CN101811019B - Dynamic hole jet reactor and method for preparing isocyanate by adopting dynamic hole jet reactor - Google Patents
Dynamic hole jet reactor and method for preparing isocyanate by adopting dynamic hole jet reactor Download PDFInfo
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- CN101811019B CN101811019B CN 201010149916 CN201010149916A CN101811019B CN 101811019 B CN101811019 B CN 101811019B CN 201010149916 CN201010149916 CN 201010149916 CN 201010149916 A CN201010149916 A CN 201010149916A CN 101811019 B CN101811019 B CN 101811019B
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Abstract
The invention relates to a dynamic hole jet reactor which comprises an internal feeding tube, an external feeding tube, a tubular mixed reaction nozzle, a gear box, a transmission shaft and a transmission side roller, wherein the transmission shaft, the internal feeding tube and the external feeding tube are coaxially arranged from inside to outside, the external feeding tube and the gear box are communicated and coaxially arranged from top to down, the gear box is internally provided with a gear and the tubular mixed reaction nozzle provided with a plurality of material entering pore paths, the gear and the tubular mixed reaction nozzle are mutually fit with each other, the internal feeding tube and the tubular mixed reaction nozzle are communicated and are coaxially arranged from top to down, and the tubular mixed reaction nozzle coaxially rotates under the driving of the transmission shaft and the transmission side roller so as to drive the gear of the gear box to rotate, and the transmission side roller can move up and down in the tubular mixed reaction nozzle. The invention also provides a method for preparing isocyanate by adopting the dynamic hole jet reactor. Since mechanical transmission is adopted to realize the automatic online cleaning of pore paths in a mixed reaction area, the invention can also increase productivity and improve the quality of products.
Description
Technical field
The present invention relates to a kind of dynamic aperture shooting flow type reactor, and adopt this reactor to make aliphatic or aromatic amine type organic and phosgene in liquid phase, carry out the method for prepared in reaction isocyanates.
Background technology
Since Wurtz in 1849 prepared alkyl isocyanate first, the mankind were just exploring the various methods and the various isocyanate products with special construction and performance of preparation that prepare isocyanates always.Facts have proved that light phosgenation remains the synthetic route that has industrial value most up to now, is main flow technology with the liquid phase light phosgenation especially wherein.
The liquid phase light phosgenation prepares isocyanates and has mild condition, controls stable characteristics.In this technical process, aliphatic or aromatic amine type organic at first photoreactive gas react generation carbamyl chloride and HCl in solvent, and HCl can rapid and other amidos reaction generation semicarbazide hydrochlorides.Excessive phosgene can continue to react the generation carbamyl chloride and emit HCl with semicarbazide hydrochloride in the system.This is the cold course of reaction in the cold and hot two step phosgenation technologies that generally adopt.
Carbamyl chloride in this course of reaction and semicarbazide hydrochloride all are the intermediate products of synthesizing isocyanate, and all are solid matters.The certainty that solid intermediate product exists has been brought numerous difficulties to DESIGN OF REACTOR; Reactor will provide enough mixing intensities on the one hand; Guarantee hybrid reaction efficiently; Want on the other hand can effectively prevent the solid intermediate product wall built-up or stop up the hybrid reaction passage, and when clogging takes place, can be convenient to cleaning.Fact proved that the hybrid reaction part has become one of main bottleneck that limits each kind isocyanate process units production capacity and energy consumption index.For many years, academia and business circles are all being done unremitting effort and exploration for this same problem.
US5931579, US4915509 have described a kind of rotor-stator type mixing reactor.In this blender, a fluid streams gets into hybrid chamber through the circular hole at header board center, and another fluid streams is through being a series of holes entering hybrid chambers that concentric circles is arranged on the header board.Be provided with in the hybrid chamber that the multilayer sieve plate is staggered respectively to be fixed on stator and the rotor, the stator that reaction under high pressure liquid can be rotated during through sieve plate layer by layer grinds, thereby reaches good rapid mixing and even dispersion effect.But this structure of reactor is complicated, in case stop up, it is very difficult that cleaning will become.
US5117048 has described a kind of reaction mixer of hole jet type, and one material plays the effect of enhancing mixed through getting in another strand material in a plurality of holes of tube chamber.However, the mixed effect of this reaction mixer is still very limited in industrial amplification process, and the frequent jams problem of reactor can not be solved in time in the manufacturing of isocyanates.
CN200910069917 has described a kind of shell and tube impact flow reactor of producing toluene di-isocyanate(TDI); One material sprays into through the jet orifice jet on the lower perforated plate; Another road fluid is the tubulation jet orifice jet stream penetrating at a certain angle mixed zone of tubulation and the tubulation expanding reach through vertical lower perforated plate then, clashes into first strand of material and realizes mixing.The mixing intensity of this reactor a little less than, reaction time is longer, and often has bulk solid to assemble, this reactor of easy blocking not only, even can stop up or the contaminate subsequent consersion unit.
CN200910306519 has described the tubular reactor that a kind of centre is provided with the central-injection device, on its center injector taper hydraulic barrier and nozzle is arranged, and the tubular reactor tube wall is provided with hydraulic barrier.The mixed effect of this reactor is very limited, and solid product is easy to wall built-up, the cleaning in case the obstruction reactor just need stop.
Can find out that through above comparison the process that the liquid phase light phosgenation prepares isocyanates is a gas-liquid-solid phase reaction process, mix and do not cause the solid intermediate product bulk deposition at once.The accumulation of solid intermediate product can destroy the hybrid reaction effect on the one hand, causes the vicious circle of more solid accumulations, thereby reduces the device load or influence product quality; More likely force device to shut down on the other hand because stop up feeding-passage fully.Thereby mixing rate that requires mixing reactor to possess to be exceedingly fast and good anti-clogging ability.Therefore, the reactor that needs research and development to have higher mixing efficiency and be convenient to artificial Hand scarf or can clear up automatically faces the frequency of stopping overhauling to reduce device, improves running efficiency.
Summary of the invention
The object of the present invention is to provide a kind of dynamic aperture jetting type mixing reactor and adopt this reactor to make aliphatic or aromatic amine type organic and phosgene in liquid phase, carry out the method for prepared in reaction isocyanates, to overcome the defective of above-mentioned pre-existing reactors.
Dynamic aperture jetting type mixing reactor provided by the present invention is following: this reactor comprises interior feed pipe, outer feed pipe, tubular type hybrid reaction shower nozzle, gear-box, power transmission shaft and transmission side roller; Wherein, Said power transmission shaft, interior feed pipe and the coaxial setting of outer feed pipe from-inner-to-outer; Said outer feed pipe is communicated with gear-box and coaxial from top to bottom setting, is provided with gear and the tubular type hybrid reaction shower nozzle with a plurality of materials entering duct in the said gear-box, and said gear and tubular type hybrid reaction shower nozzle get into the mutual match in duct through material; And, also be provided with in the gear-box and be used for spacing gear axis track with the match of gear-box circumferential inner wall; Feed pipe is communicated with and coaxial from top to bottom setting with tubular type hybrid reaction shower nozzle in said; Said tubular type hybrid reaction shower nozzle axially rotates under the driving of power transmission shaft and transmission side roller, and then the rotation of driven gear case internal gear; Said transmission side roller can pump in said tubular type hybrid reaction shower nozzle.
In dynamic aperture shooting flow type reactor provided by the present invention, formed reaction channel is called inboard reactant channel between said power transmission shaft and the interior feed pipe, and formed reaction channel is called outside reactant channel between interior feed pipe and the outer feed pipe.The cross-sectional area of said outside reactant channel and inboard reactant channel (perpendicular to this reactor axially) ratio be 0.5～24: 1, preferred 0.75～12: 1, more preferably 1～7.5: 1.Passage in the tubular type hybrid reaction shower nozzle is 0.5～4: 1 with the ratio of the sectional area of inboard reactant channel, preferred 0.75～3: 1.
In dynamic aperture shooting flow type reactor provided by the present invention, the quantity of said gear is generally 1～8 in the gear-box, and preferred 2,4,6 or 8, more preferably 2 or 4.The root diameter of gear (internal diameter of gear) is 0.25～4 times that tubular type hybrid reaction shower nozzle material gets into position, duct external diameter, preferred 0.5～2 times.
In dynamic aperture shooting flow type reactor provided by the present invention, said material gets into duct (or being called for short the material duct) and is arranged on the tube wall of pipe reaction shower nozzle, gets into the duct in the reaction shower nozzle to form material.On the tube wall of tubular type hybrid reaction shower nozzle, said material gets into the duct can be arranged in or be distributed with 1～20 circle from top to bottom, preferred 2～12 circles, more preferably 3～8 circles; Every circle has 8～40 ducts, and preferred every circle has 12～24 ducts; The perforate direction that every circle material gets into the duct all perpendicular to this reactor axially, and be preferably in evenly being provided with in the radial direction of pipe reaction shower nozzle tube wall.The shape of cross section that said material gets into the duct is right angle or fillet rectangle, right angle or fillet square, triangle, rhombus, trapezoidal, equilateral or non-equilateral polygon, circle or ellipse etc.When two circles or the material entering duct more than two circles were set, the material of two adjacent rings gets into the duct can adopt identical or different duct shape of cross section, duct size and alignment thereof.All the materials size sum (being the cross-sectional area sum) that gets into the duct should be guaranteed under the material pressure and the material pressure in the inboard material channel in the outside material channel that sets, and gets into the flow velocity of the reaction mass in tubular type hybrid reaction shower nozzles from outside material channel via gear-box and these ducts and satisfies this mass ratio that reacts needed two kinds of reactants or molar ratio requirement with the ratio that outlet (having certain cross-sectional area) from inboard material channel bottom gets into the flow velocity of the reaction mass in the tubular type hybrid reaction shower nozzle.For example, when phosgene and TDA reaction, pure phosgene is about 3.4-4.2 with the ratio of the quality of pure TDA: 1, or about 3.8: 1.Certainly; After the cross-sectional area of the outlet of size sum in whole materials duct of designing knowing (being the cross-sectional area sum) and inboard material channel bottom; Calculate according to common process, also can regulate quality or the molar ratio that gets into two kinds of reactants in the tubular type hybrid reaction shower nozzle through material pressure and the material pressure in the inboard material channel regulated in the material channel of the outside.This is that those skilled in the art realize easily, can regulate according to the actual needs of reaction.
In dynamic aperture shooting flow type reactor provided by the present invention, preferably, said tubular type hybrid reaction shower nozzle has different wall thickness up and down, but preferably its internal diameter is identical up and down; Further preferably, the wall thickness at material entering position of living in, duct is 1～5 times of tubular type hybrid reaction shower nozzle lower part outlet end thickness of pipe wall, preferred 1.5～3 times.That is to say, tube wall that a plurality of materials get into the position in duct is set is (thickness of pipe wall that for example reacts the shower nozzle end with other position of pipe reaction shower nozzle Comparatively speaking) equal thickness or thicker on the pipe reaction shower nozzle.
In dynamic aperture shooting flow type reactor provided by the present invention; On the inwall of said tubular type hybrid reaction shower nozzle, be provided with at least 1 with the isometric slideway of tubular type hybrid reaction shower nozzle; Preferably be provided with 2～3 with the isometric slideway of tubular type hybrid reaction shower nozzle; So that make said transmission side roller in tubular type hybrid reaction shower nozzle, realize pumping, preferably, realize pumping through mechanical automated manner through manual or automated manner.In the present invention, said transmission side roller is when keeping rotation, to pump, and reciprocating frequence is 1 time/day～1 time/minute, preferred 5～288 times/day, and more preferably 5～48 times/day.Further preferably, the reciprocating frequence of transmission side roller can be regulated step by step.Generally speaking, the velocity of rotation of transmission side roller is 1～120r/min, preferred 6～60r/min.That is to say that the velocity of rotation that the transmission side roller drives tubular type hybrid reaction shower nozzle is 1～120r/min, preferred 6～60r/min refers to both rotating speeds (promptly with speed) together here.
Generally process at dynamic aperture shooting flow type reactor provided by the present invention by steel, glass, pottery, alloy, carborundum or enamel steel.
Aliphatic, the method alicyclic or aromatic isocyanate of employing dynamic aperture jetting type mixing reactor preparation provided by the present invention shown in general formula (I) is following:
R(NCO)
n (I)
R(NH
2)
n (II)
Wherein R is aliphatic or aromatic hydrocarbyl, and has two carbon atom arrangement at least between any two adjacent (NCO) of general formula (I), and n >=2, preferred n=2-4, and more preferably 2 or 3, said method comprising the steps of:
(a). have one or more amine of general formula (II) or the organic solution of amine and get into the tubular type hybrid reaction shower nozzle of rotation through inboard reactant channel; Perhaps get into gear-box, get into the duct to inject the tubular type hybrid reaction shower nozzle of rotation perpendicular to the flow direction of interior side flow through material then through outside reactant channel;
(b). pure phosgene liquid or phosgene solution get in the gear-box through outside reactant channel, get into the duct to inject the tubular type hybrid reaction shower nozzle of rotation perpendicular to the flow direction of interior side flow through material then; Perhaps get into the tubular type hybrid reaction shower nozzle of rotation through inboard reactant channel;
(c). amine side photoreactive gas side material is mixing fast, is reacting in the both sides reactant channel collects in the tubular type hybrid reaction shower nozzle of rotation respectively under the raw material discharge pressure effect separately, and reactant liquor gets in the agitated reactor through tubular type hybrid reaction shower nozzle rapidly and proceeds and accomplish reaction.
In the method for the invention; Preferred R is aliphatic C2-C50 alkyl, alicyclic C2-C50 alkyl or aromatic series C6-C50 alkyl; More preferably R is aliphatic C4-C30 alkyl, alicyclic C4-C30 alkyl or aromatic series C6-C30 alkyl, and further preferred R is aliphatic C5-C18 alkyl, alicyclic C5-C18 alkyl or aromatic series C6-C20 alkyl.
In the method for the invention; It is 2 of 100/0-80/20 or 65/35 that said isocyanates with general formula (I) is generally isomer proportion; 4-/2,6 toluene di-isocyanate(TDI)s, diphenyl methane 4,4 '-vulcabond, dicyclohexyl methyl hydride 4; 4 '-vulcabond, IPDI, 1; Hexamethylene-diisocyanate, 1,4-hexamethylene vulcabond, 1,8-two isocyanato-s-4-(isocyanatomethyl) octane, three isocyano nonanes, 1; 4-fourth vulcabond, naphthalene diisocyanate, PPDI, XDI, cyclohexanedimethyleterephthalate vulcabond, trimethyl-1,6-hexamethylene diisocyanate, tetramethyl m-phenylenedimethylim-vulcabond, dimethyl diphenyl vulcabond, Methylcyclohexyl diisocyanate etc.Wherein preferred XDI, diphenyl methane 4,4 '-vulcabond, toluene di-isocyanate(TDI), more preferably toluene di-isocyanate(TDI).
In the method for the invention, said amine organic matter with general formula (II) generally be isomer proportion be 80/20 or 65/35 2,4-/2; 6 toluenediamine mixtures or pure 2,4-toluenediamine, diphenyl methane 4,4 '-diamines, dicyclohexyl methyl hydride 4; 4 '-diamines, IPD, 1; 6-hexamethylene diamine, 1,4-cyclohexanediamine, 1,8-diaminourea-4-(aminomethyl) octane, triaminononane, 1; 4-butanediamine, naphthylenediamine, p-phenylenediamine (PPD), phenylenedimethylidyne diamines, cyclohexanedimethyleterephthalate diamines, trimethyl-1,6-hexamethylene diamine, tetramethyl m-phenylenedimethylim-diamines, dimethyl diphenyl diamines or methylcyclohexyl diamines etc.; Preferred phenylenedimethylidyne diamines, diphenyl methane 4,4 '-diamines or toluenediamine; More preferably toluenediamine.
In the method for the invention; Step (a) and (b) comprise and utilize atent solvent that the amine photoreactive gas is diluted that said atent solvent generally is selected from: one or more in benzene, toluene, chlorobenzene, o-dichlorohenzene, paracide, a chlordiphenyl, dimethyl terephthalate ester or the diethyl phthalate.The concentration of polyamines organic solution is generally 12.5wt%～45wt%, preferred 15～25wt%; Phosgene organic solution concentration generally is not less than 60wt%, preferred 60-90wt%, more preferably 75-85wt%.
In the method for the invention, said inboard reactant channel inner fluid axial flow linear velocity is generally 0.8～14.6m/s, preferred 2.0～8.2m/s; The material of outside reactant channel gets into the duct through material, and vertically to inject the linear velocity of tubular type hybrid reaction shower nozzle be 1～9 times of interior side flow axial flow linear velocity, preferred 1.2～5.5 times.
In the method for the invention, the material pressure of said inboard reactant channel and outside reactant channel generally is 1～20bar, preferred 5～15bar; The gross area that gets into the duct when material is during greater than the cross-sectional area of inboard reactant channel; Need to promote outside reactant pressures separately, thereby guarantee that linear velocity that reactant gets into the duct through material is 1～9 times of inboard reactant channel internal reaction flow linear velocity; Tubular type hybrid reaction shower nozzle outlet pressure is generally 1～15bar, preferred 5～10bar.
For cold and hot two-step method liquid phase phosgenation reaction; First step reaction will inevitably produce carbamyl chloride and semicarbazide hydrochloride; The certainty that this solid intermediate product exists makes to spray in the reaction mixer very easily accumulates solid; The accumulation of solid intermediate product can destroy the hybrid reaction effect on the one hand, causes the vicious circle of more solid accumulations, thereby reduces the device load or influence product quality; More likely make device have to shut down on the other hand because stop up feeding-passage fully.Traditional method is to wash with high pressure solvent or phosgene earlier, faces after the discovery flushing is invalid and stops maintenance, promptly manually clears up reactor.This way greatly reduces the running efficiency of device, and has increased many potential safety hazards.
Reactor provided by the present invention is provided with gear, the tubular type hybrid reaction shower nozzle of continuous rotation and the transmission side roller that can pump; The washing capacity that is equipped with reaction mass itself can successfully be released conversion zone with solid intermediate product, thereby has guaranteed the long-term high load capacity steady running of the unobstructed and whole device in conversion zone duct.In addition; Reactor provided by the present invention has one and has the tubular type hybrid reaction shower nozzle that a plurality of materials get into the hole, and the material of two adjacent rings gets into the duct can adopt different sizes, shape and alignment thereof, thereby has better improved mixing of materials efficient; Phosgene and solvent are further reduced with respect to the proportioning of raw material amine; Improve the production capacity of original device, improved product quality, also reduced energy consumption simultaneously.
Description of drawings
Fig. 1 is the structural representation of the dynamic aperture shooting flow type reactor of a preferred embodiment of the invention.
Fig. 2 is a reactor shown in Figure 1 profile along the A-A direction.
Fig. 3 is the structural representation according to the dynamic aperture shooting flow type reactor of another kind of preferred implementation of the present invention.
Fig. 4 is a reactor shown in Figure 3 profile along A '-A ' direction.
The specific embodiment
Further specify dynamic aperture shooting flow type reactor provided by the present invention and adopt the method for this reactor made isocyanates below in conjunction with accompanying drawing, but therefore the present invention does not receive any restriction.
In this application, generally speaking, " axially " and " radially " refer to respectively reactor axially with radially, only if specially indicate in addition.In addition, when mentioning " amine " or " polyamines " or " amine (organic) solution " or " (organic) polyamines solution " in this application, " amine " or " polyamines " or " amine aqueous solution " or " polyamines solution " can exchange use.For the ease of explanation and understanding; The present invention illustrates the position relation between the reactor member with the reactor of vertical installation; For example level, vertical, laterally, go up inferiorly, but the present invention does not get rid of other possible mounting means, the mode that for example tilts to install a little.Therefore, should be with the restriction that is interpreted as reactor according to the invention and preparation method vertically is installed.
Dynamic aperture shooting flow type reactor provided by the present invention comprises inboard reactant channel 2, outside reactant channel 3 and the power transmission shaft 1 all coaxial with above-mentioned two wing passages with coaxial sleeve tube structure.With gear 7 is housed in the gear-box 6 that outside reactant channel 3 links to each other and has the tubular type hybrid reaction shower nozzle 5 that a plurality of materials get into duct 8.Material gets into duct 8 and all belongs to gear match district 9 with the gear-box circumferential inner wall, and is equipped with the spacing of gear axis track 10.Be installed in the outside motor of reactor through gearbox and power transmission shaft 1 and transmission side roller 4 drive tubular type hybrid reaction shower nozzles 5 axial rotation; Because getting into duct 8, material has tooth, the crack structure that cooperatively interacts simultaneously with gear 7, can driven gear 7 rotation and revolution in gear-box 6.
Generally speaking, the present invention does not have special demands for the rotating speed of gear 7 rotation in gear-box 6, and does not have special demands for its rotating speed along the revolution of reactor main shaft yet.The rotating speed of gear depends on the root diameter of gear and the ratio of hybrid reaction shower nozzle external diameter, and its rotating speed is unimportant, as long as change.
Structure of reactor illustrated in figures 1 and 2 is one of preferred embodiment of the present invention, and 2 gears are set in its gear-box, and tubular type hybrid reaction shower nozzle is provided with 1 circle material and gets into duct 8, and the shape of cross section in material entering duct is a rectangle.Therefore, the gear that is meshed with said material entering duct should have tooth, the crack structure suitable with rectangular duct.Gear is by the tubular type hybrid reaction shower nozzle driven rotary of (being that material duct or material get into the duct) with holes; The transmission side roller that is arranged at simultaneously between power transmission shaft and the tubular type hybrid reaction shower nozzle can be in tubular type hybrid reaction shower nozzle up and down reciprocatingly automatically, thereby realized the automatic on-line cleaning of reactor according to the invention.
Fig. 3 and structure of reactor shown in Figure 4 are another preferred embodiment of the present invention; As shown in the figure; 2 gears are set in the gear-box; Tubular type hybrid reaction shower nozzle is provided with 2 circle materials and gets into ducts 8, and up and down 2 circle materials to get into shape of cross section, size and the alignment thereof thereof in ducts all inequality.Therefore, with the material of this reactor get into gear that the duct is meshed should have with shown in material get into suitable tooth, the crack structure in duct.Gear is by perforated pipe formula hybrid reaction shower nozzle driven rotary, and the transmission side roller that is arranged at simultaneously between power transmission shaft and the tubular type hybrid reaction shower nozzle can be automatically up and down reciprocatingly, thereby realized the automatic on-line cleaning of mixing reactor.
Though the application does not provide the structure of reactor that is provided with plural gear in gear-box sketch map; Do not provide yet and the above material of two circles is set on the tubular type hybrid reaction shower nozzle gets into duct and material and get into the structure of reactor sketch map that the duct is triangle, rhombus, other shape such as trapezoidal; But those skilled in the art should be understood that the structural adjustment and the change that have the reactor of said structure characteristics and combine common practise to do all can realize the present invention.
Enumerate several kinds of isocyanates preparation methods' provided by the present invention embodiment below in conjunction with accompanying drawing, but therefore the present invention does not receive any restriction.
Embodiment one:
Adopt reactor as depicted in figs. 1 and 2, make to have general formula the organic solution of one or more amine or amine of (II) gets in the tubular type hybrid reaction shower nozzle 5 of rotation through inboard reactant channel 2; Simultaneously, pure phosgene liquid or phosgene solution get in the gear-box 6 through outside reactant channel 3, get into duct 8 to inject the tubular type hybrid reaction shower nozzle 5 of rotation perpendicular to the flow direction of interior side flow through material then; Amine side photoreactive gas side material is carrying out hybrid reaction fast respectively under the raw material discharge pressure effect separately in the both sides reactant channel collects in the tubular type hybrid reaction shower nozzle 5 of rotation; Reactant liquor passes through tubular type hybrid reaction shower nozzle 5 rapidly under the cooperation of raw material pushed at high pressure and gear 7 and transmission side roller 4, thereby proceeds and finally accomplish reaction in the agitated reactor in entering downstream.
Embodiment two:
Adopt reactor as depicted in figs. 1 and 2; Make to have general formula the organic solution of one or more amine or amine of (II) gets into gear-boxes 6 through outside reactant channel 3, and then get into duct 8 to inject the tubular type hybrid reaction shower nozzle 5 of rotation perpendicular to the flow direction of interior side flow through material; Simultaneously, pure phosgene liquid or phosgene solution get into the tubular type hybrid reaction shower nozzle 5 of rotation through inboard reactant channel 2; Amine side photoreactive gas side material is carrying out hybrid reaction fast respectively under the raw material discharge pressure effect separately in the both sides reactant channel collects in the tubular type hybrid reaction shower nozzle 5 of rotation; Reactant liquor passes through tubular type hybrid reaction shower nozzle 5 rapidly under the cooperation of raw material pushed at high pressure and gear 7 and transmission side roller 4, thereby proceeds and finally accomplish reaction in the agitated reactor in entering downstream.
Embodiment three:
Adopt like Fig. 3 and reactor shown in Figure 4, make in the tubular type hybrid reaction shower nozzle 5 that the have general formula organic solution of one or more amine or amine of (II) rotates through inboard reactant channel 2 entering; Simultaneously, pure phosgene liquid or phosgene solution get in the gear-box 6 through outside reactant channel 3, get into duct 8 to inject the tubular type hybrid reaction shower nozzle 5 of rotation perpendicular to the flow direction of interior side flow through material then; Amine side photoreactive gas side material is carrying out hybrid reaction fast respectively under the raw material discharge pressure effect separately in the both sides reactant channel collects in the tubular type hybrid reaction shower nozzle 5 of rotation; Reactant liquor passes through tubular type hybrid reaction shower nozzle 5 rapidly under the cooperation of raw material pushed at high pressure and gear 7 and transmission side roller 4, thereby proceeds and finally accomplish reaction in the agitated reactor in entering downstream.
Embodiment four:
Adopt like Fig. 3 and reactor shown in Figure 4; Make to have general formula the organic solution of one or more amine or amine of (II) gets into gear-boxes 6 through outside reactant channel 3, and then get into duct 8 to inject the tubular type hybrid reaction shower nozzle 5 of rotation perpendicular to the flow direction of interior side flow through material; Simultaneously, pure phosgene liquid or phosgene solution get into the tubular type hybrid reaction shower nozzle 5 of rotation through inboard reactant channel 2; Amine side photoreactive gas side material is carrying out hybrid reaction fast respectively under the raw material discharge pressure effect separately in the both sides reactant channel collects in the tubular type hybrid reaction shower nozzle 5 of rotation; Reactant liquor passes through tubular type hybrid reaction shower nozzle 5 rapidly under the cooperation of raw material pushed at high pressure and gear 7 and transmission side roller 4, thereby proceeds and finally accomplish reaction in the agitated reactor in entering downstream.
Below will carry out more detailed elaboration to the present invention, but following embodiment should not be construed as the restriction to content of the present invention through embodiment.
As shown in Figure 1; The material that one circle rectangle is set in the tube wall of tubular type hybrid reaction shower nozzle gets into the duct; The quantity that its material gets into the duct is that 12 and said material get into the duct and on the cross section perpendicular to the reactor axial direction of tubular type hybrid reaction shower nozzle, be in alignment with each other, equidistantly arrange, and the length-width ratio in rectangle duct is 2: 1; The root diameter of gear is 1.5 times of position, tubular type hybrid reaction shower nozzle duct external diameter, and two gears are set in the gear-box altogether; The internal diameter of tubular type hybrid reaction shower nozzle equates with the internal diameter of inboard reactant channel; Tubular type hybrid reaction shower nozzle rotating speed is 60r/min, and transmission side roller up and down reciprocatingly frequency is 2 times/hour.
O-dichlorohenzene (ODCB) the solution quality concentration of toluenediamine (TDA) (2,4-2,6 isomer proportions are 80/20, down together) is 37%, phosgene (COCl
2) ODCB solution quality concentration be 75%, pure phosgene is 3.8: 1 with the ratio of the quality of pure TDA, pure TDA feed rate is 5kg/h.Reactant channel gets into gear-box to phosgene solution through the outside, and further gets into duct injection tubular type hybrid reaction shower nozzle via material; TDA solution gets into tubular type hybrid reaction shower nozzle through inboard reactant channel; The discharge pressure of two strands of materials is 7.5bar.The phosgene solution temperature is 0 ℃, and the TDA solution temperature is 85 ℃.Two bursts of material contact and reactions fast in tubular type hybrid reaction shower nozzle, formed reactant liquor comes out to get into the subsequent reactor from tubular type hybrid reaction shower nozzle, about 125 ℃ of follow-up stirring reaction temperature, 45 minutes time of staying in subsequent reactor.
Evidence: this device steady running did not react in 1000 hours, and device pollutes or clogging.The reactant liquor sampling is viewed as claret and clear, slightly a small amount of suspension, and the liquid-phase chromatographic analysis result shows that its TDI selectivity is 97.2%.
Of Fig. 3, two circle rectangle materials are set in the tube wall of tubular type hybrid reaction shower nozzle get into ducts, every circle duct quantity is 12 and on each circle, be in alignment with each other, equidistantly arrange, and the length-width ratio in rectangle duct is 2: 1, and two circle ducts are staggered up and down; The root diameter of gear is 1.5 times of position, tubular type hybrid reaction shower nozzle duct external diameter, has two gears, and tubular type hybrid reaction shower nozzle internal diameter equates with the internal diameter of inboard reactant channel; Tubular type hybrid reaction shower nozzle rotating speed is 60r/min, and transmission side roller up and down reciprocatingly frequency is 6 times/hour.
O-dichlorohenzene (ODCB) the solution quality concentration of toluenediamine (TDA) (2,4-2,6 isomer proportions are 80/20, down with) is 42%, phosgene (COCl
2) ODCB solution quality concentration be 75%, pure phosgene is 4: 1 with the ratio of the quality of pure TDA, pure TDA feed rate is 5kg/h.Reactant channel gets into gear-box to phosgene solution through the outside, and further gets into duct injection tubular type hybrid reaction shower nozzle via material; TDA solution gets into tubular type hybrid reaction shower nozzle through inboard reactant channel; The discharge pressure of two strands of materials is 7.5bar.The phosgene solution temperature is 0 ℃; The TDA solution temperature is 85 ℃, two bursts of material contact and reactions fast in tubular type hybrid reaction shower nozzle, and formed reactant liquor comes out to enter into subsequent reactor from tubular type hybrid reaction shower nozzle; About 125 ℃ of follow-up stirring reaction temperature, the time of staying is 45 minutes and 20 seconds.
Evidence: this device steady running did not react in 1000 hours, and device pollutes or clogging.The reactant liquor sampling is viewed as claret and transparent, obviously has suspension, and the liquid-phase chromatographic analysis result shows that its TDI selectivity is 96.7%.
In the reactor that this embodiment adopted, three circle rectangle material ducts are set in the tube wall of tubular type hybrid reaction shower nozzle, every from the top down circle duct quantity is followed successively by 24,18,12.Because duct alignment on each circle, equidistantly arrangement so three circle ducts increase from top to bottom successively, are a with first lap duct, upper strata width, then second, third circle duct width is followed successively by 4a/3 and 2a.The two adjacent rings duct is staggered up and down.The length-width ratio in rectangle duct is 2: 1; The root diameter of gear is 1.5 times of tubular type hybrid reaction nozzle openings position external diameter.Be provided with four gears in the gear-box altogether; The internal diameter of tubular type hybrid reaction shower nozzle equates with inboard reactant channel bore; Tubular type hybrid reaction shower nozzle rotating speed is 60r/min, and transmission side roller up and down reciprocatingly frequency is 6 times/hour.
O-dichlorohenzene (ODCB) the solution quality concentration of toluenediamine (TDA) (2,4-2,6 isomer proportions are 80/20, down with) is 25%, phosgene (COCl
2) ODCB solution quality concentration be 75%, pure phosgene is 3.5: 1 with the ratio of the quality of pure TDA, pure TDA feed rate is 5kg/h.Reactant channel gets into gear-box to phosgene solution through the outside, and further gets into duct injection tubular type hybrid reaction shower nozzle via material; TDA solution gets into tubular type hybrid reaction shower nozzle through inboard reactant channel; The discharge pressure of two strands of materials is 7.5bar.The phosgene solution temperature is 0 ℃; The TDA solution temperature is 85 ℃, two bursts of material contact and reactions fast in tubular type hybrid reaction shower nozzle, and formed reactant liquor comes out to enter into subsequent reactor from tubular type hybrid reaction shower nozzle; About 125 ℃ of follow-up stirring reaction temperature, the time of staying is 40 minutes and 20 seconds.
Evidence: this device steady running did not react in 1000 hours, and device pollutes or clogging.The reactant liquor sampling is viewed as claret and clear, does not have suspension, and the liquid-phase chromatographic analysis result shows that its TDI selectivity is 98.1%.
In the reactor that this embodiment adopted, the circular material of three circles duct is set in the tube wall of tubular type hybrid reaction shower nozzle, the quantity in every from the top down circle duct is followed successively by 24,18,12, and the length-width ratio in rectangle duct is 2: 1.Because material gets into duct alignment on each circle, equidistantly arranges, so three circle ducts increase from top to bottom successively, is a with first lap duct, upper strata width, then second, third circle duct width is followed successively by 4a/3 and 2a.The two adjacent rings duct is staggered up and down.The root diameter of gear is 1.5 times of tubular type hybrid reaction nozzle openings position external diameter, and two gears are set in the gear-box altogether; Tubular type hybrid reaction shower nozzle internal diameter equates with inboard reactant channel bore; Tubular type hybrid reaction shower nozzle rotating speed is 90r/min, and transmission side roller up and down reciprocatingly frequency is 12 times/hour.
O-dichlorohenzene (ODCB) the solution quality concentration of toluenediamine (TDA) (2,4-2,6 isomer proportions are 80/20, down with) is 30%, phosgene (COCl
2) ODCB solution quality concentration be 75%, pure phosgene is 3.5: 1 with the ratio of the quality of pure TDA, pure TDA feed rate is 5kg/h.Reactant channel gets into gear-box to phosgene solution through the outside, and further gets into duct injection tubular type hybrid reaction shower nozzle via material; TDA solution gets into tubular type hybrid reaction shower nozzle through inboard reactant channel; The discharge pressure of two strands of materials is 7.5bar.The phosgene solution temperature is 0 ℃; The TDA solution temperature is 85 ℃, two bursts of material contact and reactions fast in tubular type hybrid reaction shower nozzle, and formed reactant liquor comes out to enter into subsequent reactor from tubular type hybrid reaction shower nozzle; About 125 ℃ of follow-up stirring reaction temperature, the time of staying is 43 minutes and 40 seconds.
Evidence: this device steady running did not react in 1000 hours, and device pollutes or clogging.The reactant liquor sampling is viewed as claret and clear, does not have suspension, and the liquid-phase chromatographic analysis result shows that its TDI selectivity is 97.7%.
Claims (38)
1. a dynamic aperture shooting flow type reactor comprises interior feed pipe, outer feed pipe, tubular type hybrid reaction shower nozzle, gear-box, power transmission shaft and transmission side roller; Wherein, Said power transmission shaft, interior feed pipe and the coaxial setting of outer feed pipe from-inner-to-outer; Said outer feed pipe is communicated with gear-box and coaxial from top to bottom setting, is provided with gear and a tubular type hybrid reaction shower nozzle that is provided with a plurality of materials entering duct in the said gear-box, and said gear and tubular type hybrid reaction shower nozzle get into the mutual match in duct through material; And, also be provided with in the gear-box and be used for spacing gear axis track with the match of gear-box circumferential inner wall; Feed pipe is communicated with and coaxial from top to bottom setting with tubular type hybrid reaction shower nozzle in said; Said tubular type hybrid reaction shower nozzle axially rotates under the driving of power transmission shaft and transmission side roller, and then the rotation of driven gear case internal gear; Said transmission side roller can pump in said tubular type hybrid reaction shower nozzle.
2. according to the described dynamic aperture shooting flow type reactor of claim 1, it is characterized in that: the shape of cross section that said material gets into the duct is selected from: any in equilateral polygon, non-equilateral polygon, circle or the ellipse.
3. according to the said dynamic aperture shooting flow type reactor of claim 1, it is characterized in that: the shape of cross section that said material gets into the duct is selected from: any in the square of the rectangle of right angle or fillet, right angle or fillet, triangle, rhombus, trapezoidal, circle or the ellipse.
4. according to the described dynamic aperture shooting flow type reactor of claim 2, it is characterized in that: get into the duct at the above a plurality of material of tubular type hybrid reaction shower nozzle and be set to 1～20 circle.
5. according to the described dynamic aperture shooting flow type reactor of claim 4, it is characterized in that: get into the duct at the above a plurality of material of tubular type hybrid reaction shower nozzle and be set to 2～12 circles.
6. according to the described dynamic aperture shooting flow type reactor of claim 5, it is characterized in that: get into the duct at the above a plurality of material of tubular type hybrid reaction shower nozzle and be set to 3～8 circles.
7. according to the described reactor of claim 4, it is characterized in that: when said tubular type hybrid reaction shower nozzle was provided with two circles or the material entering duct more than two circles, the material of two adjacent rings got into duct align or interlaced arrangement; The material of said two adjacent rings gets into quantity, the shape and big or small identical or different in duct; The quantity that the included material of every circle gets into the duct is 8～40.
8. according to the described reactor of claim 4, it is characterized in that: the quantity that the included material of every circle gets into the duct is 12～24.
9. according to any described dynamic aperture shooting flow type reactor among the claim 1-8, it is characterized in that: said tubular type hybrid reaction shower nozzle is along having different wall thickness on its axial direction but have identical internal diameter.
10. according to the described dynamic aperture shooting flow type reactor of claim 9, it is characterized in that: the wall thickness that said material gets into position of living in, duct is thick 1～5 times of tubular type hybrid reaction shower nozzle lower part outlet end wall.
11. according to the described dynamic aperture shooting flow type reactor of claim 10, it is characterized in that: the wall thickness that said material gets into position of living in, duct is thick 1.5～3 times of tubular type hybrid reaction shower nozzle lower part outlet end wall.
12. according to the described dynamic aperture shooting flow type reactor of claim 9, it is characterized in that: the internal diameter of said gear is 0.25～4 times that tubular type hybrid reaction shower nozzle material gets into position, duct external diameter.
13. according to the described dynamic aperture shooting flow type reactor of claim 12, it is characterized in that: the internal diameter of said gear is 0.5～2 times that tubular type hybrid reaction shower nozzle material gets into position, duct external diameter.
14. according to the described dynamic aperture shooting flow type reactor of claim 12, it is characterized in that: the quantity of said gear is 1～8.
15. according to the described dynamic aperture shooting flow type reactor of claim 14, it is characterized in that: the quantity of said gear is 2,4,6 or 8.
16. according to any described dynamic aperture shooting flow type reactor among claim 1-8, the 12-15; It is characterized in that: the inwall of said tubular type hybrid reaction shower nozzle be provided with at least 1 with the isometric slideway of tubular type hybrid reaction shower nozzle so that said transmission side roller can pump in said tubular type hybrid reaction shower nozzle when keeping axial rotation.
17. according to the described dynamic aperture shooting flow type reactor of claim 16, it is characterized in that: the inwall of said tubular type hybrid reaction shower nozzle is provided with 2～3 slideways.
18. according to the described dynamic aperture shooting flow type reactor of claim 16, it is characterized in that: said transmission side roller can be realized pumping through manual or automatic mode; The reciprocating frequency of said transmission side roller is 1 time/day～1 time/minute.
19. according to the described dynamic aperture shooting flow type reactor of claim 18, it is characterized in that: the reciprocating frequency of said transmission side roller is 5～288 times/day; The reciprocating frequency of said transmission side roller can be regulated through gearbox step by step.
20. according to the described dynamic aperture shooting flow type reactor of claim 19, it is characterized in that: the reciprocating frequency of said transmission side roller is more preferably 5～48 times/day.
21. according to the described dynamic aperture shooting flow type reactor of claim 18, it is characterized in that: the speed of said tubular type hybrid reaction shower nozzle axial rotation is 1～120r/min.
22. according to the described dynamic aperture shooting flow type reactor of claim 21, it is characterized in that: the speed of said tubular type hybrid reaction shower nozzle axial rotation is 6～60r/min.
23. according to claim 1 or 21 described dynamic aperture shooting flow type reactors; It is characterized in that: formed reaction channel is inboard reactant channel between said power transmission shaft and the interior feed pipe, and formed reaction channel is an outside reactant channel between said interior feed pipe and the outer feed pipe; Outside reactant channel is 0.5～24: 1 with the ratio of the cross-sectional area of inboard reactant channel.
24. according to the described dynamic aperture shooting flow type reactor of claim 23, it is characterized in that: outside reactant channel is 0.75～12: 1 with the ratio of the cross-sectional area of inboard reactant channel.
25. according to the described dynamic aperture shooting flow type reactor of claim 24, it is characterized in that: outside reactant channel is 1～7.5: 1 with the ratio of the cross-sectional area of inboard reactant channel.
26. according to the described dynamic aperture shooting flow type reactor of claim 23, it is characterized in that: the passage in the said tubular type hybrid reaction shower nozzle is 0.5～4: 1 with the ratio of the cross-sectional area of inboard reactant channel.
27. according to the described dynamic aperture shooting flow type reactor of claim 26, it is characterized in that: the passage in the said tubular type hybrid reaction shower nozzle is 0.75～3: 1 with the ratio of the cross-sectional area of inboard reactant channel.
28. a method that adopts aliphatic shown in general formula (I) of each described hole shooting flow type reactor preparation among the claim 1-27, alicyclic or aromatic isocyanate,
R(NCO)
n (I)
R(NH
2)
n (II)
Wherein R is aliphatic C2-C50 alkyl, alicyclic C4-C50 alkyl or aromatic series C6-C50 alkyl, and has two carbon atom arrangement at least between any two adjacent (NCO) of general formula (I), and n >=2, said method comprising the steps of:
(a). have one or more amine of general formula (II) or the organic solution of amine and get into the tubular type hybrid reaction shower nozzle of rotation through inboard reactant channel; Perhaps get into gear-box, get into the duct to inject the tubular type hybrid reaction shower nozzle of rotation perpendicular to the flow direction of interior side flow through material then through outside reactant channel;
(b). pure phosgene liquid or phosgene solution get in the gear-box through outside reactant channel, get into the duct to inject the tubular type hybrid reaction shower nozzle of rotation perpendicular to the flow direction of interior side flow through material then; Perhaps get into the tubular type hybrid reaction shower nozzle of rotation through inboard reactant channel;
(c). amine side photoreactive gas side material is mixing fast, is reacting in the both sides reactant channel collects in the tubular type hybrid reaction shower nozzle of rotation respectively under the raw material discharge pressure effect separately; Reactant liquor gets in the subsequent reactions still and proceeds and accomplish reaction rapidly through tubular type hybrid reaction shower nozzle.
29. according to the described method of claim 28; It is characterized in that: the isocyanates with general formula (I) is selected from: isomer proportion is 2 of 100/0-80/20 or 65/35; 4-/2,6-toluene di-isocyanate(TDI), diphenyl methane 4,4 '-vulcabond, dicyclohexyl methyl hydride 4; 4 '-vulcabond, IPDI, 1; Hexamethylene-diisocyanate, 1,4-hexamethylene vulcabond, 1,8-two isocyanato-s-4-(isocyanatomethyl) octane, three isocyano nonanes, 1; 4-fourth vulcabond, naphthalene diisocyanate, PPDI, XDI, cyclohexanedimethyleterephthalate vulcabond, trimethyl-1,6-hexamethylene diisocyanate, tetramethyl m-phenylenedimethylim-vulcabond, dimethyl diphenyl vulcabond or Methylcyclohexyl diisocyanate.
30. according to the described method of claim 28; It is characterized in that: the amine organic matter with general formula (II) is selected from: isomer proportion be 80/20 or 65/35 2,4-/2,6-toluenediamine mixture or pure 2; 4-toluenediamine, diphenyl methane 4; 4 '-diamines, dicyclohexyl methyl hydride 4,4 '-diamines, IPD, 1,6-hexamethylene diamine, 1; 4-cyclohexanediamine, 1; 8-diaminourea-4-(aminomethyl) octane, triaminononane, 1,4-butanediamine, naphthylenediamine, p-phenylenediamine (PPD), phenylenedimethylidyne diamines, cyclohexanedimethyleterephthalate diamines, trimethyl-1,6-hexamethylene diamine, tetramethyl m-phenylenedimethylim-diamines, dimethyl diphenyl diamines or methylcyclohexyl diamines.
31., it is characterized in that according to the described method of claim 28: step (a) and (b) described in polyamines organic solution photoreactive gas solution be to utilize atent solvent that the amine photoreactive gas is diluted; Said atent solvent is selected from: one or more in benzene, toluene, chlorobenzene, o-dichlorohenzene, paracide, a chlordiphenyl, dimethyl terephthalate ester or the diethyl phthalate; The concentration of said polyamines organic solution is 12.5%～45wt%; Phosgene organic solution concentration is not less than 60wt%.
32. according to the described method of claim 31, it is characterized in that: the concentration of said polyamines organic solution is 15～25wt%.
33. according to any described method among the claim 28-32, it is characterized in that: the linear velocity of inboard reactant channel inner fluid axial flow is 0.8～14.6m/s; The material of the outside in the reactant channel gets into the duct through material, and vertically to inject the linear velocity of tubular type hybrid reaction shower nozzle be 1～9 times of interior side flow axial flow linear velocity.
34. according to the described method of claim 33, it is characterized in that: the linear velocity of inboard reactant channel inner fluid axial flow is 2.0～8.2m/s; The material of the outside in the reactant channel gets into the duct through material, and vertically to inject the linear velocity of tubular type hybrid reaction shower nozzle be 1.2～5.5 times of interior side flow axial flow linear velocity.
35. according to the described method of claim 33, it is characterized in that: the material pressure in inboard reactant channel and the outside reactant channel is 1～20bar; The total cross-sectional area that gets into the duct when material is during greater than the cross-sectional area of inboard reactant channel; Through independent lifting outside reactant pressures, be 1～9 times of inboard reactant channel internal reaction flow linear velocity to guarantee linear velocity that reactant gets into the duct through material.
36. according to the described method of claim 35, it is characterized in that: the material pressure in inboard reactant channel and the outside reactant channel is 5～15bar.
37. according to the described method of claim 35, it is characterized in that: the outlet pressure of said tubular type hybrid reaction shower nozzle is 1～15bar.
38. according to the described method of claim 37, it is characterized in that: the outlet pressure of said tubular type hybrid reaction shower nozzle is 5～10bar.
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| WO2011130901A1 (en) * | 2010-04-19 | 2011-10-27 | 烟台万华聚氨酯股份有限公司 | Jet reactor with dynamic spray nozzle and method for preparing isocyanates using the same |
| EP2486975B1 (en) * | 2010-12-29 | 2015-09-23 | Wanhua Chemical Group Co., Ltd. | Fast mixing reactor and use thereof |
| CN103084134B (en) * | 2012-12-12 | 2015-04-22 | 万华化学集团股份有限公司 | Dynamic hole jet mixed reactor and method for producing diphenyl methane series diamine and polyamine by using same |
| CN114085166B (en) * | 2020-08-25 | 2023-05-05 | 万华化学集团股份有限公司 | Method for preparing high-purity high-stability isocyanate in high yield |
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| CN1830540A (en) * | 2006-02-15 | 2006-09-13 | 烟台万华聚氨酯股份有限公司 | Liquid film colliding type jet reactor |
| CN101153015A (en) * | 2006-09-28 | 2008-04-02 | 宁波万华聚氨酯有限公司 | Hole shooting flow type reactor and method for producing isocyanic ester by using the reactor |
| CN101209405A (en) * | 2006-12-27 | 2008-07-02 | 宁波万华聚氨酯有限公司 | Hole jet type injecting reactor |
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| JPH1190277A (en) * | 1997-09-18 | 1999-04-06 | Tosoh Corp | Rotary sprayer and reactor having the same |
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| CN1830540A (en) * | 2006-02-15 | 2006-09-13 | 烟台万华聚氨酯股份有限公司 | Liquid film colliding type jet reactor |
| CN101153015A (en) * | 2006-09-28 | 2008-04-02 | 宁波万华聚氨酯有限公司 | Hole shooting flow type reactor and method for producing isocyanic ester by using the reactor |
| CN101209405A (en) * | 2006-12-27 | 2008-07-02 | 宁波万华聚氨酯有限公司 | Hole jet type injecting reactor |
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