or eliminate in reaction process reaction hot spot at
For the key of reaction process control.
In actual application, reactor occurs one of hot spot the reason is that reaction raw materials air flow method is uneven.Specially
Sharp CN201310018157.2 discloses a kind of gas pre-distributor, the gas pre-distributor include horizontal flow deflector, diversion pipe,
Tapered cap is distributed with solving reaction stream present in conventional art after the gas pre-distributor of fixed bed reactors entrance
Unevenness, reaction-ure conversion-age is low and the selectively low problem of purpose product, the patent have the drawback that the components such as flow deflector
Shapes and sizes are limited by reactor inner space, dismantle that difficult, overhaul procedure is cumbersome.
Another reason for hot spot, which occurs, in reactor to be reacted at the entrance of reactor due to normal butane, and reaction is made
The bed temperature of device inlet steeply rises.Patent CN201110236413.6 proposes a kind of maleic anhydride production reaction temperature adjusting
Control device and method, the core technology of the patent is to use a kind of shell/tube-type reactor, using a kind of molten in reactor shell side
The shortcomings that potassium nitrate and sodium nitrite mixture melted is used as moving the cooling medium of heat by pump for liquid salts reciprocation cycle, the patent be：
Fused salt can also reduce the temperature at the other positions of bed while reducing hot(test)-spot temperature, and n-butane conversion and cis-butenedioic anhydride is caused to be received
Rate reduces.Patent USP4855459 passes through the heat in reaction tube using the method for inert sial ball and catalyst dilution filling
Point generating unit is diluted filling, reacts hot(test)-spot temperature to achieve the purpose that reduce, the shortcomings that above-mentioned patent is inertia goods and materials
Addition reduce the effective volume of reactor, also reduce production efficiency.Patent CN201510806387.4 discloses one kind
The method for reducing reactor reaction hot spot, the core technology of the patent are to use three concatenated vanadium-phosphor oxide catalyst beds, this
The shortcomings that average valence of vanadium is in first high, rear low, raised trend again successively in three concatenated catalyst beds, the patent be
Require height, exploitativeness poor catalyst preparation and activating process.
Invention content
In view of the deficiencies of the prior art, the object of the present invention is to provide a kind of selective oxidation of n -butane to produce maleic anhydride process,
To solve the problems, such as that reactor local temperature overheats, catalyst activity is improved, extends the service life of catalyst, the present invention also carries
Maleic anhydride unit is produced for a kind of selective oxidation of n -butane.
Selective oxidation of n -butane of the present invention produces maleic anhydride process, includes the following steps：
(1) normal butane vaporizes in normal butane evaporator, enters normal butane/auxiliary agent in normal butane superheater after overheat successively
It is mixed with auxiliary agent in mixer, subsequently enters air/normal butane mixer；
(2) air mixes in humidification mixer with humidification steam, and air/normal butane is entered after air heater heats
Normal butane that mixer is obtained with step (1), agent mixture mix；
(3) mixed material enters reactor reaction, generates gas and is discharged into next unit；
Wherein：It is equipped with more tubulations in reactor, loading catalyst in tubulation, using partition board by the shell side outside tubulation point
Be segmented into it is multiple it is not connected up and down take hot chamber, be each all connected with by thermal medium inlet pipe by hot chamber import, each take the outlet of hot chamber
It is all connected with and takes thermal medium exit tube, each take hot chamber and by being respectively provided with flow control valve on the pipeline between thermal medium inlet pipe.
By temperature in flow control valve control tubulation at 380-430 DEG C.
Auxiliary agent is phosphorus simple substance, the oxide of phosphorus, hypophosphorous acid, phosphinate, phosphate dialkyl ester, carbonic acid trialkyl ester or coke
One or more of phosphoric acid tetraalkyl ester.
It is one kind in water, steam, fused salt or conduction oil by thermal medium, preferably fused salt, fused salt are preferably nitrate and Asia
The mixture of nitrate.
Reactor inlet normal butane, air, humidification steam and the molar ratio of auxiliary agent are：1:51~62:0.5~6.5:
0.05~0.3.
Reactor inlet n-butane feed air speed is 1000-1700h-1。
The pressure of normal butane evaporator is 0.2-0.5Mpa, and gas phase normal butane temperature is 40-60 DEG C；Normal butane superheater is just
Butane outlet temperature is 100-150 DEG C.
Air heater air exit temp is 150-180 DEG C.
The present invention also provides a kind of selective oxidation of n -butane to produce maleic anhydride unit, including normal butane evaporator, and normal butane steams
It sends out device import and connects normal butane inlet pipe, normal butane evaporator outlet is sequentially connected normal butane superheater, normal butane/help by pipeline
Agent mixer and air/normal butane mixer are additionally provided with auxiliary agent inlet pipe on normal butane/auxiliary agent mixer, and humidification mixer is successively
Air heater and air/normal butane mixer are connected, air inlet lines and humidification steam inlet tube are additionally provided on the mixer that is humidified, it is empty
Gas/normal butane mixer connects reactor by pipeline, and more tubulations are equipped in reactor, using partition board by the shell outside tubulation
Journey be divided into it is multiple it is not connected up and down take hot chamber, be each all connected with by thermal medium inlet pipe by hot chamber import, each by hot chamber
Outlet is all connected with by thermal medium exit tube, each takes hot chamber and by being respectively provided with flow control valve on the pipeline between thermal medium inlet pipe.
Reactor outlet connection generates gas discharge pipe；Air/pipeline between normal butane mixer and reactor is equipped with
Static mixer.
In use, the raw material normal butane in normal butane inlet pipe enters in normal butane evaporator, in the work of low-pressure steam
It is vaporized with lower normal butane, subsequently into normal butane superheater, the normal butane after overheat enters normal butane/auxiliary agent mixer and comes from
The auxiliary agent of auxiliary agent inlet pipe mixes, auxiliary agent type be phosphorus simple substance, the oxide of phosphorus, hypophosphorous acid, phosphinate, phosphate dialkyl ester,
One or more of carbonic acid trialkyl ester or pyrophosphoric acid tetraalkyl ester, subsequently into air/normal butane mixer.
Air from air inlet lines mixes in humidification mixer with the humidification steam from humidification steam inlet tube, through sky
It is mixed into air/normal butane mixer with normal butane, auxiliary agent after hot-air heater heating.Mixed unstripped gas is by static mixed
Enter reactor reaction after clutch, generates gas by generating gas discharge pipe and be discharged into next unit.
Tubulation quantity is 10000-30000 roots in reactor, and preferably 24900, reactor size is preferred：Internal diameter × height
Degree is 5600 × 6000mm of Φ, and tubulation size is preferred：Internal diameter × highly it is 5 × 6000mm of Φ.
It is equipped with more tubulations in reactor, loading catalyst in tubulation, catalyst is preferably that commercially available compounding vanadium phosphorus oxygen is urged
Agent.Unstripped gas is in row inner reaction tube.Shell side outside tubulation is divided by multiple heat of taking not connected up and down using partition board
Chamber is each all connected with by hot chamber import by thermal medium inlet pipe, and the outlet of hot chamber is each taken to be all connected with by thermal medium exit tube.It is each to take heat
Chamber and by being respectively provided with flow control valve on the pipeline between thermal medium inlet pipe.It flows through by hot chamber, is realized in tubulation by thermal medium
The control of temperature.The present invention controls each flow that thermal medium is taken by hot chamber by controlling flow control valve, to realize to each
By the control of hot intracavitary reaction bed temperature.
In initial reaction stage, most of normal butane reacts at reactor inlet, and the bed temperature of inlet steeply rises simultaneously
Reach hot spot, subsequent bed temperature drastically declines and tends to be steady, and the present invention is increased out by the aperture of control flow control valve
The tubulation of existing hot spot, which corresponds to take, takes thermal medium internal circulating load in hot chamber, remaining takes hot chamber due to corresponding tubulation thermal discharge very little, can
Thermal medium internal circulating load is taken to reduce.Over time, reaction hot spot can be moved to reactor outlet direction, should suitably be increased
Occur reaction hot spot tubulation it is corresponding by hot chamber take thermal medium flow, control tubulation in temperature at 380-430 DEG C.This method
While ensureing high n-butane conversion, yield of maleic anhydride, the problem of reaction temperature hot-spot can effectively prevent.
Compared with prior art, the present invention has the following advantages：
(1) it is mixed to enter air/normal butane after the vaporization of normal butane evaporator, normal butane superheater overheat for raw material normal butane
Clutch, it is not in liquid phase normal butane that the advantages of this method, which is in pipeline, and gas phase normal butane has preferably distribution equal with air
Even property, can effectively overcome the reaction hot issue occurred because gas is unevenly distributed.
(2) by be humidified mixer vapor is added into unstripped gas, this method while improving catalysis oxidation environment,
Hot(test)-spot temperature can be reduced.
(3) auxiliary agent phosphorus is added into unstripped gas by normal butane/auxiliary agent mixer, this method is slowing down catalyst inactivation speed
While spending, reaction hot spot can be reduced.
(4) under conditions of normal butane evaporator is set, a small amount of light dydrocarbon heavy constituent being mingled in n-butane feedstock will not vapour
Change and enter reactor, to avoid the problem of light dydrocarbon carbon distribution on a catalyst.
(5) static mixer can make unstripped gas distribution more uniform, and have the characteristics that maintenance is convenient.
(6) reaction temperature hot-spot can effectively prevent using this reactor, reduces the heat for even being eliminated catalyst bed
Point problem, improves catalyst activity, extends the service life of catalyst.
(7) reactor local temperature overheat can effectively prevent using this technique, catalyst activity can be improved, extend catalyst
Service life.
Description of the drawings
Fig. 1 is the structural schematic diagram of inventive embodiments selective oxidation of n -butane production maleic anhydride unit；
Fig. 2 is the structural schematic diagram of reactor of the embodiment of the present invention；
In figure：1- air inlet lines, 2- humidification mixers, 3- air heaters, 4- air/normal butane mixer, 5- humidifications
Steam inlet tube, 6- normal butane inlet pipes, 7- normal butane evaporators, 8- normal butane superheaters, 9- normal butanes/auxiliary agent mixer, 10- are helped
Agent inlet pipe, 11- static mixers, 12- take thermal medium exit tube, 13- reactors, 14- generate gas discharge pipe, 15- take thermal medium into
Pipe, 16- flow control valves, 17- partition boards, 18- take hot chamber, 19- tubulations.
Specific implementation mode
With reference to embodiment, the present invention will be further described.
Embodiment 1
A kind of selective oxidation of n -butane production maleic anhydride process, includes the following steps：
(1) normal butane successively in the normal butane evaporator 7 vaporization, enter normal butane/help in normal butane superheater 8 after overheat
It is mixed with auxiliary agent in agent mixer 9, subsequently enters air/normal butane mixer 4；
(2) air mixes in humidification mixer 2 with humidification steam, enters air/positive fourth after the heating of air heater 3
Normal butane that alkane mixer 4 is obtained with step 1, agent mixture mix；
(3) mixed material enters the reaction of reactor 13, generates gas and is discharged into next unit；
Wherein：It is equipped with more tubulations 19 in reactor 13, loading catalyst in tubulation 19 will be outside tubulation 19 using partition board 17
The shell side in portion be divided into about 4 it is not connected take hot chamber 18, be each all connected with by thermal medium inlet pipe 15 by 18 import of hot chamber,
It each takes the outlet of hot chamber 18 to be all connected with by thermal medium exit tube 12, each takes hot chamber 18 and by the pipeline between thermal medium inlet pipe 15
It is respectively provided with flow control valve 16.
It is fused salt by thermal medium, specifically potassium nitrate is 1 in mass ratio with sodium nitrite:0.8 mixture.
Auxiliary agent is the mixture of trimethyl phosphate and pyrophosphoric acid tetraalkyl ester, mass ratio 1:1.
13 entrance normal butane of reactor, air, humidification steam and the molar ratio of auxiliary agent are：1:55:5:0.05.
13 entrance n-butane feed air speed of reactor is 1700h-1。
The pressure of normal butane evaporator 7 is 0.4Mpa, and gas phase normal butane temperature is 60 DEG C；8 normal butane of normal butane superheater
Outlet temperature is 120 DEG C.
3 air exit temp of air heater is 150 DEG C.
The selective oxidation of n -butane that the technique uses produces maleic anhydride unit, including normal butane evaporator 7, normal butane evaporator
7 imports connect normal butane inlet pipe 6, and the outlet of normal butane evaporator 7 is sequentially connected normal butane superheater 8, normal butane/help by pipeline
Agent mixer 9 and air/normal butane mixer 4 are additionally provided with auxiliary agent inlet pipe 10 on normal butane/auxiliary agent mixer 9, and be humidified mixer
2 are sequentially connected air heater 3 and air/normal butane mixer 4, and air inlet lines 1 are additionally provided on the mixer 2 that is humidified and humidification steams
Vapour inlet pipe 5, air/normal butane mixer 4 connect reactor 13 by pipeline, are equipped with more tubulations 19 in reactor 13, use
Partition board 17 by the shell side outside tubulation 19 be divided into about 4 it is not connected take hot chamber 18, each connect by 18 import of hot chamber
It connects and takes thermal medium inlet pipe 15, the outlet of hot chamber 18 is each taken to be all connected with by thermal medium exit tube 12, each take hot chamber 18 and take thermal medium
Flow control valve 16 is respectively provided on pipeline between inlet pipe 15.
19 quantity of tubulation is 24900 in reactor 13,13 size internal diameter of reactor × highly it is 5600 × 6000mm of Φ,
19 size internal diameter of tubulation × highly it is 5 × 6000mm of Φ.
The catalyst used is commercially available compound vanadium-phosphor oxide catalyst.
The outlet of reactor 13 connection generates gas discharge pipe 14；The pipeline of air/between normal butane mixer 4 and reactor 13
It is equipped with static mixer 11.
Temperature in tubulation is controlled by flow control valve 16, the mean temperature for specifically each hot chamber 18 being taken to correspond to tubulation 19 is shown in
Table 1, present apparatus operating condition are shown in Table 1.
Table 1
As can be seen from Table 1, catalyst hot spot is no in 24 months moves.
Embodiment 2
A kind of selective oxidation of n -butane production maleic anhydride process, includes the following steps：
(1) normal butane successively in the normal butane evaporator 7 vaporization, enter normal butane/help in normal butane superheater 8 after overheat
It is mixed with auxiliary agent in agent mixer 9, subsequently enters air/normal butane mixer 4；
(2) air mixes in humidification mixer 2 with humidification steam, enters air/positive fourth after the heating of air heater 3
Normal butane that alkane mixer 4 is obtained with step 1, agent mixture mix；
(3) mixed material enters the reaction of reactor 13, generates gas and is discharged into next unit；
Wherein：It is equipped with more tubulations 19 in reactor 13, loading catalyst in tubulation 19 will be outside tubulation 19 using partition board 17
The shell side in portion be divided into about 4 it is not connected take hot chamber 18, be each all connected with by thermal medium inlet pipe 15 by 18 import of hot chamber,
It each takes the outlet of hot chamber 18 to be all connected with by thermal medium exit tube 12, each takes hot chamber 18 and by the pipeline between thermal medium inlet pipe 15
It is respectively provided with flow control valve 16.
It is steam by thermal medium.
Auxiliary agent is trimethyl phosphate.
13 entrance normal butane of reactor, air, humidification steam and the molar ratio of auxiliary agent are：1:60:6.5:0.1.
13 entrance n-butane feed air speed of reactor is 1500h-1。
The pressure of normal butane evaporator 7 is 0.2Mpa, and gas phase normal butane temperature is 50 DEG C；8 normal butane of normal butane superheater
Outlet temperature is 150 DEG C.
3 air exit temp of air heater is 180 DEG C.
The selective oxidation of n -butane that the technique uses produces maleic anhydride unit, including normal butane evaporator 7, normal butane evaporator
7 imports connect normal butane inlet pipe 6, and the outlet of normal butane evaporator 7 is sequentially connected normal butane superheater 8, normal butane/help by pipeline
Agent mixer 9 and air/normal butane mixer 4 are additionally provided with auxiliary agent inlet pipe 10 on normal butane/auxiliary agent mixer 9, and be humidified mixer
2 are sequentially connected air heater 3 and air/normal butane mixer 4, and air inlet lines 1 are additionally provided on the mixer 2 that is humidified and humidification steams
Vapour inlet pipe 5, air/normal butane mixer 4 connect reactor 13 by pipeline, are equipped with more tubulations 19 in reactor 13, use
Partition board 17 by the shell side outside tubulation 19 be divided into about 4 it is not connected take hot chamber 18, each connect by 18 import of hot chamber
It connects and takes thermal medium inlet pipe 15, the outlet of hot chamber 18 is each taken to be all connected with by thermal medium exit tube 12, each take hot chamber 18 and take thermal medium
Flow control valve 16 is respectively provided on pipeline between inlet pipe 15.
19 quantity of tubulation is 24900 in reactor 13,13 size internal diameter of reactor × highly it is 5600 × 6000mm of Φ,
19 size internal diameter of tubulation × highly it is 5 × 6000mm of Φ.
The catalyst used is commercially available compound vanadium-phosphor oxide catalyst.
The outlet of reactor 13 connection generates gas discharge pipe 14；The pipeline of air/between normal butane mixer 4 and reactor 13
It is equipped with static mixer 11.
Temperature in tubulation is controlled by flow control valve 16, the mean temperature for specifically each hot chamber 18 being taken to correspond to tubulation 19 is shown in
Table 2, present apparatus operating condition are shown in Table 2.
Table 2
As can be seen from Table 2, catalyst hot spot is no in 24 months moves.
Embodiment 3
A kind of selective oxidation of n -butane production maleic anhydride process, includes the following steps：
(1) normal butane successively in the normal butane evaporator 7 vaporization, enter normal butane/help in normal butane superheater 8 after overheat
It is mixed with auxiliary agent in agent mixer 9, subsequently enters air/normal butane mixer 4；
(2) air mixes in humidification mixer 2 with humidification steam, enters air/positive fourth after the heating of air heater 3
Normal butane that alkane mixer 4 is obtained with step 1, agent mixture mix；
(3) mixed material enters the reaction of reactor 13, generates gas and is discharged into next unit；
Wherein：It is equipped with more tubulations 19 in reactor 13, loading catalyst in tubulation 19 will be outside tubulation 19 using partition board 17
The shell side in portion be divided into about 4 it is not connected take hot chamber 18, be each all connected with by thermal medium inlet pipe 15 by 18 import of hot chamber,
It each takes the outlet of hot chamber 18 to be all connected with by thermal medium exit tube 12, each takes hot chamber 18 and by the pipeline between thermal medium inlet pipe 15
It is respectively provided with flow control valve 16.
It is conduction oil by thermal medium.
Auxiliary agent is the mixture of phosphorus simple substance, phosphinate and pyrophosphoric acid tetraalkyl ester, mass ratio 1:0.5:0.5.
13 entrance normal butane of reactor, air, humidification steam and the molar ratio of auxiliary agent are：1:51:1:0.2.
13 entrance n-butane feed air speed of reactor is 1000h-1。
The pressure of normal butane evaporator 7 is 0.1Mpa, and gas phase normal butane temperature is 40 DEG C；8 normal butane of normal butane superheater
Outlet temperature is 130 DEG C.
3 air exit temp of air heater is 160 DEG C.
The selective oxidation of n -butane that the technique uses produces maleic anhydride unit, including normal butane evaporator 7, normal butane evaporator
7 imports connect normal butane inlet pipe 6, and the outlet of normal butane evaporator 7 is sequentially connected normal butane superheater 8, normal butane/help by pipeline
Agent mixer 9 and air/normal butane mixer 4 are additionally provided with auxiliary agent inlet pipe 10 on normal butane/auxiliary agent mixer 9, and be humidified mixer
2 are sequentially connected air heater 3 and air/normal butane mixer 4, and air inlet lines 1 are additionally provided on the mixer 2 that is humidified and humidification steams
Vapour inlet pipe 5, air/normal butane mixer 4 connect reactor 13 by pipeline, are equipped with more tubulations 19 in reactor 13, use
Partition board 17 by the shell side outside tubulation 19 be divided into about 4 it is not connected take hot chamber 18, each connect by 18 import of hot chamber
It connects and takes thermal medium inlet pipe 15, the outlet of hot chamber 18 is each taken to be all connected with by thermal medium exit tube 12, each take hot chamber 18 and take thermal medium
Flow control valve 16 is respectively provided on pipeline between inlet pipe 15.
19 quantity of tubulation is 24900 in reactor 13,13 size internal diameter of reactor × highly it is 5600 × 6000mm of Φ,
19 size internal diameter of tubulation × highly it is 5 × 6000mm of Φ.
The catalyst used is commercially available compound vanadium-phosphor oxide catalyst.
The outlet of reactor 13 connection generates gas discharge pipe 14；The pipeline of air/between normal butane mixer 4 and reactor 13
It is equipped with static mixer 11.
Temperature in tubulation is controlled by flow control valve 16, the mean temperature for specifically each hot chamber 18 being taken to correspond to tubulation 19 is shown in
Table 3, present apparatus operating condition are shown in Table 3.
Table 3
As can be seen from Table 3, catalyst hot spot is no in 24 months moves.
Embodiment 4
A kind of selective oxidation of n -butane production maleic anhydride process, includes the following steps：
(1) normal butane successively in the normal butane evaporator 7 vaporization, enter normal butane/help in normal butane superheater 8 after overheat
It is mixed with auxiliary agent in agent mixer 9, subsequently enters air/normal butane mixer 4；
(2) air mixes in humidification mixer 2 with humidification steam, enters air/positive fourth after the heating of air heater 3
Normal butane that alkane mixer 4 is obtained with step 1, agent mixture mix；
(3) mixed material enters the reaction of reactor 13, generates gas and is discharged into next unit；
Wherein：It is equipped with more tubulations 19 in reactor 13, loading catalyst in tubulation 19 will be outside tubulation 19 using partition board 17
The shell side in portion be divided into about 2 it is not connected take hot chamber 18, be each all connected with by thermal medium inlet pipe 15 by 18 import of hot chamber,
It each takes the outlet of hot chamber 18 to be all connected with by thermal medium exit tube 12, each takes hot chamber 18 and by the pipeline between thermal medium inlet pipe 15
It is respectively provided with flow control valve 16.
It is fused salt by thermal medium, lava is potassium nitrate and sodium nitrite is 1 in mass ratio:0.8 mixture.
Auxiliary agent is hypophosphorous acid.
13 entrance normal butane of reactor, air, humidification steam and the molar ratio of auxiliary agent are：1:55:3:0.05.
13 entrance n-butane feed air speed of reactor is 1600h-1。
The pressure of normal butane evaporator 7 is 0.2Mpa, and gas phase normal butane temperature is 50 DEG C；8 normal butane of normal butane superheater
Outlet temperature is 100 DEG C.
3 air exit temp of air heater is 130 DEG C.
The selective oxidation of n -butane that the technique uses produces maleic anhydride unit, including normal butane evaporator 7, normal butane evaporator
7 imports connect normal butane inlet pipe 6, and the outlet of normal butane evaporator 7 is sequentially connected normal butane superheater 8, normal butane/help by pipeline
Agent mixer 9 and air/normal butane mixer 4 are additionally provided with auxiliary agent inlet pipe 10 on normal butane/auxiliary agent mixer 9, and be humidified mixer
2 are sequentially connected air heater 3 and air/normal butane mixer 4, and air inlet lines 1 are additionally provided on the mixer 2 that is humidified and humidification steams
Vapour inlet pipe 5, air/normal butane mixer 4 connect reactor 13 by pipeline, are equipped with more tubulations 19 in reactor 13, use
Partition board 17 by the shell side outside tubulation 19 be divided into about 2 it is not connected take hot chamber 18, each connect by 18 import of hot chamber
It connects and takes thermal medium inlet pipe 15, the outlet of hot chamber 18 is each taken to be all connected with by thermal medium exit tube 12, each take hot chamber 18 and take thermal medium
Flow control valve 16 is respectively provided on pipeline between inlet pipe 15.
19 quantity of tubulation is 24900 in reactor 13,13 size internal diameter of reactor × highly it is 5600 × 6000mm of Φ,
19 size internal diameter of tubulation × highly it is 5 × 6000mm of Φ.
The catalyst used is commercially available compound vanadium-phosphor oxide catalyst.
The outlet of reactor 13 connection generates gas discharge pipe 14；The pipeline of air/between normal butane mixer 4 and reactor 13
It is equipped with static mixer 11.
Temperature in tubulation is controlled by flow control valve 16, the mean temperature for specifically each hot chamber 18 being taken to correspond to tubulation 19 is shown in
Table 4, present apparatus operating condition are shown in Table 4.
Table 4
As can be seen from Table 4, catalyst hot spot is no in 24 months moves.
Claims (10)
1. a kind of selective oxidation of n -butane produces maleic anhydride process, it is characterised in that：Include the following steps：
(1) normal butane successively in the normal butane evaporator (7) vaporization, enter normal butane/help in normal butane superheater (8) after overheat
It is mixed with auxiliary agent in agent mixer (9), subsequently enters air/normal butane mixer (4)；
(2) air mixes in humidification mixer (2) with humidification steam, enters air/positive fourth after air heater (3) heating
Normal butane that alkane mixer (4) is obtained with step (1), agent mixture mix；
(3) mixed material enters reactor (13) reaction, generates gas and is discharged into next unit；
Wherein：It is equipped with more tubulations (19) in reactor (13), tubulation (19) interior loading catalyst, using partition board (17) by tubulation
(19) external shell side be divided into it is multiple it is not connected up and down take hot chamber (18), each hot chamber (18) import is taken to be all connected with by hot
Medium inlet pipe (15) each takes hot chamber (18) outlet to be all connected with by thermal medium exit tube (12), each hot chamber (18) is taken to be situated between with by heat
Flow control valve (16) is respectively provided on pipeline between matter inlet pipe (15).
2. selective oxidation of n -butane according to claim 1 produces maleic anhydride process, it is characterised in that：Pass through flow control valve
(16) control tubulation (19) interior temperature is at 380-430 DEG C.
3. selective oxidation of n -butane according to claim 1 produces maleic anhydride process, it is characterised in that：Auxiliary agent be phosphorus simple substance,
One kind in the oxide of phosphorus, hypophosphorous acid, phosphinate, phosphate dialkyl ester, carbonic acid trialkyl ester or pyrophosphoric acid tetraalkyl ester
Or it is several；It is one kind in water, steam, fused salt or conduction oil by thermal medium.
4. selective oxidation of n -butane according to claim 1 produces maleic anhydride process, it is characterised in that：Reactor (13) entrance
Normal butane, air, humidification steam and the molar ratio of auxiliary agent are：1:51~62:0.5~6.5:0.05~0.3.
5. selective oxidation of n -butane according to claim 1 produces maleic anhydride process, it is characterised in that：Reactor (13) entrance
N-butane feed air speed is 1000-1700h-1。
6. selective oxidation of n -butane according to claim 1 produces maleic anhydride process, it is characterised in that：Normal butane evaporator
(7) pressure is 0.2-0.5Mpa, and gas phase normal butane temperature is 40-60 DEG C；Normal butane superheater (8) normal butane outlet temperature is
100-150℃。
7. selective oxidation of n -butane according to claim 1 produces maleic anhydride process, it is characterised in that：Air heater (3)
Air exit temp is 150-180 DEG C.
8. selective oxidation of n -butane according to claim 1 produces maleic anhydride process, it is characterised in that：Row in reactor (13)
Pipe (19) quantity is 10000-30000 roots, reactor (13) size：Internal diameter × highly it is 5600 × 6000mm of Φ, tubulation (19)
Size：Internal diameter × highly it is 5 × 6000mm of Φ.
9. a kind of selective oxidation of n -butane produces maleic anhydride unit, it is characterised in that：Including normal butane evaporator (7), normal butane steams
Device (7) import connection normal butane inlet pipe (6) is sent out, normal butane evaporator (7) outlet is sequentially connected normal butane superheater by pipeline
(8), normal butane/auxiliary agent mixer (9) and air/normal butane mixer (4) are additionally provided on normal butane/auxiliary agent mixer (9) and help
Agent inlet pipe (10), humidification mixer (2) are sequentially connected air heater (3) and air/normal butane mixer (4), humidification mixing
Air inlet lines (1) and humidification steam inlet tube (5) are additionally provided on device (2), air/normal butane mixer (4) connects anti-by pipeline
Device (13) is answered, more tubulations (19) are equipped in reactor (13), is divided into the external shell side of tubulation (19) using partition board (17)
It is multiple it is not connected up and down take hot chamber (18), be each all connected with by thermal medium inlet pipe (15) by hot chamber (18) import, each take
Hot chamber (18) outlet is all connected with by thermal medium exit tube (12), each takes hot chamber (18) and by the pipeline between thermal medium inlet pipe (15)
On be respectively provided with flow control valve (16).
10. selective oxidation of n -butane according to claim 9 produces maleic anhydride unit, it is characterised in that：Reactor (13) goes out
Mouth connection generates gas discharge pipe (14)；Air/pipeline between normal butane mixer (4) and reactor (13) is equipped with static mixed
Clutch (11).
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| CN115463618A (en) * | 2022-08-08 | 2022-12-13 | 北京鑫缘化工有限公司 | Reactor for preparing maleic anhydride by oxidizing n-butane |
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