CN101811017A - Stirring and grinding reactor and method for preparing isocyanate with same - Google Patents
Stirring and grinding reactor and method for preparing isocyanate with same Download PDFInfo
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- CN101811017A CN101811017A CN201010154068.7A CN201010154068A CN101811017A CN 101811017 A CN101811017 A CN 101811017A CN 201010154068 A CN201010154068 A CN 201010154068A CN 101811017 A CN101811017 A CN 101811017A
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Abstract
The invention relates to a stirring and grinding integrated reactor and a method for preparing isocyanate by using the reactor. The reactor comprises a reactor shell, a first reactant feeding hole, a first reactant distributing tray, a second reactant main feeding hole, an annular second reactant distributing tray, a stirring shaft, an axial stirring paddle, a radial stirring paddle, a dynamic grinding sheet, a static grinding sheet and at least one second reactant sub feeding hole, wherein the dynamic and static grinding sheets are provided with a plurality of passage holes. Quick mixing and quick reaction between the raw materials are realized by axial and radial strong stirring and a feeding method of a strongest mixing area, and the solid reaction product is further pulverized by hole passage type quick grinding combined through multilayer dynamic and static grinding trays so as to enhance the reaction effect, improve the yield and quality of the isocyanate, reduce the using amount of a solvent and the excess ratio of phosgene, improve the yield of the device, improve the quality of the product and reduce the energy consumption.
Description
Technical field
The present invention relates to a kind of agitation grinding reactor and application thereof, more particularly, relate to a kind of method that can realize that (gas-gas or liquid-liquid) rapid mixing, rapid-action integrate stirring, the reactor that grinds and utilize this reactor made isocyanates between fluid.
Background technology
In chemical process, when complicated fast and parallel competitive reaction taking place between reaction mass or connecting competitive reaction fast, certain component in product or intermediate product and the raw material may further react; The CONCENTRATION DISTRIBUTION situation of degree that these reactions are carried out and various material (for example raw material, intermediate product etc.) has direct relation.So the initial mixing effect between the raw material can influence greatly that final product distributes, the yield and the quality of purpose product, and influence indexs such as the design of all round process and energy consumption simultaneously.For example, when adopting phosgenation processes to produce isocyanates (TDI or MDI), this course of reaction mainly comprises cold light gasifying stage and hot phosgenation stage.At the cold light gasifying stage, the polyamines of liquid state and liquid phosgene are dissolved in respectively in the atent solvent, for example dichloro-benzenes, chlorobenzene, toluene, chlorinated naphthalene, 1,2,4-trichloro-benzenes etc., and polyamines and phosgene are reacted under 0～100 ℃ low temperature.In this stage, mainly generate the hydrochloride of acid amides and polyamines, and a spot of carbamide compounds.Key reaction is as follows:
RNH
2+COCl
2RNHCOC?l+HCl (1)
RNH
2+HCl→RNH
2·HCl (2)
RNH
2+RNHCOCl→RNCO+RNH
2·HCl (3)
RNH
2+RNCO→RNHCONHR (4)
In the cold stage of reaction, polyamines at first reacts with phosgene (1), generates carbamyl chloride, and this is a quick exothermic reaction; Simultaneously, HCl and polyamines generation fast reaction (2) that reaction (1) produces generate the polyamines hydrochloride.Carbamyl chloride and polyamines hydrochloride all are the solid matters that is insoluble to reaction system.When the local mixed effect of phosgene and polyamines is relatively poor, local excessive polyamines will react (3) and (4) with carbamyl chloride or isocyanates in the solution, generation accessory substance urea, and urea is the thick material that is not dissolved in reaction system.This process is complicated multistep series connection competitive reaction.Main reaction is fast reaction, and the time scale of its reaction is at Millisecond or following; The product that generates further with raw material generation fast reaction, generate the accessory substance that is not dissolved in reaction system.Therefore, the initial mixing effect of two kinds of raw materials will directly influence the yield and the selectivity of principal product.Successfully design the liquid fast-mixing reactor, improve the initial mixing effect of two strands of feed streams, for the yield and the selectivity that increase principal product, the generation that reduces accessory substance has great importance.In addition, generate a large amount of solid matters, be easy to cause the parcel of this solid matter, thereby cause main reaction minimizing, side reaction to increase polyamines owing to adopt phosgenation processes to produce isocyanates.Therefore, the minimizing solid particle also has very important significance for improving reaction yield to the parcel of polyamines.
Current domestic and international patent mainly is that cross-flow mixes, its mesopore jet is a kind of main method, enter main body stream thigh by burst injection of a lot of tiny streams, injecting each little fluid streams of back rapidly by burst encirclement of main body stream, thereby realize that by the turbulence state of fluid two flow the mixing between the thigh, for example U.S. Pat 3,226,410 described a kind of hole jet type injecting devices, one fluid streams is in an other fluid streams during cross-flow jet, because the interaction between the fluid, when entering in the main fluid, the jet stream thigh can only reach certain jet degree of depth, like this when the pipeline diameter of main body stream hour, can realize the rapid mixing between two fluid streams, but when production capacity is big, the pipeline diameter of main body stream is also corresponding bigger, spraying the stream thigh that enters from jet orifice can not fully be distributed to the main body stream in the short period of time, certainly will cause main body stream pipe center in long segment distance, not mixed, the corresponding prolongation of incorporation time, when incorporation time yardstick one timing that requires to reach, also there is greatest limit in the production capacity of reactor, therefore, rely on simple static mixing, can not realize the quick moment mixing of big flow storeroom, and need concentration of reactants is reduced greatly in order to obtain satisfied productive rate, cause and bigger energy consumption to reclaim solvent.Therefore, need a kind of more efficiently mixing apparatus of exploitation, to realize rapid mixing and the fast reaction between the reaction raw materials under the large-scale production ability.
Summary of the invention
The objective of the invention is to the method developing a kind of high efficiency reactor and utilize this reactor made isocyanates, realize the moment rapid mixing between the reaction raw materials under the big production capacity, to strengthen main reaction, to suppress side reaction, simultaneously the solid product that produces is further ground refinement, reduce the parcel of solid product particle, improve the yield and the quality of target product liquid charging stock.
In specification of the present invention, if not special regulation, " axially " and " radially " refer to respectively the axial of reactor with radially." phosgene " mentioned in the present invention can exchange use with " phosgene solution ", and " amine ", " organic solution of amine " can be exchanged use with " amine aqueous solution ".The present invention illustrates the position relation of each member with the reactor of vertical installation, but does not get rid of the mode that other mounting means for example tilt to install a little.
Reactor provided by the present invention is based on following design concept: one logistics (gas or liquid) is by the axial thrust of axial paddle generation along shaft, another burst logistics to the high turbulent area that is in this paddle below is axially sheared, and then by further strong dispersion the after radially paddle mixes these two bursts of logistics, the incorporation time of such two strands of materials is very short, has realized rapid mixing, fast reaction; For the solid matter that produces in the course of reaction, grind facility by design, make the further dispersion and fining of solid product, avoid raw material to be wrapped up by solid matter, improve the yield of target product.
The invention provides a kind of agitation grinding reactor, it comprises: the second reactant distribution dish of reactor shell, the first reaction-ure feeding mouth, the first reactant distribution dish, the second reactant combined feed mouth, ring-type, shaft, axially paddle, radially paddle, moving abrasive sheet, quiet abrasive sheet and at least one second reactant divide charging aperture; Wherein, reactor shell and the coaxial setting of shaft, and below reactor shell inside is positioned at the first reactant distribution dish, form reaction channel; The first reactant distribution dish of first reactant through being arranged on this reactor top that be arranged so that of the first reaction-ure feeding mouth enters reaction channel; Axially paddle and radially paddle be arranged on the shaft from top to bottom; Moving abrasive sheet and quiet abrasive sheet are arranged on the radially below of paddle spaced reciprocally, and moving abrasive sheet is fixed on the shaft, and quiet abrasive sheet is fixed on the inwall of reactor shell, also are provided with access opening on moving abrasive sheet and the quiet abrasive sheet; Second reactant divides charging aperture to be arranged on axial paddle and radially between the paddle, so that second reactant divides charging aperture to be delivered to reaction channel through the second reactant distribution dish and second reactant of the second reactant combined feed mouth, ring-type.
According to reactor provided by the invention, the wherein said first reactant distribution dish is a cavity structure, is that first reactant enters described reaction channel prerequisite for the circulation place.
According to reactor provided by the invention, wherein, axially paddle makes the logistics of first reactant produce axial thrust, and the logistics realization of one or more strands of second reactants is axially sheared, and strengthens the initial mixing effect.Therefore, the 1-6 of can on shaft, be arrangeding in parallel, preferred 1-3 axial paddle, and according to the flow direction of material described axial paddle is carried out progression and arrange; Each axial paddle has 2-20 sheet, preferred 3-15, more preferably 3-8 sheet blade; The external profile diameter of described axial paddle blade is 40-1000mm, is preferably 60-800mm.
According to reactor provided by the invention, the described second reactant distribution dish is a cavity structure, is that second reactant divides charging aperture to enter the reaction channel prerequisite for the circulation place by second reactant; Described second reactant divides charging aperture to be arranged on the reactor shell and is positioned at reaction channel, and the cross sectional shape of described minute charging aperture is circle, triangle, rectangle, rhombus, trapezoidal, polygon or ellipse etc., is preferably circle, rectangle, triangle; The quantity of described minute charging aperture is 3-200, is preferably 3-100, more preferably 5-80; Described minute charging aperture can be even distribution on reactor shell, also can be non-homogeneous distribution.But, be preferably even distribution.Charging aperture can be positioned on the identical or different horizontal plane in described minute.When second reactant divided the cross section of charging aperture to be circle, its diameter was 2-30mm, is preferably 2-20mm, more preferably 2-15mm.For convenience of explanation, when elected usefulness had the branch charging aperture of other cross sectional shapes, its sectional area calculated according to the equivalent section of circular charging aperture is long-pending.Each divides the axial distance of the lower edge of the top edge of charging aperture and the axial paddle blade of afterbody is 1-50mm, is preferably 2-30mm; Charging aperture was 1-100mm from the radial distance of the extremely axial paddle blade outer most edge of most proximal end of shaft in described minute, was preferably 2-40mm.
According to reactor provided by the invention, wherein, described second reactant divides charging aperture level (promptly perpendicular to shaft) to be arranged on the reactor shell and is positioned at reaction channel; Preferably, described second reactant divides that charging aperture is downward-sloping to be arranged on the reactor shell, and each divides the central shaft of charging aperture and the angle of shaft is 20-90 °, is preferably 60-90 °.
According to reactor provided by the invention, the 1-6 of can on shaft, be arrangeding in parallel, preferred 1-3 paddle radially, and according to the flow direction of material described radially paddle is carried out progression and arrange; Each radially paddle have 2-20 sheet, preferred 3-15 sheet, more preferably 3-8 sheet blade; The external profile diameter of described radially paddle blade is 40-1000mm, is preferably 60-700mm; The first order radially the upper limb of paddle blade and second reactant to divide the axial distance (being vertical range) of the lower limb of charging aperture be 1-200mm, be preferably 2-100mm.In the present invention, by being set, second reactant divide charging aperture to make the high turbulent area charging of second reactant below paddle radially, and radially paddle radial shear power that produces and the axial shearing force one that axial paddle produces reacts on reactant stream, thereby realizes quick, the sufficient mixing.
According to reactor provided by the invention, the moving abrasive sheet of one or more (or from top to bottom one or more levels) and the quiet abrasive sheet of one or more (or from top to bottom one or more levels) can be set below paddle radially spaced reciprocally, and respectively moving abrasive sheet and quiet abrasive sheet be carried out progression according to the flow direction of material and arrange; Wherein the quiet abrasive sheet of the first order is arranged on the below of the moving abrasive sheet of the first order, and the upper surface of the moving abrasive sheet of the first order and the afterbody radially axial distance of the lower edge of paddle blade are 1-200mm, are preferably 10-100mm.
According to reactor provided by the invention, described moving abrasive sheet also has centre bore, make shaft pass this centre bore, and will move abrasive sheet and be fixed on the shaft and be positioned at reaction channel, the progression that moving abrasive sheet is set from top to bottom is the 2-6 level, is preferably the 2-4 level, and the shape of described moving abrasive sheet is not particularly limited, but be preferably external profile diameter is the disk of 40-1200mm, preferred 60-800mm, and rotates together with shaft; Each moving abrasive sheet is provided with 10-1000, preferred 15-100 access opening, and the cross sectional shape of described access opening is circle, triangle, rectangle, rhombus, trapezoidal, polygon or ellipse etc., is preferably circle, rectangle, triangle; Although total circulation area of these access openings depends on the size of reaction channel and moving abrasive sheet, this circulation area is preferably 8-600mm
2, 10-400mm more preferably
2Described access opening can be even distribution on moving abrasive sheet, for example equidistantly distributes in a circumferential direction, and also can be non-homogeneous distribution, still, be preferably even distribution.Described access opening is 10-80% with respect to the percent opening of reaction channel, is preferably 20-70%.The outer most edge of described moving abrasive sheet to the radial distance of reaction channel inwall is 1-20mm, preferred 1-10mm.
According to reactor provided by the invention, described quiet abrasive sheet also has centre bore, makes shaft pass this centre bore, and quiet abrasive sheet is fixed on the inwall of reactor shell and is positioned at reaction channel, the progression that quiet abrasive sheet is set from top to bottom is the 1-6 level, is preferably the 2-4 level; Axial distance between the moving abrasive sheet of every grade of quiet abrasive sheet and adjacent level is 1-50mm, is preferably 1-30mm, and more preferably 1-25mm most preferably is 2-15mm; Shape to described quiet abrasive sheet is not particularly limited, but is preferably the disk that external profile diameter is 40-1200mm, preferred 60-800mm; Each quiet abrasive sheet is provided with 10-1000, preferred 15-100 access opening, and the cross sectional shape of described access opening is circle, triangle, rectangle, rhombus, trapezoidal, polygon or ellipse etc., is preferably circle, rectangle, triangle; Although total circulation area of these access openings depends on the size of reaction channel and quiet abrasive sheet, this circulation area is preferably 8-600mm
2, 10-400mm more preferably
2Described access opening can be equally distributed on quiet abrasive sheet, and is for example radially or on the circumferencial direction the equidistantly distributing of annulus, also can right and wrong equally distributed.But, be preferably equally distributed.Described access opening is 10-80% with respect to the percent opening of reaction channel, is preferably 20-70%.The inner edge of described quiet abrasive sheet to the radial distance of shaft outer most edge is 1-10mm, preferred 1-5mm.
According to reactor provided by the invention, in the end one-level radially is provided with moving abrasive sheet of multilayer and quiet abrasive sheet in the paddle below spaced reciprocally, grind the solid product particle that the refinement reaction generates fast by the duct formula of being association of activity and inertia, avoid raw material liq to be wrapped up by the solid product particle, reduce side reaction, improve target product yield.
According to reactor provided by the invention, the cross sectional shape of reaction channel is circle, ellipse, polygon or rectangle etc., circular, polygon; When the cross section of reaction channel was circle, its channel diameter was 30-1400mm, is preferably 60-800mm, and when selecting difform reaction channel for use, its channel cross-sectional area calculates according to the equivalent section of circular channel is long-pending.
The material of reactor provided by the invention itself is the material of this area routine, includes but not limited to be made by steel, glass, pottery, alloy, carborundum or glassed steel etc.
The present invention also provides a kind of method that adopts the agitation grinding reactor by the aliphatic of the amine preparation with general formula I shown in general formula I I, alicyclic or aromatic isocyanate,
R(NH
2)
n I
R(NCO)
n II
Wherein, R is aliphatic, alicyclic or aromatic hydrocarbyl, and n=1 or n 〉=2 said method comprising the steps of:
(a) pure phosgene liquid or phosgene solution enter reactor by the first reaction-ure feeding mouth, enter in the reaction channel through the first reactant distribution dish then;
(b) organic solution with amine of general formula I enters the second reactant distribution dish by the second reactant combined feed mouth, divides charging aperture to enter the lower zone of the axial paddle of afterbody by second reactant then;
(c) at axial paddle with radially under the effect of paddle, phosgene stream thigh flows to the below of reaction channel, burst injection of amine stream enters phosgene stream thigh, two strands of materials mix rapidly, react, under the turning effort of shaft, the solid particle that reaction generates grinds refinement through moving abrasive sheet and quiet abrasive sheet, and the reactant liquor that comes out from reaction channel enters proceeds and finish reaction in the subsequent reactions still.
The present invention adopts in the method for agitation grinding reactor made isocyanates, and formed concentration is the phosgene solution of 50-100wt% to described phosgene solution in the inert organic solvents in order pure phosgene or phosgene are dissolved in; The organic solution of described amine is for being 10-60wt% with the formed concentration in inert organic solvents of the amine solvent shown in the general formula I, being preferably the amine aqueous solution of 20-50wt%.
The present invention adopts in the method for agitation grinding reactor made isocyanates, and the rotating speed of described shaft is 80-10000r/min, is preferably 100-5000r/min.
The present invention adopts in the method for agitation grinding reactor made isocyanates, described amine aqueous solution is in the axially lower zone charging of paddle, this zone is high turbulent area, thereby it is the strongest at the turbulent extent of this zone amine stream thigh, the most favourable to mixing, phosgene stream thigh from the reaction channel above the axial paddle is axially sheared this part amine stream thigh by axial paddle, make by paddle radially again that mixture is further strong to be disperseed, make the incorporation time of two strands of materials very short, can realize rapid mixing, fast reaction.
The present invention adopts in the method for agitation grinding reactor made isocyanates, under the high speed rotation of shaft, the solid product that reaction generates grinds refinement through dynamic and static abrasive sheet, can avoid material liquid to be wrapped up by solid, reduce the generation of side reaction, realize the high yield of product.
The present invention adopts in the method for agitation grinding reactor made isocyanates, and in the described general formula I, when n=1, the amine that this general formula is represented is the C2-C20 Armeen or the C6-C20 primary aromatic amine of simple function group; When n 〉=2, the amine that this general formula is represented includes but not limited to toluenediamine, 4,4 '-diaminodiphenyl-methane, polymethylene polyphenyl polyamine, IPD, hexamethylene diamine, cyclohexanediamine, naphthylenediamine, p-phenylenediamine (PPD), phenylenedimethylidyne diamines, cyclohexanedimethyleterephthalate diamines, trimethyl-1,6-hexamethylene diamine, tetramethyl m-phenylenedimethylim-diamines, dimethyl diphenyl diamines or methylcyclohexyl diamines are preferably toluenediamine.
The present invention adopts in the method for agitation grinding reactor made isocyanates, the inert organic solvents of dissolving phosgene and amine can be identical or different, is selected from benzene, toluene, chlorobenzene, o-dichlorohenzene, paracide, a chlordiphenyl, dimethyl terephthalate ester or the diethyl phthalate one or more respectively.
Compared with prior art, adopt agitation grinding reactor provided by the invention and using method thereof to prepare isocyanates and have following beneficial effect:
(1) adopt reactor provided by the present invention, amine stream thigh is in the strong turbulence regime charging, and the initial mixing degree is greatly improved,
(2) adopt reactor provided by the present invention,, realized rapid mixing, the fast reaction of multiply material, avoided the generation of side reaction, improved the yield of target product by combined hybrid mode axial and radially.
(3) adopt reactor provided by the present invention, mixed logistics is under the effect of axial paddle, and back-mixing degree minimum approaches desirable " laminar flow " form, has strengthened mixed effect, has improved reaction rate.
(4) adopt reactor provided by the present invention, quick grinding by multilayer duct formula sound abrasive sheet, make solid product further by dispersion and fining, reduced the possibility of solid particle parcel material liquid, farthest reduced side reaction, reduced the excessive ratio of phosgene in the consumption of solvent and the reaction-ure feeding, improved the production capacity of device, improved product quality and cut down the consumption of energy.
(5) reactor of the present invention can infinitely amplify in theory, and enlarge-effect is less, can realize the quick moment mixing between the following two bursts of logistics of large-scale production ability (gas-gas or liquid-liquid), overcome traditional static mixing reactor enlarge-effect obvious defects.
Description of drawings
Fig. 1 is the structural representation of agitation grinding reactor;
Fig. 2 is the structural representation of the moving abrasive disk of agitation grinding reactor;
Fig. 3 is the structural representation of the quiet abrasive disk of agitation grinding reactor;
Fig. 4 is the structural representation of the axial paddle of agitation grinding reactor;
Fig. 5 is the structural representation that second reactant of agitation grinding reactor divides charging aperture;
Fig. 6 is a U.S. Pat 3,226, the structure of reactor schematic diagram shown in 410.
The specific embodiment
Below further specify the present invention in conjunction with the accompanying drawings by a specific embodiment, but the present invention is not limited thereto embodiment.Only otherwise depart from aim of the present invention and scope, the present invention can have other change form.
Fig. 1 is a kind of preferred agitation grinding reactor provided by the present invention.Described agitation grinding reactor comprise the amine aqueous solution distributing disc 3, shaft 4 of reactor shell 1, phosgene charging aperture 1a, phosgene distributing disc 2, amine aqueous solution combined feed mouth 1b, ring-type, axially paddle 5, radially paddle 6, moving abrasive sheet 8, quiet abrasive sheet 9 and amine aqueous solution divide charging aperture 10; Wherein, reactor shell 1 and shaft 4 coaxial settings form reaction channel 7 below reactor shell inside is positioned at phosgene distributing disc 2; Axially paddle 5 and radially paddle 6 from top to down be arranged on the shaft; Moving abrasive sheet 8 is fixed on the shaft and is positioned at reaction channel, and quiet abrasive sheet 9 is fixed on the inwall of reactor shell 1 and is positioned at reaction channel 7, and moving abrasive sheet 8 and quiet abrasive sheet 9 are arranged on the radially below of paddle 6 spaced reciprocally; Amine aqueous solution divides charging aperture 3 to be arranged on axial paddle 5 and radially between the paddle 6.
Fig. 2, Fig. 3 are the structural representation of abrasive sheet 8 and quiet abrasive sheet 9 respectively, are equipped with a centre bore and a plurality of equally distributed circular access hole of circumferential that is on the described dynamic and static abrasive sheet.Fig. 4 is the structural representation of axial paddle 5.Fig. 5 is the structural representation that amine aqueous solution divides charging aperture 10, wherein each amine aqueous solution divide charging aperture 10 from shaft most proximal end and the distance between the inwall of reactor shell be l.
In the agitation grinding reactor provided by the present invention, phosgene solution and amine aqueous solution enter this reactor through 1a and 1b respectively, phosgene solution enters reaction channel 7 through the phosgene distributing disc 2 with cavity structure, under the effect of axial paddle 5, flows to the below of reaction channel 7.Amine aqueous solution is divided charging aperture 10 to spray to enter in the phosgene solution stream strand by amine aqueous solution through the cyclic amine solution distributing disc 3 of cavity structure, two bursts of material rapid mixing, fast reaction, and incorporation time is a Millisecond.The solid matter that the material reaction that mixes generates continues to move downward under the gravity effect, enter into dynamic and static abrasive sheet, through rotation at a high speed, the diameter of solid particle diminishes, reduced the possibility that material liquid is wrapped, the reactant liquor that comes out from reaction channel enters proceeds and finishes reaction in the subsequent reactions still.
Following examples will further specify agitation grinding reactor provided by the present invention and utilize the method for this reactor made isocyanates, but therefore the present invention is not subjected to any restriction.
In the process of producing toluene di-isocyanate(TDI) (TDI), the initial mixing of reaction raw materials toluenediamine and phosgene is to the yield important influence of final products, generally require two strands of materials in the time scale in initial mixing stage at Millisecond, to suppress the generation of side reaction, improve the yield of target product.
Adopt reactor as shown in Figure 1 to produce toluene di-isocyanate(TDI) (TDI), wherein: reaction channel adopts circular, diameter 100mm, agitator shaft speed is 400r/min, adopts axial paddle as shown in Figure 4, and axially paddle is 1 grade, have 3 blades, blade external profile diameter 90mm; It is 4 that amine aqueous solution divides charging aperture, circular hole design, bore dia is 2mm, and is vertical with shaft, this charging aperture apart from the reaction channel inwall apart from l=15mm; Radially paddle is 2 grades, and each level has 3 blades, blade external profile diameter 60mm; Adopt as shown in Figures 2 and 3 moving, quiet abrasive sheet, moving abrasive sheet outer most edge to the radial distance of reaction channel inwall is 2mm, the inner edge of quiet abrasive sheet to the radial distance of shaft outer most edge is 2mm, moving, access opening on the quiet abrasive sheet all is circular, the diameter of both access openings all is 10mm, and the percent opening with respect to reaction channel is 30%, moving, quiet abrasive sheet is respectively 3 grades (promptly being arranged alternately 3 moving abrasive sheets and 3 quiet abrasive sheets from top to bottom successively), the more close radially paddle of moving abrasive sheet (promptly moving abrasive sheet is above quiet abrasive sheet), moving, gap between the quiet abrasive sheet is 5mm.With flow is the mixed solution (being amine aqueous solution) of the toluenediamine (TDA) of 200Kg/h and o-dichlorohenzene (ODCB) composition that flow is 900Kg/h, injects continuously from amine aqueous solution charging aperture 1b; With flow is phosgene-o-dichlorobenzene solution (the phosgene mass percent is 50%) injection continuously from phosgene charging aperture 1a of 1200Kg/h; The reactant liquor that comes out from reaction channel enters into 100 ℃, 125 ℃ and each volume and is 0.8m
3Two stirred tanks in carry out phosgenation reaction, until solution clarification, product is after packed tower removes phosgene, desolventizes distillation, the yield of toluene di-isocyanate(TDI) (TDI) is 98.4%.
Adopt reactor of the present invention shown in Figure 1 to produce toluene di-isocyanate(TDI) (TDI), wherein: reaction channel adopts circular, diameter 100mm, agitator shaft speed is 300r/mi n, adopt axial paddle as shown in Figure 4, axially paddle is 1 grade, has 3 blades, blade external profile diameter 90mm; It is 4 that amine aqueous solution divides charging aperture, square hole design, the length of side is 2mm, and is vertical with shaft, each divide charging aperture apart from the reaction channel inwall apart from l=15mm; Radially paddle is 2 grades, and each level has 3 blades, blade external profile diameter 60mm; Adopt as shown in Figures 2 and 3 moving, quiet abrasive sheet, moving abrasive sheet outer most edge to the radial distance of reaction channel inwall is 2mm, the inner edge of quiet abrasive sheet to the radial distance of shaft outer most edge is 2mm, moving, quiet abrasive sheet has 3 grades (promptly being arranged alternately 3 moving abrasive sheets and 3 quiet abrasive sheets from top to bottom) respectively, the more close radially paddle of moving abrasive sheet (promptly moving abrasive sheet is above quiet abrasive sheet), moving, quiet abrasive sheet access opening all is circular, the diameter of both access openings all is 10mm, and the percent opening with respect to reaction channel is 40%, and is moving, the gap of quiet abrasive sheet is 5mm.With flow is the mixed solution (being amine aqueous solution) of the toluenediamine (TDA) of 200Kg/h and o-dichlorohenzene (ODCB) composition that flow is 900Kg/h, injects continuously from charging aperture 1b; With flow is phosgene-o-dichlorobenzene solution (the phosgene mass percent is 50%) injection continuously from charging aperture 1a of 1200Kg/h; The reactant liquor that comes out from reaction channel enters into 100 ℃, 125 ℃ and each volume and is 0.8m
3Two stirred tanks in carry out phosgenation reaction, until solution clarification, product is after packed tower removes phosgene, desolventizes distillation, the yield of toluene di-isocyanate(TDI) (TDI) is 98.1%.
Adopt reactor of the present invention shown in Figure 1 to produce toluene di-isocyanate(TDI) (TDI), wherein: reaction channel adopts circular, diameter 120mm, agitator shaft speed is 400r/min, adopt axial paddle as shown in Figure 4, axially paddle is 1 grade, has 3 blades, blade external profile diameter 90mm; It is 4 that amine aqueous solution divides charging aperture, circular hole design, diameter is 2mm, amine aqueous solution divides downward-sloping its central shaft that makes of charging aperture to become 70 ° of angles with shaft, each branch charging aperture apart from the reactor shell inwall apart from l=10mm; Radially paddle is 1 grade, has 3 blades, blade external profile diameter 65mm; Adopt dynamic and static abrasive sheet as shown in Figures 2 and 3, moving abrasive sheet outer most edge to the radial distance of reaction channel inwall is 2mm, the inner edge of quiet abrasive sheet to the radial distance of the outer most edge of shaft is 2mm, dynamic and static abrasive sheet has 3 grades (promptly being arranged alternately 3 moving abrasive sheets and 3 quiet abrasive sheets from top to bottom) respectively, the more close radially paddle of moving abrasive sheet, dynamic and static abrasive sheet access opening all is circular, the diameter of both access openings all is 10mm, percent opening with respect to reaction channel is 40%, and the gap of dynamic and static abrasive sheet is 5mm.With flow is the mixed solution of the toluenediamine (TDA) of 200Kg/h and o-dichlorohenzene (ODCB) composition that flow is 900Kg/h, injects continuously from charging aperture 1b; With flow is phosgene-o-dichlorobenzene solution (the phosgene mass percent is 50%) injection continuously from charging aperture 1a of 1200Kg/h; The reactant liquor that comes out from reaction channel enters into 100 ℃, 125 ℃ and each volume and is 0.8m
3Two stirred tanks in carry out phosgenation reaction, until solution clarification, product is after packed tower removes phosgene, desolventizes distillation, the yield of toluene di-isocyanate(TDI) (TDI) is 97.6%.
Adopt reactor of the present invention shown in Figure 1 to produce toluene di-isocyanate(TDI) (TDI), wherein: reaction channel adopts circular, diameter 90mm, agitator shaft speed is 500r/min, adopt axial paddle as shown in Figure 4, axially paddle is 1 grade, has 3 blades, blade external profile diameter 86mm; It is 4 that amine aqueous solution divides charging aperture, circular hole design, diameter is 2mm, its central shaft becomes 900 angles with shaft, each branch charging aperture apart from the reactor shell inwall apart from l=10mm (as Fig. 5); Radially paddle is 2 grades, and each grade paddle has 3 blades, blade external profile diameter 60mm; Dynamic and static abrasive sheet has 3 grades (promptly being arranged alternately 3 moving abrasive sheets and 3 quiet abrasive sheets from top to bottom) respectively, the more close radially paddle of moving abrasive sheet, moving abrasive sheet outer most edge to the radial distance of reaction channel inwall is 2mm, the inner edge of quiet abrasive sheet to the radial distance of the outer most edge of shaft is 2mm, dynamic and static abrasive sheet access opening is a rectangle, and wide is 3mm, and long is 10mm, percent opening with respect to reaction channel is 50%, and the gap of dynamic and static abrasive sheet is 5mm.With flow is the mixed solution of the toluenediamine (TDA) of 200Kg/h and o-dichlorohenzene (ODCB) composition that flow is 800Kg/h, injects continuously from charging aperture 1b; With flow is phosgene-o-dichlorobenzene solution (the phosgene mass percent is 50%) injection continuously from charging aperture 1a of 1100Kg/h; The reactant liquor that comes out from reaction channel enters into 100 ℃, 125 ℃ and each volume and is 0.8m
3Two stirred tanks in carry out phosgenation reaction, until solution clarification, product is after packed tower removes phosgene, desolventizes distillation, the yield of toluene di-isocyanate(TDI) (TDI) is 98.8%.
Adopt reactor of the present invention shown in Figure 1 to produce toluene di-isocyanate(TDI) (TDI), wherein: reaction channel adopts circular, diameter 150mm, agitator shaft speed is 400r/mi n, axially paddle is 1 grade, has 3 blades (as Fig. 4), blade external profile diameter 140mm; It is 4 that amine aqueous solution divides charging aperture, circular design, diameter is 3mm, its central shaft becomes 900 angles with shaft, each divide charging aperture apart from the reactor shell inwall apart from l=15mm; Radially paddle is 2 grades, and each level radially paddle has 3 blades, blade external profile diameter 90mm; Dynamic and static abrasive sheet has 3 grades (promptly being arranged alternately 3 moving abrasive sheets and 3 quiet abrasive sheets from top to bottom) respectively, the more close radially paddle of moving abrasive sheet, the outer most edge of moving abrasive sheet to the radial distance of reaction channel inwall is 2mm, the inner edge of quiet abrasive sheet to the radial distance of the outer most edge of shaft is 2mm, dynamic and static abrasive sheet access opening all is a rectangle, and wide is 3mm, and long is 10mm, percent opening with respect to reaction channel is 45%, and the gap of dynamic and static abrasive sheet is 4mm.With flow is the mixed solution of the toluenediamine (TDA) of 400Kg/h and o-dichlorohenzene (ODCB) composition that flow is 1500Kg/h, injects continuously from charging aperture 1b; With flow is phosgene-o-dichlorobenzene solution (the phosgene mass percent is 55%) injection continuously from charging aperture 1a of 2000Kg/h; The reactant liquor that comes out from reaction channel enters into 115 ℃, 130 ℃ and each volume and is 0.8m
3Two stirred tanks in carry out phosgenation reaction, until solution clarification, product is after packed tower removes phosgene, desolventizes distillation, the yield of toluene di-isocyanate(TDI) (TDI) is 98.1%.
The vulcabond crude product is analyzed, find when utilizing reactor made isocyanates provided by the invention, the less side products that resulting accessory substance produces when preparing isocyanates than the hole jet reactor that adopts usually at present, usually can reduce 1-4wt%, the preferred 2wt% (based on the total amount of vulcabond crude product) that reduces has obtained bigger economic benefit.
Claims (24)
1. agitation grinding reactor, it comprises: the second reactant distribution dish of reactor shell, the first reaction-ure feeding mouth, the first reactant distribution dish, the second reactant combined feed mouth, ring-type, shaft, axially paddle, radially paddle, moving abrasive sheet, quiet abrasive sheet and at least one second reactant divide charging aperture; Wherein, reactor shell and the coaxial setting of shaft, and below reactor shell inside is positioned at the first reactant distribution dish, form reaction channel; The first reactant distribution dish of first reactant through being arranged on this reactor top that be arranged so that of the first reaction-ure feeding mouth enters reaction channel; Axially paddle and radially paddle be arranged on the shaft from top to bottom; Moving abrasive sheet and quiet abrasive sheet are arranged on the radially below of paddle spaced reciprocally, and moving abrasive sheet is fixed on the shaft, and quiet abrasive sheet is fixed on the inwall of reactor shell, also are provided with access opening on moving abrasive sheet and the quiet abrasive sheet; Second reactant divides charging aperture to be arranged on axial paddle and radially between the paddle, so that second reactant divides charging aperture to be delivered to reaction channel through the second reactant distribution dish and second reactant of the second reactant combined feed mouth, ring-type.
2. reactor according to claim 1 is characterized in that, the described first reactant distribution dish and the second reactant distribution dish are cavity structure.
3. reactor according to claim 1 is characterized in that, 1-6, preferred 1-3 axial paddle be arranged in parallel on shaft; Each axial paddle has 2-20 sheet, preferred 3-15 sheet, more preferably 3-8 sheet blade; The external profile diameter of described axial paddle blade is 40-1000mm, is preferably 60-800mm.
4. reactor according to claim 1 is characterized in that, the cross sectional shape that described second reactant divides charging aperture is preferably circle, rectangle, triangle for circle, triangle, rectangle, rhombus, trapezoidal, polygon or ellipse; It is 3-200 that described second reactant divides the quantity of charging aperture, is preferably 3-100, more preferably 5-80.
5. reactor according to claim 4, it is characterized in that, described second reactant divides charging aperture flatly or dip down and tiltedly be arranged on the reactor shell and be positioned at reaction channel, and each divides the central shaft of charging aperture and the angle of shaft is 20-90 °, is preferably 60-90 °; Described second reactant divides charging aperture evenly or anisotropically to be distributed on the reactor shell, is preferably even distribution.
6. reactor according to claim 5 is characterized in that, it is 1-50mm that described second reactant divides the axial distance of the lower edge of the top edge of charging aperture and the axial paddle blade of afterbody, is preferably 2-30mm; It is 1-100mm from the radial distance of the extremely axial paddle blade outer most edge of most proximal end of shaft that described second reactant divides charging aperture, is preferably 2-40mm.
7. reactor according to claim 1 is characterized in that, 1-6, the individual radially paddle of preferred 1-3 be arranged in parallel on shaft; Each radially paddle have 2-20 sheet, preferred 3-15 sheet, more preferably 3-8 sheet blade; The external profile diameter of described radially paddle blade is 40-1000mm, is preferably 60-700mm.
8. reactor according to claim 7 is characterized in that, the first order radially upper limb to the second reactant of paddle blade to divide the axial distance of the lower limb of charging aperture be 1-200mm, be preferably 2-100mm.
9. reactor according to claim 1 is characterized in that, also is provided with centre bore on the described moving abrasive sheet, makes shaft pass this centre bore, and from top to bottom the 2-6 level is set on shaft, the moving abrasive sheet of preferred 2-4 level; Described moving abrasive sheet is that diameter is the disk of 40-1200mm, preferred 60-800mm; Described moving abrasive sheet outer most edge to the radial distance of reaction channel inwall is 1-20mm, preferred 1-10mm.
10. reactor according to claim 9 is characterized in that, the upper surface of the moving abrasive sheet of the first order to afterbody radially the axial distance of the lower edge of paddle blade be 1-200mm, be preferably 10-100mm.
11. reactor according to claim 10 is characterized in that, each moving abrasive sheet is provided with 10-1000, preferred 15-100 access opening; The cross sectional shape of described access opening is circle, triangle, rectangle, rhombus, trapezoidal, polygon or ellipse, is preferably circle, rectangle, triangle.
12. reactor according to claim 11 is characterized in that, described access opening evenly or anisotropically is distributed on the moving abrasive sheet, preferred evenly distribution; Described access opening is 10-80% with respect to the percent opening of whole moving abrasive sheet, is preferably 30-60%; Total circulation area of described access opening is 8-600mm
2, be preferably 10-400mm
2
13. reactor according to claim 1 is characterized in that, also is provided with centre bore on the described quiet abrasive sheet, makes shaft pass this centre bore, and from top to bottom the 1-6 level is set on the inwall of reactor shell, the preferred quiet abrasive sheet of 2-4 level; Described quiet abrasive sheet is that diameter is the disk of 40-1200mm, preferred 60-800mm; The inner edge of described quiet abrasive sheet to the radial distance of shaft outer most edge is 1-10mm, preferred 1-5mm.
14. reactor according to claim 13, it is characterized in that, the moving abrasive sheet of the first order is arranged on the top of the quiet abrasive sheet of the first order, and the axial distance between the moving abrasive sheet of every grade of quiet abrasive sheet and adjacent level is 1-50mm, be preferably 1-30mm, more preferably 1-25mm most preferably is 2-15mm.
15. reactor according to claim 14 is characterized in that, each quiet abrasive sheet is provided with 10-1000, preferred 15-100 access opening; The cross sectional shape of described access opening is circle, triangle, rectangle, rhombus, trapezoidal, polygon or ellipse, is preferably circle, rectangle, triangle.
16. reactor according to claim 15 is characterized in that, described access opening evenly distributes or anisotropically is distributed on the quiet abrasive sheet, preferred evenly distribution; Described access opening is 10-80% with respect to the percent opening of whole quiet abrasive sheet, is preferably 30-60%; Total circulation area of described access opening is 8-600mm
2, 10-400mm more preferably
2
17. reactor according to claim 1 is characterized in that, the cross sectional shape of described reaction channel is circle, ellipse, polygon or rectangle, is preferably circle, polygon.
18. reactor according to claim 17 is characterized in that, the diameter of described circular reaction channel is 30-1400mm, is preferably 60-800mm.
19. a method that adopts each described reactor among the claim 1-18 by the aliphatic of the amine preparation with general formula I shown in general formula I I, alicyclic or aromatic isocyanate,
R(NH
2)
n I
R(NCO)
n II
Wherein, R is aliphatic, alicyclic or aromatic hydrocarbyl, and n=1 or n 〉=2 said method comprising the steps of:
(a) pure phosgene liquid or phosgene solution enter reactor by the first reaction-ure feeding mouth, enter in the reaction channel through the first reactant distribution dish then;
(b) organic solution with amine of general formula I enters the second reactant distribution dish by the second reactant combined feed mouth, divides charging aperture to enter in the reaction channel by second reactant then;
(c) at axial paddle with radially under the effect of paddle, phosgene stream thigh and amine stream thigh mix rapidly, react, the solid particle that reaction generates grinds refinement through moving abrasive sheet and quiet abrasive sheet, and the reactant liquor that comes out from reaction channel enters proceeds and finish reaction in the subsequent reactions still.
20. method according to claim 19 is characterized in that, formed concentration is the phosgene solution of 50-100wt% to described phosgene solution in the inert organic solvents in order pure phosgene or phosgene are dissolved in.
21. method according to claim 19 is characterized in that, the organic solution of described amine is for being 10-60wt% with the formed concentration in inert organic solvents of the amine solvent shown in the general formula I, being preferably the amine aqueous solution of 20-50wt%.
22. method according to claim 19, it is characterized in that, R among described general formula I and the II is C2-C50 alkyl, alicyclic C2-C50 alkyl or aromatic series C6-C50 alkyl, be preferably C4-C30 alkyl, alicyclic C4-C30 alkyl or aromatic series C6-C30 alkyl, more preferably C5-C18 alkyl, alicyclic C5-C18 alkyl or aromatic series C6-C20 alkyl; N=2-4 among described general formula I and the II.
23. method according to claim 19, it is characterized in that, amine shown in the general formula I is selected from: toluenediamine, 4,4 '-diaminodiphenyl-methane, polymethylene polyphenyl polyamine, IPD, hexamethylene diamine, cyclohexanediamine, naphthylenediamine, p-phenylenediamine (PPD), phenylenedimethylidyne diamines, cyclohexanedimethyleterephthalate diamines, trimethyl-1,6-hexamethylene diamine, tetramethyl m-phenylenedimethylim-diamines, dimethyl diphenyl diamines or methylcyclohexyl diamines are preferably toluenediamine.
24. according to each described method among the claim 20-21, it is characterized in that, the inert organic solvents of dissolving phosgene and amine can be identical or different, and it is selected from benzene, toluene, chlorobenzene, o-dichlorohenzene, paracide, a chlordiphenyl, dimethyl terephthalate ester or the diethyl phthalate one or more respectively.
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