Classifications

• • 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
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
  • B01D3/14—Fractional distillation or use of a fractionation or rectification column
  • B01D3/16—Fractionating columns in which vapour bubbles through liquid
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
  • B01D3/42—Regulation; Control
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C263/00—Preparation of derivatives of isocyanic acid
  • C07C263/18—Separation; Purification; Stabilisation; Use of additives
  • C07C263/20—Separation; Purification
• • 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
• • 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
  • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J2219/00002—Chemical plants
  • B01J2219/00027—Process aspects
  • B01J2219/00033—Continuous processes

Definitions

• the invention relates to a process for the preparation of isocyanates by reacting primary amines with phosgene in the stoichiometric excess in the gas phase, in which the excess phosgene is subsequently recovered and recycled to the reaction.
• the present invention relates to a process for the controlled recycling of the recovered phosgene, particularly when the phosgene stream to be recycled is split between several gas phase reactors operated in parallel.
• Isocyanates are produced in large quantities and serve mainly as starting materials for the production of polyurethanes. They are usually prepared by reacting the corresponding amines with phosgene, wherein phosgene is used in stoichiometric excess. The reaction of the amines with the phosgene can be carried out both in the gas phase and in the liquid phase. In these syntheses, the excess phosgene generally precipitates at least partially together with the gaseous by-product hydrogen chloride liberated in the reaction, so that it is indispensable for economical operation of an isocyanate synthesis to separate the excess phosgene from the hydrogen chloride by-product and to return it to the reaction.
• GB 737 442 describes a process for the recovery of liquid phosgene from gas mixtures containing hydrogen chloride and phosgene, in which the gas mixture flows upwards through a cooler cooled to -40 to -60 ° C, the phosgene condensing and draining into a storage tank.
• the recovered liquid phosgene can be used in reactions with amines because of its low hydrogen chloride content of less than 0.7% by weight without further purification.
• it does not give any information on how the recovered liquid phosgene can be used in an economically advantageous manner in a gas phase reaction.
• US 2,764,607 describes a process for the recovery of phosgene from a gas mixture with hydrogen chloride from the production of chloroformates.
• the phosgene-hydrogen chloride gas mixture leaving the condenser which is mounted on the reaction vessel, is first brought into contact with cold solvent, the phosgene preferably being absorbed in the solvent.
• the feed is fed between the output and the amplifier part and, with the aid of a top condenser, a reflux to the distillation column is generated, which completely removes solvent from the gas mixture taken off at the top.
• the phosgene is completely liquefied and fed to a storage container.
• a disadvantage of the disclosed method is the high demand for cooling performance at a low temperature level.
• the document describes that the hydrogen chloride-phosgene separation can be carried out under high pressure, but this increases the safety risk.
• the generation of high pressure is energetically complex.
• the separation is described at very low temperatures, which, however, is also energetically complex and also leads to high levels of hydrogen chloride in the liquid, phosgene-containing phase.
• WO 2007/014936 discloses a process for the preparation of diisocyanates by reacting diamines with stoichiometric excess phosgene in the gas phase, wherein the excess phosgene is at least partially recycled to the reaction and wherein the phosgene flow to the reactor before mixing with the amine is less than Contains 15 wt .-% hydrogen chloride.
• the service life of the reactors should be improved because precipitations of amine hydrochlorides are to be reduced.
• a disadvantage of such high levels of inert hydrogen chloride gas in the phosgene gas is that this leads to an increase in operating costs and larger equipment and thus high plant construction costs through increased circulation.
• the excess phosgene and the resulting hydrogen chloride is first separated from the substantially gaseous reaction mixture, then the excess phosgene is at least partially recycled back into the reaction, from this recycled phosgene hydrogen chloride is separated so that the phosgene before the mixing with the amine stream less than 15 wt .-% hydrogen chloride.
• the reference teaches that the separation is preferably carried out via a combination of a distillation and a wash.
• the phosgene is washed out of the hydrogen chloride-containing stream with a detergent.
• the separation of the phosgene and the hydrogen chloride from this loaded washing medium is preferably carried out by distillation.
• the laundry and the distillation can be operated according to description at pressures of 1 to 10 bar absolute. Further explanation of the separation of phosgene from the loaded detergent does not disclose the Scriptures.
• the phosgene in a gas phase phosgenation reaction, the phosgene must not contain more than 1000 ppm by weight of chlorine before mixing with the amine, otherwise the risk of material damage would occur due to the high temperatures. According to this teaching, due to the cleavage of phosgene at high temperatures always forms a certain amount of chlorine, so that a separation of this chlorine is necessary.
• the document discloses an embodiment in which the phosgene, hydrogen chloride and chlorine-containing gas mixture is first subjected to partial condensation (S. 18, Z.30) and laundry (page 19, Z.18) is subjected. In this case, a liquid phase containing phosgene, washing medium, hydrogen chloride and chlorine is obtained.
• a first rectification (called c)) of the low-boiling components chlorine and hydrogen chloride.
• phosgene and washing medium are separated from one another in a second rectification (called e)) (page 20, lines 26 to page 21, line 1).
• the document discloses two embodiments of the second rectification column: In the first, the rectification column has only one stripping section, so that the top product is removed without purification via separation-active internals at the top. The characterization of the composition of the bottom product is not unique; it is attributed to the phosgenation reaction. About the further use of the low-current current eL is not specified.
• the second rectification additionally has an amplifier part which, with a corresponding reflux ratio, makes it possible for the top stream to consist essentially of pure phosgene, which can be used in the phosgenation without further purification.
• the bottom stream consists in this embodiment with amplifier part substantially pure washing liquid.
• WO 2009/037179 discloses a process for the preparation of isocyanates in the gas phase, wherein the freshly produced phosgene is fed without prior condensation of the gas phase reaction.
• the phosgene holdup of the plant is reduced and the energy saved for vaporizing the phosgene is saved (page 5, lines 32-42).
• a disadvantage of this process is the inability to separate accompanying components contained in the fresh phosgene, which otherwise contaminate the hydrogen chloride stream discharged from the process.
• this document describes the process for the separation of phosgene from a gas mixture with hydrogen chloride and for recycling the separated phosgene for gas phase phosgenation by a combined wash and multi-stage distillation.
• the document states that first a washing liquid laden with phosgene and hydrogen chloride is obtained in a first step by washing the phosgene-hydrogen chloride gas mixture with a washing liquid. This is followed by a first distillation step, in which the hydrogen chloride is largely removed from the phosgene-containing wash solution and returned to the preceding washing step, followed by a second distillation step in which the previously obtained wash solution is separated into gaseous phosgene and largely free from phosgene scrubbing liquid , The gaseous phosgene is passed into the gas phase phosgenation, while the Washing liquid is used again for washing the phosgene-hydrogen chloride gas mixture.
• the document does not disclose how the phosgene washing liquid separation is configured in terms of apparatus or which purity of the recycled phosgene stream is achieved.
• a two-stage distillation process for recovering gaseous phosgene from a phosgene-laden washing medium for recycling to the phosgenation reaction is the method of choice.
• the elimination of fresh phosgene condensation and storage is the only concrete measure that the scripture calls for to achieve a lower phosgene hold-up.
• a process procedure consisting of two distillation steps (and thus the use of separation apparatuses with significant phosgene hold-up) is proposed as the preferred embodiment, no detailed information is provided on the apparatus design of the two distillation steps, in particular not on the phosgene hold. up minimizing apparatus design.
• WO 2011/003 532 discloses a process for the preparation of isocyanates by reacting primary amines with phosgene in the stoichiometric excess in the gas phase, in which the excess phosgene is subsequently recovered and recycled to the reaction.
• the recovery of phosgene from the phosgene and hydrogen chloride-containing gas mixture is carried out in two stages.
• the hydrogen chloride and phosgene-containing gas mixture leaving the reactor is separated into a gaseous substantially hydrogen chloride-containing stream and a liquid stream containing phosgene, and in a second step (phosgene gas production) receiving liquid stream transferred into a gaseous, phosgene-containing stream, wherein the pressure in the first process step is less than the pressure in the second process step.
• the process is advantageous because it enables the recovery of phosgene from the liquid, phosgene-containing detergent solution in just one step (phosgene gas production).
• the phosgene gas production takes place in a distillation column with 2 to 45 theoretical plates.
• the column can contain a stripping section and / or an amplifier section, preferably the column contains both an output section and an amplifier section, with a preferred supply of the input flow between the output section and the amplifier section.
• the column is preferably operated at a bottom temperature of 140-220 ° C.
• the column is provided with a top condenser.
• the top condenser is preferably operated at a coolant inlet temperature of -25 to 0 ° C.
• the condensate produced by the top condenser can be wholly or partially recycled to the column and / or removed, preferably the condensate is completely recycled to the column.
• a disadvantage of the preferred embodiment is the large dimension of the column for phosgene gas production, as well as the expensive use of cold to produce a return stream.
• the phosgene gas production is carried out so that the liquid stream containing phosgene is separated from the hydrogen chloride-phosgene separation by partial evaporation into a gaseous stream containing phosgene and possibly inert gases and into a liquid stream.
• the liquid stream obtained from the hydrogen chloride-phosgene separation is passed into an evaporator whose bottom temperature is preferably 100-220 ° C.
• the phosgene-containing liquid stream from the hydrogen chloride-phosgene separation is preferably passed indirectly into the phosgene gas production, i. H. heated by heat exchange with other process streams to particular preferred 5 - 175 ° C heated the phosgene gas is supplied.
• the production of phosgene gas is in the form of a stripping column, ie without a reinforcing part.
• the stream to be distilled is fed at the top of the distillation column so that a stripping column does not have an enrichment section.
• the phosgene solution obtained from the hydrogen chloride-phosgene separation is pumped directly to the top of the stripping column at a temperature below 10 ° C., ie without pre-evaporation.
• gaseous phosgene is taken, containing about 0.2% by weight of solvent.
• a disadvantage of this embodiment is that due to the low head temperature of the desorption column no energy-saving heat integration can be realized by preheating and partial pre-evaporation. Furthermore, the phosgene solution due to varied process parameters (including phosgene excess in the reaction, reactor outlet temperature, amount of solvent to the quencher, amount of solvent for phosgene absorption) and due to process variations have different compositions and temperature. In the case of direct application to the top of the stripping column, this inevitably leads to a changed and possibly fluctuating composition and temperature of the phosgene recycling stream, since a stabilizing, controllable top condenser is not available in this embodiment. Varying conditions of the phosgene recycle stream can lead to lower energy efficiency, reduced reaction yield, increased operating costs, and reduced availability.
• WO 2011/003 532 mentions the possibility that hydrogen chloride-phosgene gas mixtures from several reaction lines are treated in a single hydrogen chloride-phosgene separation.
• gas phase reactors have a narrow favorable load range, the fast operating point change is e.g. advantageous when starting and stopping individual reactors.
• the apparatus design allows a smaller maximum production capacity than the desired total capacity of the production plant (see “Rules of Thumb for
• EP-A-570 799 describes that gas phase reactors for the phosgenation of amines have only a narrow favorable load range, and that solid formation can occur in the reactors, which may necessitate production stoppages for cleaning purposes. U. a. For these reasons, the installation of several parallel operable reaction lines for phosgenation may be advantageous. On the other hand, in order to reduce the apparatus costs, it may be advantageous to design upstream and / or downstream process steps (eg phosgene generation, amine evaporation, hydrogen chloride phosgene separation) together for all reaction sections.
• upstream and / or downstream process steps eg phosgene generation, amine evaporation, hydrogen chloride phosgene separation
• EP-A-2 196 455 describes u. a. an embodiment of a production process for isocyanates, in which the crude product of two reaction sections of a common reaction termination zone (quench) is supplied.
• phosgene gas production and the reactors are connected to each other via a gas space, so that a change in the process pressure in an apparatus affects the connected apparatus. This is especially true when there are no actively controllable booster or pressure reduction elements in the connection between phosgene gas production and reactors. Above all, sudden changes in process parameters (eg safety shutdown or load change in a reaction line) lead to undesirable instabilities in the overall system, possibly even up to the necessity of decommissioning the entire system.
• An essential parameter for the trouble-free and stable operation of the reaction is the guarantee of a constant phosgene excess in the phosgenation reaction.
• a constant supply pressure of the phosgene gas source ie z. B. a distillation column, essential.
• the pressure control of this distillation column is of essential importance for the overall process stability.
• the elimination of the head capacitor complicates the pressure control.
• the prior art does not disclose a method that would combine eliminating the amplifier part with energy efficient preheat / pre-evaporation of the phosgene gas generation feed.
• the gas phase reaction is an inert substance, for.
• solvent can be supplied, wherein the range of possible solvent contents described in Phosgen Wegfabstrom reaches 10% by mass.
• the lowest possible solvent content in the phosgene stream is obviously desired in practice (see, for example, the document WO 2011 / discussed in detail above).
• 003 532 according to this, only a few ppm of solvent is allowed to minimize energy input, in example 5 a solvent concentration of 0.2% is mentioned, which is the maximum value disclosed in a particular embodiment).
• phosgene-solvent separation column is equipped with an amplifier part and operated with a reflux, or by a low temperature level is maintained at the top of the column (in WO 2011/003 532, a temperature of the feed to the top of column maximum 10 ° C called).
• an object of the present invention is a continuous process for the preparation of an isocyanate by phosgenation of the corresponding primary amine, comprising the steps:
• step (v) discharging the two-phase process product from step (iv) at the top of a distillation column from which a gaseous phosgene-containing stream is taken overhead;
• step (vi) recycling the gaseous phosgene-containing stream from step (v) in step (i) (recycling "re-phosgene”);
• step (vii) working up of the liquid, solvent and isocyanate-containing stream (ii-2) obtained in step (ii) to obtain the desired isocyanate.
• the procedure according to the invention makes it possible to evaporate only partially the liquid phosgene-containing stream (iii-1) in step (iv) and to feed a two-phase process product into the distillation column in step (v), the pre-evaporator used in step (iv) Control device to use, whereby the hitherto conventional top condenser of this distillation column, which also takes over control tasks in the art, is dispensed in principle and is preferably not used in the inventive method.
• the solvent content in the gaseous phosgene-containing top product can be adjusted in a targeted manner (for example to 5.0% by mass at a temperature of the two-phase process product when fed into the distillation column at 100 ° C.), as described below is carried out closer.
• a targeted manner for example to 5.0% by mass at a temperature of the two-phase process product when fed into the distillation column at 100 ° C.
• this quality of the pressure regulation can be achieved in a preferred embodiment by using an (at least partially) vaporous, phosgene-containing feed stream for the generation of gaseous recycle phosgene as the manipulated variable of the pressure control.
• Step (i) of the invention the actual gas phase phosgenation, can in principle be carried out according to a method described in the prior art, as described, for example, in EP-A-570 799 and WO-A-2007/014936. It is possible to use both aliphatic and aromatic mono- and polyamines. Aromatic amines are preferably used, in particular aromatic diamines which can be converted into the gas phase without appreciable decomposition.
• TDA toluenediamine
• NDA naphthyldiamine
• TDA 2,4-TDA and 2,6-TDA and mixtures thereof.
• NDA naphthyldiamine
• TDA 2,4-TDA and 2,6-TDA and mixtures thereof.
• amines especially diamines, based on aliphatic or cycloaliphatic hydrocarbons having 2 to 18 carbon atoms are particularly suitable.
• Particularly suitable amines are 1,6-diamino-hexane, l-amino-3,3,5-trimethyl-5-aminomethylcyclohexane (IPDA) and 4.4, -Diaminodicyclohexylamin.
• the starting amines are usually evaporated before carrying out the process according to the invention and heated to 200 ° C to 600 ° C, preferably 200 ° C to 500 ° C, more preferably 250 ° C to 450 ° C and optionally diluted with an inert gas such as N2 , He, Ar or with the vapors of an inert solvent, e.g. B. aromatic hydrocarbons optionally with halogen substitution, such as. As chlorobenzene or o-dichlorobenzene, fed to the reaction space.
• an inert gas such as N2 , He, Ar
• an inert solvent e.g. B.
• aromatic hydrocarbons optionally with halogen substitution, such as.
• chlorobenzene or o-dichlorobenzene fed to the reaction space.
• the evaporation of the starting amines can be carried out in all known evaporation equipment, preference is given to evaporation systems in which a small working content with a high circulation capacity is passed through a falling film evaporator, wherein to minimize the thermal load of the output amines of the evaporation process - as stated above - if necessary with the addition of Inert gas and / or vapors of an inert solvent can be supported.
• the evaporation can also take place in special evaporation apparatus with very short residence times, as described for example in EP-A-1 754 698.
• phosgene is used in excess with respect to the amine groups to be reacted.
• a molar ratio of phosgene to amine groups of 1.1 to 20, preferably from 1.2 to 5, before.
• the phosgene is heated to temperatures of 200 ° C to 600 ° C and optionally diluted with an inert gas such as N 2 , He, Ar or with the vapors of an inert solvent, eg.
• an inert gas such as N 2 , He, Ar or with the vapors of an inert solvent, eg.
• aromatic hydrocarbons with or without halogen substitution such as.
• chlorobenzene or 0-dichlorobenzene fed to the reaction space.
• the inventive method is preferably carried out in step (i) so that the separately heated reactants via at least one mixing device in at least introduced a reaction space, mixed and reacted under consideration of suitable reaction times under preferably adiabatic reaction. Subsequently, by cooling the gas stream, the isocyanate is condensed, wherein the cooling to a temperature above the decomposition temperature of the corresponding carbamic, so for example Toluylendiaminklachlorid in the case of TDA, takes place.
• the necessary residence time for the reaction of the amine groups with the phosgene to form isocyanate is between 0.05 and 15 seconds, depending on the type of amine used, the starting temperature, the adiabatic temperature increase in the reaction space, the molar ratio of amine and phosgene used, any Dilution of the reactants with inert gases and the selected reaction pressure.
• Reactors having substantially rotationally symmetrical reaction spaces are particularly preferably used in step (i), in which the gaseous educts, optionally diluted with inerts, at least one mixing chamber according to the jet mixer principle (Chemie-Ing. Techn. 44 (1972) p , Fig.10).
• the components are thus preferably adiabatically converted; the adiabatic temperature increase in the mixing unit and reactor or reactor is adjusted solely via the temperatures, compositions and relative dosages of the educt streams and the residence time in the mixing units and the reactors , It is also possible in the inventive method, a non-adiabatic reaction of the components.
• the gaseous reaction mixture which comprises the isocyanate, phosgene and hydrogen chloride formed is freed from the isocyanate formed in step (ii) by treatment with a solvent and any reactions still occurring are quenched ("quenching").
• the treatment with solvent is carried out at a temperature which is below the boiling temperature of the isocyanate and above the decomposition temperature of the corresponding carbamic acid chloride, so that a gaseous, hydrogen chloride and unreacted phosgene-containing stream (ii-1) and a liquid, solvent and isocyanate containing stream (ii-2) can be obtained.
• isocyanate For selective recovery of the isocyanate from the gaseous reaction mixture are particularly suitable at a temperature of 80 ° C to 200 ° C, preferably 80 ° C to 180 ° C held solvent such as chlorobenzene and / or dichlorobenzene, or held in these temperature ranges isocyanate or Mixtures of the isocyanate with chlorobenzene and / or dichlorobenzene. It is easily predictable for a person skilled in the art on the basis of the physical data at a given temperature, pressure and composition, which mass fraction of the isocyanate condenses in the quenche or passes through it uncondensed. Likewise, it is easy to predict which mass fraction of the excess phosgene, hydrogen chloride and inert gas optionally used as diluent passes through the quench uncondensed or dissolves in the quench liquid.
• solvent such as chlorobenzene and / or dichlorobenzene
• the gas mixture (ii-1) leaving the condensation or quenching stage is preferably freed from residual isocyanate in a downstream gas scrubber with a suitable scrubbing liquid.
• the purification of the isocyanate is preferably carried out subsequently by distillative workup of the stream (ii-2), optionally after it has been combined with further isocyanate from the gas scrubber.
• step (iii) the hydrogen chloride and phosgene contained in stream (ii-1) are separated to obtain a liquid phosgene-containing stream (iii-1) and a gaseous hydrogen chloride-containing stream (iii-2).
• the gas mixture entering into the separation in step (iii) generally contains 1 to 50% by mass of HCl, preferably 3 to 40% by mass of HCl, particularly preferably 5 to 35% by mass of HCl and very particularly preferably 7.5 to 30 Mass% HCl, based on the mass of the gas mixture.
• This gas mixture generally contains 5 to 90% by mass of phosgene, preferably 15 to 85% by mass of phosgene, particularly preferably 25 to 80% by mass of phosgene and very particularly preferably 40 to 75% by mass of phosgene, based on Mass of the gas mixture.
• the content of solvent in the gas mixture is generally 0.01 to 60% by mass, preferably 0.05 to 40% by mass and more preferably 0.1 to 10% by mass, based on the mass of the gas mixture.
• the solvent may be in the form of vapor or liquid.
• the gas mixture may additionally contain inert gases in the sum of generally 0 to 10% by mass, preferably 0.0001 to 8% by mass and more preferably 0.001 to 5% by mass, based on the masses of the gas mixture.
• the gas mixture may generally contain from 0 to 10% by mass, preferably from 0.001 to 7.5% by mass and more preferably from 0.05 to 5% by mass, based on the mass of the gas mixture, of reaction product.
• step (iii) can be carried out by various embodiments, as described in detail, for example, in WO 2011/003532 (page 11, line 31 to page 19 line 11) and can also be used in the method according to the invention.
• absorption in a solvent is just as suitable as partial condensation with subsequent washing or complete or partial condensation with subsequent distillation or stripping.
• a particularly preferred embodiment for this process step is absorption in a solvent. Most preferably, the absorption is carried out on the solvent which is also used for the quench (step (ii)).
• the absorption takes place in a sequence of at least two absorption steps, optionally in combination with partial condensation stages, wherein at least one absorption step is performed isothermally and at least one absorption step is performed adiabatically.
• the first absorption step is performed isothermally, the following absorption step adiabatically.
• the same solvent used in step (ii) is used for the adiabatic and isothermal absorption step. It is furthermore preferred to further purify the gas leaving the last absorption stage by cooling it by means of a heat exchanger of any remaining traces of phosgene and solvent by condensation.
• step (iii) is carried out by partial condensation with subsequent washing.
• the gas mixture is first partially condensed.
• the remaining gas stream is introduced from below into an absorption column and washed in countercurrent with the solvent.
• the removal of the heat of absorption is carried out by external heat exchangers.
• the liquid can be completely or partially, preferably completely, removed and cooled by an external cooler.
• step (iii) is the partial or complete condensation of phosgene, followed by distillation or stripping in a column for removing the dissolved HCl from the bottoms product phosgene, and then washing the overhead product HCl obtained in the first step a solvent for absorption of the remaining after condensation in the gas stream phosgene.
• the liquid stream obtained in the bottom of the distillation or stripping has only a small charge of dissolved HCl and / or inert gases and can be passed in step (iv).
• step (iii) all provide a gaseous stream (iii-2) and a liquid stream (iii-1).
• the HCl-containing gas stream (iii-2) has sufficient purity and can generally be further processed without further purification.
• the fresh phosgene to be added to supplement the phosgene consumed in step (i) is added in step (iii) and thus becomes part of the liquid phosgene-containing stream (iii-1) obtained in this step.
• this step comprises the absorption in a solvent
• fresh phosgene can be added to the bottom of the corresponding absorption column.
• Gas stream (iii-2) leaving step (iii) contains essentially HCl and optionally traces of phosgene.
• the stream may also contain inert gases and / or solvents as well as traces of reaction by-products.
• the stream contains 80 to 100% by mass, preferably 90 to 100% by mass, and particularly preferably 95 to 100% by mass of HCl, based on the mass of the gas stream (iii-2).
• This gas stream contains not more than 0.8% by mass of phosgene, preferably not more than 0.4% by mass and more preferably not more than 0.2% by mass of phosgene, based on the mass of the gas stream (iü-2).
• the gas stream (iii-2) leaving step (iii) is generally at the outlet from the process step under a pressure of 1.00 to 4.00 bar absolute, preferably 1.01 to 3.00 bar absolute, and particularly preferably 1 , 02 to 2.00 bar absolute.
• the gas stream obtained from step (iii) generally has a temperature of -40 to 30 ° C., preferably -20 to 20 ° C. and particularly preferably -15 to 10 ° C., at the exit from the process step.
• the outlet from the process step is understood to be the gas outlet connection of the last apparatus belonging to this method step.
• stream (iii- 1) leaving this step contains, in addition to phosgene, solvent (incompletely separated solvent from step (ii) and optionally the absorption solvent from step (iii)). ). If appropriate, dissolved HCl and / or dissolved inert substances and optionally dissolved reaction by-products may also be present.
• the stream (iii- 1) contains 30 to 90% by mass, preferably 35 to 85% by mass and more preferably 40 to 70% by mass of> phosgene, based on the mass of the liquid phosgene-containing stream (iii-1).
• this stream contains 10 to 70% by mass, preferably 15 to 65% by mass, and particularly preferably 30 to 60% by mass of solvent, based on the mass of the liquid phosgene-containing stream (iii-1). Furthermore, this liquid stream (iii-1) 0 to 5% by mass, preferably 0.1 to 3.5% by mass and more preferably 0.5 to 2.5% by mass) of dissolved hydrogen chloride, based on the Weight of the stream containing liquid phosgene (iii-1).
• the liquid phosgene stream (iii-1) leaving step (iii) generally has a temperature of -40 to 20 ° C, preferably -25 to 15 ° C, and more preferably -20 to 10 ° C.
• This stream is usually at exit from the process step under a pressure of 1.00 to 4.00 bar absolute, preferably 1, 01 to 3.00 bar absolute and more preferably from 1.02 to 2.00 bar absolute.
• the liquid outlet nozzle is understood to mean the apparatus or apparatuses belonging to this process stage. The pressure measured there is adjusted by the hydrostatic pressure of the liquid column in the apparatus (s).
• This stream (iii-1) is now partially evaporated in step (iv).
• This partial evaporation of the stream (iii-1) can be carried out, for example, by:
• a controlled pre-evaporator ie heat supply at about the pressure of the distillation column from step (v), thereby forming a vapor phase
• controlled flash evaporation partial evaporation by pressure reduction
• the preheating and partial evaporation reduces energy costs by partially replacing the heat input in the bottom of the distillation column from step (v) at a high temperature level with heat at a lower temperature level in the column feed.
• the preheating and partial evaporation can also take place in several steps (that is, with the aid of several apparatuses and / or several heating media).
• the preheating and partial evaporation may, in particular due to the low to moderate temperature levels possibly also by heat integration with suitable process streams and / or waste heat streams (condensate, low-tension steam) done and thus allows a particularly energy-efficient plant operation, in contrast to the prior art regardless of the Execution of the distillation column from step (v) with or without reinforcing part.
• step (iv) makes it possible to reduce the pressure in the distillation column of the following step (v) (the gaseous rephosphorogen generation step which is recycled in step (vi) to the reaction of step (i)), by regulating the amount of steam directly supplied to the substance mixture to be separated in this distillation column.
• the term "pressure in the distillation column from step (v)” is understood to mean the pressure measured at the top of the column. the with the in the distillation column to be separated mixture in material So, in particular, contact refers to the vapor fraction obtained in step (iv) (but, as will be explained later, phosgene vapor components from another source may be present).
• directly supplied steam is also used in abbreviated form: A distinction is to be made between heating steam supplied via indirect heating and not in material contact with the substance mixture to be separated in the distillation column.
• a stable column pressure in step (v) can be regulated particularly well by using a (at least partially) vaporous, phosgene-containing feed stream (the two-phase process product from step (iv)) to produce the gaseous rephosphorus is used as a control variable of the pressure control.
• the parameters column pressure and phosgene removal at the top of the distillation column of step (v) are closely coupled to each other, so that the pressure control according to the invention, which influences both parameters in parallel, is particularly effective.
• the steam supplied directly to the distillation column from step (v) consists exclusively of the vapor portion of the two-phase process product from step (iv).
• the fresh phosgene to be added to supplement the phosgene consumed in step (i), if not already supplied in step (iii), may already be part of the phosgene contained in the two-phase process product of step (iv) , with the gaseous phosgene-containing stream from step (v) (ie the "re-phosgene") before it is fed to the reaction of step (i), but it is also conceivable that the re-phosgene and the fresh phosgene are separated from one another to carry out the reaction of step (i)
• fresh phosgene can be supplied to the reactor without being liquefied, including any inert gases and any excess carbon monoxide which may be present from its production, if the desired type of reuse of the hydrogen chloride produced in the process permits this with respect to
• step (ii) it is also conceivable to introduce fresh phosgene in the liquid phase, for example dissolved in a solvent, preferably dissolved in the solvent to be used in step (ii), or preferably in pure form, to be introduced into the distillation column of step (v), e.g. B. in the bottom of this column, which then takes over the function of a phosgene evaporator.
• liquid fresh phosgene is fed to the top of this column, so that the liquid fresh phosgene can partially replace the function of the reflux.
• a top condenser of the distillation column from step (v) should not be dispensed with, fresh phosgene can also be liquefied in this top condenser and fed as reflux to the distillation column.
• the variation of the amount of the steam supplied to the distillation column from step (v) is carried out by varying the vapor content of the two-phase process product produced in step (iv). This is preferably done by varying the temperature of the two-phase process product from step (iv): the higher its temperature is, the larger the vapor content and vice versa.
• the temperature of the two-phase process product can be adjusted for steam heating, for example, via a suitable control of the heating steam.
• the stripping column from step (v) is fed with vaporous fresh phosgene in addition to the biphasic process product from step (iv), ie the steam fed directly to the distillation column comprises the vapor portion of the biphasic process product from step (iv) and separately provided - Frischphosgendampf. It is not necessary to use a completely vaporous phosgene stream for this purpose; Rather, it is also possible to supply the distillation column from step (v) a further two-phase (ie containing liquid and gaseous portions) stream.
• the variation of the amount of vapor supplied to the distillation column of step (v) can be made by varying the vapor content of the biphasic process product produced in step (iv). But it can also be made by varying the vapor content of the further, phosgene vapor-containing stream (if the stream is not already completely is vaporous, but instead has variable liquid content). A combination of both measures is conceivable.
• step (v) it may be advantageous to the variation of the amount of the distillation column from step (v) directly supplied steam by varying the total amount supplied to this column (ie the sum of the liquid and vapor portion) two-phase process product from step (iv) and / or by varying the total amount of this column supplied separately provided, possibly two-phase, phosgene vapor-containing stream.
• the proportion of vapor expressed as mass fraction of the total mass flow from step (iv), of the two-phase process product produced in step (iv) substantially constant.
• Substantially constant means that a vapor content set once is not more than one If the control task also or exclusively the variation of the total amount of an additionally supplied, possibly two-phase, phosgene vapor-containing stream described above is used, it is preferred that its vapor content be "Substantially constant” means that a vapor content set once varies by a maximum amount corresponding to 3% of the target value desired for the vapor fraction.
• This embodiment makes it possible to use the vaporous fresh phosgene as a pressure-regulating feed stream.
• a higher feed temperature leads to an increased solvent content in the recirculating phosgene, but on the other hand also reduces energy costs through a higher rate of heat integration and waste heat utilization for feed heating and a reduced energy requirement for heating the re-phosgene flow.
• a feed temperature (ie the temperature of the two-phase process product from step (iv) fed into the distillation column of step (v)) of 50 ° C to 150 ° C, preferably from 80 ° C to 120 ° C, more preferably from 90 ° C to 110 ° C and a solvent content in the gaseous phosgene-containing stream from step (v) of 1.0% by mass to 15% by mass, preferably from 2.5% by mass to 10% by mass , particularly preferably from 3.0 mass% to 7.5 mass% have, at a pressure in the distillation column from step (v) of 10 mbar to 1500 mbar above ambient pressure (measured at the top of the column) as particularly favorable.
• step (vi) the gaseous phosgene-containing stream obtained in step (v), if appropriate after addition of fresh phosgene (see above), is recycled to the reaction from step (i).
• the work-up of the liquid, solvent and isocyanate-containing stream (ii-2) obtained in step (ii) to obtain the desired isocyanate in step (vi) can be carried out by any process known in the art.
• the workup is preferably carried out by distillation. This step is sufficiently known from the prior art and is preferably carried out as described in EP 1 371 635 B1, in particular in paragraphs [0014] to [0018].
• the liquid hold-up with a high phosgene content in the distillation column from step (v) is significantly reduced.
• the phosgene hold-up becomes significant, i. H. reduced by about 10% to 20%.
• Dispensing with the overhead condenser in the preferred embodiments reduces apparatus costs, plant complexity and, at the same time, operating costs for condensing energy.
• step (v) By dispensing with the reinforcing part, the volume of the distillation column from step (v) is reduced by up to 80%, which leads to significantly lower apparatus costs.
• step (v) The elimination of the reinforcing part also leads to a significantly reduced pressure drop of the distillation column from step (v). At the same head pressure, the pressure in the sump and the corresponding evaporator temperature drop, so that the
• Evaporator can be dimensioned with smaller area.
• Bottom stream can be used, if it is a substantially pure binary mixture with widely separated boiling points (eg solvents and phosgene). If it is ensured that only the two-component mixture solvent / phosgene is permanently present in the bottom of the column, in practice the column will be operated reliably enough to be used as an apparatus for
• Solvent diphosgenation use and dispense with dedicated additional apparatus for this task.
• step (v) The mixture withdrawn in step (v) as a liquid bottom product, which consists essentially of solvent, is preferably recycled to the process.
• This stream has due to its usually close to the boiling point
• This bottom product stream is therefore particularly suitable for in-process heat recovery with cooling of this bottom product stream, z.
• To evaporate liquid fresh phosgene present to heat the vaporous phosgene stream passed to the reaction, to evaporate or overheat the amine before entering the gas phase reactor, to superheat the hydrogen chloride stream to be removed from step (iii), to preheat or partially vaporize in step (iv). for heating sump evaporators in the liquid quench product processing sequence or elsewhere in this process.
• reaction products (ii-1) from, for example, three reaction sections over two processing sections. This can be done, for example, so that the individual streams (ii-l) i to (ii-l) 3 are first combined and then divided into two streams.

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• 2016
  • 2016-07-12 JP JP2018501949A patent/JP6804512B2/ja active Active
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