WO2007028715A1 - Verfahren zur herstellung von isocyanaten - Google Patents
Verfahren zur herstellung von isocyanaten Download PDFInfo
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- WO2007028715A1 WO2007028715A1 PCT/EP2006/065593 EP2006065593W WO2007028715A1 WO 2007028715 A1 WO2007028715 A1 WO 2007028715A1 EP 2006065593 W EP2006065593 W EP 2006065593W WO 2007028715 A1 WO2007028715 A1 WO 2007028715A1
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- phosgene
- amine
- reaction
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C263/00—Preparation of derivatives of isocyanic acid
- C07C263/10—Preparation of derivatives of isocyanic acid by reaction of amines with carbonyl halides, e.g. with phosgene
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F25/00—Flow mixers; Mixers for falling materials, e.g. solid particles
- B01F25/30—Injector mixers
- B01F25/31—Injector mixers in conduits or tubes through which the main component flows
- B01F25/313—Injector mixers in conduits or tubes through which the main component flows wherein additional components are introduced in the centre of the conduit
- B01F25/3132—Injector mixers in conduits or tubes through which the main component flows wherein additional components are introduced in the centre of the conduit by using two or more injector devices
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F25/00—Flow mixers; Mixers for falling materials, e.g. solid particles
- B01F25/30—Injector mixers
- B01F25/31—Injector mixers in conduits or tubes through which the main component flows
- B01F25/313—Injector mixers in conduits or tubes through which the main component flows wherein additional components are introduced in the centre of the conduit
- B01F25/3132—Injector mixers in conduits or tubes through which the main component flows wherein additional components are introduced in the centre of the conduit by using two or more injector devices
- B01F25/31322—Injector mixers in conduits or tubes through which the main component flows wherein additional components are introduced in the centre of the conduit by using two or more injector devices used simultaneously
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F25/00—Flow mixers; Mixers for falling materials, e.g. solid particles
- B01F25/30—Injector mixers
- B01F25/31—Injector mixers in conduits or tubes through which the main component flows
- B01F25/313—Injector mixers in conduits or tubes through which the main component flows wherein additional components are introduced in the centre of the conduit
- B01F25/3133—Injector mixers in conduits or tubes through which the main component flows wherein additional components are introduced in the centre of the conduit characterised by the specific design of the injector
- B01F25/31332—Ring, torus, toroidal or coiled configurations
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F25/00—Flow mixers; Mixers for falling materials, e.g. solid particles
- B01F25/40—Static mixers
- B01F25/42—Static mixers in which the mixing is affected by moving the components jointly in changing directions, e.g. in tubes provided with baffles or obstructions
- B01F25/43—Mixing tubes, e.g. wherein the material is moved in a radial or partly reversed direction
- B01F25/433—Mixing tubes wherein the shape of the tube influences the mixing, e.g. mixing tubes with varying cross-section or provided with inwardly extending profiles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F25/00—Flow mixers; Mixers for falling materials, e.g. solid particles
- B01F25/40—Static mixers
- B01F25/42—Static mixers in which the mixing is affected by moving the components jointly in changing directions, e.g. in tubes provided with baffles or obstructions
- B01F25/43—Mixing tubes, e.g. wherein the material is moved in a radial or partly reversed direction
- B01F25/433—Mixing tubes wherein the shape of the tube influences the mixing, e.g. mixing tubes with varying cross-section or provided with inwardly extending profiles
- B01F25/4335—Mixers with a converging-diverging cross-section
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/26—Nozzle-type reactors, i.e. the distribution of the initial reactants within the reactor is effected by their introduction or injection through nozzles
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C265/00—Derivatives of isocyanic acid
- C07C265/12—Derivatives of isocyanic acid having isocyanate groups bound to carbon atoms of six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C265/00—Derivatives of isocyanic acid
- C07C265/14—Derivatives of isocyanic acid containing at least two isocyanate groups bound to the same carbon skeleton
Definitions
- the present invention relates to a process for the preparation of isocyanates and a device suitable therefor, and to their use.
- the gas phase phosgenation is characterized in that the reaction conditions are chosen so that at least the reaction components diamine, diisocyanate and phosgene are gaseous at these conditions.
- the present invention relates exclusively to gas phase phosgenation.
- EP 1 275 639 A1 describes the gas-phase phosgenation of (cyclo) aliphatic diamines in a reaction zone with constrictions of the walls.
- EP 1 275 640 A1 describes the gas phase phosgenation of (cyclo) aliphatic di- and triamines in a mixing tube with a reactor, in which the gas flow in the mixing region is accelerated.
- a reactor geometry with an inner and an outer tube, with a gas phase phosgenation on a scale of only about 211 g of hexamethylenediamine-1, 6 per hour is possible.
- a disadvantage of the reactors disclosed in these two documents is that with a simple transfer of this reactor geometry to industrially meaningful sizes of the diameter of the inner tube would have to be increased so that a mixing of the metered through the two tubes streams due to the long transverse to the flow direction in short mixing times is no longer possible.
- EP 1 449 826 A1 discloses a pre-distribution of the amine-containing stream to at least two individual amine feeds. However, these are hydrodynamically decoupled from each other. If the cross section of a single of these tubes decreases, for example as a result of the formation of the amine hydrochlorides, then the throughput through this tube automatically becomes smaller because of the pressure drop increase and leads to a reduced throughflow. Smaller throughputs, however, lead to even more solids settling on the wall, so that the blockage progresses even faster.
- DE 10359627 A1 discloses a gas phase phosgenation in which amine is mixed in through a concentric annular gap between two phosgene streams, the surface cross sections of both phosgene streams being in a ratio of 1: 0.5 to 1: 4.
- Another disadvantage of this reactor geometry is that, given a simple transfer of this reactor geometry to industrially meaningful sizes, the internal diameter of the mixing element can only be increased up to a certain limit so that this area ratio can be maintained.
- WO 02/02217 describes various methods for mixing reactant streams, inter alia for liquid phase phosgenation.
- the object of the present invention was to develop a reaction regime for a gas phase phosgenation, with which a large-scale implementation is possible.
- the object is achieved by processes for the preparation of isocyanates by reacting the corresponding amines with phosgene, optionally in the presence of at least one inert medium, in the gas phase, in which in a reactor n
- Amine streams are reacted with n + 1 phosgene streams, where n is a positive integer of at least 1, and all amine and phosgene streams are metered via annular gaps for mixing in the reactor.
- annular gap and “annular gap” are used as follows:
- annular gap is considered as a generalization of a hollow cylinder (for the definition of the hollow cylinder, see Bronstein, "Taschenbuch der Mathematik", 21st edition, p. 199):
- An annular gap space is the volume of an outer and an inner, respectively spatially enclosed, curved lateral surface and the limiting end faces, wherein the two lateral surfaces do not penetrate each other.
- the annular gap is understood as a generalization of a circular ring surface (for the definition of the annular surface see Bronstein, "Taschenbuch der Mathematik", 21st edition, p. 194):
- the annular gap has the shape of the end face, which limits the above-described annular gap space at its end face.
- the annular gap space (see FIG. 1) also has a longitudinal axis 5 in the case of an irregular shape.
- this longitudinal axis 5 To construct this longitudinal axis 5, one chooses a point in the interior of the inner shell 2 and searches for the plane containing this point and the one with the lowest annular gap Cut surface, but completely in the form of an annular gap cuts.
- the center of gravity of this annular gap-shaped sectional area with the annular gap space lies on the longitudinal axis of the annular gap space.
- Other points of the longitudinal axis 5 can be determined by the same procedure when choosing other points inside the inner shell 2.
- the longitudinal axis 5 results as a whole of all focal points of such cut surfaces.
- the longitudinal axis forms a straight line.
- the phosgene-containing and amine-containing educt streams to be metered into the annular gap in the process pass through (2n + 1), for example three annular gap-shaped surfaces, into the annular gap space on one side.
- These annular gaps are arranged relative to one another in such a way that their centers of gravity lie substantially on a straight line, the center of gravity of the annular gap projecting furthest into the annular gap space lying on the longitudinal axis of the annular gap space.
- the centers of gravity of the annular gaps used for metering are preferably located in one point, so that the surfaces are arranged concentrically. Then the totality of all annular gaps used for metering, including the webs therebetween, results in an annular gap which represents one of the two end faces of the annular gap space.
- Rotationally symmetric means that a body, here the annular gap space, or a surface, here the associated annular gap, has a rotational symmetry when rotating about the axis of rotation. This may be, for example, a twofold rotational axis C2, a three-axis C3 ⁇ of the four-axis rotation axis C 4 , or preferably a complete rotational symmetry (C ⁇ ).
- a planar annular gap bordered by two ellipses each having coinciding longitudinal and transverse main axes has a twofold rotational axis.
- a circular ring surface has complete rotational symmetry.
- the amines that can be used in a gas phase phosgenation must meet certain requirements (see below).
- These may be monoamines, diamines, triamines or higher amines, preferably diamines. Accordingly, the corresponding mo- noisocyanates, diisocyanates, triisocyanates or higher isocyanates, preferably diisocyanates.
- the amines and isocyanates may be aliphatic, cycloaliphatic or aromatic, preferably aliphatic or cycloaliphatic and more preferably aliphatic.
- Cycloaliphatic isocyanates are those which contain at least one cycloaliphatic ring system.
- Aliphatic isocyanates are those which have exclusively isocyanate groups attached to straight or branched chains.
- Aromatic isocyanates are those which have at least one isocyanate group bonded to at least one aromatic ring system.
- aromatic diisocyanates are preferably those having 6-20 carbon atoms, for example monomeric 2,4'- or 4,4'-methylene-di (phenyl isocyanate (MDI), 2,4- and / or 2,6-tolylene diisocyanate (TDI) and 1, 5- or 1, 8-naphthyl diisocyanate (NDI).
- MDI phenyl isocyanate
- TDI 2,4- and / or 2,6-tolylene diisocyanate
- NDI 1, 5- or 1, 8-naphthyl diisocyanate
- Diisocyanates are preferably (cyclo) aliphatic diisocyanates, particularly preferably (cyclo) aliphatic diisocyanates having 4 to 20 C atoms.
- customary diisocyanates are aliphatic diisocyanates such as 1,4-tetramethylene diisocyanate, hexamethylene diisocyanate (1,6-diisocyanatohexane), 1,8-octamethylene diisocyanate, 1,10-decamethylene diisocyanate, 1,12-dodecamethylene diisocyanate, 1,14-tetradecamethylene diisocyanate, derivatives of lysine diisocyanate, tetramethylxylylene diisocyanate (TMXDI), trimethylhexane diisocyanate or tetra methylhexane diisocyanate, and also 3 (or 4), 8 (or 9) -bis (isocyanatomethyl) -tricyclo [5.2.1.0 26 ] decane isomer mixtures, and also cycloaliphatic diisocyanates such as 1 , 4, 1, 3 or 1, 2-diisocyanatocyclohexan
- 1,6-diisocyanatohexane 1-isocyanato-3,3,5-trimethyl-5- (isocyanato-methyl) cyclohexane, 4,4'-di (isocyanatocyclohexyl) methane and tolylene diisocyanate isomer mixtures.
- Particular preference is given to 1,6-diisocyanatohexane, 1-isocyanato 3,3,5-trimethyl-5- (isocyanatomethyl) cyclohexane and 4,4'-di (isocyanato-cyclohexyl) methane.
- amines for the reaction it is possible to use those amines for the reaction to the corresponding isocyanates in which the amine, its corresponding intermediates and the corresponding isocyanates are present in gaseous form under the reaction conditions chosen.
- Particularly suitable here are amines, in particular diamines, based on aliphatic or cycloaliphatic hydrocarbons having 2 to 18 carbon atoms.
- Examples of these are 1, 6-diaminohexane, 1-amino-3,3,5-trimethyl-5-aminomethylcyclohexane (IPDA) and 4,4'-diaminodicyclohexylmethane. Preference is given to using 1,6-diaminohexane (HDA).
- IPDA 1-amino-3,3,5-trimethyl-5-aminomethylcyclohexane
- HDA 1,6-diaminohexane
- aromatic amines can be used for the process according to the invention, which can be converted into the gas phase without significant decomposition.
- preferred aromatic amines are toluenediamine (TDA), as a 2,4- or 2,6-isomer or as a mixture thereof, for example as 80:20 to 65:35 (mol / mol) mixture, diaminobenzene, 2,6 Xylidine, naphthyldiamine (NDA) and 2,4'- or 4,4'-
- MDA Methylene (diphenylamine) (MDA) or isomeric mixtures thereof. Preferred among these are the diamines, more preferably 2,4- and / or 2,6-TDA.
- the compounds occurring in the course of the reaction ie starting materials (diamine and phosgene), intermediates (in particular the intermediately formed mono- and dicarbamoyl chlorides), end products (diisocyanate), and optionally metered inert compounds, among the Reaction conditions remain in the gas phase.
- starting materials diamine and phosgene
- intermediates in particular the intermediately formed mono- and dicarbamoyl chlorides
- end products diisocyanate
- optionally metered inert compounds among the Reaction conditions remain in the gas phase.
- these or other components e.g. deposited on the reactor wall or other apparatus components, it can be changed by these deposits, the heat transfer or the flow through the affected components undesirable. This is especially true for occurring amine hydrochlorides, which are formed from free amino groups and hydrogen chloride (HCl), since the resulting amine hydrochlorides are easily precipitated and are difficult to re-evaporate.
- the educts can be metered into the mixing chamber together with at least one inert medium.
- the inert medium is a medium which is gaseous in the reaction space at the reaction temperature and does not react with the compounds occurring in the course of the reaction.
- the inert medium is generally mixed before the reaction with amine and / or phosgene, but can also be separated from the educt streams be dosed.
- nitrogen, noble gases such as helium or argon, or aromatics such as chlorobenzene, chlorotoluene, o-dichlorobenzene, toluene, xylene, chloronaphthalene, decahydronaphthalene, carbon dioxide or carbon monoxide can be used.
- nitrogen and / or chlorobenzene is used as the inert medium.
- the inert medium is used in an amount such that the ratio of the gas volumes of inert medium to amine or to phosgene is more than 0.0001 to 30, preferably more than 0.01 to 15, particularly preferably more than 0.1 to 5 is.
- the starting amines are evaporated before carrying out the process according to the invention and heated to 200 ° C to 600 ° C, preferably 300 ° C to 500 ° C and optionally diluted with an inert gas or with the vapors of an inert solvent fed through the mixer to the reactor.
- the phosgene used in the phosgenation is also heated to a temperature within the range of 200 ° C to 600 ° C, preferably 300 ° C to 500 ° C before carrying out the inventive method optionally diluted with an inert gas or with the vapors of an inert solvent.
- the n amine streams are heated to a temperature up to 50 ° C higher than the (n + 1) phosgene streams, preferably up to 30 ° C, more preferably up to 24 and most preferably up to 20 ° C. higher.
- the temperature of the n amine streams is at least 5 ° C, more preferably at least 10 ° C above that of the (n + 1) phosgene streams.
- phosgene is used in excess with respect to amino groups.
- a molar ratio of phosgene to amino groups 1, 1: 1 to 20: 1, preferably from 1, 2: 1 to 5: 1 before.
- the mixing and reaction of the two gaseous educts takes place by the novel process after the introduction of the educt streams diamine and phosgene via the annular gaps as entry surfaces in the annular gap space as the reaction space.
- the reaction usually starts with contact of the reactants immediately after mixing.
- the mixing of the educts, optionally mixed with inert medium takes place (mixing space).
- the preheated stream containing amine or mixtures of amines and the preheated stream containing phosgene are passed continuously into the reactor, preferably a tubular reactor.
- the reactors are generally made of steel, glass, alloyed or enameled steel and have a length sufficient to allow complete reaction of the diamine with the phosgene under the process conditions.
- the (n + 1) phosgene streams and n amine streams are generally fed to a residence time reactor at one end of the reactor via a mixing unit. Between each 2 phosgene streams, an amine stream is fed at high speed through an annular gap. The supply of all phosgene streams and amine streams takes place in each case via annular gaps.
- the annular gaps with which adjacent phosgene streams and the amine stream between them are supplied are preferably those whose centroids lie on a straight line, particularly preferably those whose centroids coincide in one point.
- the supply via rotationally symmetric annular gaps.
- the shape of the annular gaps can be arbitrary. Conceivable are irregular shapes, trapezoidal, rectangular, square, polygonal, oval, elliptical or circular annular gaps, preferably rectangular, square, oval, elliptical or circular and more preferably circular annular gaps. Due to the shape of the annular gaps, the shape of the annular gap spaces is usually determined as well. However, it may also be conceivable, although less preferred, to form the annular gap spaces differently than the annular gaps.
- the amine stream is mixed via an annular gap between two phosgene streams, which in turn are metered via an annular gap.
- This inventive principle is analogous to the dosage of n amine streams, for example, 2, 3, 4 or more, between two layers of (n + 1) phosgene streams generalized.
- the interior of the annular gap and of the subsequent annular gap space is filled by a solid body or displacer as the core, which extends from the end face of the reaction space into the reaction space.
- the innermost and outermost streams are each a phosgene stream which keeps the amine stream (s) away from the walls of the reactor, both from the outer wall and from the inner bulk body.
- the ratio of the total area of the amine streams to the total area of the phosgene streams is greater than 0.00002, preferably greater than 0.0002, more preferably greater than 0.002, and most preferably greater than 0.02.
- the ratio of the total area of the amine streams to the total area of the phosgene streams is less than 5, preferably less than 1, more preferably less than 0.5 and most preferably less than 0.2.
- the area ratio of two phosgene-carrying annular gaps which are separated by an amine-conducting annular gap is 0.1 to 10, preferably 0.2 to 5, particularly preferably 0.4 to 2.5, very particularly 0.8 to 1, 25, in particular 0.9 to 1, 1 and especially 1.
- the area ratio of two amine-conducting annular gaps, which are separated by a phosgene-leading annular gap from 0.1 to 10, preferably 0.2 to 5, more preferably 0.4 to 2.5, most preferably 0.8 to 1 , 25, in particular 0.9 to 1, and especially 1.
- the individual educts are fed into the mixing device at a flow rate of 20 to 400 meters / second into the reactor, preferably from 25 to 300 meters / second, more preferably 30 to 250, most preferably 50 to 200, in particular more than 150 to 200 and especially 160 to 180 meters / second.
- the phosgene streams in particular the outer phosgene stream with a higher flow velocity through the annular gap in the mixing chamber, as the amine stream they envelop, more preferably at least 10 m / s more, especially preferably at least 20 m / s more and in particular at least 50 m / s more.
- the phosgene streams in particular the outer phosgene stream with a lower flow rate through the annular gaps in the mixing chamber, as the amine stream they envelop, more preferably with at least 50 m / s less, completely more preferably at least 120 m / s less, very preferably 160 m / s less and in particular at least 180 m / s less.
- the (n + 1) ring gaps of the phosgene streams are connected to precisely one phosgene feed line with little pressure loss, without additional control means, so that the rate at which the phosgene flows out of the (n + 1) ring columns is approximately equal.
- n ring gaps of the amine streams are preferably exactly one
- the educts enter the mixing chamber with a velocity vector.
- the velocity vector can be subdivided into an axial, radial and tangential directional component.
- the directional component of the velocity vector is understood to be parallel to the longitudinal axis of the mixing chamber.
- Radial direction is understood to mean the directional component of the velocity vector from the outside to the longitudinal axis, thus enclosing a right angle with the longitudinal axis.
- the directional component of the velocity vector is understood to be parallel to the boundary of the annular gap space, ie an annular circulating movement.
- an improvement in the mixing that results from the incorporation of elements producing a tangential velocity can be achieved, for example in the feed line of the partial streams of the excess components into the mixing chamber.
- a suitable tangential-speed generating element would be, for example, a spirally twisted band (spiral) embedded in the supply line, round or angular guide plates (guide vanes) or the like. The effect of the tangential velocity-generating internals is to increase the shear between flow layers of different composition in the flow of the nozzle.
- tangential entry of the feed line of one or more reactant streams is also possible or, in the case of a radial inflow of one or more reactant streams, a blade ring.
- the phosgene and amine streams with opposite tangential velocity in the mixing chamber may be useful to introduce the phosgene and amine streams with opposite tangential velocity in the mixing chamber, for example by the phosgene streams with a tangential velocity along the longitudinal axis of the reactor looking clockwise, and the intervening amine stream with a tangential speed counterclockwise in the mixing chamber be metered.
- the angle enclosed by the sum vector from the vectors of the tangential velocity and from the vector of the axial velocity of the streams metered in this way with the longitudinal axis of the reactor can range from 5 to 85 °, preferably 17 to 73 °, particularly preferably 30 to 60 ° which may be one stream, for example the phosgene streams, and from -5 to -85 °, preferably -17 to -73 °, more preferably -30 to -60 ° for the other streams, for example the amine stream.
- an angle between the sum vector from the radial velocity vector and from the axial velocity vector with the longitudinal axis is established. This angle usually corresponds to the angle of the associated metering channel with the longitudinal axis of the mixing chamber.
- a negative angle means a metering from the inside out
- an angle of 0 ° means a parallel to the longitudinal axis of the mixing chamber flow and an angle of 90 ° to the longitudinal axis of the mixing chamber vertical flow.
- the outer phosgene stream can be metered into the mixing space through the mixing device at a radial angle of 0 to 85 °, preferably 5 to 85 °, particularly preferably 7 to 65 °, very particularly preferably 15 to 35 ° and in particular 18 to 30 ° ,
- the amine stream can be metered into the mixing chamber through the mixing device at a radial angle of -50 ° to + 50 °, preferably -25 to 25 °, more preferably -10 to 10 ° and most preferably -3 to + 3 °.
- the inner phosgene stream can be passed through the mixing device at a radial angle of 0 to -85 °, preferably -5 to -85 °, particularly preferably -7 to -65 °, very particularly preferably -15 to -35 ° and in particular -18 to - 30 ° are metered into the mixing chamber.
- the outer phosgene stream and the amine stream relative to each other include a radial angle of 1 to 45 °, preferably 7 to 40, particularly preferably 15 to 35 and particularly preferably 18 to 30 °.
- the amine stream and the internal phosgene stream relative to one another include a radial angle of 1 to 45 °, preferably 10 to 40 °, particularly preferably 15 to 35 ° and particularly preferably 18 to 30 °.
- the reaction space in the front region comprises the mixing space, in which predominantly the mixing of the gaseous mixture of phosgene, amine, optionally mixed with inert medium takes place, which is usually accompanied by the onset of the reaction.
- the mixing space in which predominantly the mixing of the gaseous mixture of phosgene, amine, optionally mixed with inert medium takes place, which is usually accompanied by the onset of the reaction.
- the rear part of the reaction space then essentially only the reaction takes place and at most subordinate the mixing.
- the mixing space can be defined as the area of the reaction space in which the mixing of the educts takes place to a degree of 99%.
- the conversion in the mixing space ie the consumption of the amine used, is less than 15%.
- the degree of mixing is given as the ratio of the difference between the local average mixture fraction and the initial mixture fraction before mixing to the difference between the mean final mixture fraction after mixing and the initial mixture fraction before mixing.
- reactor is meant the technical device containing the reaction space.
- reaction spaces which are suitable for the non-catalytic, single-phase gas reaction, preferably for the continuous, non-catalytic, single-phase gas reaction, and which withstand the required moderate pressures.
- Suitable materials for contact with the reaction mixture are, for example, metals, such as steel, tantalum, silver or copper, glass, ceramic, enamel or homogeneous or heterogeneous mixtures thereof. Preference is given to using steel reactors.
- the walls of the reactor can be hydraulically smooth or profiled. As profiles are, for example, scratches or waves.
- reactors are known from EP-B1 289840, Sp. 3, Z. 49 - Sp. 4, Z. 25, EP-B1 593334, WO 2004/026813, S. 3, Z. 24 - P. 6, Z 10, WO 03/045900, page 3, Z. 34 - page 6, line 15, EP-A1 1275639, page 4, line 17 - page 5, line 17 and EP-B1 570799, Sp. 2, Z. 1 - Sp. 3, Z. 42, which are expressly referred to within the scope of this disclosure.
- a particularly preferred plate reactor has a width to height ratio of at least 2: 1, preferably at least 3: 1, more preferably at least 5: 1 and especially at least 10: 1.
- the upper limit of the ratio of width to height depends on the desired capacity of the reaction space and is in principle not limited. Reaction spaces with a ratio of width to height up to 5000: 1, preferably up to 1000: 1, have proven to be technically useful.
- the reaction of phosgene with amine in the reaction space takes place at absolute pressures of more than 0.1 bar to less than 20 bar, preferably between 0.5 bar and 15 bar and particularly preferably between 0.7 and 10 bar.
- the absolute pressure is very particularly preferably between 0.7 bar and 5 bar, in particular from 0.8 to 3 bar and especially 1 to 2 bar.
- the pressure in the feed lines to the mixing device is higher than the above-mentioned pressure in the reactor. Depending on the choice of mixing device drops at this pressure.
- the pressure in the supply lines is preferably 20 to 2000 mbar, particularly preferably 30 to 1000 mbar, higher than in the reaction space.
- the reactor consists of a bundle of reactors.
- the mixing unit does not have to be an independent apparatus, but rather it may be advantageous to use the mixing unit. unit to be integrated into the reactor.
- An example of an integrated unit of mixing unit and reactor is a tubular reactor with flanged nozzles.
- reaction in the gas phase is understood to mean that the conversion of the educt streams and intermediates to the products in the gaseous state react with each other and in the course of the reaction during the passage through the reaction space to at least 95%, preferably at least 98%, more preferably at least 99%, very particularly preferably at least 99.5%, in particular at least 99.8 and especially at least 99.9% remain in the gas phase.
- Intermediates are, for example, the monomino-monocarbamoyl chlorides, dicarbamoyl chlorides, monoamino monoisocyanates and monoisocyanato monocarbamoyl chlorides formed from the diamines, and the hydrochlorides of the amino compounds.
- the temperature in the reaction space is chosen so that it is above the boiling point of the diamine used, based on the pressure conditions prevailing in the reaction space.
- an advantageous temperature in the reaction space of more than 200.degree. C., preferably more than 260.degree. C. and particularly preferably more than 300.degree. C., usually results.
- the temperature is up to 600, preferably up to 570 0 C.
- the average contact time of the reaction mixture in the process according to the invention is generally between 0.001 seconds and less than 5 seconds, preferably from more than 0.01 seconds to less than 3 seconds, more preferably from more than 0.015 seconds to less than 2 seconds.
- the average contact time can be very particularly preferably from 0.015 to 1.5 seconds, in particular from 0.015 to 0.5 seconds, especially from 0.020 to 0.1 seconds and often from 0.025 to 0.05 Seconds.
- the term "average contact time” is understood to mean the period of time from the start of the mixing of the educts until they leave the reaction space in the workup stage.
- the flow in the reactor of the process according to the invention is characterized by a Bodenstein number of more than 10, preferably more than 100, and more preferably more than 500.
- the dimensions of the reaction space and the flow rates are selected such that a turbulent flow, ie a flow with a Reynolds number of at least 2300, preferably at least 2700, is present for the reaction mixture, wherein the Reynolds number is formed with the hydraulic diameter of the reaction space.
- the gaseous reaction mixture passes through the reaction space at a flow rate of 10 to 300 meters / second, preferably from 25 to 250 meters / second, more preferably 40 to 230, most preferably 50 to 200, in particular more than 150 to 190 and especially 160 to 180 meters / second.
- the turbulent flow results in narrow residence time distributions with a low standard deviation of usually not more than 6% as described in EP 570799 and good mixing is achieved. Measures such as the constriction described in EP-A-593 334, which is also prone to blockage, are not necessary.
- the reaction volume can be tempered over its outer surface.
- several reactor tubes can be connected in parallel.
- the reaction can also be carried out preferably adiabatically. This means that heating or cooling energy flows do not flow via the outer surface of the reaction volume with technical measures.
- the reaction conditions are selected such that the reaction gas at the outlet from the reaction space has a phosgene concentration of more than 25 mol / m 3 , preferably from 30 to 50 mol / m 3 .
- an inert medium concentration of more than 25 mol / m 3 preferably from 30 to 100 mol / m 3, is generally present at the outlet from the reaction space.
- the reaction space can be structurally decomposed essentially into up to four longitudinal sections along the longitudinal axis of the reactor in the course of the flow:
- a fourth section of length L 4 which represents a tube reactor without an internal displacer body and to which a quench (see below) adjoins.
- the reaction space is described as the volume in which at least 98% of the conversion, ie the consumption of the amine used, takes place, preferably at least 99%, more preferably 99.5%, very preferably 99.7%, in particular 99.9% and specifically 99.99%.
- R for the total diameter of the tubular reactor, i. from inner wall to inner wall, including the volume body in the reactor, and r for the outer diameter of this volume.
- angles ⁇ and ⁇ of which ⁇ describes the angle of the outer wall with the longitudinal axis of the tubular reactor and ⁇ the angle of the volume body with the longitudinal axis of the tubular reactor.
- a positive angle ⁇ thus describes an outer wall of the tubular reactor which widens in the course of the flow, whereas a negative angle ⁇ denotes a taper.
- a negative angle ⁇ describes a volumetric body that tapers in the flow direction, a positive one widening.
- the flow area F of the reactor is determined indirectly, by ⁇ and ß their course in the flow direction.
- the values of R and r may coincide or, by change, lead to a sudden expansion / constriction.
- the present invention furthermore relates to various preferred constructions of the reaction space, which differ in the size of the cross-sectional areas along the longitudinal axis of the reactor in the course of the flow:
- the flow-through surface F does not change in the course of the reactor, ie no structural distinction is made between sections, instead there is only a single section 1.
- ⁇ i and ⁇ i are each 0 °.
- the entire reactor is thus formed from an annular gap space, preferably from a rotationally symmetrical annular gap space, particularly preferably from a hollow cylinder.
- the area Fi flowing through increases in a section 1 and then remains constant in a second section 2.
- the angle ⁇ i is then 0 ° and the angle ßi from -1 to -10 °, preferably from -2 to -8 °, more preferably from -3 to -7 ° and most preferably from -4 to -6 °.
- the angle ⁇ i may also vary along the course of the section 1.
- the length U results from the diameter n at the beginning of the section 1 and the angle ßi by simple trigonometric calculation.
- R2 remains constant and r2 zero, 02 and ß2 are each 0 °.
- the second design alternative can also be achieved by increasing Ri and keeping n constant.
- the angle ⁇ i is 0 ° and the angle ⁇ i is from 0.0001 to 10 °, preferably from 0.0002 to 8 °, more preferably from 0.0003 to 7 °, and most preferably from 0.0003 to 6 ° ,
- the area Fi remains the same in a section 1 and expands in the second section to remain constant in the third section.
- ⁇ 2 is equal to zero and O 2 is, for example, from 0.0001 to 10 °, preferably from 0.0002 to 8 °, particularly preferably from 0.0003 to 7 ° and very particularly preferably from 0.0003 to 6 °.
- this third design alternative can also be achieved by keeping R2 constant in the second section and reducing r2 to zero.
- the angle 02 is then 0 ° and the angle ß2 from -1 to -10 °, preferably from -2 to -8 °, more preferably from -3 to -7 ° and most preferably from -4 to -6 °.
- the constant area in sections 1 and 3 is again achieved by keeping Ri and n constant and keeping R3 and r3 constant.
- the area Fi is kept the same in a section 1, in section 2 F2 is then reduced and increased in section 3 F3 and kept constant in section 4.
- ⁇ 2 is kept at 0 °
- O 2 is for example less than 0 ° and more than -90 °, preferably -7 to -65 °, particularly preferably -15 to -35 ° and very particularly preferably -20 to -30 °.
- F3 increases, which is achieved by an increasing R3 and a constant r3, which means that ⁇ 3 is zero and 03, for example, from 0.0001 to 10 °, preferably from 0.0002 to 8 °, more preferably from 0.0003 to 7 ° and most preferably from 0.0003 to 6 °.
- this fourth design alternative can also be achieved as follows:
- ⁇ 2 is kept at 0 °
- O 2 is for example less than 0 ° and more than -90 °, preferably -7 to -65 °, particularly preferably -15 to -35 ° and very particularly preferably -20 to -30 °.
- the area reduction F3 is achieved by a zero-reducing r3 and constant R3.
- the angle 03 is then 0 ° and the angle ß3 from -1 to -10 °, preferably from -2 to -8 °, more preferably from -3 to -7 ° and most preferably from -4 to -6 °.
- the area Fi is reduced in the first section, enlarged in the second section F2 and kept constant in the third section F3.
- Fi decreases, which is achieved by decreasing Ri and constant n.
- ⁇ i is kept at 0 °, ⁇ i is for example less than 0 ° and more than -90 °, preferably -7 to -65 °, more preferably -15 to -35 ° and most preferably -20 to -30 °.
- F 2 increases, which is achieved by an increasing R 2 and a constant r 2, which means that ⁇ 2 is zero and, for example, from 0.0001 to 10 °, preferably from 0.0002 to 8 °, more preferably from 0.0003 to 7 ° and most preferably from 0.0003 to 6 °.
- Fi decreases, which is achieved by decreasing Ri and constant n.
- ⁇ i is kept at 0 °, ⁇ i is for example less than 0 ° and more than -90 °, preferably -7 to -65 °, more preferably -15 to -35 ° and most preferably -20 to -30 °.
- the area reduction F2 is now achieved by keeping constant in the second section R2 and reducing r2 to zero.
- the angle 02 is then 0 ° and the angle ß2 from -1 to -10 °, preferably from -2 to -8 °, more preferably from -3 to -7 ° and most preferably from -4 to -6 °.
- the area Fi is reduced, remains constant in section two, is enlarged again in section 3, and then remains constant in the fourth section.
- Fi decreases, which is achieved by decreasing Ri and constant n.
- ⁇ i is kept at 0 °, ⁇ i is for example less than 0 ° and more than -90 °, preferably -7 to -65 °, more preferably -15 to -35 ° and most preferably -20 to -30 °.
- the third section F3 increases, which is achieved by an increasing R3 and a constant r3, which is also equal to r2, which means that ⁇ 3 equals zero and 03 for example from 0.0001 to 10 °, preferably from 0.0002 to 8 °, particularly preferably from 0.0003 to 7 ° and very particularly preferably from 0.0003 to 6 °.
- Fi decreases, which is achieved by a decreasing Ri and constant n.
- ⁇ i is kept at 0 °, ⁇ i is for example less than 0 ° and more than -90 °, preferably -7 to -65 °, more preferably -15 to -35 ° and most preferably -20 to -30 °.
- the area reduction of F3 is now achieved by keeping R3 constant in the third section and reducing r3 to zero.
- the angle 03 is then 0 ° and the angle ß3 from -1 to -10 °, preferably from -2 to -8 °, more preferably from -3 to -7 ° and most preferably from -4 to -6 °.
- the length of the section 2 is chosen differently depending on the amine used:
- isocyanates such as, for example, (cyclo) aliphatic isocyanates and in particular 1,6-hexamethylene diisocyanate
- a short section 2 is preferred.
- the length of zone 2 L2 is generally less than 30 times the resulting gap width (R2-r2), preferably less than 15 times, more preferably less than 10 times, most preferably less than 6 times , in particular smaller than five times and in particular smaller than three times. Often L2 is less than twice and even smaller than the simple of the gap width (R2 - ⁇ 2).
- the length of zone 2 in the case of such isocyanates is greater than the simple of the resulting gap width (R2-r2), preferably greater than 5 times, particularly preferably greater than 10 times, very particularly preferably greater than 15 times and in particular larger than 30 times.
- the length of each of the last section with gleichbeschender area F, that is, in the sixth alternative construction, L 4 is chosen so that on the one hand reaches the desired average contact time in the reactor and on the other hand, a L 4 / (2 * R 4) - ratio of greater than 2 , preferably greater than 4, more preferably greater than 6, most preferably greater than 10 and in particular greater than 15 achieved.
- F is chosen such that the average velocity of the reaction mixture is generally greater than 60 m / s, preferably greater than 100, more preferably greater than 160 m / s and most preferably greater than 180 m / s is and in particular greater 200 m / s.
- F is chosen such that the average velocity is generally less than 250 m / s, preferably less than 240, more preferably less than 230 m / s, even more preferably less than 220 m / s and in particular less than 210 m /s is.
- the change of the parameters R and r can be linear or non-linear within the sections.
- the angles ⁇ and ⁇ within the sections remain the same and only change at the transitions between the sections.
- the course may be concave, i. inclined in the flow space, convex, i. pointing away from the flow space, or mixed concavo-convex or convex-concave.
- a concave curve means for the angle ⁇ , that this increases or becomes more positive in the course of the flow, and for the angle ⁇ , that it becomes smaller or more negative. Preference is given to a linear course.
- transitions between the respective sections 1 to 4 can be carried out stepwise or rounded independently of each other. Preferred is a rounded design.
- FIG. 2 (not to scale):
- the reaction space 10 is bounded by an outer reactor wall 1 1 and an inner volume body 12 and divided along the course of the reaction into four sections of length Li, L2, L3 and L 4 , which differ in their area through which flows.
- the area Fi traversed is reduced by decreasing Ri and increasing n, remaining the same in section 2, expanding again in section 3 by increasing R3 and decreasing r3 to zero, then stay constant in the fourth section.
- the solid in the interior of the tube reactor is preferably connected to the walls of the reactor for stabilization, preferably via struts or baffles.
- the shape of these struts is preferably as streamlined as possible, for example with a drop cross section. But it is also possible to use these attachments to further increase the tangential velocity of the reaction mixture, so that this leads to an additional mixing.
- the flow-through volume of the reactor can be filled with static mixers, for example, packings, moldings, fabrics, perforated or slotted sheets, but the volume is preferably as free of internals as possible.
- a suitable turbulence generating element would be, for example, a recessed spirally twisted band, round or square slant plates or the like.
- the gaseous reaction mixture is preferably washed at temperatures greater than 130 ° C. with a solvent (quench).
- Suitable solvents are preferably hydrocarbons which are optionally substituted by halogen atoms, such as hexane, benzene, nitrobenzene, anisole, chlorobenzene, chlorotoluene, o-dichlorobenzene, trichlorobenzene, diethyl isophthalate (DEIP), tetrahydrofuran (THF), dimethylformamide (DMF), Xylene, chloronaphthalene, decahydronaphthalene and toluene.
- the solvent used is particularly preferably monochlorobenzene.
- the solvent used may also be the isocyanate.
- the isocyanate is selectively transferred to the wash solution. Subsequently, the remaining gas and the resulting wash solution are preferably separated by rectification in isocyanate, solvent, phosgene and hydrogen chloride.
- the reaction mixture After the reaction mixture has been reacted in the reaction space, it is passed into the workup device with quench.
- This is preferably a so-called scrubbing tower, the isocyanate formed being separated off from the gaseous mixture by condensation in an inert solvent, while excess phosgene, hydrogen chloride and optionally the inert medium pass through the work-up device in gaseous form.
- the temperature of the inert solvent above the solution temperature of the carbamoyl chloride belonging to the amine is preferably maintained in the selected quench medium. In this case, the temperature of the inert solvent is particularly preferably kept above the melting temperature of the carbamyl chloride belonging to the amine
- the pressure in the workup device is lower than in the reaction space.
- the pressure is preferably 50 to 500 mbar, more preferably 80 to 150 mbar, lower than in the reaction space.
- the laundry can be carried out, for example, in a stirred tank or in other conventional apparatus, for example in a column or mixer-settler apparatus.
- a suitable quench is known, for example, from EP-A1 1403248, Sp. 2, Z. 39 - Sp. 3, Z. 18, to which reference is expressly made in the scope of this disclosure.
- the reaction mixture which consists essentially of the isocyanates, phosgene and hydrogen chloride, is mixed intensively with the injected liquid.
- the mixing takes place in such a way that the temperature of the reaction mixture is lowered from 200 to 570 ° C. to 100 to 200 ° C., preferably to 140 to 180 ° C., and the isocyanate contained in the reaction mixture passes completely or partially into the sprayed liquid droplets by condensation, while the phosgene and hydrogen chloride remain substantially completely in the gas phase.
- the proportion of the isocyanate contained in the gaseous reaction mixture, which passes into the liquid phase in the quench zone, is preferably from 20 to 100% by weight, more preferably from 50 to 99.5% by weight and in particular from 70 to 99% by weight, based on the isocyanate contained in the reaction mixture.
- the reaction mixture preferably flows through the quench zone from top to bottom.
- a collecting container is arranged, in which the liquid phase is separated off, collected and removed from the reaction chamber via an outlet and subsequently worked up.
- the remaining gas phase is removed via a second outlet from the reaction space and also worked up.
- the quench may be, for example, as described in EP 1403248 A1, or as described in unpublished International Application Serial No. PCT / EP / 05/006745 and filing date 22.06.2005.
- the liquid droplets are for this purpose by means of single- or Zweistoffzerstäuberdüsen, preferably Einstoffzerstäuberdüsen generated and produce depending on the embodiment, a spray cone angle of 10 to 140 °, preferably from 10 to 120 °, particularly preferably from 10 ° to 100 °.
- the liquid that is injected via the atomizer nozzles must have a good solubility for isocyanates.
- organic solvents are used.
- aromatic solvents which may be substituted by halogen atoms.
- the immersed liquid is a mixture of isocyanates, a mixture of isocyanates and solvent or isocyanate, it being possible for the particular quench liquid used to comprise proportions of low-boiling components, such as HCl and phosgene.
- the isocyanate is used, which is prepared in the respective process. Since the reaction comes to a standstill due to the lowering of the temperature in the quench zone, side reactions with the injected isocyanates can be ruled out.
- the advantage of this embodiment is in particular that can be dispensed with a separation of the solvent.
- the inert medium used together with at least one of the educts and the solvent used in the quench are the same compound, most preferably monochlorobenzene is used in this case.
- Small amounts of by-products which remain in the isocyanate can be separated from the desired isocyanate by means of additional rectification, by stripping with an inert gas or else by crystallization, preferably by rectification.
- the isocyanate is separated off from the solvent, preferably by distillation.
- the separation of residual impurities including hydrogen chloride, inert medium and / or phosgene, can also take place here, as described, for example, in DE-A1 10260092.
- the cross-sectional area of the reaction space enclosed between the inner wall of the tubular reactor and the outer wall of the solid can preferably be constructed as described in the above-mentioned design alternatives.
- connection may be a connection to another device at the opposite end face of the tube reactor, in which there is at least one atomizer nozzle with which a liquid can be brought into contact with the reaction mixture leaving the tube reactor.
- the device can be designed so that the supply lines of the educt streams, preferably the Aminströ- me at the transition to the annular gaps narrow towards the annular gaps (13 in Figure 2) and thereby the Zuzhouwandept with half an opening angle , ie the angle between the longitudinal axis of the feed line and the narrowing Zumoni- tion wall, from more than 0 ° up to and including 70 ° leak, preferably 1 to 60 °, more preferably 2 to 50 °, particularly preferably 3 to 45 °, completely particularly preferably 5 to 40, in particular 7 to 30 and especially 7 to 20 °.
- the length of the constriction results from the selected angle and the outer diameter of the annular gap and the inner diameter of the feeding pipeline.
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Abstract
Description
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CN2006800326067A CN101258127B (zh) | 2005-09-06 | 2006-08-23 | 制备异氰酸酯的方法 |
US12/065,964 US8258337B2 (en) | 2005-09-06 | 2006-08-23 | Method for producing isocyanates |
EP06792972.9A EP1924552B1 (de) | 2005-09-06 | 2006-08-23 | Verfahren und vorrichtung zur herstellung von isocyanaten |
JP2008529589A JP5264489B2 (ja) | 2005-09-06 | 2006-08-23 | イソシアネートの製造方法 |
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DE102005042392.2 | 2005-09-06 | ||
DE102005042392A DE102005042392A1 (de) | 2005-09-06 | 2005-09-06 | Verfahren zur Herstellung von Isocyanaten |
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EP (1) | EP1924552B1 (de) |
JP (1) | JP5264489B2 (de) |
KR (1) | KR101339601B1 (de) |
CN (1) | CN101258127B (de) |
DE (1) | DE102005042392A1 (de) |
HU (1) | HUE042073T2 (de) |
SG (1) | SG166091A1 (de) |
WO (1) | WO2007028715A1 (de) |
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JP7486914B2 (ja) | 2015-04-21 | 2024-05-20 | コベストロ、ドイチュラント、アクチエンゲゼルシャフト | 1,5-ジイソシアナトペンタンを基礎とするポリイソシアネート混合物 |
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WO2018184980A1 (de) | 2017-04-03 | 2018-10-11 | Covestro Deutschland Ag | Reinigungsvorrichtung für gasströme aus der isocyanatherstellung |
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Publication number | Publication date |
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CN101258127B (zh) | 2012-06-13 |
SG166091A1 (en) | 2010-11-29 |
US8258337B2 (en) | 2012-09-04 |
JP5264489B2 (ja) | 2013-08-14 |
CN101258127A (zh) | 2008-09-03 |
JP2009507059A (ja) | 2009-02-19 |
US20090221846A1 (en) | 2009-09-03 |
KR101339601B1 (ko) | 2013-12-10 |
DE102005042392A1 (de) | 2007-03-08 |
KR20080043872A (ko) | 2008-05-19 |
HUE042073T2 (hu) | 2019-06-28 |
EP1924552B1 (de) | 2018-10-10 |
EP1924552A1 (de) | 2008-05-28 |
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