CN101612547A - Tubular impingement flow reactor and operating system for producing toluene diisocyanate - Google Patents
Tubular impingement flow reactor and operating system for producing toluene diisocyanate Download PDFInfo
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- CN101612547A CN101612547A CN200910069917A CN200910069917A CN101612547A CN 101612547 A CN101612547 A CN 101612547A CN 200910069917 A CN200910069917 A CN 200910069917A CN 200910069917 A CN200910069917 A CN 200910069917A CN 101612547 A CN101612547 A CN 101612547A
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- tubulation
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- tube
- mixed zone
- jet orifice
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- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 title abstract 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 78
- 238000002156 mixing Methods 0.000 claims abstract description 32
- 239000007921 spray Substances 0.000 claims abstract description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 96
- 239000012948 isocyanate Substances 0.000 claims description 45
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 claims description 35
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 claims description 32
- 239000000243 solution Substances 0.000 claims description 23
- 238000004519 manufacturing process Methods 0.000 claims description 15
- 238000002347 injection Methods 0.000 claims description 10
- 239000007924 injection Substances 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 8
- 239000000463 material Substances 0.000 abstract description 13
- 238000000034 method Methods 0.000 description 20
- 239000000203 mixture Substances 0.000 description 17
- 239000012530 fluid Substances 0.000 description 14
- 150000002513 isocyanates Chemical class 0.000 description 13
- 239000002904 solvent Substances 0.000 description 11
- 239000000376 reactant Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 239000000126 substance Substances 0.000 description 8
- 239000007789 gas Substances 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 238000010348 incorporation Methods 0.000 description 5
- 238000006552 photochemical reaction Methods 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- -1 amido hydrochloride Chemical compound 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000002309 gasification Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- OADNRFNXACMWMJ-UHFFFAOYSA-N benzene;isocyanic acid Chemical class N=C=O.C1=CC=CC=C1 OADNRFNXACMWMJ-UHFFFAOYSA-N 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 206010020843 Hyperthermia Diseases 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000036031 hyperthermia Effects 0.000 description 1
- 230000003116 impacting effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 238000009527 percussion Methods 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- WOZVHXUHUFLZGK-UHFFFAOYSA-N terephthalic acid dimethyl ester Natural products COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明涉及一种生产甲苯二异氰酸酯的列管式撞击流反应器及操作系统。列管式撞击流反应器上封头与筒体相连，筒体上设置有筒体进料口(4)，列管穿过筒体并均布于筒体内的上下板管上，下管板射流口(10)均布于下管板上；列管下端与列管扩大段相连，列管下端和列管扩大段上设置有列管射流口(9)。一股物料通过下管板射流口(10)射流喷入，下管板射流口周围垂直于下管板平行排列有列管和列管扩大段，另一股流体则通过分布于列管和列管扩大段上的列管射流口(9)以一定角度射流喷入撞击混合区内，并与第一股物料撞击快速混合，反应物料进入第二反应区(12)进一步反应。撞击混合区的大小可通过混合区结构参数的调整灵活的改变，因此适应性强。
The invention relates to a shell and tube impinging flow reactor and an operating system for producing toluene diisocyanate. The upper head of the tube-and-tube impingement flow reactor is connected to the cylinder, and the cylinder is provided with a cylinder feed port (4). The tubes pass through the cylinder and are evenly distributed on the upper and lower plate tubes in the cylinder, and the lower tube plate The jet openings (10) are evenly distributed on the lower tube plate; the lower end of the tube array is connected with the tube expansion section, and the tube jet openings (9) are arranged on the lower end of the tube tube and the tube expansion section. One stream of material is sprayed in through the jet opening (10) of the lower tube plate. Around the jet opening of the lower tube plate, there are tubes and tube expansion sections arranged in parallel to the lower tube plate. The tube jet port (9) on the tube expansion section sprays into the impact mixing zone at a certain angle, and collides with the first material to mix quickly, and the reaction material enters the second reaction zone (12) for further reaction. The size of the impact mixing zone can be flexibly changed by adjusting the structural parameters of the mixing zone, so it has strong adaptability.
Description
Technical field
The present invention relates to a kind of Apparatus and method for of producing organic isocyanate, especially relate to a kind of shell and tube impact flow reactor and operating system of producing toluene di-isocyanate(TDI).
Background technology
Organic isocyanate is a kind of important organic intermediate, is widely used in the industry such as polyurethane, coating, dyestuff.Isocyanates mainly contains: toluene di-isocyanate(TDI) (TDI), methyl diphenylene diisocyanate (MDI), poly-methyl polyphenyl isocyanates (PAPI) and benzene isocyanates (PI) etc.The production of organic isocyanate can be divided into phosgenation and two kinds of routes of non-phosgene, and wherein industrial production promptly prepares isocyanates with corresponding amine and phosgene reaction based on light phosgenation.
The method that light phosgenation is produced isocyanates can be divided into two kinds of gas phase phosgenation method and liquid phase light phosgenations.Disclosed at present gas phase phosgenation method patent is a lot, as WO2007014936, and CN1458150A, CN101372463A, CN1425647A, US20050113601A1, US20080146834A1, US2003216597A1, CA2258194A etc.The characteristics of vapor phase method are that the time of staying of reactant in reactor is short, but reactant need be heated to the temperature more than the boiling point of reactant, different according to pressure and the amine that is adopted, 200 ℃～600 ℃ of reaction temperature selections.
The liquid phase light phosgenation is the method that present commercial Application prepares TDI the most widely, and the key reaction that wherein comprises has:
(1) cold light gasification
(2) hot phosgenation
(3) side reaction have between the product TDI polymerization and with the reaction of toluenediamine, reaction equation is
Cold light gasification reaction (1) has very fast reaction rate, and promptly can carry out under lower reaction temperature.And the reaction (3) of the further reaction (2) of intermediate product amido hydrochloride that generates and phosgene and two amido formyl chlorides decomposition generation isocyanates and hydrogen chloride is slower, thereby need carry out under higher reaction temperature.The accessory substance that side reaction (4) generates is a solid toughness material, and growing amount can cause the obstruction of reactor for a long time, and production can't be carried out.For this reason, the two-step methods that adopt are carried out the preparation of isocyanates more in the disclosed patent, as CN1194962C, CA813928A, CN101100447A, US20070299279A1, US2007012577A1 etc., the advantage of two-step method is and can in the first step amine be consumed fully as much as possible, reduces the chance of accessory substances such as isocyanates and amine reaction generation urea in second step.
In the preparation process of organic isocyanate, first step gasification reaction speed is big, and therefore mixing rate and the effect of two kinds of reaction raw materials in first step phosgenation reactor is most important, and it is directly connected to the selectivity of isocyanates and the stability of operation.The reactor of first step phosgenation reaction is the blender of two strands of reaction masses.Mainly comprise: dynamic mixer (as stirred tank reactor, stator-rotor reaction device etc.) and static mixer (as injection reactor, impact flow reactor etc.).The reactor that carries out the second step photochemical reaction mainly contains tower reactor, tubular reactor etc.
Chinese patent CN1304927A discloses the method and the reactor of a kind of a kind of toluene di-isocyanate(TDI) of preparation (TDI): adopt injection reactor to finish the rapid mixing and the first step photochemical reaction of material, wherein liquid phosgene of first strand of material or the toluenediamine solution that is dissolved in solvent enter blender after rotary atomizer is atomized into drop, and another strand material be dissolved in the toluenediamine solution of solvent or phosgene by the annular space of reactor spray enter and with first burst of material high-speed mixing, this injection reactor has special striker structure, this patent thinks that there is not blocking problem in the employing nozzle, but this structure is comparatively complicated.The reaction mass that comes out to finish first step photochemical reaction from injection reactor enters and carries out the second step photochemical reaction the tower reactor and reclaim excessive phosgene.
Chinese patent CN1830540A discloses a kind of liquid film colliding type jet reactor, this injection reactor comprises two reaction mixed zones, wherein the fluid more than two strands or two strands is to clash into and rapid mixing and reaction behind the liquid film that forms of several millimeters slit by thickness in first mixed zone, and unmixed material completely carries out further mixing and reaction in second mixed zone in first mixed zone.This patent is not described the effect that this reactor is used for isocyanates production.
World patent WO2009002900-A3 discloses a kind of method for preparing toluene di-isocyanate(TDI) (TDI), this method adopt High shear device with the gaseous phosgene high degree of dispersion in liquid toluenediamine, formed phosgene bubble diameter can reach micron or submicron order, dispersion liquid further reacts subsequently and prepares toluene di-isocyanate(TDI) (TDI), and disclosed high-shear device is a kind of one or more levels rotor-stator system.Adopt this method,, may be difficult to avoid the generation of accessory substance such as urea etc. owing to inevitably exist localized hyperthermia in the mixed process.
U.S. Pat 3226410, US5117048 and Chinese patent application CN101209405A disclose hole jet type injecting reactor respectively, the principal character of reactor is to open some holes on the inner sleeve circumference, polyamines solution enters in the inner sleeve by the hole, and mixes with the phosgene that flows by inner sleeve.Difference is the circular inner sleeve that US3226410 adopts, and CN101209405A has then adopted the inner sleeve of rectangle or approximate rectangular structure, and both compare the latter and have littler enlarge-effect.The inner sleeve that US5117048 adopts is similar to Venturi tube, the effect when mixing to improve.Above-mentioned mixed method can not reach good mixed effect, and accessory substance may take place stop up the duct.
In sum, existing method is produced the subject matter that exists in the process of toluene di-isocyanate(TDI), and to be that accessory substance generates inevitable, reactor have potential obstruction may and enlarge-effect big etc.
Summary of the invention
Have been found that at present the mixing of carrying out first step phosgenation reaction is the most remarkable to the influential effect of phosgenation in liquid phase method production toluene di-isocyanate(TDI) (TDI) process.Design irrational blender, not only can reduce the yield and the quality of product toluene di-isocyanate(TDI) (TDI), simultaneously because the deposition of the high viscosity accessory substance that generates in the course of reaction also can cause the obstruction of reactor and pipeline, and then influence production is stable.
The purpose of this invention is to provide a kind of liquid phase method and produce the mixing reactor and the operating system of toluene di-isocyanate(TDI) (TDI), in this blender, two fluid streams can realize that quick microcosmic mixes, thereby effectively suppress the formation of side reaction and accessory substance, and may dropping to of reactor plugs is minimum.
Technical scheme of the present invention is as follows:
The shell and tube impact flow reactor of production toluene di-isocyanate(TDI) of the present invention as shown in Figure 1, comprise with lower member: upper cover 1, cylindrical shell 2, upper cover charging aperture 3, cylindrical shell charging aperture 4, tubulation 5, tubulation expanding reach 6, upper perforated plate 7, lower perforated plate 8, tubulation jet orifice 9, lower perforated plate jet orifice 10, jet mixed zone 11, second reaction zone 12; Wherein: upper cover is provided with upper cover charging aperture 3, and cylindrical shell 2 is provided with cylindrical shell charging aperture 4, and tubulation passes cylindrical shell 2 and is distributed on cylindrical shell interior the upper plate pipe 7 and lower plate pipe 8, and lower perforated plate jet orifice 10 is distributed on the lower perforated plate 8; Tubulation 5 lower ends link to each other with tubulation expanding reach 6, and tubulation 5 lower ends and tubulation expanding reach 6 are provided with tubulation jet orifice 9.
The operating system of the shell and tube impact flow reactor of production toluene di-isocyanate(TDI) of the present invention, be two strands of reaction masses, one material is wherein sprayed into by jet orifice 10 jets on the lower perforated plate 8, show tubulation 5 and tubulation expanding reach 6 perpendicular to lower perforated plate 8 parallel around the jet orifice 10 on the lower perforated plate 8, another fluid streams is then by being distributed in the tubulation jet orifice 9 jet stream penetrating at a certain angle mixed zone 11 on tubulation 5 and the tubulation expanding reach 6, and clash into first strand of material and realize that rapid mixing, mixed subsequently reaction mass enter second reaction zone 12 and further mix and reaction.
Described bump mixed zone 11 is surrounded by tubulation 5, tubulation expanding reach 6 and lower perforated plate 8, its number can be by set tubulation number flexible modulation, but at least 1, is preferably greater than to equal 6, have similar structure between the different jet mixed zone 11, and adjacent bump mixed zone 11 communicates with each other.Mixing reactor of the present invention is not limited to vertically downward to be arranged, and other all can as vertically upward or horizontal mode etc.
Described two strands of reaction masses are respectively toluenediamine solution photoreactive gas solution; Phosgene enters in the bump mixed zone with the form of liquid state or with the form of bubble; Toluenediamine solution photoreactive gas solution is 0.5-20m/s by the flow velocity of jet orifice.The mean residence time of fluid-mixing in the bump mixed zone is 0.015～0.6s.
Compared with prior art, percussion flow mixing reactor of the present invention has following advantage:
(1) reactor is made of some bumps mixed zone, and the reactor of different scales can be realized by the increase of mixed zone number amplifying, thereby enlarge-effect is little;
(2) two strands of reacting fluids carry out multiple spot in a plurality of bumps mixed zone, spray at many levels and clash into, and the both macro and micro good mixing effect can at utmost reduce the generation of accessory substance.
(3) the big I of bump mixed zone changes flexibly by the adjustment of mixed zone structural parameters, so adaptability is strong.
Description of drawings
Fig. 1: be impact flow reactor structural representation of the present invention;
Fig. 2 (a): be of the present invention by 3 tubulations and 1 impact flow reactor that the bump mixed zone is formed;
Fig. 2 (b): be of the present invention by 7 tubulations and 6 impact flow reactors that the bump mixed zone is formed;
Fig. 2 (c): be of the present invention by 19 tubulations and 24 impact flow reactors that the bump mixed zone is formed;
Fig. 3: be bump of the present invention mixed zone structural representation;
Fig. 4 (a): be the lower perforated plate jet orifice schematic diagram with borehole structure of the present invention;
Fig. 4 (b): be the lower perforated plate jet orifice schematic diagram with multilayer concentric annular space structure of the present invention.
The specific embodiment
Be detailed description of the present invention and embodiment below, by describing, can clearer understanding the present invention.
Impact flow reactor cylindrical shell charging aperture number of the present invention is more than or equal to 1, and preferred 2-4, during a plurality of charging aperture, charging aperture is arranged at the same axial location of cylindrical shell and evenly distributes along angle.Tubulation is arranged in parallel perpendicular to last lower perforated plate, and its diameter d is 5-50mm, preferred 10-35mm, and tubulation stringing mode has equilateral triangle type, square etc., but preferred equilateral triangle, tubulation centre-to-centre spacing L is 1.2-6d, preferred 1.5-4d; Tubulation expanding reach end diameter is 1.2-5d times, preferred 1.5-3d; Described tubulation jet orifice is distributed in tubulation and tubulation expanding reach.
Two strands of reacting fluids of production toluene di-isocyanate(TDI) (TDI) enter the bump mixed zone by lower perforated plate jet orifice and the injection of tubulation jet orifice respectively and carry out rapid mixing and reaction.The factor of decision mixed effect comprises the structural parameters and the operating parameter of mixed zone.The mixed zone structural parameters comprise the size of mixed zone, the spray angle of the size of jet orifice, layout, number and tubulation jet orifice etc.Second reaction zone communicates with the bump mixed zone among the present invention.Two strands of reacting fluids enter second reaction zone by the mixed zone outlet after the rapid mixing and further react in the bump mixed zone.Fluid is complete mixing flow in the mixed zone or near the complete mixing flow flow pattern at bump, and is laminar flow or near the laminar flow flow pattern in second reaction zone.
Fig. 3 clashes into the mixed zone structural representation for the present invention.The volume of bump mixed zone can be by the characteristic size L of mixed zone
2, L
3, h, h
1Calculate.The upper end characteristic size L of mixed zone
2Equal the poor of tubulation centre-to-centre spacing L and tubulation outside diameter d.Lower end, mixed zone characteristic size L
3With upper end size L
2Relevant, general L
3Be 0.1-0.9L
2, preferred L
3Be 0.2-0.8L
2
The present invention is clashed into mixed zone tubulation jet orifice and is arranged at tubulation and tubulation expanding reach, and circular is distributed on the tube wall, and the jet orifice diameter is 0.1-5mm, preferred 0.2-3mm, and the jet orifice number is 3-40 on the same circumference, preferred 6-30; Jet orifice also can be square, highly is 0.1-5mm, preferred 0.2-2mm.The tubulation jet orifice is set to be no less than 2 layers, and jet orifice center and tubulation center angle α are 0-90 °.The lower perforated plate jet orifice is arranged on the lower perforated plate, diameter d
1Be 0.1-5mm, preferred 0.2-3mm; Jet orifice is arranged preferred equilateral triangle, square, hole centre-to-centre spacing L
1Be 1.2d
1-4d
1, preferred 1.5d
1-3d
1, a mixed zone inner lower tube plate jet orifice number should not be less than 4, preferably is no less than 9; Jet orifice also can be the multilayer concentric annular space, annular space width b
1Be 0.1-5mm, preferred 0.2-2mm, annular space spacing b
2Be 0.5-5b
1, preferred 0.5-3b
1, the annular space number of plies is no less than 2 layers, preferably is no less than 4 layers, and the increase of the jet orifice number and the annular space number of plies helps improving mixed effect.
Adopt impact flow reactor of the present invention to produce toluene di-isocyanate(TDI) (TDI) system to be: a kind of reaction mass toluenediamine is diluted in the atent solvent, add after 10 injections of lower perforated plate jet orifice enter bump mixed zone 11 by cylinder charging aperture 4, another kind of reaction mass phosgene maybe will be diluted in phosgene in the atent solvent by upper cover charging aperture 3 through upper cover 1, tubulation 5, tubulation expanding reach 6 and 9 injections of tubulation jet orifice enter reaction mixed zone 11 and realize rapid mixing and reaction with the toluenediamine bump, and mixing back material enters into second reaction zone 12 through the mixed zone outlet and continues reaction; Toluenediamine solution photoreactive gas solution also can enter the bump mixed zone by tubulation jet 9 and lower perforated plate jet orifice 10 respectively.The reactant phosgene can be liquid form also can bubble form in jet enters the mixed zone.Leave second reaction zone reaction intermediate can by in the prior art disclosed method further carry out the second step photochemical reaction to generate toluene di-isocyanate(TDI) (TDI), as tubular type and tower reactor etc.
The solvent of dilution toluenediamine photoreactive gas is benzene, dimethylbenzene, chlorobenzene, o-dichlorohenzene among the present invention, diethyl phthalate, dimethyl terephthalate ester etc., these solvents can be used alone or as a mixture, wherein toluenediamine concentration is 5%-40% in the toluenediamine solution, and preferred 8%-30% is when adopting phosgene solution, the concentration of phosgene is 40%-95%, be preferably 50%-90%, in the charging phosgene than the excessive 10%-150% of toluenediamine, preferred excessive 25%-100%.
The following examples will further specify the effect of impact flow reactor of the present invention in toluene di-isocyanate(TDI) (TDI) is produced.
Embodiment 1:
Adopt impact flow reactor of the present invention to carry out the toluenediamine phosgenation reaction and produce toluene di-isocyanate(TDI) (TDI), structure of reactor as shown in Figure 1,2 of its middle cylinder body charging apertures; The arrangement mode of tubulation on following distribution grid is shown in Fig. 2 b: 7 of tubulations are equilateral triangle to be arranged, 6 of mixed zones, and the mixed zone height is 36mm, single mixed zone volume is about 23800mm
3Barrel diameter D is 150mm, and the tubulation diameter d is 32mm, and tubulation centre-to-centre spacing L is 52mm.Lower perforated plate jet orifice diameter d
1Be 0.5mm, equilateral triangle is arranged, centre-to-centre spacing L
1Be 2mm, single mixed zone inner lower tube plate jet orifice is 222.Tubulation expanding reach end diameter is 44.8mm, and the tubulation jet orifice is three layers of arrangement at tubulation and expanding reach, and diameter is 1.0mm, and the tubulation jet orifice adds up to 40 in the single mixed zone.The second reaction zone length is the twice of barrel diameter D.
Volume flow is 5.4m
3/ h, temperature is-5 ℃, phosgene content is that 67% phosgene and o-dichlorohenzene mixture are added by the upper cover charging aperture, is sprayed by the tubulation jet orifice to enter the bump mixed zone behind tubulation, tubulation expanding reach; Another burst volume flow is 8.3m
3/ h, temperature is 65 ℃, toluenediamine content is that 25% toluenediamine and o-dichlorohenzene mixture are added by the cylindrical shell charging aperture, enter the bump mixed zone through the injection of lower perforated plate jet orifice, and realize rapid mixing and reaction with the phosgene material impacting, wherein phosgene is 8m/s with respect to the flow velocity of excessive 50%, two fluid streams of toluenediamine by lower perforated plate jet orifice and tubulation jet orifice, the time of staying (incorporation time) of fluid-mixing in the bump mixed zone is 37.5ms, and reaction temperature is 95 ℃.
Above-mentioned reactant mixture enters tower reactor through second mixed zone, and first step phosgenation reaction product carries out the second step phosgenation reaction and generates toluene di-isocyanate(TDI) (TDI) product in the tower still, and reaction temperature is 162 ℃.The tower reactor condition is: the number of plates 25, operating pressure 1.65MPa.Can be by tower reactor with HCl, phosgene and toluene di-isocyanate(TDI) (TDI) and separated from solvent.
Mixture at the bottom of the analysis tower, toluene di-isocyanate(TDI) (TDI) molar yield is 93.5%.
Embodiment 2:
The structure and parameter that changes impact flow reactor among the embodiment 1 carries out toluene di-isocyanate(TDI) (TDI) production.
Structure of reactor as shown in Figure 1,2 of its middle cylinder body charging apertures; The arrangement of tubulation on following distribution grid is shown in Fig. 2 c: 19 of tubulations are equilateral triangle to be arranged, 24 of mixed zones, and the mixed zone height is 21.6mm, single mixed zone volume is 4938mm
3Tube sheet diameter D is 150mm, and the tubulation diameter d is 18mm, and tubulation centre-to-centre spacing L is 30mm.Lower perforated plate jet orifice diameter d
1Be 0.5mm, equilateral triangle is arranged, centre-to-centre spacing 2mm, and single mixed zone inner lower tube plate jet orifice is 76.Tubulation expanding reach end diameter is 25.2mm, and the tubulation jet orifice is three layers of arrangement at tubulation and expanding reach, and diameter is 1.0mm, and the tubulation jet orifice adds up to 24 in the single mixed zone.The second reaction zone length is the twice of barrel diameter D.
Volume flow is 10.8m
3/ h, temperature is-5 ℃, phosgene content is that 67% phosgene solution and volume flow are 12.5m
3/ h, temperature is 65 ℃, toluenediamine content is that 27.5% toluenediamine solution sprays from lower perforated plate jet orifice and tubulation jet orifice respectively and enters bump mixed zone rapid mixing and reaction (o-dichlorohenzene is an atent solvent), wherein phosgene is with respect to toluenediamine excessive 50%, two fluid streams are 8m/s by the flow velocity at jet orifice place, the time of staying (incorporation time) of fluid-mixing in impact flow reactor is 17.5ms, and reaction temperature is 99 ℃.
Above-mentioned reactant mixture enters through second mixed zone and carries out the second step phosgenation reaction in the tower reactor, and reaction temperature is 162 ℃, and other condition is with embodiment 1.
Mixture at the bottom of the analysis tower, toluene di-isocyanate(TDI) (TDI) molar yield is 98.1%.
Embodiment 3:
The structure and parameter that changes impact flow reactor among embodiment 1 and the embodiment 2 carries out toluene di-isocyanate(TDI) (TDI) production.
Structure of reactor as shown in Figure 1,2 of its middle cylinder body charging apertures; The arrangement of tubulation on following distribution grid is shown in Fig. 2 a: 3 of tubulations are equilateral triangle to be arranged, 1 of mixed zone, and the mixed zone height is 50.4mm, single mixed zone volume is 70129mm
3Tube sheet diameter D is 150mm, and the tubulation diameter d is 50mm, and tubulation centre-to-centre spacing L is 78mm.Lower perforated plate jet orifice diameter d
1Be 0.5mm, equilateral triangle is arranged, centre-to-centre spacing 2mm, and single mixed zone inner lower tube plate jet orifice is 76.Tubulation expanding reach end diameter is 28mm, and the tubulation jet orifice is three layers of arrangement at tubulation and expanding reach, and diameter is 1.0mm, and the tubulation jet orifice adds up to 56 in the single mixed zone.The second reaction zone length is the twice of barrel diameter D.
Volume flow is 1.3m
3/ h, temperature is-5 ℃, phosgene content is that 75% phosgene solution and volume flow are 3m
3/ h, temperature is 65 ℃, toluenediamine content is that 20% toluenediamine solution sprays from tubulation jet orifice and lower perforated plate jet orifice respectively and enters bump mixed zone rapid mixing and reaction (o-dichlorohenzene is an atent solvent), phosgene is with respect to toluenediamine excessive 50% in the reactant mixture, two fluid streams are 8m/s by the flow velocity at jet orifice place, the time of staying (incorporation time) of fluid-mixing in impact flow reactor is 59.6ms, and reaction temperature is 93 ℃.
Above-mentioned reactant mixture enters by second mixed zone and carries out the second step phosgenation reaction in the tower reactor, and reaction temperature is 162 ℃, and other condition is with embodiment 1 and embodiment 2.
Mixture at the bottom of the analysis tower, toluene di-isocyanate(TDI) (TDI) molar yield is 86.7%.
Embodiment 4:
The structure and parameter that keeps the impact flow reactor among the embodiment 1 changes the flow velocity of two strands of reacting fluids by the jet orifice place and carries out toluene di-isocyanate(TDI) (TDI) production.
Volume flow is 13.7m
3/ h, temperature is-5 ℃, phosgene content is that 67% phosgene solution and volume flow are 20.7m
3/ h, temperature is 65 ℃, toluenediamine content is 25% sprayed by tubulation jet orifice and lower perforated plate jet orifice respectively with toluenediamine solution and enter impact flow reactor and mix and react (o-dichlorohenzene is an atent solvent), wherein phosgene is with respect to toluenediamine excessive 50%, two fluid streams are 20m/s by the flow velocity of lower perforated plate jet orifice and tubulation jet orifice, the time of staying (incorporation time) of fluid-mixing in the bump mixed zone is 15ms, and reaction temperature is 98 ℃.
Above-mentioned reactant mixture enters by second mixed zone and carries out the second step phosgenation reaction in the tower reactor, and reaction temperature is 162 ℃, and other condition is with embodiment 1.
Mixture at the bottom of the analysis tower, the toluenediamine conversion ratio is 100%, toluene di-isocyanate(TDI) (TDI) molar yield is 95.7%.
Embodiment 5:
The structure and parameter that keeps impact flow reactor among embodiment 1 and the embodiment 4 changes the flow velocity of two strands of reaction mass fluids by the jet orifice place and carries out toluene di-isocyanate(TDI) (TDI) production.
Volume flow is 0.33m
3/ h, temperature is-5 ℃, phosgene content is that 67% phosgene solution and volume flow are 0.52m
3/ h, temperature is 65 ℃, toluenediamine content is 25% sprayed by tubulation jet orifice and lower perforated plate jet orifice respectively with toluenediamine solution and enter impact flow reactor and mix and react (o-dichlorohenzene is an atent solvent), wherein phosgene is with respect to toluenediamine excessive 50%, two fluid streams are 0.5m/s by the flow velocity of lower perforated plate jet orifice and tubulation jet orifice, the time of staying (incorporation time) of fluid-mixing in the bump mixed zone is 0.6s, and reaction temperature is 95 ℃.
Above-mentioned reactant mixture enters by second mixed zone and carries out the second step phosgenation reaction in the tower reactor, and reaction temperature is 162 ℃, and other condition is with embodiment 1 and embodiment 4.
Mixture at the bottom of the analysis tower, toluene di-isocyanate(TDI) (TDI) molar yield is 91.9%.
Claims (8)
1. shell and tube impact flow reactor of producing toluene di-isocyanate(TDI), comprise with lower member: upper cover (1), cylindrical shell (2), upper cover charging aperture (3), cylindrical shell charging aperture (4), tubulation (5), tubulation expanding reach (6), upper perforated plate (7), lower perforated plate (8), tubulation jet orifice (9), lower perforated plate jet orifice (10), jet mixed zone (11), second reaction zone (12); It is characterized in that upper cover is provided with upper cover charging aperture (3), cylindrical shell is provided with cylindrical shell charging aperture (4), and tubulation passes cylindrical shell and is distributed on the interior upper and lower plates pipe of cylindrical shell, and lower perforated plate jet orifice (10) is distributed on the lower perforated plate; The tubulation lower end links to each other with the tubulation expanding reach, and tubulation lower end and tubulation expanding reach are provided with tubulation jet orifice (9).
2. the shell and tube impact flow reactor of production toluene di-isocyanate(TDI) as claimed in claim 1 is characterized in that having level and smooth being connected between tubulation expanding reach and the tubulation.
3. the shell and tube impact flow reactor of production toluene di-isocyanate(TDI) as claimed in claim 1, it is characterized in that tubulation is parallel evenly distributed perpendicular to last lower perforated plate, tubulation is at least 3, and tubulation jet orifice (9) is distributed in lower perforated plate (8) following tubulation lower end and tubulation expanding reach.
4. the system as claimed in claim 1 is characterized in that clashing into mixed zone (11) and is surrounded by tubulation, tubulation expanding reach and lower perforated plate, and the mixed zone number is relevant with the tubulation number, and is at least 1, preferably is no less than 6; Different bumps communicate with each other between the mixed zone; Second reaction zone (12) communicates with the bump mixed zone.
5. the shell and tube impact flow reactor system of the production toluene di-isocyanate(TDI) of claim 1, after it is characterized in that one reaction mass enters cylindrical shell by cylindrical shell charging aperture (4), enter bump mixed zone (11) from lower perforated plate jet orifice (10) injection that is distributed on the lower perforated plate, and with enter tubulation by upper cover charging aperture (3) after, spray another strand reaction mass bump that enters the bump mixed zone at a certain angle from tubulation jet orifice (9) and realize rapid mixing and reaction, reaction mass enters second reaction zone (12) and further mixes and react subsequently.
6. reaction system as claimed in claim 5 is characterized in that one reaction mass is a toluenediamine solution, and another strand reaction mass is a phosgene solution; Phosgene enters in the bump mixed zone with the form of liquid state or with the form of bubble.
7. as claim 5 and 6 described reaction systems, it is characterized in that toluenediamine solution photoreactive gas solution is 0.5-20m/s by the flow velocity of jet orifice.
8. as claim 5 and 6 described reaction systems, it is characterized in that the mean residence time of fluid-mixing in the bump mixed zone is 0.015～0.6s.
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| CN2009100699176A CN101612547B (en) | 2009-07-28 | 2009-07-28 | Column tube type impinging stream reactor and operating system for producing toluene diisocynate |
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| CN2009100699176A CN101612547B (en) | 2009-07-28 | 2009-07-28 | Column tube type impinging stream reactor and operating system for producing toluene diisocynate |
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| CN101612547B CN101612547B (en) | 2012-05-30 |
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