Process for diisocyanate distillation

Abstract

The present invention relates to a process for diisocyanate distillation, comprising steps A) providing a distillation system, B) distilling, in the distillation system, a composition essentially containing pentamethylene diisocyanate, characterized in that after step B), step C) is carried out, consisting in distilling, in the distillation system, a composition essentially containing a diisocyanate other than pentamethylene diisocyanate, so as to obtain a distillate.

Description

[0001] Diisocyanate distillation process

[0002] The invention relates to a process for diisocyanate distillation, comprising a purification of the distillation system and a distillation system for carrying out the process and a use of certain diisocyanates for purifying a distillation system which was used for the distillation of pentamethylene diisocyanate.

[0003] Pentamethylene diisocyanate (hereinafter also referred to as PDI, 1,5-PDI, or 1,5-pentane diisocyanate) is a valuable raw material for the production of polyurethanes. PDI is produced industrially advantageously by phosgenation of pentamethylenediamine (PDA). The reaction can take place either in the condensed phase (liquid-phase phosgenation, hereinafter also referred to as FPP) or in the gas phase (gas-phase phosgenation, hereinafter also referred to as GPP). After the phosgenation reaction, the PDI is usually obtained as a largely liquid crude product stream, from which the PDI is isolated in a multi-stage distillation sequence.

[0004] A previously unsolved problem in the distillation of monomeric diisocyanates is their tendency to form deposits during extended operation of the distillation systems. These deposits can occur in various areas of the distillation system and require periodic production interruptions to clean the distillation systems or replace internals.

[0005] CN 114 133 343 A describes the distillation of monomeric diisocyanates under high vacuum. The distillation of 1,5-PDI and HDI is described as an example. Nowhere in the document does it indicate that both distillations are carried out consecutively in the same apparatus. Problems caused by deposits during extended operation of the PDI distillation process are not addressed.

[0006] EP 3 533 785 A1 describes a method for producing 1,5-PDI, wherein the distillation takes place in a multi-stage distillation sequence. The purification steps disclosed include solvent removal, heat treatment, residue separation, and purification distillation. A comparative example describes the production and distillation of HDI. This document also does not disclose the distillation of PDI followed by the distillation of HDI in the same apparatus. Problems caused by deposits during prolonged operation of the PDI distillation are not addressed here either.

[0007] WO2017 / 076551 A1 describes a dividing-wall column suitable for the distillation of isocyanates such as TDI, MDI, HDI, PDI, isophorone diisocyanate (IPDI), XDI, or dicyclohexylmethane diisocyanate (HnMDI). The desired isocyanate is withdrawn as a side stream, while low-boiling components are collected at the top of the column. Problems caused by deposits during prolonged operation of the distillation system are also not addressed here.

[0008] US 6,550,485 B2 describes a method for cleaning distillation systems containing polymerizable nitrogen-containing compounds or deposits formed from such compounds. The method consists of rinsing the distillation system with an acidic liquid, preferably with organic or inorganic acids in aqueous solution. This is preferably followed by a further rinsing of the distillation system with water to remove the acid from the system. Even though diisocyanates in general and pentamethylene diisocyanate in particular are polymerizable nitrogen-containing compounds, the disclosed method is completely unsuitable for distillation systems used for the distillation of diisocyanates. Due to the known reactivity of diisocyanates or even of oligomers already formed, this method would lead to the formation of further sparingly soluble deposits, e.g.in the form of isocyanurates or ureas, and thus make the problem even worse.

[0009] US 7,182,839 B2 discloses a method for suppressing the formation of deposits during distillation, particularly solvent separation, from fouling-prone media. Diisocyanates, for example, are also listed as fouling-prone media. The method requires the presence of N,N'-dialkylamides or fatty acids, which are intended to ensure the dispersion of solid or semi-solid particles before they can form deposits. This method requires the introduction and removal of otherwise foreign substances into the distillation system and thus entails considerable additional effort. Furthermore, not all areas of a diisocyanate distillation system can be protected in this way without inevitably causing contamination of the distilled product.There was therefore a need for a process for the distillation of diisocyanate monomers in which cleaning of the distillation system could be carried out without the disadvantages usually associated with it.

[0010] Surprisingly, it has been found that this object is achieved for certain diisocyanates by a process for diisocyanate distillation, comprising the steps

[0011] A) Providing a distillation system and

[0012] B) Distillation of a first composition containing essentially pentamethylene diisocyanate in the distillation system, characterized in that after step B) the step

[0013] C) distilling a second composition containing essentially a diisocyanate other than pentamethylene diisocyanate (PDI) in the distillation system to obtain a distillate.

[0014] Diisocyanate distillation is understood here as a thermal separation process in which a monomeric diisocyanate is evaporated and recondensed at least once to separate it from other, particularly higher-boiling, impurities and obtain it in high purity. The term encompasses, in particular, repeated evaporation and condensation using a distillation column with a plurality of separation stages. Such processes are also referred to as rectification and, unless expressly stated otherwise, are encompassed herein by the terms distillation and diisocyanate distillation.

[0015] In the present case, a distillation system comprises at least one distillation column and the associated peripheral equipment, such as evaporators, heat exchangers, condensers, pumps, and the piping connecting them. The distillation column can be equipped with any device known to those skilled in the art for increasing separation efficiency. These include, in particular, beds, packings, and trays of various designs.

[0016] During the distillation of 1,5-pentane diisocyanate in a distillation system consisting of a column with a side takeoff for the distilled product, a top condenser, and a circulation evaporator, it was observed that, over extended periods of operation, deposits can form at various points within the distillation system, negatively impacting its operation. White to light yellow deposits occurred particularly on the cooling surfaces of the distillation system, i.e., the heat exchange surfaces of the top condenser. These deposits impaired heat transfer and required cleaning. These deposits were observed repeatedly and varied in consistency, from powdery to jelly-like or foam-like.

[0017] Surprisingly, it has now been discovered that changing the raw material to be distilled from the first composition containing essentially PDI to a second composition containing essentially a diisocyanate different from PDI is accompanied by a cleaning effect. Not only is any remaining pentane diisocyanate dissolved in the second composition and ultimately carried away, but the deposits caused by the PDI distillation are also significantly reduced or even dissolved. This cleaning was sufficient to allow the distillation system to continue operating for an extended period. It did not have to be completely shut down for mechanical cleaning, such as high-pressure cleaning, or even for the replacement of parts of the distillation system, such as the packings.

[0018] In a preferred embodiment of the process described above, the first composition in step B) contains at least 80% by weight, preferably at least 90% by weight, and particularly preferably at least 95% by weight of pentamethylene diisocyanate. These figures refer to the provided composition, ie, the so-called raw material.

[0019] In a further preferred embodiment, the second composition in step C) contains at least 80% by weight, preferably at least 90% by weight, and particularly preferably at least 95% by weight of the diisocyanate other than pentamethylene diisocyanate. These figures refer to the provided composition, i.e., to the so-called raw material. The diisocyanate is preferably selected from the group comprising or consisting of hexamethylene diisocyanate, isophorone diisocyanate, and 4,4'-diisocyanatodicyclohexylmethane, particularly preferably selected from the group comprising or consisting of hexamethylene diisocyanate and isophorone diisocyanate, and very particularly preferably the diisocyanate is hexamethylene diisocyanate.In a preferred embodiment, the pentamethylene diisocyanate was prepared by phosgenation of pentamethylenediamine, preferably by phosgenation of bio-based pentamethylenediamine, and / or the diisocyanate other than PDI was prepared by phosgenation of the corresponding diamine.

[0020] In a particularly preferred embodiment, the phosgenation of the diamine other than pentamethylenediamine is carried out at least partially, preferably entirely, in the same apparatus as the previous phosgenation of pentamethylenediamine. The phosgenation apparatus in this embodiment is therefore a multipurpose phosgenation apparatus designed to react 1,5-diaminopentane and at least one diamine, preferably selected from the group consisting of 1,6-diaminohexane, isophoronediamine, and bis(4-aminocyclohexyl)methane, with phosgene in a campaign-by-campaign manner to form the corresponding isocyanates. This embodiment has the advantage that economies of scale can be utilized even when there is only a limited demand for the individual isocyanates. The campaign-by-campaign operation makes it particularly easy to utilize the purification effect underlying this invention.

[0021] In a preferred embodiment of the process, contents of the distillation system between steps B) and C) are transferred at least partially, preferably predominantly, into a first drain vessel and / or contents of the distillation system after step C) are transferred at least partially, preferably predominantly, into a second drain vessel.

[0022] This embodiment has the advantage that the distillate obtained in step C) has only a very low content of PDI from the outset and the time until it is completely free of PDI is shortened and / or that a PDI distillate possibly produced subsequently has only a very low content of diisocyanate from step C) other than PDI from the outset and the time until it is completely free of this is shortened.

[0023] The distillation system comprises a sump tank. The drain tank is connected to the sump tank via a supply line. Preferably, the supply line has at least one shut-off valve. This can be opened to transfer contents or partial contents of the distillation system into the drain tank, or closed to prevent the transfer of contents or partial contents of the distillation system into the drain tank during operation.

[0024] Preferably, at least one of the drain tanks is arranged relative to the sump tank such that the contents of the distillation system to be transferred into the drain tank can flow into the drain tank solely due to its hydrostatic pressure (i.e., without the need for a transfer device to effect the transfer). Particularly preferably, all drain tanks have this arrangement relative to the sump tank.

[0025] The transfer to a drain tank having the aforementioned arrangement opposite the sump tank can be additionally accelerated by means of at least one transfer device. However, this is not preferred.

[0026] If a drain tank does not have the above-mentioned arrangement relative to the sump tank, the transfer into the sump tank takes place by means of at least one transfer device.

[0027] The drain vessel(s) may be connected to other parts of the distillation system via additional supply lines.

[0028] It is also possible, in principle, to rinse at least parts of the distillation system with an organic solvent in a further step. This solvent should be largely chemically inert toward isocyanate groups. Suitable organic solvents in the context of the present invention are not one of the isocyanates involved in steps B) or C).

[0029] Suitable organic solvents would be, for example, aromatic hydrocarbons. Preferred solvents are chlorobenzene, o-dichlorobenzene, p-dichlorobenzene, trichlorobenzenes, the corresponding chlorotoluenes or chloroxylenes, chloro- or ethylbenzene, monochlorodiphenyl, α- or β-naphthyl chloride, ethyl benzoate, dialkyl phthalate, diisodiethyl phthalate, toluene, xylenes or mixtures thereof. Particularly preferred solvents are chlorobenzene, o-dichlorobenzene, p-dichlorobenzene, toluene, xylene or mixtures thereof, and very particularly preferred solvents are chlorobenzene and / or o-dichlorobenzene. It should be noted, however, that such rinsing entails great effort for the provision, treatment and disposal of the solvent, and contamination of the subsequently produced distillate cannot always be completely avoided.It is therefore particularly preferred that between steps B) and C), no substantial, preferably no, rinsing of the distillation system with an organic solvent and / or with an aqueous solution as rinsing agent takes place. Rinsing of the distillation system is considered non-substantial in the present case if the resulting rinsing solution preferably contains less than 50% by weight of the rinsing agent, more preferably less than 30% by weight of the rinsing agent, and particularly preferably less than 10% by weight of the rinsing agent, or if preferably only up to two individual apparatuses of the distillation system are rinsed, preferably isolated and then rinsed, from the rest of the system.

[0030] As a result of maintenance-related shutdowns during which equipment in the distillation system is opened, atmospheric moisture can enter the distillation system. This can react with isocyanate as the process progresses and lead to poorly soluble urea deposits on the surfaces of the distillation system that are in contact with the process media. In a further preferred embodiment, the process therefore comprises, as a further step A1), drying at least parts of the distillation system. Drying is preferably carried out by applying a negative pressure. Particularly preferably, the parts of the distillation system to be dried are evacuated several times and then ventilated with dry inert gas. The aforementioned drying can be carried out at any time if required, for example also after step B) or C).

[0031] In a further embodiment, step C) comprises the following sub-steps: c1) incipient distillation of a composition comprising essentially a diisocyanate selected from the group consisting of hexamethylene diisocyanate, isophorone diisocyanate and 4,4'-diisocyanatodicyclohexylmethane in the at least one distillation system, c2) transferring at least a partial content of the distillation system into a second drain vessel, c3) continuous distillation of a composition comprising essentially the same diisocyanate as the composition in step (c1) in the distillation system to obtain a distillate and c4) optionally and if appropriate after passing through at least one processing step, blending the partial content transferred in sub-step c2) from the drain vessel by introducing it into the continuous distillation in sub-step c3) or the distillate obtained in sub-step c3).

[0032] In one embodiment, the composition c1) or c3) contains at least 80% by weight, preferably at least 90% by weight and particularly preferably at least 95% by weight of the diisocyanate.

[0033] In the present case, incipient distillation means that the corresponding composition is introduced into the distillation system and at least partially evaporated there by introducing thermal energy. The resulting vapors are condensed and preferably returned entirely as reflux. Alternatively, but less preferably, some or all of the condensed vapors can be removed from the distillation system and disposed of. The advantage of this embodiment is that the distillation system is already supplied with the following diisocyanate by the incipient distillation and any residues of pentamethylene diisocyanate are effectively removed from the system. If the optional step c4) is carried out, rinsing losses can be avoided and the product yield can thus be optimized.It is important to ensure that the quantity flow to be blended is selected to be only large enough to ensure that the product specification of the diisocyanate to be distilled in step C) is met at all times, if possible.

[0034] The purifying effect of step C) on the distillation system can be best utilized by ultimately using the distillation system to alternately distill a composition containing essentially PDI and a composition containing a diisocyanate other than PDI. This can even eliminate the use of solvents, for example, to flush the distillation system for extended periods, and eliminate downtime due to otherwise required cleaning phases, since the purifying effect is achieved by also distilling a diisocyanate as a valuable product.In a preferred embodiment of the process, a composition comprising essentially pentamethylene diisocyanate is thus distilled again in the distillation system after step C), and it is particularly preferred that no substantial, preferably no, rinsing of the distillation system with an organic solvent and / or with an aqueous solution takes place between steps C) and the renewed distillation of a composition comprising essentially pentamethylene diisocyanate after step C).

[0035] In a further embodiment, the invention relates to a process for diisocyanate distillation, comprising the steps

[0036] A) Providing a distillation system

[0037] B) Distillation of a composition containing essentially pentamethylene diisocyanate in the distillation system, characterized in that after step B) the step

[0038] C) Distilling a composition containing essentially a diisocyanate other than pentamethylene diisocyanate in the distillation system to obtain a distillate, and after step C), steps B) and C) are preferably repeated one or more times alternately. The above-mentioned embodiments and preferences apply equally to this process.

[0039] The drain tanks are suitable for use as intermediate storage. The contents can either be blended later while the other diisocyanate is distilled, or, preferably, stored until the same diisocyanate is distilled again and then blended.

[0040] The discharge vessels therefore preferably have at least one discharge line with a transport device configured to blend contents from one of the discharge vessels with a previously distilled product from the diisocyanate distillation system and / or to recirculate contents from one of the discharge vessels so that they pass through the fractionation column again. The discharge line also preferably has a device for measuring and / or controlling the flow. Optionally, the discharge vessel has a heating device.

[0041] Another object of the invention is a diisocyanate distillation system for

[0042] Carrying out the process according to claims 1 to 12, comprising or consisting of (a) at least one feed device for introducing diisocyanate compositions into the diisocyanate distillation system,

[0043] (b) a sump tank with an associated fractionating column with or without a dividing wall;

[0044] (c) at least one evaporator for at least partially evaporating at least a portion of the contents from the sump tank

[0045] (d) a vacuum device to reduce the internal pressure in the column

[0046] (e) at least one condenser for at least partial condensation of the vapors from the fractionation column

[0047] (f) at least two drain tanks designed to receive at least part of the contents of the diisocyanate distillation system,

[0048] (g) a withdrawal device adapted to discharge distilled product from the diisocyanate distillation system and / or return it to the fractionation column

[0049] (h) optionally at least one conveying device for conveying the sump content to the at least one evaporator,

[0050] (i) optionally at least one transport device adapted to blend contents from one of the discharge vessels with an already distilled product from the diisocyanate distillation system and / or to recirculate contents from one of the discharge vessels so that they pass through the fractionation column again and / or to withdraw them from the diisocyanate distillation system.

[0051] A further object of the invention is the use of a composition comprising essentially a diisocyanate selected from the group comprising or consisting of hexamethylene diisocyanate, isophorone diisocyanate and 4,4'-diisocyanatodicyclohexylmethane for purifying at least one distillation system which was used for the distillation of at least one composition comprising essentially pentamethylene diisocyanate.

[0052] Preferably, a composition is used for cleaning the at least one distillation system which contains at least 80% by weight, preferably at least 90% by weight and particularly preferably at least 95% by weight of the diisocyanate.

[0053] Preferably, the distillation system to be purified was used for the distillation of at least one composition containing at least 80 wt.%, preferably at least 90 wt.% and particularly preferably at least 95 wt.% pentamethylene diisocyanate.

[0054] In the following, the invention is described in more detail using examples, but is not limited to these.

[0055] Example

[0056] A crude product from the phosgenation of 1,5-pentanediamine, previously freed of solvents, was continuously distilled in a pilot plant. This crude product consisted of approximately 98% by weight of pentamethylene diisocyanate, with the remainder consisting of 100% low-boiling and high-boiling secondary components. Distillation took place at a column head pressure of 16 mbar. The gaseous vapors were removed from the top of the column and condensed in a condenser. A small portion of the condensate was withdrawn to remove low-boiling components, and the remainder was fed back to the column as reflux. Pentamethylene diisocyanate with a purity of 99.8% by weight was withdrawn from the side stream, and a concentrate of the high-boiling secondary components in pentamethylene diisocyanate was discharged from the bottom.

[0057] After one week, a white, partially yellowish coating appeared on the cooling surfaces of the top condenser. Distillation was discontinued after three weeks, and the residues remaining in the test system were drained into a waste container.

[0058] Subsequently, without flushing the distillation system, the raw material was switched to a raw material from the phosgenation of 1,6-hexanediamine, which had also already been freed of solvent, and the distillation was restarted. It was observed that the deposits on the cooling surfaces partially dissolved.

Claims

1. A process for diisocyanate distillation, comprising the steps A) Providing a distillation system B) Distillation of a composition containing essentially pentamethylene diisocyanate in the distillation system, characterized in that after step B) the step C) distilling a composition containing essentially a diisocyanate other than pentamethylene diisocyanate in the distillation system to obtain a distillate.

2. Process according to claim 1, characterized in that the composition in step B) contains at least 80% by weight, preferably at least 90% by weight and particularly preferably at least 95% by weight of pentamethylene diisocyanate.

3. Process according to claim 1 or 2, characterized in that the composition in step C) contains at least 80% by weight, preferably at least 90% by weight and particularly preferably at least 95% by weight of the diisocyanate other than pentamethylene diisocyanate.

4. The process according to claim 1, 2 or 3, characterized in that the diisocyanate other than PDI is selected from the group comprising or consisting of hexamethylene diisocyanate, isophorone diisocyanate and 4,4'-diisocyanatodicyclohexylmethane, preferably selected from the group comprising or consisting of hexamethylene diisocyanate and isophorone diisocyanate and particularly preferably hexamethylene diisocyanate.

5. The process according to any one of claims 1 to 4, characterized in that the pentamethylene diisocyanate was prepared by phosgenation of pentamethylenediamine, preferably by phosgenation of bio-based pentamethylenediamine, and / or the diisocyanate other than pentamethylene diisocyanate was prepared by phosgenation of the corresponding diamine.

6. Process according to claim 5, characterized in that the phosgenation of the diamine different from pentamethylenediamine, at least partly in the same apparatus as the phosgenation of pentamethylenediamine.

7. The method according to any one of claims 1 to 6, characterized in that contents of the distillation system between steps B) and C) are at least partially transferred into a first drain vessel and / or that contents of the distillation system after step C) are at least partially transferred into a second drain vessel.

8. Process according to one of claims 1 to 7, characterized in that the distillation system is not substantially rinsed, preferably not rinsed at all, with an organic solvent and / or with an aqueous solution between steps B) and C).

9. Method according to one of claims 1 to 8, characterized in that the method comprises a further step Al) drying at least parts of the distillation system.

10. The process according to any one of claims 1 to 9, characterized in that step C) comprises the following sub-steps c1) incipient distillation of a composition comprising essentially a diisocyanate selected from the group consisting of hexamethylene diisocyanate, isophorone diisocyanate and 4,4'-diisocyanatodicyclohexylmethane in the at least one distillation system, c2) transferring at least a portion of the contents of the distillation system into a second drain vessel, c3) continuously distilling a composition comprising essentially the same diisocyanate as the composition in step (c1) in the distillation system to obtain a distillate and c4) optionally and if appropriate after passing through at least one processing step, blending the contents transferred in sub-step c) from the drain vessel by introducing it into the continuous distillation in sub-step c3) or the distillate obtained in sub-step c3).

11. Process according to one of claims 1 to 10, characterized in that after step C) a composition containing essentially pentamethylene diisocyanate is again distilled in the distillation system.

12. The process according to claim 11, characterized in that the composition which is distilled after step C) contains at least 80% by weight, preferably at least 90% by weight and particularly preferably at least 95% by weight of pentamethylene diisocyanate.

13. The process according to claim 11 or 12, characterized in that between steps C) and the renewed distillation of a composition containing essentially pentamethylene diisocyanate after step C), no substantial, preferably no, rinsing of the distillation system with an organic solvent and / or with an aqueous solution takes place.

14. Diisocyanate distillation system for carrying out the process according to claims 1 to 13, comprising or consisting of (a) at least one feed device for introducing diisocyanate compositions into the diisocyanate distillation system, (b) a sump tank with an associated fractionating column with or without a dividing wall; (c) at least one evaporator for at least partially evaporating at least a portion of the contents from the sump tank (d) a vacuum device to reduce the internal pressure in the column (e) at least one condenser for at least partial condensation of the vapors from the fractionation column (f) at least two drain tanks designed to receive at least part of the contents of the diisocyanate distillation system, (g) a withdrawal device adapted to discharge distilled product from the diisocyanate distillation system and / or return it to the fractionation column (h) optionally at least one conveying device for conveying the sump content to the at least one evaporator, (i) optionally at least one transport device adapted to blend contents from one of the discharge vessels with an already distilled product from the diisocyanate distillation system and / or to recirculate contents from one of the discharge vessels so that they pass through the fractionation column again and / or to withdraw them from the diisocyanate distillation system.

15. Use of a composition containing essentially a diisocyanate selected from the group comprising or consisting of hexamethylene diisocyanate, isophorone diisocyanate and 4,4'-diisocyanatodicyclohexylmethane for purifying at least one distillation system which was used for the distillation of at least one composition containing essentially pentamethylene diisocyanate.

Images