CN105032307A - Dynamic self-cleaning reactor and method for preparing isocyanate - Google Patents
Dynamic self-cleaning reactor and method for preparing isocyanate Download PDFInfo
- Publication number
- CN105032307A CN105032307A CN201510428651.5A CN201510428651A CN105032307A CN 105032307 A CN105032307 A CN 105032307A CN 201510428651 A CN201510428651 A CN 201510428651A CN 105032307 A CN105032307 A CN 105032307A
- Authority
- CN
- China
- Prior art keywords
- feed pipe
- reactor
- scraper
- phosgene
- blender
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a dynamic self-cleaning reactor and method for preparing isocyanate through the dynamic self-cleaning reactor by means of gas phase phosgenation reaction. The dynamic self-cleaning reactor comprises a shell (1), an auxiliary feeding opening (N3), a scraping piece (2), a supporting shaft (5), a mixer and a reaction region (3). The mixer is composed of inner feeding pipes (N1) and outer feeding pipes (N2), wherein the outer feeding pipes (N2) are located on the peripheries of the inner feeding pipes (N1) and coaxial with the inner feeding pipes (N1). The scraping piece (2) can rotate with the supporting shaft (5) as the axis. Phosgene entering from the auxiliary feeding opening (N3) forms rotational flow to enhance vortex, amine steam and the phosgene are promoted to be quickly mixed and react, generation of reaction by-products is reduced, rotating power is provided for the scrapping piece, deposition of the reactor is cleared, and the operation cycle is prolonged.
Description
Technical field
The present invention relates to a kind of reactor preparing isocyanates, be specifically related to a kind of dynamically self-cleaning reactor, also relate to the method using this reactor to prepare isocyanates.
Background technology
Gas phase phosgenation method prepares isocyanates just has report in the forties in 20th century, gas phase reaction process usually carries out in tubular reactor, it is fast that it has reaction rate, the feature that phosgene hold-up is low, if but mix improper, during as mixed slow, then generate more polymeric by-products, these accessory substances are wall built-up coking, caking in reactor, final blocking reactor, particularly material more easily produces coking material at first make contact place, and then causes the progressively deterioration of mixing flow field, shortens the cycle of operation of reactor.Therefore need high-temperature reaction process to strengthen mixing on the one hand, shorten the time of staying; On the other hand, adopt the reactor of high mixing efficiency, to avoid generating solid matter in reactor, the third aspect, effectively will remove inevitable reactive deposition thing, the extension reactor cycle of operation.
European patent EP 0289840A have employed a kind of barrel type reactor not with movable member, and reaction logistics is reacted under turbulence state.Gas phase phosgenation process due to aliphatic amine is an extremely fast course of reaction, belongs to the course of reaction that mixing velocity controls.Usually due to back-mixing, cause isocyanates and amine to react, thus form solid pollution reactor, and cause airway blockage.
European patent EP 0593334A describes a kind of method preparing aromatic isocyanate in the gas phase, any dynamic tumbler is not comprised in the tubular reactor that the method adopts, contractile response wall is only utilized to increase disturbance, compared with the mixed effect obtained with the standard of use hybrid element, its mixed effect is poor, and this bad mixing will cause forming undesirable solid product.
European patent EP 0699657A describes a kind of method preparing aromatic isocyanate in the gas phase, the reaction of aromatic diamine and phosgene is carried out in mixing reactor, this reactor is divided into two regions, inner region is the Mixed Zone of diamines photoreactive gas mixing, accounts for 20 ~ 80% of total reactor volume; Exterior domain is the conversion zone close to plug flow, accounts for 80 ~ 20% of total reaction volume.But the reaction volume due at least 20% there will not be desirable back-mixing, therefore cause uneven residence time destribution, form undesirable solid product.
European patent EP 1362847A describes a kind of method preparing isocyanates in the gas phase, in the method, by the measure relevant to flowing as added Homogenizing Element in the reactor and determining the center of gas phase educt, improve the response characteristic in tubular reactor, thus avoid the formation of the secondary species of deposit in reactor and the polymerization that causes reactor lifetime to shorten.
US Patent No. 4847408A adopts the prevailing reactor of turbulent flow to strengthen mixing, reaction logistics is reacted under strong turbulence state, and its internal diameter is 2.5mm, and length is 17.5mm, amine steam is injected in reactor by nozzle at high speeds, has prepared HDI under the high temperature of 400 DEG C.Barrel type reactor simple in US4847408A is improved as similar Venturi type blender by CN1396152A, and this design can reduce contact and the back-mixing of reaction zone and wall.
Chinese patent application CN1651406A discloses a kind of tubular reactor without moveable element, this reactor has the double wall conduit that tubular reactor rotating shaft direction extends along center, the concentric annular gap formed between the inner and outer wall of double wall conduit, makes the amine photoreactive gas fast reaction being heated to 200 ~ 600 ° in this format.The method is the improvement carried out on the basis of straight feed pipe by amine feed pipe, adds somewhat to the diffusion admittance of amine, improves mixed effect, but this blender equally also exists the problem that solid matter lumps in inside.
The process that gas phase phosgenation prepares isocyanates is a fast reaction process, even if under the mixing rate be exceedingly fast, also cannot avoid the formation of the high polymers such as accessory substance urea, therefore need to find and a kind ofly can make the efficient rapid mixing of reactant and effectively can remove reactor and the method for reactive deposition thing.
Summary of the invention
The object of the invention is to, a kind of dynamically self-cleaning reactor is provided, it can increase eddy current and turbulating effect, the remarkable mixed effect improving reactant, simultaneously inevitable deposit in effective removing course of reaction, the efficient rapid mixing of realization response thing also reaches the object of the extension reactor cycle of operation.
Another object of the present invention is to, provide a kind of and adopt described dynamic self-cleaning reactor to prepare the method for isocyanates.
The present invention is by the following technical solutions:
A kind of dynamically self-cleaning reactor, it comprises: housing 1, auxiliary charging aperture N3, scraping blade 2, back shaft 5, blender, conversion zone 3, described blender is by interior feed pipe N1 and be positioned at the peripheral and outer feed pipe N2 coaxial with feed pipe N1 of feed pipe N1 and form, annular space 4 is formed between interior feed pipe N1 and outer feed pipe N2, back shaft 5 one end is fixed in inner walls, the other end is connected with scraping blade 2 axle, described scraping blade 2 is positioned at housing 1 and exports for axle rotates cleaning feed pipe N1 with back shaft 5, the outlet of outer feed pipe N2 and the sidewall 6 of conversion zone 3, auxiliary charging aperture N3 is positioned on the sidewall 6 of conversion zone 3.
The outlet of interior feed pipe N1 of the present invention and outer feed pipe N2 is positioned in same level, between the region that the horizontal plane at the horizontal plane of this horizontal plane at the peak place of auxiliary charging aperture N3 and minimum point place limits.
The outlet material of interior feed pipe N1 of the present invention, outer feed pipe N2, auxiliary charging aperture N3 enters conversion zone 3.Reaction mass exports N4 by the housing 1 of reactor and discharges reactor.
Reactor of the present invention is provided with 2 ~ 12 groups of blenders, preferably 3 ~ 8 groups, more preferably 4 ~ 6 groups.
Of the present inventionly often organize the axis of blender and the axis being parallel of reactor, the distance often organizing the axis of blender axis and reactor is respectively 0.2r ~ 0.8r, preferred 0.4r ~ 0.7r.
R of the present invention is the radius of conversion zone 3.
Preferably, the axis of blender is often organized equal with the distance of the axis of reactor; More preferably often organizing blender axis is evenly distributed in the imaginary circles 8 coaxial with reactor, and the radius of imaginary circles 8 is 0.2r ~ 0.8r, preferred 0.4r ~ 0.7r.
The number of auxiliary charging aperture N3 of the present invention is 2 ~ 12, preferably 3 ~ 8, more preferably 4-6.
Auxiliary charging aperture N3 of the present invention is preferably evenly distributed on the sidewall 6 of conversion zone 3, the axis of each auxiliary charging aperture N3 is located in the same horizontal plane, the axis of described auxiliary charging aperture N3 follows the distance L of reactor axis to be 0.1r ~ 0.9r, preferred 0.2r ~ 0.7r, more preferably 0.3r ~ 0.5r.
Scraping blade 2 of the present invention has 2 ~ 12 scrapers, preferably has 3 ~ 8, more preferably 4 ~ 6.
Described each scraper comprises radial scraper, axial scraper.
Described scraping blade 2 is with back shaft 5 for axle rotates, and the outlet of interior feed pipe N1 and outer feed pipe N2 pressed close to by radial scraper, the deposit of removing outlet; The sidewall 6 of conversion zone 3 pressed close to by axial scraper, the deposit of cleaning sidewall 6.
The position that described radial scraper and axial scraper export with interior feed pipe N1 respectively, outer feed pipe N2 exports, the inwall of conversion zone 3 is pressed close to is comparatively sharp-pointed, can play and strike off sedimental effect.
The cross section of preferred radial scraper is quadrangle, the angle α of described quadrangle is 20 ° ~ 90 °, preferably 30 ° ~ 70 °, more preferably 40 ° ~ 50 °, described angle α and interior feed pipe N1 exports, outer feed pipe N2 exports, and the ratio of the length of base L1 and the thickness W of scraper is 2 ~ 8:1, preferably 3 ~ 5:1, make radial scraper form the structure of similar blade, this structure and interior feed pipe N1 export, the outlet contact of outer feed pipe N2, for removing deposit.
The cross section more preferably right-angled trapezium of radial scraper of the present invention, the angle α of right-angled trapezium is 20 ° ~ 90 °, preferably 30 ° ~ 70 °, more preferably 40 ° ~ 50 °, the ratio of the length of base L1 and the thickness W of scraper is 2 ~ 8:1, preferably 3 ~ 5:1.
The cross section of preferred axial scraper is quadrangle, the angle β of described quadrangle is 20 ° ~ 90 °, preferably 30 ° ~ 70 °, more preferably 40 ° ~ 50 °, described angle β and the inwall of conversion zone 3 are pressed close to, and the ratio of the length of base L3 and the thickness W of scraper is 2 ~ 8:1, preferably 3 ~ 5:1, make axial scraper form the structure of similar blade, this structure contacts with the sidewall 6 of conversion zone 3, for removing deposit.
The cross section more preferably right-angled trapezium of axial scraper of the present invention, the angle β of right-angled trapezium is 20 ° ~ 90 °, preferably 30 ° ~ 70 °, more preferably 40 ° ~ 50 °, the ratio of the length of base L3 and the thickness W of scraper is 2 ~ 8:1, preferably 3 ~ 5:1.
The length L2 of described radial scraper is 0.3r ~ 1.0r, preferred 0.4r ~ 0.9r.
The length L2 of described radial scraper is more than or equal to imaginary circles 7 radius at blender outer rim place, is less than or equal to the radius of conversion zone 3, thus can remove the deposit that interior feed pipe N1 exports and outer feed pipe N2 exports.
The height H of described axial scraper is 0.2r ~ 1.5r, preferred 0.4r ~ 1.0r.The height of axial scraper will meet the sidewall 6 that axial scraper extends to conversion zone 3, plays the sedimental effect of cleaning sidewall 6.
Described radial scraper can be connected by any-mode with between axial scraper, preferably, is connected by oblique scraper, now, the cross section of oblique scraper and the cross section of radial scraper identical or different, preferably identical.
Described back shaft 5 is coaxially arranged with reactor, be arranged in reactor shell 1, described scraping blade 2 is connected with back shaft 5 by arbitrary rotatable device, the rotary power of scraping blade 2 is provided by the kinetic energy of the charging of auxiliary charging aperture N3, without the need to adding power-equipment, what effectively solve turn parts adds the sealing problem brought to reactor.
Adopt dynamic self-cleaning reactor of the present invention to prepare a method for isocyanates, the method comprises:
A amine photoreactive gas heats by () respectively, make it gasification;
B () one phosgene enters blender by interior feed pipe N1, amine steam enters blender by outer feed pipe N2; Or one phosgene enters blender by outer feed pipe N2, amine steam enters blender by interior feed pipe N1;
C () second strand of phosgene enters reactor from auxiliary charging aperture N3;
React at conversion zone 3 d () phosgene mixes with amine steam after, obtain isocyanates.
Amine of the present invention, for can be converted into gas phase and Undec primary amine, has general formula R (NH
2)
n, wherein R has the alicyclic or aromatic alkyl of the aliphatic being no more than 15 carbon atoms, preferably 3 ~ 15 carbon atoms, more preferably aliphatic, the alicyclic or aromatic hydrocarbyl of 4 ~ 13 carbon atoms, and n is the integer in 1 ~ 10.As: the example of suitable aliphatic monoamine has methylamine, ethamine, propylamine, cyclohexylamine etc.; The example of suitable aliphatic diamine has amino-3,3,5-trimethyl-5-aminomethyl cyclohexane (IPDA) of Putriscine, 1,6-hexamethylene diamine, Isosorbide-5-Nitrae-DACH, 1-, 4,4 '-diamino-dicyclohexyl methane (H
12mDA) etc.; The example of suitable aliphatic triamine has 1,8-diaminourea-4-(aminomethyl) octane, triaminononane etc.; The example of suitable aromatic series monoamine has aniline etc.; The example of suitable aromatic diamine has toluenediamine, diaminobenzene, naphthylenediamine etc.
Described amine can also be containing heteroatomic amine, as 2-oxolane amine.
Described amine is 1,6-hexamethylene diamine, IPDA, H preferably
12mDA and triaminononane.
In described (a), the temperature of heating is 120 ~ 600 DEG C, preferably 250 ~ 500 DEG C.
Can also use in (a) of the present invention and utilize the steam of inert gas or atent solvent to dilute amine steam, described inert gas is selected from nitrogen and/or argon gas, and described atent solvent is selected from the one or two or more in toluene, dimethylbenzene, o-dichlorohenzene and decahydronaphthalenes.
In the steam of (a) of the present invention inert gas or atent solvent and amine, contained amino mol ratio is 0.1 ~ 2:1, preferably 0.2 ~ 1:1.
In (b) of the present invention, the mol ratio of the amino of phosgene and amine steam is 1.25 ~ 4.5:1, preferably 1.5 ~ 3.5:1.
5 ~ 100:1 of the mol ratio of the phosgene inlet amount of (c) of the present invention auxiliary charging aperture N3 and the amino of (b) amine steam, preferably 10 ~ 50:1.
In (b) of the present invention, the flow velocity of phosgene is 1 ~ 60m/s, preferably 3 ~ 40m/s, and the flow velocity of amine steam is 12 ~ 80m/s, preferably 20 ~ 60m/s; Described (c) second the phosgene flow velocity of charging aperture N3 be 6 ~ 120m/s, preferably 15 ~ 100m/s.
The absolute pressure of interior feed pipe N1 of the present invention and outer feed pipe N2 is 200 ~ 3000mbar, and the outlet N4 absolute pressure of the housing 1 of auxiliary charging aperture N3 and reactor is preferably 150 ~ 1500mbar.
According to the present invention, the phosgene entered by auxiliary charging aperture can form the eddy current of rotation, strengthens the mixing of phosgene and amine, reduces the generation of accessory substance, reduces sedimental generation; Further, the phosgene entered from secondary charging aperture provides kinetic energy, the dynamic self-cleaning of realization response device for scraping blade rotates, and removes the deposit be attached in reactor, extends the cycle of operation.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of the preferred dynamically profilograph of self-cleaning reactor of the present invention, 1 is wherein housing, 2 is scraping blade, 3 is conversion zone, 4 is annular space, 5 is back shaft, 6 is sidewall, N1 is interior feed pipe, N2 is outer feed pipe, N3 is auxiliary charging aperture, N4 is outlet.
Fig. 2 for along A-A line in Fig. 1 the cross-sectional view (upward view) that cuts, the radius that the distance that L is the axis of auxiliary charging aperture N3 and reactor axis, r are conversion zone 3.
Fig. 3 for along A-A line in Fig. 1 the cross-sectional view (top view) that cuts, 7 is the imaginary circles, 8 at blender outer rim place is the imaginary circles at blender axis place.
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 scraper, and L4 is the length of oblique scraper;
Fig. 5-2 is the cross-sectional view of radial scraper along B-B line, and wherein L1 is quadrangle base, and W is the thickness of scraper, and α is the angle of quadrangle;
Fig. 5-3 is the cross-sectional view of axial scraper along C-C line, and wherein L3 is quadrangle base, and W is the thickness of scraper, and β is the angle of quadrangle.
Detailed description of the invention
Following examples will further illustrate dynamic self-cleaning reactor provided by the present invention and adopt this reactor to prepare the method for isocyanates, but the present invention is not therefore subject to any restriction.
Embodiment 1:
Reactor:
Adopt dynamic self-cleaning reactor as shown in Figure 1.It comprises: housing 1, auxiliary charging aperture N3, scraping blade 2, back shaft 5, blender, conversion zone 3, outlet N4, described blender is by interior feed pipe N1 and be positioned at the peripheral and outer feed pipe N2 coaxial with feed pipe N1 of feed pipe N1 and form, annular space 4 is formed between interior feed pipe N1 and outer feed pipe N2, described scraping blade 2 is with back shaft 5 for axle rotates feed pipe N1 outlet, the outlet of outer feed pipe N2 and the sidewall 6 of conversion zone 3 in cleaning, and auxiliary charging aperture N3 is positioned on the sidewall 6 of conversion zone 3.
Described reactor is provided with 4 groups of blenders; Often organize the axis of blender and the axis being parallel of reactor, the axis often organizing blender is evenly distributed in the imaginary circles 8 that radius is 250mm, and the radius r of conversion zone 3 is 500mm.The internal diameter of interior feed pipe N1 is 80mm, external diameter 90mm; The internal diameter of outer feed pipe N2 is 170mm, external diameter 180mm.
The outlet of interior feed pipe N1 and outer feed pipe N2 is positioned in same level, between the region that the horizontal plane at the horizontal plane of described horizontal plane at auxiliary charging aperture N3 peak place and minimum point place limits.
The number of described auxiliary charging aperture N3 is 4, and it is evenly distributed on the sidewall 6 of conversion zone 3, and the axis of each auxiliary charging aperture N3 is located in the same horizontal plane, and each axis of auxiliary charging aperture N3 and the distance L of reactor axis are 300mm.
Described scraping blade 2 has 3 scrapers; Described scraper comprises radial scraper, oblique scraper and axial scraper, and the cross section of radial scraper, oblique scraper, axial scraper is right-angled trapezium, and angle α and β of described right-angled trapezium is 45 °; The length of L1 is 80mm, and the thickness W of scraper is the length of 20mm, L3 is 80mm; The length L2 of radial scraper is 340mm; The height H of axial scraper is 500mm, and oblique scraper length L4 is 180mm.The internal diameter of auxiliary charging aperture N3 is 160mm, and the axis of the outlet of interior feed pipe N1, the outlet of outer feed pipe N2 and auxiliary charging aperture N3 is positioned in same level.
Prepare isocyanates:
4,4 '-dicyclohexyl methyl hydride diamines (H
12mDA), phosgene and nitrogen are preheated to 360 ° respectively.Mol ratio is the N of 1:1
2with H
12the gaseous mixture of MDA enters reactor, H by interior feed pipe N1
12the flow of MDA is 400kg/h, and flow velocity is 16m/s.The phosgene entered by outer feed pipe N2 and H
12the mol ratio of the amino of MDA is 4:1, and flow velocity is 30m/s, and the absolute pressure of interior feed pipe N1 and outer feed pipe N2 is 2400mbar, the phosgene entered by auxiliary charging aperture N3 and H
12the amino mol ratio of MDA is 10:1, and flow velocity is 20m/s, the pressure 750mbar of auxiliary charging aperture N3 and outlet N4.
The material obtained after conversion zone 3 has reacted absorbs trapping through solvent chlorobenzene and obtains H
12the isocyanate solution of MDI, by gas chromatographic analysis (area normalization), H
12mDI yield is 98.0%.Through macrocyclic operation, after operation 4 months, parking maintenance, mixer outlet and conversion zone sidewall are showed no obvious coking material.
Embodiment 2:
The dynamic self-cleaning reactor adopted has 2 groups of blenders, and the axis often organizing blender is evenly distributed in the imaginary circles 8 that radius is 200mm, and the number of auxiliary charging aperture N3 is 3, and each axis of auxiliary charging aperture N3 and the distance L of reactor axis are 200mm.Scraping blade 2 has 6 scrapers, and scraper is directly connected with axial scraper by radial scraper, and without oblique scraper, the cross section of radial scraper and axial scraper is right-angled trapezium, and the angle α of described right-angled trapezium is 35 °, and angle β is 40 °; The length of L1 is 80mm, and the thickness W of scraper is the length of 20mm, L3 is 80mm; The length L2 of radial scraper is 500mm; The height H of axial scraper is 450mm.All the other structures are with the reactor of embodiment 1.
Adopt the reaction condition of preparing isocyanates identical with embodiment 1.Shown by gas chromatographic analysis, H
12the yield 97.9% of MDI, through long-term operation, in operation after 3.5 months, parking maintenance, mixer outlet and conversion zone sidewall are showed no obvious coking material.
Embodiment 3:
The dynamic self-cleaning reactor adopted has 6 groups of blenders, and the axis of blender is evenly distributed in the imaginary circles 8 that radius is 300mm, and the number of auxiliary charging aperture N3 is 6, and each axis of auxiliary charging aperture N3 and the distance L of reactor axis are 250mm.Scraping blade has 8 scrapers, and the length of L1 is 75mm, and the thickness W of scraper is the length of 25mm, L3 is 60mm; The length L2 of radial scraper is 400mm; The height H of axial scraper is 450mm, and oblique scraper length L4 is 150mm.All the other structures are with the reactor of embodiment 1.
Adopt the reaction condition of preparing isocyanates identical with embodiment 1.Shown by gas chromatographic analysis, H
12the yield of MDI is 97.9%, and through long-term operation, in operation after 3.6 months, parking maintenance, mixer outlet and conversion zone sidewall are showed no obvious coking material.
Embodiment 4:
Angle α, β of cross section of the scraper of the scraping blade of the dynamic self-cleaning reactor adopted is 60 °, and the length of the length of L1 to be 60mm, W be 15mm, L2 is 400mm, H is 600mm, and all the other structures are with the reactor of embodiment 1.
Adopt the reaction condition of preparing isocyanates identical with embodiment 1.Shown by gas chromatographic analysis, H
12the yield of MDI is 98.0%, and through long-term operation, in operation after 4 months, parking maintenance, mixer outlet and conversion zone sidewall are showed no obvious coking material.
Embodiment 5:
Adopt the dynamic self-cleaning reactor identical with embodiment 1.
1,6-hexamethylene diamine (HDA), phosgene and nitrogen are preheated to 300 DEG C respectively.Mol ratio is the N of 1:2
2enter reactor with the gaseous mixture of HDA by interior feed pipe N1, the flow of HDA is 600kg/h, and flow velocity is 29m/s.The mol ratio of the phosgene entered by outer feed pipe N2 and the amino of HDA is 3:1, and flow velocity is 40m/s, and the phosgene entered by auxiliary charging aperture N3 and the amino mol ratio of HDA are 20:1, and flow velocity is 70m/s, and remaining reaction condition is with embodiment 1.Shown by gas chromatographic analysis, the yield of HDI is 99.0%.Through macrocyclic operation, after operation 5 months, parking maintenance, mixer outlet and conversion zone sidewall are showed no obvious coking material.
Embodiment 6
Adopt the dynamic self-cleaning reactor identical with embodiment 1.
IPD (IPDA), phosgene and nitrogen are preheated to 320 DEG C respectively, and remaining reaction condition is with embodiment 1.Shown by gas chromatographic analysis, the yield of IPDI is 98.8%.Through macrocyclic operation, after operation 4 months, parking maintenance, mixer outlet and conversion zone sidewall are showed no obvious coking material.
Comparative example 1:
The reactor adopted does not install scraping blade, and all the other structures are with the reactor of embodiment 1.
Adopt the reaction condition of preparing isocyanates identical with embodiment 1.Shown by gas chromatographic analysis, H
12mDI yield is 97.8%, runs after 1.5 months after parking maintenance, all visible significantly coking material of mixer outlet and conversion zone sidewall.
Comparative example 2:
The reactor adopted does not install scraping blade and auxiliary charging aperture, and all the other structures are with the reactor of embodiment 1.
The phosgene entered by outer feed pipe N2 and H
12the mol ratio of the amino of MDA is 4:1, adopts the reaction condition of preparing isocyanates identical with embodiment 1.Shown by gas chromatographic analysis, H
12mDI yield is H
12mDI97.4%, runs after 1.5 months after parking maintenance, all visible significantly coking material of mixer outlet and conversion zone sidewall.
Claims (10)
1. a dynamic self-cleaning reactor, it comprises: housing (1), auxiliary charging aperture (N3), scraping blade (2), back shaft (5), blender, conversion zone (3), described blender is by interior feed pipe (N1) and be positioned at the peripheral and outer feed pipe (N2) coaxial with feed pipe (N1) of feed pipe (N1) and form, annular space (4) is formed between interior feed pipe (N1) and outer feed pipe (N2), back shaft (5) one end is fixed on housing (1) inwall, the other end is connected with scraping blade (2) axle, described scraping blade (2) is positioned at housing (1) and exports for axle rotates cleaning feed pipe (N1) with back shaft (5), the outlet of outer feed pipe (N2) and the sidewall (6) of conversion zone (3), auxiliary charging aperture (N3) is positioned on the sidewall (6) of conversion zone (3).
2. reactor according to claim 1, it is characterized in that, the outlet of described interior feed pipe (N1) and outer feed pipe (N2) is positioned in same level, and described horizontal plane is positioned between the region of the horizontal plane at auxiliary charging aperture (N3) peak place and the horizontal plane restriction at minimum point place.
3. reactor according to claim 1, is characterized in that, described reactor is provided with 2 ~ 12 groups of blenders, preferably 3 ~ 8 groups, more preferably 4 ~ 6 groups; Often organize the axis of blender and the axis being parallel of reactor, the distance often organizing the axis of blender and the axis of reactor is respectively 0.2r ~ 0.8r, preferred 0.4r ~ 0.7r; Preferably often organize the axis of blender equal with the distance of the axis of reactor; More preferably blender axis is evenly distributed in the imaginary circles (8) coaxial with reactor, and the radius of imaginary circles (8) is 0.2r ~ 0.8r, preferred 0.4r ~ 0.7r; R is the radius of conversion zone (3).
4. reactor according to claim 1, is characterized in that, the number of described auxiliary charging aperture (N3) is 2 ~ 12, preferably 3 ~ 8, more preferably 4 ~ 6; It is evenly distributed on the sidewall (6) of conversion zone (3), the distance (L) of its axis and reactor axis is 0.1r ~ 0.9r, preferred 0.2r ~ 0.7r, more preferably 0.3r ~ 0.5r, r are the radius of conversion zone (3).
5. reactor according to claim 1, is characterized in that, described scraping blade (2) has 2 ~ 12 scrapers, preferably 3 ~ 8, more preferably 4 ~ 6; Each scraper comprises radial scraper and axial scraper, and the length (L2) of radial scraper is 0.3r ~ 1.0r, preferred 0.4r ~ 0.9r; The height (H) of axial scraper is 0.2r ~ 1.5r, preferred 0.4r ~ 1.0r; R is the radius of conversion zone (3); The cross section of described radial scraper is quadrangle, the angle (α) of described quadrangle is 20 ° ~ 90 °, preferably 30 ° ~ 70 °, more preferably 40 ° ~ 50 °, the ratio of the length on quadrangle base (L1) and the thickness (W) of scraper is 2 ~ 8:1, preferably 3 ~ 5:1; The cross section of described axial scraper is quadrangle, the angle (β) of described quadrangle is 20 ° ~ 90 °, preferably 30 ° ~ 70 °, more preferably 40 ° ~ 50 °, the ratio of the length on quadrangle base (L3) and the thickness (W) of scraper is 2 ~ 8:1, preferably 3 ~ 5:1.
6. adopt the reactor according to any one of claim 1-5 to prepare a method for isocyanates, the method comprises:
A amine photoreactive gas heats by () respectively, make it gasification;
B () one phosgene enters blender by interior feed pipe (N1), amine steam enters blender by outer feed pipe (N2); Or one phosgene enters blender by outer feed pipe (N2), amine steam enters blender by interior feed pipe (N1);
C () second strand of phosgene enters reactor by auxiliary charging aperture (N3);
D () phosgene and amine steam react at conversion zone (3), obtain isocyanates.
7. method according to claim 6, is characterized in that, the general formula R (NH of described amine
2)
n, wherein R has the aliphatic or alicyclic or aromatic hydrocarbyl that are no more than 15 carbon atoms, and n is the integer in 1 ~ 10; It is preferably from methylamine, ethamine, propylamine, cyclohexylamine, 1,4-butanediamine, 1,6-hexamethylene diamine, 1,4-DACH, 1-amino-3,3,5-trimethyl-5-aminomethyl cyclohexane, 4, the one or two or more in 4 '-diamino-dicyclohexyl methane diamines, 1,8-diaminourea-4-(aminomethyl) octane, triaminononane, aniline, toluenediamine, diaminobenzene and naphthylenediamine.
8. method according to claim 6, is characterized in that, in described (b), the mol ratio of the amino of phosgene and amine steam is 1.25 ~ 4.5:1, preferably 1.5 ~ 3.5:1; The phosgene inlet amount of described (c) auxiliary charging aperture (N3) and 5 ~ 100:1 of the mol ratio of the amino of amine steam in (b), preferably 10 ~ 50:1.
9. the method according to claim 6 or 8, is characterized in that, in described (b), the flow velocity of phosgene is 1 ~ 60m/s, preferably 3 ~ 40m/s, and the flow velocity of amine steam is 12 ~ 80m/s, preferably 20 ~ 60m/s; The phosgene flow velocity of described (c) auxiliary charging aperture (N3) is 6 ~ 120m/s, preferably 15 ~ 100m/s.
10. method according to claim 6, it is characterized in that, the absolute pressure of described interior feed pipe (N1) and outer feed pipe (N2) is 200 ~ 3000mbar, and the absolute pressure of auxiliary charging aperture (N3) is 150 ~ 1500mbar.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510428651.5A CN105032307B (en) | 2015-07-21 | 2015-07-21 | A kind of dynamic self-cleaning reactor and its method for preparing isocyanates |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510428651.5A CN105032307B (en) | 2015-07-21 | 2015-07-21 | A kind of dynamic self-cleaning reactor and its method for preparing isocyanates |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105032307A true CN105032307A (en) | 2015-11-11 |
| CN105032307B CN105032307B (en) | 2017-07-21 |
Family
ID=54439626
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510428651.5A Active CN105032307B (en) | 2015-07-21 | 2015-07-21 | A kind of dynamic self-cleaning reactor and its method for preparing isocyanates |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105032307B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112574068A (en) * | 2020-11-17 | 2021-03-30 | 万华化学（宁波）有限公司 | Preparation method of carbodiimide modified isocyanate with low color number and high stability |
| US11542228B2 (en) | 2021-01-05 | 2023-01-03 | Anhui Dongzhi Guangxin Agrochemical Co., Ltd | Method and device for preparing diisocyanate |
| CN117101588A (en) * | 2023-10-23 | 2023-11-24 | 万华化学集团股份有限公司 | Reactor for producing isocyanate and method for producing isocyanate by using same |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4847408A (en) * | 1987-04-30 | 1989-07-11 | Bayer Aktiengesellschaft | Process for the preparation of (cyclo)aliphatic diisocyanates |
| CN1094395A (en) * | 1992-10-16 | 1994-11-02 | 罗纳·布朗克化学公司 | The method that in gas phase, prepares aromatic isocyanate type composition |
| CN1530361A (en) * | 2003-02-20 | 2004-09-22 | Preparation of (poly) isocyanic ester in gas phase | |
| CN1651406A (en) * | 2003-12-18 | 2005-08-10 | 拜尔材料科学股份公司 | Process for preparing diisocyanates |
| CN101372463A (en) * | 2007-08-21 | 2009-02-25 | 宁波万华聚氨酯有限公司 | Draft tube type jet flow reactor and method for preparing isocyanate using the same |
| CN101879425A (en) * | 2010-07-16 | 2010-11-10 | 烟台万华聚氨酯股份有限公司 | Reactor and method for preparing isocyanate |
| CN202590677U (en) * | 2012-08-02 | 2012-12-12 | 阿克苏诺贝尔防护涂料(苏州)有限公司 | Scratch board stirring device |
| CN202962441U (en) * | 2012-09-07 | 2013-06-05 | 中国石油化工集团公司 | Reactor for producing acetylene by hydrocarbon |
-
2015
- 2015-07-21 CN CN201510428651.5A patent/CN105032307B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4847408A (en) * | 1987-04-30 | 1989-07-11 | Bayer Aktiengesellschaft | Process for the preparation of (cyclo)aliphatic diisocyanates |
| CN1094395A (en) * | 1992-10-16 | 1994-11-02 | 罗纳·布朗克化学公司 | The method that in gas phase, prepares aromatic isocyanate type composition |
| CN1530361A (en) * | 2003-02-20 | 2004-09-22 | Preparation of (poly) isocyanic ester in gas phase | |
| CN1651406A (en) * | 2003-12-18 | 2005-08-10 | 拜尔材料科学股份公司 | Process for preparing diisocyanates |
| CN101372463A (en) * | 2007-08-21 | 2009-02-25 | 宁波万华聚氨酯有限公司 | Draft tube type jet flow reactor and method for preparing isocyanate using the same |
| CN101879425A (en) * | 2010-07-16 | 2010-11-10 | 烟台万华聚氨酯股份有限公司 | Reactor and method for preparing isocyanate |
| CN202590677U (en) * | 2012-08-02 | 2012-12-12 | 阿克苏诺贝尔防护涂料(苏州)有限公司 | Scratch board stirring device |
| CN202962441U (en) * | 2012-09-07 | 2013-06-05 | 中国石油化工集团公司 | Reactor for producing acetylene by hydrocarbon |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112574068A (en) * | 2020-11-17 | 2021-03-30 | 万华化学（宁波）有限公司 | Preparation method of carbodiimide modified isocyanate with low color number and high stability |
| US11542228B2 (en) | 2021-01-05 | 2023-01-03 | Anhui Dongzhi Guangxin Agrochemical Co., Ltd | Method and device for preparing diisocyanate |
| CN117101588A (en) * | 2023-10-23 | 2023-11-24 | 万华化学集团股份有限公司 | Reactor for producing isocyanate and method for producing isocyanate by using same |
| CN117101588B (en) * | 2023-10-23 | 2024-02-02 | 万华化学集团股份有限公司 | Reactor for producing isocyanate and method for producing isocyanate by using same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105032307B (en) | 2017-07-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1197643C (en) | Method for reducing byproducts in the mixture of educt trreams | |
| CN101104595B (en) | Process for preparing isocyanate | |
| CN101796022B (en) | Prepare the method for isocyanic ester | |
| CN101372463B (en) | Draft tube type jet flow reactor and method for preparing isocyanate using the same | |
| KR102159044B1 (en) | Reactor and alkylation process using the reactor | |
| CN101279923B (en) | Preparation of polymethylene polyphenyl polyamine | |
| CN105032307B (en) | A kind of dynamic self-cleaning reactor and its method for preparing isocyanates | |
| KR20130099200A (en) | Fast mixing reactor and use thereof | |
| CN101879425A (en) | Reactor and method for preparing isocyanate | |
| WO2011120374A1 (en) | Heterogeneous catalytic tower type collision flow reactor | |
| CN1194962C (en) | Method and apparatus for continuously preparing tolylene diisocyanate | |
| CN102532504A (en) | Synthetic reaction kettle suitable for preparation of carbon dioxide-epoxypropane copolymer | |
| CN104402766B (en) | Single reflection hypergravity device and process for continuous preparation of toluene diisocyanate | |
| CN201791525U (en) | High shear reactor with feeding-material distribution device | |
| CN206139165U (en) | A high shear reactor for quick competing reaction | |
| CN101811019B (en) | Dynamic hole jet reactor and method for preparing isocyanate by adopting dynamic hole jet reactor | |
| CN104874335A (en) | Reactor for preparing isocyanate and method of reactor for preparing isocyanate | |
| CN104496852A (en) | III-shaped hypergravity device and technology for continuous preparation of toluene diisocyanate | |
| CN104496851B (en) | A kind of device and process for continuously preparing toluene diisocyanate | |
| CN206139164U (en) | A high shear reactor for quick competing reaction | |
| CN101670263B (en) | Reactor for preparing toluene diisocynate by gaseous phase method and operation method | |
| CN204125406U (en) | A kind of river shape super-gravity device of continuous production tolylene diisocyanate | |
| WO2008122148A1 (en) | A process for preparation of polymethylene polyphenyl polyamine | |
| CN104549116B (en) | Segmented charging alkylation reactor and alkylation reaction technique | |
| KR101879020B1 (en) | A multi-phase reactor system with slinger liquid reflux distributor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20151111 Assignee: Wanhua chemical (Ningbo) Co.,Ltd. Assignor: Wanhua Chemical Group Co.,Ltd. Contract record no.: 2017990000326 Denomination of invention: Dynamic self-cleaning reactor and method for preparing isocyanate Granted publication date: 20170721 License type: Common License Record date: 20170818 |
|
| EE01 | Entry into force of recordation of patent licensing contract | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: The invention relates to a dynamic self-cleaning reactor and a method for preparing isocyanate Effective date of registration: 20211123 Granted publication date: 20170721 Pledgee: Bank of China Limited by Share Ltd. Yantai branch Pledgor: Wanhua Chemical Group Co.,Ltd. Registration number: Y2021980013026 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Date of cancellation: 20220622 Granted publication date: 20170721 Pledgee: Bank of China Limited by Share Ltd. Yantai branch Pledgor: Wanhua Chemical Group Co.,Ltd. Registration number: Y2021980013026 |
|
| PC01 | Cancellation of the registration of the contract for pledge of patent right |