Method for preparing aliphatic diisocyanates in the gas phase

Abstract

The invention relates to a method for producing aliphatic diisocyanates by reacting the corresponding aliphatic diamines with phosgene in the gas phase.

Description

[0001] Process for the preparation of aliphatic diisocyanates in the gas phase

[0002] The invention relates to a process for the preparation of aliphatic diisocyanates by reacting the corresponding aliphatic diamines with phosgene in the gas phase.

[0003] Isocyanates are produced in large quantities and are mainly used as starting materials for the production of polyurethanes. Since the usual monomeric diisocyanates generally have a high vapor pressure, polyisocyanates made from them are used, particularly in paint applications, for reasons of occupational hygiene. These include uretdiones, isocyanurates, iminooxadiazinediones, biurets, urethanes, allophanates or ureas, which are often produced from the monomeric diisocyanates in the presence of catalysts. However, this places particularly high demands on the purity of the monomers, since secondary components usually contained therein can sometimes significantly reduce the activity of the catalysts. Higher catalyst concentrations or longer reaction times must then be used, which significantly impairs the quality of the resulting polyisocyanates, for example with regard to color and storage stability.

[0004] It is therefore desirable that as few secondary components as possible, especially chlorine-containing secondary components, are formed during the production of the monomeric diisocyanates in order to subsequently limit the effort required to remove or minimize them, e.g. by fractional distillation.

[0005] Examples of such secondary components that cause increased effort in the purification of the monomeric diisocyanates are, in the case of aliphatic diisocyanates, the corresponding chloroalkyl isocyanates, in which an NCO group is replaced by a Cl atom. In the case of 1,5-pentane diisocyanate (hereinafter abbreviated as 1,5-PDI or PDI), for example, this is 5-chloropentyl isocyanate (hereinafter abbreviated as CPI) and in the case of 1,6-hexane diisocyanate (hereinafter abbreviated as 1,6-HDI or HDI), this is 6-chlorohexyl isocyanate (hereinafter abbreviated as CHI). On the one hand, the formation of these chloroalkyl isocyanates reduces the yield of diisocyanate in the phosgenation, and on the other hand, they act as chain terminators in subsequent oligo- or polymerizations due to their monofunctionality.A high content of so-called hydrolyzable chlorine (HC value) also interferes with the further processing of monomeric aliphatic diisocyanates into polyisocyanates because, as previously explained, it leads to the deactivation of the usual catalysts used in further processing. Therefore, monomeric aliphatic diisocyanates with HC values ​​of < 100 ppm, preferably < 50 ppm, are generally used. The separation of chloroalkyl isocyanates such as CPI or CHI from the corresponding diisocyanate by distillation is difficult because their vapor pressures usually differ only slightly from those of the respective diisocyanate. It is therefore desirable to achieve the lowest possible levels of chloroalkyl isocyanates in the raw material in order to minimize subsequent purification costs and the associated thermal stress on the product.

[0006] The preparation of aliphatic diisocyanates from the corresponding amines is known per se and can be carried out without phosgene (T. Lesiak, K. Seyda, Journal für Praktische Chemie (Leipzig), 1979, 321 (1), 161 - 163) or by reaction with phosgene (e.g. W. Siefken, Justus Liebigs Ann. Chem. 562, 1949, p. 25 ff., (p. 122) or DE 2 625 075 A1).

[0007] In the phosgene-free preparation cited above, the amine is first reacted with formic acid to form formamide and then oxidized with halogen in the presence of tertiary amines to form the isocyanate. The disadvantage of this process is that it is a complex two-step process, producing considerable amounts of byproducts. The resulting yield losses and the required high purification effort reduce the economic viability of this process.

[0008] DE 2 625075 A1 claims a process for the preparation of carbamic acid chlorides and isocyanates, characterized in that salts of primary amines in solid form are reacted with phosgene in the presence of a liquid at elevated temperature in a rotary kiln, a paddle dryer, or in a fluidized-bed reactor. A disadvantage of this process is that it is also a multi-stage process in which, in the first stage, an amine salt is initially prepared in a solvent, which then has to be removed again before the reaction with phosgene, e.g., by filtration or centrifugation followed by drying. This is time-consuming and costly and reduces the economic viability of this process.

[0009] EP 0 100 047 A1 describes the formation of CHI as a problem in the phosgenation of HDA, and proposes a solution to this problem by producing hexamethylene diisocyanate by thermal cleavage of corresponding hexamethylene dialkyl urethanes instead of by phosgenation of HDA. Although no CHI is formed in this process due to the absence of chlorine, the process requires additional steps for the synthesis of these dialkyl urethanes. Such processes are prone to failure, and both the complexity and yield of the process are ultimately unsatisfactory, so that it has not been able to prevail over the phosgenation of HDA on an industrial scale.

[0010] WO 2008 / 015134 A1 claims a process for producing PDI in which bio-based lysine is converted into PDA, which is subsequently converted into PDI. The conversion of PDA to PDI can be carried out phosgene-free or in the presence of phosgene, with the latter variant being possible in the liquid phase or the gas phase. Any interfering impurities present in PDI and measures to avoid or minimize them are not mentioned.

[0011] WO 2016 / 042125 A1 describes a process for producing 1,5-PDI in the gas phase, wherein the gas temperatures of the reactants before entering the reactor are in the range of 230-320 °C, and the two reactant streams are fed to the reactor via an annular gap nozzle. An inert gas stream is introduced into the annular gap of this nozzle and thus between the two reactant streams. This process allows raw materials to be obtained with a relatively low CPI content of <0.5 wt. %, preferably <0.3 wt. %, excluding the solvent. For example, the lowest value disclosed in a GC analysis is 0.286 FI%.

[0012] EP 3 533 785 A1 describes a method for producing 1,5-PDI, wherein the main focus is not on suppressing the formation of chlorine-containing secondary components during the reaction, but rather on removing them later through a combination of purification steps, in particular comprising a heat treatment step. For the raw material after degassing and removal of the solvent, HO values ​​of between 2000 ppm and 20,000 ppm are generally disclosed. Nothing is stated about the presence of the secondary component CPI or its removal. In view of the high HC values ​​in the raw material, however, it is reasonable to assume that CPI must also have been produced in larger quantities. This process also requires additional steps, at least in the form of heat treatment, which has an adverse effect on its economic viability.

[0013] WO 2010 / 115908 A1 describes the production of isocyanates in the gas phase, wherein the reaction gas is cooled immediately after the reaction in a quench by adding a liquid quench medium to reduce or prevent the formation of by-products. The quench liquid contains a portion of the product stream and is freed from any solid particles present to prevent deposits in pipelines and, in particular, in atomizer nozzles. Any composition between 0 and 100% isocyanate and solvent is disclosed for the composition of the quench liquid. A raw material concentration or flow rates from which this concentration could be deduced are not mentioned.Nothing is disclosed about the presence of chloroalkyl isocyanate and accordingly there is no indication of the effects of different compositions and flow rates of the quench liquid on the formation of this minor component.

[0014] WO 2018 / 224530 A1 describes a process for producing isocyanates, wherein the reaction product mixture is cooled by bringing it into contact with a quench liquid, wherein the quench liquid comprises organic solvents in a proportion of not more than 50% by weight based on its total mass and the remainder consists of 100% by weight of the isocyanate to be produced. The crude product stream cooled in this way is separated into a liquid and a gaseous stream and the liquid stream is introduced into a collection tank together with a further liquid solvent stream comprising more than 50% by weight of organic solvents. This further solvent stream controls the solvent content in the isocyanate raw material used as the quench liquid. The mass flow of solvent is dimensioned such that the desired concentration of not more than 50% by weight is achieved.-% solvent in the raw material, which is returned to the quench zone as quench liquid. No connection is made between the formation of chloroalkyl isocyanates or byproducts in general and the concentration of the isocyanate raw material. It is merely stated that the omission of an upper quench stage containing predominantly solvent, in conjunction with the introduction of the further solvent stream into a collection tank downstream of the quench zone, does not have a negative impact on the quality of the product. Specific embodiments are not disclosed.

[0015] WO 2018 / 224529 A1 describes a process for producing isocyanates, wherein the reaction product mixture is cooled in a quench zone after passing through the reaction zone. The quench liquid used comprises a maximum of 25 wt.% organic solvent. Examples of processes for producing toluene diisocyanate (TDI) are disclosed, in which the raw material in the reactor bottom, where the isocyanate raw material is initially obtained, contains 98 wt.% TDI. In the comparative example, a TDI concentration of 35 wt.% was described in the same place; the process yield in this case, at 97.6%, is somewhat lower than for the process according to the invention. Since the document primarily deals with the aromatic diisocyanate TDI, it is not surprising that the problem of chloroalkyl isocyanates is not discussed further.

[0016] There is still a need for an efficient and cost-effective process for the production of aliphatic diisocyanates with even lower contents of chloroalkyl isocyanate and preferably also overall low HC values ​​in the raw material, which avoids the disadvantages of the prior art processes.

[0017] The object was achieved according to the invention by a process for the preparation of aliphatic diisocyanates by a gas phase phosgenation of the corresponding aliphatic diamines, wherein a mass flow of at least one aliphatic diamine is reacted with phosgene to form a reaction mixture and the reaction mixture is at least partially brought into contact in a quench zone with a quench liquid containing at least one organic solvent, whereby a raw material solution is obtained, characterized in that the quench liquid is introduced into the quench zone at a mass flow and a solvent content which are such that the resulting raw material solution has a solvent content of 68 to 88 wt.%.

[0018] The process according to the invention is particularly suitable for the preparation of aliphatic diisocyanates having up to 17 carbon atoms, preferably linear aliphatic or branched linear aliphatic diisocyanates having 4 to 11 carbon atoms. Examples of such linear aliphatic or branched linear aliphatic diisocyanates are 1,4-butane diisocyanate, 1,5-pentane diisocyanate (PDI), 1,6-hexane diisocyanate (HDI), 2-methylpentane-1,5-diisocyanate, 2,2,4-trimethylhexane-1,6-diisocyanate, 2,4,4-trimethylhexane-1,6-diisocyanate, and 1,8-octane diisocyanate. Particularly preferred aliphatic diisocyanates are PDI and HDI, with PDI being particularly preferred, in which the diisocyanate PDI and the corresponding chloroalkyl isocyanate, i.e. 5-chloropentyl isocyanate (OPI), have only a very small difference in their vapor pressures.The advantage for PDI during the purification of the PDI raw material to pure PDI is correspondingly large, resulting from a low CPI content of this raw material.

[0019] The phosgenation of diamines in the gas phase is known per se and can be carried out, for example, as described in EP 0289 840 B1, EP 1 319655 A2, EP 1 555258 A1, EP 1 275 639 A1, EP 1 275 640 A1, EP 1 449 826 A1, EP 1 754 698 B1, DE 10 359 627 A1 or DE 10 2005 042392 A1. Specifically, the phosgenation of 1,5-pentanediamine in the gas phase was described, for example, in WO 2016 / 042125 A1 and can be carried out as described there.

[0020] Diamines that can be used to carry out the process according to the invention include, for example, technical diamines, each with a purity of > 99% and a water content of < 500 ppm. The respective diamine can originate from known processes both from petrochemical-based production and from bio-based production and / or sources. In particular for the production of PDI and HDI, the respective diamine or a precursor of the diamine preferably originates from bio-based production and / or sources. Diamines from bio-based production and / or sources are understood here to be diamines during the production of which fermentation, i.e. a conversion with the aid of bacteria, yeasts or enzymes, has taken place, or in which at least one of the starting materials for the production of the diamines is a renewable raw material.Particular preference is given to diamines from bio-based production and sources, i.e., those in which, for example, the diamine is produced in a fermentation starting from sugar or amino acids. Before carrying out the process according to the invention, the diamine is generally evaporated and preferably heated to 230°C to 320°C, particularly preferably to 270°C to 310°C, and then fed to the reactor, preferably a tubular reactor. An inert gas such as N2, He, Ar, or vapors from an inert solvent, e.g., aromatic hydrocarbons with or without halogen substitution, can be admixed with the diamine. However, it should be noted that solvent vapors are not always completely inert, so that N2, He, or Ar, particularly preferably N2, is preferably selected as the inert gas stream.

[0021] The phosgene used in the phosgenation is heated before being fed into the reactor, preferably to between 230°C and 320°C, particularly preferably between 270°C and 310°C. An inert gas such as N2, He, Ar, or vapors of an inert solvent, e.g., aromatic hydrocarbons with or without halogen substitution such as chlorobenzene, o-dichlorobenzene, toluene, chlorotoluene, xylene, chloronaphthalene, or decahydrodronaphthalene, can also be admixed with the phosgene. However, it should be noted that solvent vapors are not always completely inert, so the inert gas stream chosen is preferably N2, He, or Ar, particularly preferably N2.

[0022] An optionally separately supplied inert gas stream is also preferably heated to 230°C to 320°C, particularly preferably to 270°C to 310°C. This can be an inert gas such as N2, He, Ar, or vapors of an inert solvent, e.g., aromatic hydrocarbons with or without halogen substitution. However, it should be noted that solvent vapors are not always completely inert, so the inert gas stream chosen is preferably N2, He, or Ar, particularly preferably N2.

[0023] In a preferred embodiment of the invention, the two reactant streams and an inert gas stream are fed to the reactor by means of a preferably concentrically arranged annular gap nozzle, the inert gas stream being fed via the annular gap and thus between the two reactant streams, while the diamine is preferably fed through a concentric inner channel of the annular gap nozzle and the phosgene through the remaining cross-section of the reactor. The average flow velocity of the diamine stream, optionally diluted with inert gas, upon entry into the reactor is preferably in the range of 20-150 m / s, particularly preferably in the range of 20-100 m / s, while the preheated and optionally diluted with inert gas phosgene preferably passes through the remaining cross-sectional area between the outer wall of the annular gap nozzle and the inner wall of the reactor at an average flow velocity of at least 1 m / s, particularly preferably 5-15 m / s.The inert gas stream, which briefly separates the diamine and phosgene upon entering the reactor, can be fed into the reactor at an average flow velocity of 20–150 m / s, preferably 20–100 m / s. The preferred annular gap nozzle is also referred to below as the separation gap nozzle, since the inert gas stream separates the two reactant streams.

[0024] The flow rates of gaseous diamine and phosgene are preferably selected such that the molar excess of phosgene based on an amino group is 30 to 300%, preferably 60 to 200%.

[0025] Tubular reactors without internals and without moving parts inside the reactor are preferably used in the process according to the invention. The tubular reactors are generally made of steel, glass, alloyed or enameled steel and are dimensioned such that, under the process conditions, a largely complete reaction, preferably a complete reaction, of the diamine with the phosgene is possible. The gas streams are introduced into the tubular reactor as described above, for example via a separating gap nozzle at one end of the tubular reactor. The mixing zone is preferably maintained at a temperature within the range from 230°C to 320°C, preferably from 270°C to 310°C, although this temperature can be maintained if necessary by heating the tubular reactor.

[0026] The separately heated reactants, phosgene and aliphatic diamine, are mixed and reacted, with the reactor area in which the reaction takes place being defined as the reaction zone. The reaction in the reaction zone preferably proceeds adiabatically, i.e., without targeted removal of the released reaction heat. However, the temperature in the reaction zone preferably remains below 450 °C, particularly preferably below 425 °C. This can be controlled by the flow rates of diamine, phosgene, and optionally inert gas, as well as their inlet temperatures.

[0027] Mixing and reaction preferably take place in a common technical device for conducting chemical reactions, the reactor. The area in which the mixing takes place is called the mixing zone, and the area in which the reaction takes place is called the reaction zone. The mixing zone and the reaction zone are not clearly spatially demarcated from one another, but rather flow seamlessly into one another and overlap spatially accordingly.

[0028] When carrying out the process according to the invention, the pressure in the feed lines to the reaction chamber is generally between 200 and 3,000 mbar abs., preferably between 800 and 1,500 mbar abs., and at the outlet from the reaction chamber between 150 and 2,000 mbar abs., preferably between 750 and 1,440 mbar abs., whereby a flow velocity within the reaction chamber of between 3 and 120 m / s, preferably between 5 and 75 m / s, is maintained by maintaining a suitable differential pressure. Under these conditions, turbulent flow conditions generally prevail within the reaction chamber.

[0029] The average residence time of the reaction mixture in the reactor is, for example, 0.05 to 4 s, preferably 0.1 to 2 s, particularly preferably 0.2 to 0.5 s. The average residence time is calculated from the temporal throughput of the reactant streams, the reactor dimensioning and the reaction parameters pressure and temperature.

[0030] After passing through the reaction zone, at least a portion, but preferably the entire reaction mixture obtained, is rapidly cooled and at least partially condensed to obtain a crude product solution. This is achieved by introducing it into a quench zone and bringing it into contact with a quench liquid. The design and operation of a quench zone in the production of diisocyanates by phosgenation of the corresponding diamines in the gas phase are well known to those skilled in the art. Possible embodiments are disclosed, for example, in EP 1 403 248 A1 and EP 1 935 875 A1.

[0031] In a preferred embodiment, the mixing zone, reaction zone and quenching zone are arranged in a common technical device, the reactor.

[0032] The quench liquid used contains at least one organic solvent, preferably comprising aliphatic hydrocarbons, aromatic hydrocarbons without halogen substitution, aromatic hydrocarbons with halogen substitution, and mixtures of the aforementioned solvents. Preferably, the at least one organic solvent present in the quench liquid is chlorobenzene, p-dichlorobenzene, o-dichlorobenzene, chlorotoluene, and chloronaphthalene, or mixtures of the aforementioned solvents. Particularly preferably, the at least one organic solvent present in the quench liquid is chlorobenzene and o-dichlorobenzene, or a mixture of the aforementioned solvents. Very particularly preferably, the at least one organic solvent present in the quench liquid is chlorobenzene.The quench liquid preferably contains not only the solvent but also the isocyanate formed during the reaction, since at least a portion of the quench liquid is preferably taken from the resulting isocyanate raw material. In this case, to avoid solid deposits in pipes, valves, nozzles or other quench devices, it is advisable to separate off any solid particles present in the quench liquid. Measures by which such solids removal can be achieved are known to the person skilled in the art; preferably, at least a portion of the quench liquid is filtered. In order to achieve the inventive proportion of solvent in the resulting raw material solution of 68 to 88% by weight, it is expedient for the quench liquid itself to have a solvent content above this target value. The solvent content of the quench liquid is preferably at least 70% by weight, more preferably at least 72% by weight.-% and particularly preferably at least 75 wt.%. If a quench with two or more stages and possibly different quench liquids is used, the calculated solvent content of the total quench liquid used, i.e., the sum of all quench liquid streams, is crucial. If more than one solvent is present in the quench liquid, the solvent content refers to the total solvents.

[0033] In a preferred embodiment of the invention, the flow rate and solvent content of the quench liquid are selected such that the resulting raw material solution has a solvent content of 70 to 86 wt. %, preferably 72 to 85 wt. %, and particularly preferably 74 to 84 wt. Higher contents are advantageous for a particularly low content of chloroalkyl isocyanates in the raw material. On the other hand, excessively high solvent contents result in increased effort for separating and recycling the solvent, so excessive dilution of the raw material should be avoided.

[0034] The resulting raw material can be further diluted with additional solvent in a collection tank, but given the already high solvent content of the raw material, this is generally neither necessary nor advantageous. In fact, it has a negative impact on the overall process, as this additional solvent would later have to be separated from the isocyanate. An exception to this are processes in which at least a portion of the raw material solution is taken from the collection tank and used as a quench liquid. In this case, the additional solvent added to the collection tank increases the solvent content in the quench medium, so that the solvent content in the resulting raw material can be influenced and adjusted by adding more solvent to the collection tank.If sampling of the resulting raw material is not possible before its composition is further altered, or simply to reduce the effort required for process analysis, it is also possible for a person skilled in the art to determine the solvent content in the resulting raw material mathematically. Such a calculation can also be advantageously used to measure the required mass flow of quench liquid into the quench zone and its solvent content. In a preferred embodiment of the method, the mass flow and / or the solvent content of the quench liquid are measured using computer implementation, wherein an expected solvent content in the raw material solution is calculated based on operating parameters and translated into at least one manipulated variable for at least one actuator that influences the mass flow and / or the solvent content of the quench liquid.Examples of such actuators are pumps or valves, preferably control valves, which regulate the mass flow of the quench liquid or which regulate the introduction of fresh or reclaimed solvent into the quench liquid and thus influence the solvent content of the quench liquid and consequently also the solvent content in the raw material. The present invention further provides a computer-implemented method for determining the mass flow to be introduced according to the invention, characterized in that the raw material concentration is calculated using data and parameters during the production of aliphatic diisocyanates by gas-phase phosgenation of the corresponding aliphatic diamines.

[0035] The quench zone can be configured such that the quench liquid is added at only one position in the longitudinal direction of the reactor or such that the quench liquid is added at two or more positions in the longitudinal direction of the reactor. Such different positions in the longitudinal direction of the reactor with quench liquid addition are also referred to below as quench stages. Each quench stage is preferably provided with several nozzles distributed along the circumference of the reactor. The quench zone preferably comprises two or more, particularly preferably exactly two, quench stages. In this configuration, the different quench stages can be fed with different quench liquids, i.e. quench liquids of different compositions and thus also different solvent contents.Preferably, a quench liquid with the lowest solvent content is added in the furthest downstream position, i.e. the lowest position in vertically arranged tubular reactors, while quench liquids with a higher solvent content are used in positions further upstream.

[0036] The temperature of the quench liquid is preferably selected such that it is, on the one hand, above the decomposition temperature of the carbamic acid chloride corresponding to the diisocyanate and, on the other hand, below the condensation temperature of the diisocyanate under the process conditions in the quench zone. If solvent vapors have been added as a diluting inert gas, the temperature of the quench liquid is preferably also below the condensation temperature of this solvent, so that the diisocyanate and cosolvent condense or dissolve in the quench liquid, while excess phosgene, hydrogen chloride, and optionally portions of solvents and evaporated quench liquid leave the quench zone in gaseous form. Quench liquids maintained at a temperature of 60 to 200°C, preferably 90 to 170°C, are particularly suitable for the selective recovery of the diisocyanate from the mixture leaving the reaction zone in gaseous form.

[0037] The portions of the reaction mixture leaving the quench zone in gaseous form are then freed of excess phosgene in a conventional manner. This can be achieved using a cold trap, absorption in an inert solvent maintained at a temperature of -10°C to 8°C (e.g., chlorobenzene, MCB, or dichlorobenzene, ODB), or by adsorption and hydrolysis on activated carbon. The hydrogen chloride gas passing through the phosgene recovery stage can be recycled in a conventional manner to recover the chlorine required for phosgene synthesis.

[0038] The pure preparation of the diisocyanate is preferably carried out by distillative processing of the isocyanate raw material solution.

[0039] The advantages of the process according to the invention are: a) Minimal by-product formation and thus low levels of chlorine-containing by-products, especially chloroalkyl isocyanates, even in the raw materials. Excluding the solvent, the concentrations of chloroalkyl isocyanate in the raw material solution are less than 0.25 wt.%. This minimizes the effort required for subsequent distillation. b) Avoidance of solid deposits on the reactor wall and in the quench.

[0040] A further subject of the present invention is an apparatus for producing aliphatic diisocyanates by gas phase phosgenation according to the process of the invention, comprising

[0041] • a reactor having at least one reaction zone which is designed to react at least one aliphatic diamine with phosgene, and at least one quench zone which is designed to contact the reaction mixture with a quench liquid containing at least one organic solvent,

[0042] • at least one actuator which is designed to influence the mass flow and / or the solvent content of the quench liquid, • an interface unit which is designed to read in at least one operating parameter of the reactor continuously or periodically

[0043] • a processor which is configured to process the at least one continuously or periodically read operating parameter, to calculate therefrom a theoretical solvent content for the resulting raw material and, in the event of a deviation of this solvent content from a predetermined target value for this solvent content, either to output a message on a display or to transmit a new control variable to the at least one actuator and thus to adjust the solvent content in the resulting raw material.

[0044] The present invention also relates to the use of a quench liquid with a flow rate and solvent content such that the chloroalkyl isocyanate content of aliphatic diisocyanates is reduced. Furthermore, the invention also relates to the use of the device according to the invention for reducing the chloroalkyl isocyanate content of aliphatic diisocyanates.

[0045] In the following, the invention is described in more detail using examples, but is not limited to these.

[0046] Examples:

[0047] GC method for raw material analysis:

[0048] Gas Chromatograph: Agilent (formerly Hewlett PACKARD), 7890, Series A or B ( 6890 Series A or B are also possible ),

[0049] Separation column: RXI 17 (Restek), fused silica, length 30 m, inner diameter 0.32 mm, film thickness 1 .0 pm

[0050] Temperatures: Injector 250°C, Detector (FID) 350°C,

[0051] Oven: Start 80°C, holding time 0 min,

[0052] Heating rate 10°K / min to 140°C, holding time 7.5 min

[0053] Heating rate 20°K / min to 250°C, holding time 5.0 min

[0054] Running time 24 min.

[0055] Carrier gas: hydrogen

[0056] Gas setting constant flow instead of constant pressure

[0057] Column pressure approx. 0.4 bar abs., at start of analysis

[0058] Column flow approx. 100mL / min at constant flow

[0059] Split output flow 100mL / min

[0060] Ratio 50:1

[0061] Septum flush approx. 3 ml / min

[0062] The quantitative evaluation is performed using the standardized area percentage method. For each solvent, a response factor is determined within the expected concentration range by calibration with an external standard. This response factor is taken into account when determining the solvent content in the raw material solution. For chloroalkyl isocyanates and diisocyanates, a response factor of 1 is assumed to determine the standardized area percentage.

[0063] Comparison example 1:

[0064] PDA was vaporized and superheated to 310 °C, producing a flow of 8.46 kg / h of gaseous PDA. At the same time, a flow of 45 kg / h of phosgene at 310 °C and a flow of 1.48 kg / h of nitrogen at 310 °C were provided. These streams were fed to a vertically arranged, conical-cylindrical reactor comprising a mixing zone, reaction zone, quench zone, and a collection tank. The PDA was added at the top of the reactor through a coaxial central tube to a gap nozzle, and the nitrogen through the gap of this nozzle. Phosgene flowed through the remaining annular space between the nozzle and the inner reactor wall, past the nozzle. At the nozzle outlet, the nitrogen stream was thus positioned between the amine and phosgene streams. Downstream, the streams mixed spontaneously, and the reaction mixture passed through the reaction zone to form the isocyanate.The resulting reaction mixture was cooled further downstream in a two-stage quench by injecting quench liquids, whereupon a portion of the reaction mixture condensed and drained freely into a collection tank located below the quench. The portion of the reaction mixture that did not precipitate left the reactor in gaseous form and was freed from isocyanate residues in a chlorobenzene-operated scrubbing column. The resulting scrubbing solution contained approximately 98 wt.% chlorobenzene and small amounts of phosgene and PDI.

[0065] The quench liquid for the first, upper quench stage was taken from this wash solution, while in the second, lower quench stage, a raw material stream taken from the collection tank was injected into the quench zone as quench liquid, so that ultimately the isocyanate raw material was circulated via the collection tank and the second, lower quench stage.

[0066] The flow rate of quench liquid to the first quench stage was adjusted so that the raw material in the collection tank had a chlorobenzene content of 65 wt.%.

[0067] The GC analysis of the obtained crude solution showed a CPI content of 0.48 wt.% based on the raw material without solvent.

[0068] Example 1 :

[0069] The phosgenation is carried out as in Comparative Example 1, but the flow rate to the first quench stage was increased so that the chlorobenzene content in the raw material was 68 wt.%.

[0070] GC analysis of the resulting crude solution showed a CPI content of 0.22 wt.% based on the raw material without solvent. Example 2:

[0071] The phosgenation is carried out as in Comparative Example 1, but the content of chlorobenzene in the raw material and (and thus also in the quench liquid for the second, lower quench stage) was adjusted to 70 wt.% by additionally feeding chlorobenzene into the collection tank.

[0072] The GC analysis of the obtained crude solution showed a CPI content of 0.16 wt.% based on the raw material without solvent.

[0073] Example 3:

[0074] The phosgenation is carried out as in Comparative Example 1, but the flow rate to the first quench stage was increased so that the chlorobenzene content in the raw material was 74.5 wt.%.

[0075] The GC analysis of the obtained crude solution showed a CPI content of 0.09 wt.% based on the raw material without solvent.

[0076] Example 4:

[0077] The phosgenation from Example 2 was repeated, but this time, under otherwise identical conditions, a stream of 9.62 kg / h of HDA was phosgenated instead of PDA. The solvent content of the raw material solution was adjusted to 70 wt.% as in Example 2.

[0078] The GC analysis of the obtained crude solution showed a CHI content of 0.17 wt.% based on the crude product without solvent.

Claims

1. Process for the preparation of aliphatic diisocyanates by gas-phase phosgenation of the corresponding aliphatic diamines, • wherein a mass flow of at least one aliphatic diamine is reacted with phosgene to form a reaction mixture and • the reaction mixture is at least partially brought into contact in a quench zone with a quench liquid containing at least one organic solvent, whereby a raw material solution is obtained, characterized in that the quench liquid is introduced into the quench zone at a mass flow and a solvent content which are such that the raw material solution has a solvent content of 68 to 88 wt.%.

2. Process according to claim 1, characterized in that the aliphatic diisocyanate is 1,5-pentane diisocyanate.

3. Process according to claim 1 or 2, characterized in that the at least one aliphatic diamine is 1,5-pentanediamine, preferably 1,5-pentanediamine and originates from bio-based production and / or source.

4. Process according to one of claims 1 to 3, characterized in that the at least one solvent is chlorobenzene, p-dichlorobenzene, o-dichlorobenzene, chlorotoluene, chloronaphthalene or a mixture of the aforementioned solvents.

5. Process according to one of claims 1 to 4, characterized in that the solvent content of the quench liquid is at least 70 wt.%, preferably at least 72 wt.% and particularly preferably at least 75 wt.%.

6. Process according to one of claims 1 to 5, characterized in that the introduced mass flow and the solvent content of the quench liquid are such that the resulting raw material solution has a solvent content of 70 to 86 wt.%, preferably 72 to 85 wt.% and particularly preferably 74 to 84 wt.%.

7. Process according to one of claims 1 to 6, characterized in that the quenching zone comprises two or more, preferably two, quenching stages.

8. Method according to one of claims 1 to 7, characterized in that the mass flow and / or the solvent content of the quench liquid are measured by computer implementation, whereby an expected content of solvent in the raw material solution is calculated on the basis of operating parameters and in at least a control variable is translated for at least one actuator that influences the mass flow and / or the solvent content of the quench liquid.

9. Apparatus for producing aliphatic diisocyanates by gas phase phosgenation according to one of claims 1 to 7, comprising • a reactor having at least one reaction zone which is designed to react at least one aliphatic diamine with phosgene, and at least one quench zone which is designed to contact the reaction mixture with a quench liquid containing at least one organic solvent, • at least one actuator which is designed to influence the mass flow and / or the solvent content of the quench liquid, • an interface unit configured to read in at least one operating parameter of the reactor continuously or periodically • a processor which is configured to process the at least one continuously or periodically read operating parameter, to calculate therefrom a theoretical solvent content for the resulting raw material and, in the event of a deviation of this solvent content from a predetermined target value for this solvent content, either to output a message on a display or to transmit a new control variable to the at least one actuator and thus to adjust the solvent content in the resulting raw material.