A kind of dynamic self-cleaning reactor and its method for preparing isocyanates
Technical field
The present invention relates to a kind of reactor for preparing isocyanates, and in particular to a kind of dynamic self-cleaning reactor, also relates to
And the method that isocyanates is prepared using the reactor.
Background technology
Gas phase phosgenation method just has been reported that gas phase reaction process is usually in pipe to prepare isocyanates in 1940s
Carried out in formula reactor, it has reaction rate fast, the characteristics of phosgene hold-up is low, if but mixing is improper, when such as mixing slow,
More polymeric by-products are then generated, these accessory substances wall built-up coking, caking in reactor finally block reactor, especially
It is that material is more also easy to produce coking material at first make contact, and then causes the progressively deterioration of mixing flow field, shortens reactor
The cycle of operation.Therefore on the one hand need high-temperature reaction process to strengthen mixing, shorten the residence time;On the other hand, using height mixing
The reactor of efficiency, to avoid generating solid matter in reactor, the third aspect will effectively remove inevitable reaction
Deposit, the extension reactor cycle of operation.
European patent EP 0289840A employs a kind of barrel type reactor without movable member, makes reaction stream in rapids
Reacted under stream mode.Because the gas phase phosgenation process of aliphatic amine is an extremely fast course of reaction, belong to mixing velocity control
Course of reaction.Usually due to back-mixing, cause isocyanates to be reacted with amine, so as to form solid pollution reactor, and cause gas
Road is blocked.
European patent EP 0593334A describes a kind of method for preparing aromatic isocyanate in the gas phase, this method institute
Do not include any dynamic tumbler in the tubular reactor of use, increase just with contractile response wall and disturb, with using
The mixed effect that standard hybrid element is obtained is compared, and its mixed effect is poor, and this poor mixing will be resulted in and do not wished
The solid product of prestige.
European patent EP 0699657A describes a kind of method for preparing aromatic isocyanate in the gas phase, aromatic series two
The reaction of amine and phosgene is carried out in mixing reactor, and the reactor is divided into two regions, and inner region is that diamines and phosgene are mixed
Mixed Zone, account for the 20~80% of total reactor volume;Exterior domain is the conversion zone close to plug flow, accounts for overall reaction
The 80~20% of volume.However, the reaction volume due at least 20% is not in preferable back-mixing, therefore cause uneven
Residence time destribution, forms undesirable solid product.
European patent EP 1362847A describes a kind of method for preparing isocyanates in the gas phase, in the method, leads to
Cross with flow-related measure as added Homogenizing Element in the reactor and determining the center of gas phase educt, improve tubular type anti-
The response characteristic in device is answered, so as to avoid deposit and the secondary species for the polymerization for causing reactor lifetime to shorten in reactor
Formed.
United States Patent (USP) US4847408A strengthens mixing using the prevailing reactor of turbulent flow, makes reaction stream strong
Reacted under turbulence state, its internal diameter is 2.5mm, and length is 17.5mm, and amine steam is injected in reactor by nozzle at high speeds,
HDI has been prepared at a high temperature of 400 DEG C.Simple barrel type reactor in US4847408A is improved as by CN1396152A
Similar Venturi type blender, this design can reduce contact and back-mixing of the reaction zone with wall.
Chinese patent application CN1651406A discloses a kind of tubular reactor without moveable element, and the reactor has
The double wall conduit extended on tubular reactor rotation direction of principal axis along center, is formed between the inner and outer wall of double wall conduit
Concentric annular gap, makes to be heated to 200~600 ° of amine and phosgene fast reaction in this format.This method is that amine feed pipe exists
The improvement carried out on the basis of straight feed pipe, adds somewhat to the diffusion admittance of amine, improve mixed effect, but this is mixed
The problem of clutch is equally internally lumpd there is also solid matter.
The process that gas phase phosgenation prepares isocyanates is a fast reaction process, under the mixing rate being exceedingly fast,
Also the formation of the high polymers such as accessory substance urea can not be avoided, it is therefore desirable to which reactant efficiently quickly mixing and can be with can be made by finding one kind
Effectively remove the reactor and method of reactive deposition thing.
The content of the invention
It is an object of the present invention to provide a kind of dynamic self-cleaning reactor, it can increase vortex and turbulating effect, significantly
Improve the mixed effect of reactant, while effectively removing inevitable deposit in course of reaction, realize the height of reactant
The quick purpose for mixing and reaching the extension reactor cycle of operation of effect.
Another object of the present invention is to there is provided a kind of side that isocyanates is prepared using the dynamic self-cleaning reactor
Method.
The present invention uses following technical scheme:
A kind of dynamic self-cleaning reactor, it includes:It is housing 1, auxiliary charging aperture N3, scraping blade 2, support shaft 5, blender, anti-
Region 3 is answered, the blender is by interior feed pipe N1 and positioned at interior feed pipe N1 peripheries and the outer charging coaxial with interior feed pipe N1
Pipe N2 is constituted, and annular space 4 is formed between interior feed pipe N1 and outer feed pipe N2, and the one end of support shaft 5 is fixed in inner walls,
The other end is connected with the axle of scraping blade 2, and the scraping blade 2 is located in housing 1 and is that feed pipe N1 goes out in axle rotation cleaning with support shaft 5
The side wall 6 of mouth, outer feed pipe N2 outlet and conversion zone 3, auxiliary charging aperture N3 is located on the side wall 6 of conversion zone 3.
Interior feed pipe N1 and outer feed pipe N2 of the present invention outlet are located in same level, and the horizontal plane is located at auxiliary
Between the region that horizontal plane where horizontal plane and minimum point where charging aperture N3 peak is limited.
Interior feed pipe N1 of the present invention, outer feed pipe N2, auxiliary charging aperture N3 outlet material enter conversion zone 3.
Reaction mass exports N4 discharge reactors by the housing 1 of reactor.
Reactor of the present invention is provided with 2~12 groups of blenders, more preferably preferably 3~8 groups, 4~6 groups.
The axle of the axis and the diameter parallel of reactor of every group of blender of the present invention, every group of blender axis and reactor
The distance of line is respectively 0.2r~0.8r, preferably 0.4r~0.7r.
R of the present invention is the radius of conversion zone 3.
It is preferred that, the axis of every group of blender is equal with the distance of the axis of reactor;More preferably every group blender axis
It is evenly distributed in the imaginary circles 8 coaxial with reactor, the radius of imaginary circles 8 is 0.2r~0.8r, preferably 0.4r~0.7r.
Auxiliary charging aperture N3 of the present invention number is 2~12, preferably 3~8, more preferably 4-6.
Auxiliary charging aperture N3 of the present invention is preferably evenly distributed through on the side wall 6 of conversion zone 3, each auxiliary charging aperture N3's
Axis is located in the same horizontal plane, and described auxiliary charging aperture N3 axis is 0.1r~0.9r apart from L with reactor axis, excellent
Select 0.2r~0.7r, more preferably 0.3r~0.5r.
Scraping blade 2 of the present invention has 2~12 scrapers, preferably with 3~8, more preferably 4~6.
Each scraper includes radial direction scraper, axial scraper.
The scraping blade 2 is rotated with support shaft 5 for axle, and radial direction scraper presses close to interior feed pipe N1 and outer feed pipe N2 outlet,
Remove the deposit of outlet;Axial scraper presses close to the side wall 6 of conversion zone 3, clears up the deposit of side wall 6.
The radial direction scraper and axial scraper export with interior feed pipe N1 respectively, outer feed pipe N2 outlets, conversion zone 3
The position that inwall is pressed close to is more sharp, can play a part of striking off deposit.
It is preferred that the cross section of radial direction scraper be quadrangle, the angle α of the quadrangle is 20 °~90 °, preferably 30 °~
70 °, more preferably 40 °~50 °, described angle α and interior feed pipe N1 is exported, outer feed pipe N2 outlets are pressed close to, base L1 length
Ratio with the thickness W of scraper is 2~8:1, preferably 3~5:1, radial direction scraper is formed the structure of similar blade, the structure with
Interior feed pipe N1 outlets, outer feed pipe N2 outlet contact, for removing deposit.
The cross section of radial direction scraper of the present invention is more preferably right-angled trapezium, the angle α of right-angled trapezium for 20 °~
90 °, preferably 30 °~70 °, more preferably 40 °~50 °, base L1 length and the thickness W of scraper ratio are 2~8:1, preferably 3
~5:1.
It is preferred that the cross section of axial scraper be quadrangle, the angle beta of the quadrangle is 20 °~90 °, preferably 30 °~
70 °, more preferably 40 °~50 °, described angle beta and the inwall of conversion zone 3 is pressed close to, base L3 length and the thickness W's of scraper
Ratio is 2~8:1, preferably 3~5:1, axial scraper is formed the structure of similar blade, the structure and the side wall 6 of conversion zone 3
Contact, for removing deposit.
The cross section of axial scraper of the present invention is more preferably right-angled trapezium, the angle beta of right-angled trapezium for 20 °~
90 °, preferably 30 °~70 °, more preferably 40 °~50 °, base L3 length and the thickness W of scraper ratio are 2~8:1, preferably 3
~5:1.
The length L2 of the radial direction scraper is 0.3r~1.0r, preferably 0.4r~0.9r.
The radius of imaginary circles 7 that the length L2 of the radial direction scraper is more than or equal to where blender outer rim, less than or equal to reaction
The radius in region 3, so as to remove the deposit that interior feed pipe N1 outlets and outer feed pipe N2 are exported.
The height H of the axial scraper is 0.2r~1.5r, preferably 0.4r~1.0r.The height of axial scraper will meet axle
The side wall 6 of conversion zone 3 is extended to scraper, plays a part of clearing up the deposit of side wall 6.
It can be connected between the radial direction scraper and axial scraper by any-mode, it is preferable that connected by oblique scraper,
Now, the cross section of oblique scraper and the cross section of radial direction scraper are identical or different, preferably identical.
The support shaft 5 is coaxially disposed with reactor, is arranged in reactor shell 1, and the scraping blade 2 is by arbitrarily may be used
Rotating device is connected with support shaft 5, and the rotary power of scraping blade 2 is provided by the kinetic energy of auxiliary charging aperture N3 charging, dynamic without addition
Power equipment, effectively solves the sealing problem that the addition of turn part is brought to reactor.
A kind of method for preparing isocyanates using dynamic self-cleaning reactor of the present invention, this method includes:
(a) amine and phosgene are heated respectively, is allowed to gasify;
(b) one phosgene enters blender by interior feed pipe N1, and amine steam enters blender by outer feed pipe N2;Or one
Stock phosgene enters blender by outer feed pipe N2, and amine steam enters blender by interior feed pipe N1;
(c) second strand of phosgene enters reactor from auxiliary charging aperture N3;
(d) reacted after phosgene is mixed with amine steam in conversion zone 3, obtain isocyanates.
Amine of the present invention is can be converted into gas phase and Undec primary amine, with general formula R (NH2)n, wherein R is tool
There is the aliphatic for being no more than 15 carbon atoms alicyclic or aromatic alkyl, preferably 3~15 carbon atoms, more preferably 4~
The aliphatic of 13 carbon atoms, alicyclic or aromatic hydrocarbyl, and n is the integer in 1~10.Such as:Suitable aliphatic monoamine
Example have methylamine, ethamine, propylamine, cyclohexylamine etc.;The example of suitable aliphatic diamine have 1,4- butanediamine, 1,6- oneself two
Amine, 1,4- diaminocyclohexanes, 1- amino -3,3,5- trimethyl -5- aminomethyl cyclohexanes (IPDA), 4,4 '-diaminourea two
Cyclohexyl-methane (H12MDA) etc.;The example of suitable aliphatic triamine has 1,8- diaminourea -4- (aminomethyl) octane, triamido
Nonane etc.;The example of suitable aromatic series monoamine has aniline etc.;The example of suitable aromatic diamine has toluenediamine, diaminourea
Benzene, naphthylenediamine etc..
The amine can also be containing heteroatomic amine, such as 2- tetrahydrofurans amine.
The preferred 1,6- hexamethylene diamines of amine, IPDA, H12MDA and triaminononane.
The temperature of heating is 120~600 DEG C, preferably 250~500 DEG C in (a).
It can also be used in (a) of the present invention dilute to the progress of amine steam using the steam of inert gas or atent solvent
Release, the inert gas is selected from nitrogen and/or argon gas, the atent solvent is selected from toluene, dimethylbenzene, o-dichlorohenzene and decahydronaphthalene
One or both of naphthalene is a variety of.
The mol ratio of contained amino is 0.1~2 in the steam and amine of (a) of the present invention inert gas or atent solvent:
1, preferably 0.2~1:1.
The mol ratio of phosgene and the amino of amine steam is 1.25~4.5 in (b) of the present invention:1, preferably 1.5~3.5:
1。
(c) of the present invention auxiliary charging aperture N3 phosgene inlet amount and the 5~100 of the mol ratio of the amino of (b) amine steam:
1, preferably 10~50:1.
The flow velocity of phosgene is 1~60m/s in (b) of the present invention, preferably 3~40m/s, the flow velocity of amine steam for 12~
80m/s, preferably 20~60m/s;(c) second charging aperture N3 phosgene flow velocity is 6~120m/s, preferably 15~100m/s.
Interior feed pipe N1 and outer feed pipe N2 of the present invention absolute pressure are 200~3000mbar, auxiliary charging aperture N3
And the outlet N4 absolute pressures of the housing 1 of reactor are preferably 150~1500mbar.
According to the present invention, the phosgene entered by auxiliary charging aperture can form the vortex of rotation, strengthen the mixing of phosgene and amine,
The generation of accessory substance is reduced, the generation of deposit is reduced;Also, the phosgene entered from secondary charging aperture provides dynamic for scraping blade rotation
Can, the dynamic self-cleaning of reactor is realized, the deposit being attached in reactor is removed, extends the cycle of operation.
Brief description of the drawings
Fig. 1 is the schematic diagram of the profilograph of currently preferred dynamic self-cleaning reactor, wherein 1 is housing, 2 to scrape
Piece, 3 be conversion zone, 4 be annular space, 5 be support shaft, 6 be that side wall, N1 are that interior feed pipe, N2 are outer feed pipe, supplemented by N3
Charging aperture, N4 are outlet.
Fig. 2 is the cross-sectional view (upward view) that line A-A is cut along along Fig. 1, charging aperture N3 axis and reactor axis supplemented by L
The distance of line, the radius that r is conversion zone 3.
Fig. 3 is the cross-sectional view (top view) that line A-A is cut along along Fig. 1,7 is imaginary circles where blender outer rim, 8 is
Imaginary circles where blender axis.
Fig. 4 is scraping blade schematic three dimensional views.
Fig. 5-1 is scraper sectional side elevation, and wherein H is the height of axial scraper, and L2 is the length of radial direction scraper, and L4 scrapes to be oblique
The length of knife;
Fig. 5-2 is cross-sectional view of the radial direction scraper along line B-B, and wherein L1 is quadrangle base, and W is the thickness of scraper, and α is
The angle of quadrangle;
Fig. 5-3 is cross-sectional view of the axial scraper along line C-C, and wherein L3 is quadrangle base, and W is the thickness of scraper, and β is
The angle of quadrangle.
Embodiment
Following examples will be further illustrated dynamic self-cleaning reactor provided by the present invention and use the reactor system
The method of standby isocyanates, but the present invention is not therefore subject to any restriction.
Embodiment 1:
Reactor:
Using dynamic self-cleaning reactor as shown in Figure 1.It includes:Housing 1, auxiliary charging aperture N3, scraping blade 2, support shaft
5th, blender, conversion zone 3, outlet N4, the blender by interior feed pipe N1 and positioned at interior feed pipe N1 periphery and with it is interior enter
Outer feed pipe N2 coaxial expects pipe N1 is constituted, and annular space 4, the scraping blade 2 are formed between interior feed pipe N1 and outer feed pipe N2
It is the side wall 6 that axle rotates feed pipe N1 outlets, outer feed pipe N2 outlet and conversion zone 3 in cleaning, auxiliary charging with support shaft 5
Mouth N3 is located on the side wall 6 of conversion zone 3.
The reactor is provided with 4 groups of blenders;The axis of every group of blender and the diameter parallel of reactor, every group of blender
Axis be evenly distributed in the imaginary circles 8 that radius is 250mm, the radius r of conversion zone 3 is 500mm.Interior feed pipe N1's is interior
Footpath is 80mm, external diameter 90mm;Outer feed pipe N2 internal diameter is 170mm, external diameter 180mm.
Interior feed pipe N1 and outer feed pipe N2 outlet are located in same level, and the horizontal plane is located at auxiliary charging aperture N3
Between the region that horizontal plane where horizontal plane and minimum point where peak is limited.
The number of the auxiliary charging aperture N3 is 4, and it is evenly distributed on the side wall 6 of conversion zone 3, each auxiliary charging aperture N3
Axis be located in the same horizontal plane, each auxiliary charging aperture N3 axis and reactor axis apart from L be 300mm.
The scraping blade 2 has 3 scrapers;The scraper includes radial direction scraper, oblique scraper and axial scraper, radially scrapes
Knife, oblique scraper, the cross section of axial scraper are right-angled trapezium, and the angle α and β of the right-angled trapezium are 45 °;L1 length
For 80mm, the thickness W of scraper is 20mm, and L3 length is 80mm;The length L2 of radial direction scraper is 340mm;The height of axial scraper
Degree H is 500mm, and oblique scraper length L4 is 180mm.Auxiliary charging aperture N3 internal diameter is 160mm, and interior feed pipe N1's exports, outside
Feed pipe N2 outlet and auxiliary charging aperture N3 axis are located in same level.
Prepare isocyanates:
4,4 '-dicyclohexyl methyl hydride diamines (H12MDA), phosgene and nitrogen are preheated to 360 ° respectively.Mol ratio is 1:1 N2
With H12MDA gaseous mixture enters reactor, H by interior feed pipe N112MDA flow is 400kg/h, and flow velocity is 16m/s.By outer
Phosgene and H that feed pipe N2 enters12The mol ratio of MDA amino is 4:1, flow velocity is 30m/s, interior feed pipe N1 and outer feed pipe
N2 absolute pressure is 2400mbar, the phosgene and H entered by auxiliary charging aperture N312MDA amino mol ratio is 10:1, flow velocity is
20m/s, auxiliary charging aperture N3 and the pressure 750mbar for exporting N4.
The material obtained after the completion of the reaction of conversion zone 3 absorbs trapping by solvent chlorobenzene and obtains H12MDI isocyanic acid
Ester solution, passes through gas chromatographic analysis (area normalization), H12MDI yields are 98.0%.By macrocyclic operation, in operation
After 4 months, parking maintenance, mixer outlet and conversion zone side wall are showed no obvious coking material.
Embodiment 2:
The dynamic self-cleaning reactor of use has 2 groups of blenders, and the axis of every group of blender is evenly distributed on radius and is
In 200mm imaginary circles 8, auxiliary charging aperture N3 number is 3, each auxiliary charging aperture N3 axis and reactor axis apart from L
For 200mm.Scraping blade 2 has 6 scrapers, and scraper is joined directly together by radial direction scraper and axial scraper, without oblique scraper, radial direction scraper
Cross section with axial scraper is right-angled trapezium, and the angle α of the right-angled trapezium is 35 °, and angle beta is 40 °;L1 length is
80mm, the thickness W of scraper is 20mm, and L3 length is 80mm;The length L2 of radial direction scraper is 500mm;The height H of axial scraper
For 450mm.The reactor of remaining structure be the same as Example 1.
Using the reaction condition for preparing isocyanates same as Example 1.Shown by gas chromatographic analysis, H12MDI
Yield 97.9%, by long-term operation, after operation 3.5 months, parking maintenance, mixer outlet and conversion zone side wall
It is showed no obvious coking material.
Embodiment 3:
The dynamic self-cleaning reactor of use has 6 groups of blenders, and the axis of blender is evenly distributed on radius for 300mm
Imaginary circles 8 on, auxiliary charging aperture N3 number is 6, and each auxiliary charging aperture N3 axis and reactor axis are apart from L
250mm.Scraping blade has 8 scrapers, and L1 length is 75mm, and the thickness W of scraper is 25mm, and L3 length is 60mm;Radially scrape
The length L2 of knife is 400mm;The height H of axial scraper is 450mm, and oblique scraper length L4 is 150mm.Remaining structure is with implementation
The reactor of example 1.
Using the reaction condition for preparing isocyanates same as Example 1.Shown by gas chromatographic analysis, H12MDI
Yield be 97.9%, by long-term operation, after operation 3.6 months, parking maintenance, mixer outlet and conversion zone side
Wall is showed no obvious coking material.
Embodiment 4:
Angle α, β of the cross section of the scraper of the scraping blade of the dynamic self-cleaning reactor of use are 60 °, and L1 length is
60mm, W are 15mm, and L2 length is 400mm, and H is 600mm, the reactor of remaining structure be the same as Example 1.
Using the reaction condition for preparing isocyanates same as Example 1.Shown by gas chromatographic analysis, H12MDI
Yield be 98.0%, by long-term operation, after operation 4 months, parking maintenance, mixer outlet and conversion zone side wall
It is showed no obvious coking material.
Embodiment 5:
Using dynamic self-cleaning reactor same as Example 1.
1,6- hexamethylene diamines (HDA), phosgene and nitrogen are preheated to 300 DEG C respectively.Mol ratio is 1:2 N2With HDA's
Gaseous mixture enters reactor by interior feed pipe N1, and HDA flow is 600kg/h, and flow velocity is 29m/s.Entered by outer feed pipe N2
Phosgene and HDA amino mol ratio be 3:1, flow velocity is 40m/s, by the auxiliary charging aperture N3 phosgene entered and HDA amino
Mol ratio is 20:1, flow velocity is 70m/s, remaining reaction condition be the same as Example 1.Shown by gas chromatographic analysis, HDI yield
For 99.0%.By macrocyclic operation, after operation 5 months, parking maintenance, mixer outlet and conversion zone side wall are equal
Have no obvious coking material.
Embodiment 6
Using dynamic self-cleaning reactor same as Example 1.
IPD (IPDA), phosgene and nitrogen are preheated to 320 DEG C, remaining reaction condition be the same as Example 1 respectively.It is logical
Cross gas chromatographic analysis to show, IPDI yield is 98.8%.By macrocyclic operation, after operation 4 months, parking inspection
Repair, mixer outlet and conversion zone side wall are showed no obvious coking material.
Comparative example 1:
The reactor of use does not install scraping blade, the reactor of remaining structure be the same as Example 1.
Using the reaction condition for preparing isocyanates same as Example 1.Shown by gas chromatographic analysis, H12MDI
Yield is 97.8%, after running 1.5 months after parking maintenance, mixer outlet and the visible obvious coking of conversion zone side wall
Thing.
Comparative example 2:
The reactor of use does not install scraping blade and auxiliary charging aperture, the reactor of remaining structure be the same as Example 1.
The phosgene and H entered by outer feed pipe N212The mol ratio of MDA amino is 4:1, using same as Example 1
Prepare the reaction condition of isocyanates.Shown by gas chromatographic analysis, H12MDI yields are H12MDI 97.4%, operation 1.5
After month after parking maintenance, mixer outlet and the visible obvious coking material of conversion zone side wall.