CN105170033B - A kind of annular multilayer sleeve pipe membrane reactor and the method that (methyl) acrylate is produced using it - Google Patents
A kind of annular multilayer sleeve pipe membrane reactor and the method that (methyl) acrylate is produced using it Download PDFInfo
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Abstract
The invention discloses a kind of annular multilayer sleeve pipe membrane reactor, main body is ring-like three layers of sleeve structure, including the interior film casing, middle film casing, the outer tube that are coaxially disposed from inside to outside, interior film casing and middle film casing outside are fixed by supporting network and supported, a steam outlet is offered on interior film casing, a charging aperture and a discharging opening are offered on middle film casing, an air intake is offered on outer tube, middle Membrane cover tube cavity is provided with hybrid component, is provided with separate mesh in middle film casing exit, check valve is provided between charging aperture and discharging opening.(methyl) acrylate produced using reactor of the invention, can not only realize in (methyl) acroleic acid esterification course of reaction to generating the continuous removing of water, improve the conversion ratio and selectivity of reaction；The generation of polymer and ethers impurity is reduced simultaneously.
Description
Technical field
The present invention relates to a kind of annular multilayer sleeve pipe membrane reactor and using the reactor carry out (methyl) acrylic acid with
The method that the esterification of C1-C4 alcohol produces (methyl) acrylate.
Background technology
(methyl) acrylate is a kind of large industrial chemicals, (methyl) esters of acrylic acid tree that its autohemagglutination or copolymerization are formed
Fat is widely used in the production of coating, adhesive, lucite, weaving etc..(methyl) esters of acrylic acid can be by (methyl) third
Olefin(e) acid and alcohol carry out esterification and obtain by acid catalyst catalysis.
Esterification is a reversible reaction, therefore conversion ratio can only be below an equilibrium valve, and it is normal that this depends on balance
Number.To improve conversion ratio, a kind of method can make a kind of raw alcohol or sour large excess of method.This method often leads to pair
Product increases, and selectivity declines, and certain difficulty is also brought to follow-up refining；Another method is that the water of removal generation is (such as special
The method of profit 200910012161.1), this method is more effective.
The method of usual esterification water removal has directly distillation water removal and adds entrainer dehydration (such as toluene, hexamethylene).
These method energy consumptions are higher, and dehydrating effect is undesirable, and entrainer environmental pollution is larger.It is using membrane technology osmotic, evaporating and dewatering
Dehydration technique emerging in recent years, this technology has very big progress in terms of solvent dehydration, but it is anti-to be applied to esterification
Should be rarely reported.
The prevailing technology for producing (methyl) acrylate has inorganic acid catalysis (such as Ai Lefu atropics chemical patent
95109453.X), organic acid catalysis (such as BASF patent 200610073923.5), (for example sinopec is special for solid acid catalysis
201110255431.9) and cation resin catalyzing agent catalytic esterification (such as catalyst patent 200710112480) profit.
Inorganic acid (such as concentrated sulfuric acid) and organic acid (such as p-methyl benzenesulfonic acid) belong to homogeneous catalyst, and homogeneous catalysis has biography
The advantages of matter effect is good, reaction is fast, but strong acid has very strong corrosion to equipment.Solid catalyst can avoid strong acid and set
Standby directly contact, can substantially reduce corrosion of the catalyst to equipment.(methyl) acrylic acid is prepared using solid catalyst production
The equipment of esters has a Railway Project, and first, continuous dehydration cannot be realized using fixed bed unit, so as to cause turning for esterification
Rate is low；Second, solid catalyst does not flow makes material easily form channel, causes catalyst use efficiency low, mass transfer effect compared with
Difference；3rd, (methyl) acrylic acid contains unsaturated double-bond, easily produces polymer, the inhibition air of general esterification plant be from
Single-point or some addition, inhibit air skewness in reaction system；4th, using the esterification of solid catalyst,
Alcohols is in catalyst surface absorption generation ethers impurity.
For problem above, it is necessary to seek a kind of new preparation (methyl) acrylate reactions device, can realize continuous de-
Water, can be such that solid catalyst is effectively contacted with material again, and can as possible avoid the generation of side reaction.
The content of the invention
It is an object of the present invention to provide a kind of annular multilayer sleeve pipe membrane reactor, to overcome existing esterification to set
Standby a variety of deficiencies.The reactor can realize the continuous dehydration in esterification reaction process, reduce the energy consumption of water removal, and can carry
Raw material high and the mass transfer effect of catalyst, reduce the generation of ethers impurity.
Method it is another object of the present invention to provide (methyl) acrylate is produced using above-mentioned reactor, can have
Effect improves esterification conversion ratio, less ethers by-product.
To achieve the above object, technical scheme is as follows：
A kind of annular multilayer sleeve pipe membrane reactor, main body is ring-like three layers of sleeve structure, including is coaxially disposed from inside to outside
Interior film casing, middle film casing, outer tube, interior film casing and middle film casing outside by supporting network fix support, interior film casing
On offer a steam outlet, a charging aperture and a discharging opening are offered on middle film casing, offered on outer tube
One air intake, middle Membrane cover tube cavity is provided with hybrid component, and separate mesh, separate mesh are provided with middle film casing discharge outlet
It is fixed on Membrane cover inside pipe wall, check valve is installed between charging aperture and discharging opening (in the middle of preferably), check valve act as ensureing
Fluid from charging aperture along ring-like reactor flow to discharging opening, and its allow solid catalyst pass through.
In reactor of the invention, the hybrid component of described middle Membrane cover tube cavity includes pusher fin and spiral track
Road, helical orbit is centered around inner membrance outside of sleeve, projection of the helical orbit on inner membrance sleeve pipe shaft section and inner membrance casing axis
Angle be α, α=15-30 °, pusher fin is around helical orbital movement.
In reactor of the invention, the pusher fin of described hybrid component is by central ring and on central ring circumference
6~12 fins constitute, fin is uniformly or non-uniformly distributed on central ring circumference, is perfectly even distributed, described spiral
Track passes through fin central ring, and the outward flange of helical orbit to be fitted with fin central ring inner circumferential so that central ring is held in spiral shell
Rotation sliding on rails propulsion, around helical orbital movement.
The fin push structure of described hybrid component, under fluid forces, dual-axis rotation propulsion.Fin edge is advanced first
Helical orbit rotation propulsion, propulsion fin is also advanced along the spinning of central ring axis in itself.Bispin rotary-die type can effectively mix urges
Agent and reaction mass, prevent catalyst sedimentation, effectively improve the conversion ratio of reaction, and reduce when applying in esterification
The generation of ethers impurity, it changes original expansion of the alcohols in solid catalyst surface mainly due to good mixed effect
Dissipate and adsorption process, selectivity of chemical equation is more biased towards in esterification.
In reactor of the invention, pusher fin and helical orbit material be carbon steel, 304,316 or 316L in one
Kind.
In reactor of the invention, described interior film casing and middle film casing main body are ceramic film component, the ceramic membrane
The three-dimensional shape of component is cone, terrace with edge, round platform, cylinder, square or cuboid, preferably cylinder form.Ceramic membrane
Component is mainly made up of ceramic membrane, pressure hull, sealing structure.Ceramic membrane is main isolating construction, and material is by Al2O3、
SiO2、ZrO2Or TiO2One kind in middle material is made through high temperature sintering, the pottery of the ceramic film component of interior film casing and middle film casing
Porcelain film is the NF membrane of aperture 0.3-1nm；Pressure hull is the Stainless Steel Shell of 316L materials, and sealed material is connected for component
Sealing.Outer tube main body is stainless steel, and three-dimensional shape is cone, terrace with edge, round platform, cylinder, square or cuboid,
It is preferred that cylinder form.
When reactor of the present invention is applied to esterification, interior film casing as infiltration evaporation water vapor channel,
Can be connected with negative-pressure ward system.Interior film casing can bear 10~500kpa pressure, preferably 20~400kpa.Middle Membrane cover
Pipe can bear 100~600kpa pressure, preferably 150~500kpa as reaction mass and product access way, middle film casing.
Outer tube can bear 100~1000kpa pressure, preferably 150~500kpa as hot-air access way, further excellent
Elect 200~400kpa as.
In reactor of the invention, it is preferable that reactor body horizontal positioned, interior film casing, middle film casing, overcoat caliber
It is 1 to the diameter ratio in section:(2~6):(3~10), preferably 1:(3~5):(6~7).
In reactor of the invention, described supporting network tight outside interior film casing and middle film casing, supporting network
Mesh size be 0.1~1cm, preferably 0.3~0.6cm, supporting network material be carbon steel, 304,316 or 316L in one kind.
The method that (methyl) acrylate is prepared using reactor of the invention, is comprised the following steps：
The alcohol of (methyl) acrylic acid and C1~C4 is delivered to after static mixer is well mixed by raw material pump, by raw material
Pump is delivered to heat exchanger, after being preheating to uniform temperature, the middle film casing of annular multilayer sleeve pipe membrane reactor is entered by charging aperture
Inner chamber, under the immixture of hybrid component, and circulates together loaded on the solid catalyst in middle film casing, and raw material is through solid
Body catalyst catalysis carries out esterification, and the water of generation enters inner membrance cannula cavity and realizes by ceramic film component infiltration evaporation
Continuous removing, is condensed through steam outlet by negative-pressure ward discharge system and condensed device.Air is preheating to by preheater
After uniform temperature, overcoat tube cavity is entered by air intake, the hot-air into overcoat tube cavity is equal by ceramic film component
In the even reaction mass for penetrating into middle Membrane cover tube cavity, reaction mass thermally equivalent can be realized and esterification reaction temperature is maintained,
Can realize inhibiting air being uniformly distributed in material simultaneously, reduce the generation of polymer during (methyl) acroleic acid esterification.
A reacted feed liquid part is circulated in middle Membrane cover tube cavity, and another part is passed through by the discharging opening of reactor
After separate mesh separates solid catalyst, outflow reactor.The feed liquid of circulation is 4 with the volume ratio of the feed liquid of outflow：1~8：1
In the inventive method, described solid catalyst is cationic ion-exchange resin or solid acid catalyst, and catalyst is empty
Speed is 3~5h-1, based on charging acrylic acid quality, the mol ratio 1 of the alcohol of charging (methyl) acrylic acid and C1~C4:(0.5~
2.0), preferably 1：(0.7~1.5), more preferably 1:(0.8~1.3).
In the inventive method, methyl) alcohol material residence time in the reactor of acrylic acid and C1~C4 is 1~8h,
Preferably 2~5h.
In the inventive method, the temperature being mixed into after feed liquid preheating of the alcohol of (methyl) acrylic acid and C1~C4 for 60~
120 DEG C, preferably 70~100 DEG C；Temperature into overcoat tube cavity hot-air is 60~120 DEG C, preferably 70~100 DEG C；
Film casing internal reaction temperature is 60~120 DEG C, preferably 70~100 DEG C in reactor；Inner membrance cannula cavity pressure be 20~
40kpa, middle film casing chamber pressure is 100~400kpa, and outer tube chamber pressure is 100~400kpa, overcoat tube cavity pressure
Power is higher than 5~15kpa of middle film casing chamber pressure.
The positive effect of the present invention is：First, in the reactor using solid catalyst, reduce homogeneous catalyst pair
The corrosion of equipment；Second, using ceramic membrane osmotic, evaporating and dewatering technology, the continuous dehydration in esterification reaction process can be realized,
The energy consumption of water removal is reduced, while improve the conversion ratio and selectivity of the reaction of (methyl) acroleic acid esterification；3rd, solid catalysis
Agent circulates form in reactor, it is to avoid channel is formed when material is by catalyst, improves mass transfer effect；4th, it is real
The continuous uniform that air is inhibited during existing (methyl) acroleic acid esterification is added；5th, the hybrid component of reactor is reduced
The generation of ethers impurity.
Brief description of the drawings
Fig. 1 is the reaction process schematic diagram of (methyl) acroleic acid esterification reaction.
Fig. 2 is the longitudinal section view of annular multilayer sleeve membrane reactor sleeve structure.
Fig. 3 is the axial, cross-sectional view of annular multilayer sleeve membrane reactor sleeve structure.
Fig. 4 is the schematic diagram of the hybrid component in annular multilayer sleeve membrane reactor.
Wherein 1 is (methyl) acrylic raw materials tank, and 2 is raw polyol tank, and 3 is static mixer, and 4 is flowmeter, and 5 is preheating
Device, 6 is generation water storage tank, and 7 is reactor, and 8 is surge tank, and 9 is vavuum pump, and 10 is condenser, and 11 is interior film casing, and 12 is outer
Sleeve pipe, 13 is middle film casing, and 14-1 is fin propeller, and 14-2 is helical orbit, and 15 is air intake, and 16 is charging aperture, 17
It is check valve, 18 is discharging opening, and 19 is steam outlet.
Specific embodiment
Below in conjunction with drawings and Examples, the present invention is described further.
Product uses gas chromatographic analysis, and analytical conditions for gas chromatography is as follows：Chromatographic column：(specification is 30m to Agilent HP-5
× 0.32mm × 0.25mm), injector temperature：280 DEG C, split ratio：20：1 column flow：2ml/min, column temperature：50 DEG C, keep
2min, 5 DEG C/min are increased to 80 DEG C, keep 5min, 15 DEG C/min to be increased to 280 DEG C, keep 5min, detector temperature：280
DEG C, H2Flow：30ml/min, air mass flow：400ml/min.
The reaction process of (methyl) acroleic acid esterification reaction is as shown in figure 1, (methyl) acrylic acid and alcohol are respectively from (methyl)
Acrylic raw materials tank 1, and raw polyol tank 2 is flowed out by entering pre- after flowmeter 4 controls flow after the mixing of static mixer 3
Hot device 5 is preheated, and the material after preheating enters reactor 7.
As in Figure 2-4, reactor 7 is ring-like three layers of sleeve structure, including the interior film casing being coaxially disposed from inside to outside
11st, middle film casing 13 and outer tube 12, interior film casing 11 are provided with a steam outlet 19；Middle film casing 13 is provided with a charging
Mouth 16 and a discharging opening 18；Check valve 17 is installed between charging aperture 16 and discharging opening 18；Outer tube 12 is provided with a sky
Gas entrance 15.Supporting network is installed outside interior film casing 11 and middle film casing 13 additional for fixed support.Supporting network mesh size is
0.5cm, supporting network material is 316L.The inside of middle film casing 13 sets hybrid component, and it is by 316L materials push type fin 14-1
Constituted with helical orbit 14-2.9 fins of the pusher fin 14-1 by central ring and on central ring circumference are constituted, fin
It is uniformly distributed on central ring circumference, helical orbit 14-2 passes through fin central ring.Helical orbit 14-2 is centered around interior film casing
Angle α=15 ° of 11 outsides, its projection on the shaft section of interior film casing 11 and inner membrance casing axis.Inside middle film casing 13
Circulate solid catalyst.The three-dimensional shape of the ceramic film component of interior film casing and middle film casing is cylinder, long by Nanjing
I produces high-tech, model JWCM01*12, and ceramic membrane therein is the NF membrane of 0.3nm for the aperture of single channel or multichannel,
Material is ZrO2.Reaction mass enters the inner chamber of middle film casing 13 of reactor 7 by charging aperture 16, makees in the mixing of hybrid component
Under, and solid catalyst is circulated together.Raw material carries out esterification through catalysis of solid catalyst, and the water of generation is by pottery
Porcelain membrane module infiltration evaporation enters the inner chamber of interior film casing 11 and realizes continuous removing, is arranged by negative-pressure ward through steam outlet 19
Go out system (surge tank 8, vavuum pump 9) and condensed device 10 is condensed.Air enters after preheater 5 is preheating to uniform temperature
The inner chamber of outer tube 12 of reactor 7.Hot-air into the inner chamber of outer tube 12 is by ceramic film component uniformly penetrating to middle Membrane cover
In the reaction mass of the inner chamber of pipe 13, reaction mass thermally equivalent can be realized and esterification reaction temperature is maintained, while resistance can be realized
Poly- air being uniformly distributed in material, reduces the generation of polymer during (methyl) acroleic acid esterification.Reacted feed liquid
A part is circulated in the inner chamber of middle film casing 13, and another part is by the discharging opening 16 of reactor 7 through catalyst separate mesh point
After solid catalyst, outflow reactor, circulation feed liquid is 4 with the volume ratio of outflow feed liquid：1.
Embodiment 1
The annular multilayer double tube reactor provided using the present invention carries out the esterification of acrylic acid and methyl alcohol, generates propylene
Sour methyl esters.The horizontal positioned of reactor 7, radial section length is 0.92m, and diameter is followed successively by 0.1m from inside to outside for three layers of sleeve pipe,
0.48m, 0.6m.The Amberlyst 25wet cation resin catalyzings of the inner loop of middle film casing 13 flowing DOW Chemical production
Agent, acrylic acid mass space velocity is 3.65h-1.By mol ratio 1.12:1 acrylic acid and methyl alcohol is mixed by static mixer 3
It is even, preheater 5 is delivered to by raw material pump with the speed of 10kg/h and is preheating to 75 DEG C, subsequently into the middle film casing of reactor 7
In 13.The internal pressure of interior film casing 11 is 30KPa, and the internal pressure of middle film casing 13 is 300KPa, and outer tube 12 is passed through and is preheating to
75 DEG C of air, pressure is 310kpa.The raw material residence time in the reactor is 2.9h.By the esterification of 2.9h, first
The conversion ratio of alcohol reaches 72.4%, and the selectivity of methyl acrylate reaches 97.6%, and macromolecule polyalcohol contains in reactor discharging
Amount 0.09wt%, dimethyl ether impurity content 120ppm.
Comparative example 1
The esterification of acrylic acid and methyl alcohol is carried out using general fixed bed reactors, methyl acrylate is generated.It is fixed
Bed reactor is height 0.92m, the vertical vessel of diameter 0.48m.Heap filling Amberlyst 25wet sun is dissipated inside fixed bed
Ion exchange resin catalyst, acrylic acid mass space velocity is 3.65h-1.By mol ratio 1.12:1 acrylic acid and methyl alcohol is by static mixed
Clutch is well mixed, and being delivered to preheater by raw material pump with the speed of 10kg/h is preheating to 75 DEG C, anti-subsequently into fixed bed
Answer in device.Fixed bed reactors internal pressure is 300kpa.The raw material residence time in the reactor is 2.9h.By 2.9h's
Esterification, the conversion ratio of methyl alcohol reaches 60.7%, and the selectivity of methyl acrylate reaches 97.2%, divides greatly in reactor discharging
Sub- polymer content 0.32wt%, dimethyl ether impurity content 430ppm.
Embodiment 2
The annular multilayer double tube reactor provided using the present invention carries out the esterification of acrylic acid and ethanol, generates propylene
Acetoacetic ester.The horizontal positioned of reactor 7, radial section length is 0.92m, and diameter is followed successively by 0.1m from inside to outside for three layers of sleeve pipe,
0.6m, 1m.The inner loop of middle film casing 13 flows Amberlyst 25wet cation resin catalyzing agent, acrylic acid mass space velocity
It is 3.65h-1.By mol ratio 1.10:1 acrylic acid and ethanol is well mixed by static mixer 3, logical with the speed of 10kg/h
Cross raw material pump and be delivered to preheater 5 and be preheating to 80 DEG C, subsequently into reactor 7 middle Membrane cover 13 manage in.Inside interior film casing 11
Pressure is 40KPa, and the internal pressure of middle film casing 13 is 150KPa, and outer tube 12 is passed through the air for being preheating to 80 DEG C, and pressure is
160kpa.Residence time of the raw material in reactor 7 is 2.3h, and by the esterification of 2.3h, the conversion ratio of ethanol reaches
78.4%, the selectivity of ethyl acrylate reaches 95.1%, macromolecule polyalcohol content 0.10wt%, diethyl in reactor discharging
Ether impurity content 90ppm.
Comparative example 2
The esterification of acrylic acid and ethanol is carried out using general fixed bed reactors, ethyl acrylate is generated.It is fixed
Bed reactor is height 0.92m, the vertical vessel of diameter 0.48m.Heap filling Amberlyst 25wet trees are dissipated inside fixed bed
Fat catalyst, acrylic acid mass space velocity is 3.65h-1.By mol ratio 1.10:1 acrylic acid and ethanol is mixed by static mixer
Close uniform, preheater is delivered to by raw material pump with the speed of 10kg/h and is preheating to 80 DEG C, subsequently into fixed bed reactors.
Fixed bed reactors internal pressure is 160kpa.The raw material residence time in the reactor is 2.3h.Esterification by 2.3h is anti-
Should, the conversion ratio of ethanol reaches 67.0%, and the selectivity of ethyl acrylate reaches 94.3%, macromolecular polymeric in reactor discharging
Thing content 0.41wt%, diethyl ether impurity content 380ppm.
Embodiment 3
The annular multilayer double tube reactor provided using the present invention carries out the esterification of acrylic acid and n-butanol, generation third
Olefin(e) acid butyl ester.The horizontal positioned of reactor 7, radial section length is 0.92m, and diameter is followed successively by 0.1m from inside to outside for three layers of sleeve pipe,
0.3m, 0.7m.The Amberlyst39wet cation resin catalyzing agent of the inner loop of middle film casing 13 flowing Tao Shi productions, propylene
Sour mass space velocity is 3.65h-1.By mol ratio 1:1.20 acrylic acid and butanol is well mixed by static mixer 3, with
The speed of 10kg/h is delivered to preheater 5 by raw material pump, is preheating to 95 DEG C, subsequently into the middle film casing 13 in reactor 7
It is interior.The internal pressure of interior film casing 11 is 20KPa, and the internal pressure of middle film casing 13 is 350KPa, and outer tube is passed through and is preheating to 95 DEG C
Air, pressure is 360kpa.Residence time of the raw material in reactor 7 is 3h.By the esterification of 3h, acrylic acid turn
Rate reaches 68.3%, and the selectivity of butyl acrylate reaches 98.7%, macromolecule polyalcohol content in reactor discharging
0.12wt%, butyl oxide impurity content 150ppm.
Comparative example 3
Using general complete mixing flow formula agitated bed reactor, the esterification of acrylic acid and n-butanol is carried out, generate propylene
Acid butyl ester, connection water knockout drum carries out continuous dehydration at the top of agitated bed reactor.Reactor is 0.05m3Cylindrical container.Instead
The ratio of height to diameter for answering device is 1.5:1, the Amberlyst 39wet resin catalysts of Tao Shi productions are loaded, acrylic acid mass space velocity is
3.65h-1.By mol ratio 1:1.20 acrylic acid and butanol is well mixed by static mixer, is passed through with the speed of 10kg/h
Raw material pump is delivered to preheater and is preheating to 95 DEG C, and subsequently into agitated bed reactor, agitated bed internal pressure is 20KPa, folding
Leaf rotating speed of agitator is 100r/min, and the raw material residence time in the reactor is 3h.It is acrylic acid by the esterification of 3h
Conversion ratio reaches 50.4%, and the selectivity of butyl acrylate reaches 97.5%, macromolecule polyalcohol content in reactor discharging
0.56%, butyl oxide impurity content 510ppm.
The annular multilayer sleeve pipe membrane reactor of table 1 is esterified Contrast on effect with general reactor
Claims (18)
1. a kind of annular multilayer sleeve pipe membrane reactor, it is characterised in that main body is ring-like three layers of sleeve structure, including from inside to outside
Interior film casing, middle film casing, the outer tube being coaxially disposed, interior film casing and middle film casing outside are fixed by supporting network and supported,
A steam outlet is offered on interior film casing, a charging aperture and a discharging opening, outer tube are offered on middle film casing
On offer an air intake, middle Membrane cover tube cavity is provided with hybrid component, and separation is provided with middle film casing discharge outlet
Net, check valve is installed between charging aperture and discharging opening.
2. reactor according to claim 1, it is characterised in that the hybrid component of described middle Membrane cover tube cavity is comprising pushing away
Enter formula fin and helical orbit, helical orbit is centered around inner membrance outside of sleeve, throwing of the helical orbit on inner membrance sleeve pipe shaft section
Shadow is α with the angle of inner membrance casing axis, and α=15-30 °, pusher fin is around helical orbital movement.
3. reactor according to claim 2, it is characterised in that the pusher fin of described hybrid component is by central ring
Constituted with 6~12 fins on central ring circumference, fin is uniformly or non-uniformly distributed on central ring circumference, described
Helical orbit passes through fin central ring, and the outward flange of helical orbit is fitted with fin central ring inner circumferential.
4. the reactor according to any one of claim 1-3, it is characterised in that described interior film casing and middle film casing
Main body is ceramic film component, and the three-dimensional shape of the ceramic film component is cone, terrace with edge, round platform, cylinder, square or rectangular
Body；Outer tube main body is stainless steel, and three-dimensional shape is cone, terrace with edge, round platform, cylinder, square or cuboid.
5. reactor according to claim 4, it is characterised in that the three-dimensional shape cylinder of ceramic film component, outer tube
Main body three-dimensional shape is cylinder.
6. the reactor according to any one of claim 1-3, it is characterised in that reactor body horizontal positioned, inner membrance
Sleeve pipe, middle film casing, the diameter ratio of outer tube radial section are 1:(2~6):(3~10).
7. reactor according to claim 6, it is characterised in that interior film casing, middle film casing, outer tube radial section
Diameter ratio is 1:(3~5):(6~7).
8. reactor according to claim 4, it is characterised in that in the ceramic film component of interior film casing and middle film casing
Ceramic membrane is the NF membrane that aperture is 0.3-1nm, and material is Al2O3、SiO2、ZrO2Or TiO2In one kind, pusher fin
With helical orbit material be carbon steel, 304,316 or 316L in one kind.
9. reactor according to claim 1, it is characterised in that described supporting network is wrapped in interior film casing and middle Membrane cover
Outside pipe, supporting network mesh size be 0.1~1cm, supporting network material be carbon steel, 304,316 or 316L in one kind.
10. reactor according to claim 9, it is characterised in that supporting network mesh size is 0.3~0.6cm.
11. methods that (methyl) acrylate is prepared using the reactor any one of claim 1-10, its feature is existed
In comprising the following steps：The alcohol of (methyl) acrylic acid and C1~C4 be mixed into feed liquid preheating after, enter ring-like by charging aperture
The middle Membrane cover tube cavity of multilayer sleeve membrane reactor, under the immixture of hybrid component, and loaded on the solid in middle film casing
Catalyst is circulated together, and raw material carries out esterification through catalysis of solid catalyst, and the water penetration vaporization of generation enters inner membrance
Cannula cavity and realize continuous removing, flowed out through steam outlet；After air preheat, overcoat tube cavity is entered by air intake
And uniformly penetrating, in the reaction mass of middle Membrane cover tube cavity, a reacted feed liquid part is in middle Membrane cover tube cavity recycle stream
It is dynamic, after another part is by the separated net separation solid catalyst of discharging opening, outflow reactor.
12. methods according to claim 11, it is characterised in that described solid catalyst be cationic ion-exchange resin or
Solid acid catalyst, catalyst space velocities are 3~5h-1, charging (methyl) acrylic acid is 1 with the mol ratio of the alcohol of C1~C4:(0.5
~2.0).
13. methods according to claim 12, it is characterised in that the alcohol of charging (methyl) acrylic acid and C1~C4 mole
Than being 1：(0.7~1.5).
14. methods according to claim 13, it is characterised in that the alcohol of charging (methyl) acrylic acid and C1~C4 mole
Than being 1:(0.8~1.3).
15. methods according to claim 11, it is characterised in that the material residence time in the reactor is 1~8h.
16. methods according to claim 15, it is characterised in that the material residence time in the reactor is 2~5h.
17. methods according to claim 11, it is characterised in that the mixed feeding of the alcohol of (methyl) acrylic acid and C1~C4
Temperature after liquid preheating is 60~120 DEG C；Temperature into overcoat tube cavity hot-air is 60~120 DEG C；Membrane cover in reactor
Pipe internal reaction temperature is 60~120 DEG C；Inner membrance cannula cavity pressure be 20~40kpa, middle film casing chamber pressure be 100~
400kpa, outer tube chamber pressure be 100~400kpa, outer tube chamber pressure higher than middle film casing chamber pressure 5~
15kpa。
18. methods according to claim 17, it is characterised in that the mixed feeding of the alcohol of (methyl) acrylic acid and C1~C4
Temperature after liquid preheating is 70~100 DEG C；Temperature into overcoat tube cavity hot-air is 70~100 DEG C；Membrane cover in reactor
Pipe internal reaction temperature is 70~100 DEG C.
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| CA2001397A1 (en) * | 1988-10-28 | 1990-04-28 | Tadao Shimomura | Method for production of acrylate and acrylate-containing polymer |
| US5856423A (en) * | 1996-12-23 | 1999-01-05 | E. I. Du Pont De Nemours And Company | Apparatus and process for a polycondensation reaction |
| CN101862625A (en) * | 2010-06-23 | 2010-10-20 | 湘潭大学 | Membrane reactor for use in hydrocarbon oxidization reaction-separation coupling process |
| CN102093438A (en) * | 2010-11-22 | 2011-06-15 | 柳州爱格富食品科技股份有限公司 | Process for synthesizing sucrose polyester by using rotating film transesterification flow reactor |
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