METHOD OF PURIFYING NITRATED AROMATIC COMPOUNDS FROM A NITRATION PROCESS

Abstract

A process for removing impurities from crude nitrated aromatic products obtained during the nitration of aromatic compounds. The nitrated aromatic products are purified by treatment with ammonia washing followed by caustic washing. The nitrophenolic-containing wash waters are treated to recover dissolved organics and ammonia, and the stripped ammonia-wash effluent is incinerated. Carbon dioxide, which can accumulate in the process, is purged to the caustic washer.

Claims

1. A method of purifying a nitroaromatic product containing nitro-hydroxy-aromatic by-products produced in a nitration process, comprising the steps of: (a) washing the nitrated aromatic product containing nitro-hydroxy-aromatic by-products with an alkaline aqueous solution comprising ammonia to convert some of the nitro-hydroxy-aromatic by-products into their respective nitro-hydroxy-aromatic ammonium salts; (b) separating an aqueous wash stream containing the nitro-hydroxy-aromatic ammonium salts formed in step (a) from an organic stream comprising ammonia-washed nitroaromatic product; (c) washing the ammonia-washed nitroaromatic product with an aqueous alkali metal hydroxide solution to convert the nitro-hydroxy-aromatic by-products that were not removed in steps (a) and (b) into their respective nitro-hydroxy-aromatic alkali-metal salts; and (d) separating an aqueous wash stream comprising the nitro-hydroxy-aromatic alkali-metal salts produced in step (c) from an organic stream comprising alkali-metal-hydroxide-washed nitroaromatic product.

2. A method according to claim 1, further comprising the step of stripping or concentrating the aqueous wash stream of step (b) to produce a condensate stream comprising nitroaromatic product and ammonia and a stripped effluent stream.

3. A method according to claim 2, further comprising the step of recycling the condensate stream to the ammonia washing of step (a).

4. A method according to claim 2, further comprising the step of treating the stripped effluent stream by incineration or thermal oxidation.

5. A method according to claim 3, further comprising purging a portion of the condensate stream to the caustic washing of step (c).

6. A method according to claim 1, further comprising the step of stripping at least a portion of the aqueous wash stream of step (d) to produce a condensate stream comprising recovered nitroaromatic product and ammonia and a stripped caustic effluent stream.

7. A method according to claim 6, further comprising the step of conveying the condensate stream comprising recovered nitroaromatic product and ammonia to the ammonia washing of step (a).

8. A method according to claim 6, further comprising the step of biological treatment of the stripped caustic effluent stream.

9. A method according to claim 1, wherein the nitroaromatic product comprises mononitrobenzene and the nitro-hydroxy-aromatic by-products comprise nitrophenols.

10. A method according to claim 1, wherein the nitroaromatic product comprises nitrotoluenes and the nitro-hydroxy-aromatic by-products comprise nitrocresols.

11. A method according to claim 1, wherein the nitroaromatic product comprises nitroxylenes and the nitro-hydroxy-aromatic by-products comprise nitroxylenols.

12. A method according to claim 1, further comprising the step of treating the aqueous wash stream containing nitrophenolic ammonium salts by incineration or thermal oxidation.

13. A method according to claim 1, wherein the alkali metal hydroxide is sodium hydroxide.

14. A method according to claim 1, wherein the alkali metal hydroxide is potassium hydroxide.

15. A method of purifying a nitroaromatic product containing nitro-hydroxy-aromatic by-products produced in a nitration process, comprising the steps of: (a) washing the nitrated aromatic product containing nitro-hydroxy-aromatic by-products with an alkaline aqueous solution comprising ammonia to convert some of the nitro-hydroxy-aromatic by-products into their respective nitro-hydroxy-aromatic ammonium salts; (b) separating an aqueous wash stream containing the nitro-hydroxy-aromatic ammonium salts formed in step (a) from an organic stream comprising ammonia-washed nitroaromatic product; (c) washing the ammonia-washed nitroaromatic product with an aqueous solution comprising a base stronger than ammonia to convert the nitro-hydroxy-aromatic by-products that were not removed in steps (a) and (b) into their respective nitro-hydroxy-aromatic salts; and (d) separating an aqueous wash stream comprising the nitro-hydroxy-aromatic salts produced in step (c) from an organic stream comprising washed nitroaromatic product.

16. A method according to claim 15, wherein the base stronger than ammonia comprises an alkaline earth hydroxide.

17. A method according to claim 16, wherein the alkaline earth hydroxide comprises calcium hydroxide.

18. A method according to claim 15, further comprising the step of stripping or concentrating the aqueous wash stream of step (b) to produce a condensate stream comprising nitroaromatic product and ammonia and a stripped effluent stream.

19. A method according to claim 18, further comprising the step of recycling the condensate stream to the ammonia washing of step (a).

20. A method according to claim 18, further comprising the step of treating the stripped effluent stream by incineration or thermal oxidation.

21. A method according to claim 20, further comprising purging a portion of the condensate stream to the caustic washing of step (c).

22. A method according to claim 15, further comprising the step of stripping at least a portion of the aqueous wash stream of step (d) to produce a condensate stream comprising recovered nitroaromatic product and ammonia and a stripped caustic effluent stream.

23. A method according to claim 22, further comprising the step of conveying the condensate stream comprising recovered nitroaromatic product and ammonia to the ammonia washing of step (a).

24. A method according to claim 22, further comprising the step of biological treatment of the stripped caustic effluent stream.

25. A method according to claim 15, wherein the nitroaromatic product comprises mononitrobenzene and the nitro-hydroxy-aromatic by-products comprise nitrophenols.

26. A method according to claim 15, wherein the nitroaromatic product comprises nitrotoluenes and the nitro-hydroxy-aromatic by-products comprise nitrocresols.

27. A method according to claim 15, wherein the nitroaromatic product comprises nitroxylenes and the nitro-hydroxy-aromatic by-products comprise nitroxylenols.

28. A method according to claim 15, further comprising the step of treating the aqueous wash stream containing nitrophenolic ammonium salts by incineration or thermal oxidation.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0015] FIG. 1 is a schematic block diagram illustrating one embodiment of the invention for purifying nitrated aromatic products.

[0016] FIG. 2 is a schematic block diagram illustrating a second embodiment of the invention which includes stripping of the ammonia effluent and the caustic effluent.

DETAILED DESCRIPTION OF THE INVENTION

[0017] Embodiments of the invention are described below in which the selected strong base is caustic soda. However, it will be understood that caustic soda is only one example of a strong base that can be employed. Other bases that are stronger than ammonia may also be used in the invention, examples being other alkali metal hydroxides, including potassium hydroxide, and alkaline earth hydroxides, including calcium hydroxide.

[0018] Referring first to FIG. 1, a nitrated aromatic purification system 100 has an ammonia washing stage 102 followed by a caustic washing stage 104. The ammonia washing stage and the caustic washing stage both have one or more counter-current washers. For purposes of illustration, FIG. 1 shows two counter-current ammonia washers 102A and 102B and two counter-current caustic washers 104A and 104B; and it will be understood that any number of washers suitable for a particular application may be used. The washing stages 102, 104 may employ either a stirred tank, a washing column, or a static mixer followed by a separator. The purification system has an aqueous stream of ammonia 3 to feed into the ammonia washers, and an aqueous stream of caustic soda 7 to feed into the caustic washers. Fresh water or process water can be used in both washing stages 102, 104. The purification system includes a recirculating aqueous ammonia wash stream 2 to feed into the first ammonia washer 102A and an aqueous caustic wash stream 6 to feed into the first caustic washer 104A.

[0019] In the purification process, a stream of the crude nitrated aromatic product 1, such as mononitrobenzene, from a nitration process is first contacted with the aqueous ammonia wash stream 2 in the ammonia washing stage 102. Here, mineral acids and the stronger (i.e., lower pKa) organic acids are converted to their respective ammonium salt form and extracted from the nitrated aromatic product into the aqueous wash phase (stream 2). The ammonia 3 provides the necessary alkalinity for this conversion. A portion of the aqueous ammonia wash stream 2, now containing impurities as organic salts, becomes the strong effluent stream 4 and is conveyed directly to incineration/thermal oxidation 106, or to an alternative treatment process.

[0020] The ammonia-washed nitrated aromatic product stream 5, which still contains a portion of the weaker nitrophenolic organic acids, leaves the ammonia wash stage and is contacted with the aqueous caustic wash stream 6 in the caustic wash stage 104. Here, the remaining nitrophenolic organic acids are converted to their respective sodium organic salt form by the caustic soda and extracted from the nitrated organic into the aqueous caustic wash phase (stream 6). A portion of the aqueous caustic wash stream 6, now containing the remainder of the organic salt impurities, becomes the caustic effluent stream 8. This stream 8 may be sent to an effluent stripping column 108, where dissolved nitrated aromatics are recovered via either direct or indirect steam stripping. As it contains only a small portion of the nitrophenolic species and is below bio-toxicity limits after combining with other water streams produced in the process, the caustic effluent stream 8 can then be conveyed directly to biological treatment without the requirement for additional treatment.

[0021] The final washed nitrated aromatic stream 9 is essentially free of all mineral acids as well as nitrophenolics and other acidic oxidative species. This stream may then be sent to a stripping or distillation process for further purification. It may also be further water-washed to reduce the salt content in the final washed nitrated aromatic product prior to stripping or distillation.

[0022] Referring next to FIG. 2, which illustrates a second purification system 200, the purification is achieved in essentially the same way as described above and includes some additional steps. Corresponding steps and parts are indicated by the same reference characters used in FIG. 1. The purification system 200 includes stripping of the ammonia effluent 4 and the caustic effluent 8, and the addition of a neutral water wash stage 210 downstream of the caustic wash stage 104.

[0023] In the purification system 200, the strong effluent stream 4 from the ammonia wash is first sent to a strong effluent stripper 212 to recover dissolved nitrated aromatics and excess washing base prior to the stripped effluent 10 being sent to incineration/thermal oxidation 106 or to an alternative treatment process. This stripping of the strong effluent is accomplished via either direct or indirect steam stripping. The overhead condensate stream 11 from the stripper 212, containing the recovered nitrated aromatics as well as excess ammonia, is returned to the ammonia washing stage 102. Surprisingly, with a strong effluent stripper, a sub-stoichiometric consumption of ammonia was found to be required to neutralize and extract the nitrophenolics and other acidic oxidative species. Without precluding other possible explanations, it is believed that this result is possible due to an equilibrium shift as the ammonia is stripped, which results in some of the organic salts reverting back to their acidic form while still remaining dissolved in the strong effluent. This sub-stoichiometric consumption of washing base has the benefit of lowering the net consumption of chemicals.

[0024] Optionally, the strong effluent stream 4 is sent to a concentration unit 214 either as an alternative or in combination with stripper 212. The concentration unit may use low grade energy to boil off water, thereby reducing the amount of water to be vaporized in the incinerator/thermal oxidizer. The boiled-off water can be condensed and returned to washing with the condensate stream 11.

[0025] We discovered that the strong effluent stripper 212 or concentrator 214 requires a condensate purge stream 12 to be implemented. Unexpectedly, we found that carbon dioxide and other components, which are formed as part of the nitration process, will become trapped in the ammonia washing stage 102. For the case of carbon dioxide, the mechanism is thought to be that carbon dioxide entering the ammonia washing stage 102 is converted to ammonium carbonate ((NH.sub.4).sub.2CO.sub.3), which is then sent to the strong effluent stripper 212, where it decomposes back to ammonia and carbon dioxide and is returned back to the ammonia washing stage 102, thereby building up. This causes operational problems, as the carbonate will exceed solubility and begin to precipitate and plug the equipment and piping. Our solution was to purge a portion of the condensate (purge stream 12), which would contain the highest concentration of carbon dioxide, to the caustic washing system 104. By doing this, the carbon dioxide is captured and converted to sodium carbonate (Na.sub.2CO.sub.3), which is a non-volatile and stable form that will be eventually be purged from the system via the caustic effluent stream 8.

[0026] This caustic effluent stream 8 is sent to an ammonia stripper 216, where dissolved nitrated aromatics and ammonia which entered the caustic washing stage either by water entrainment in the ammonia-washed organic stream 5 or by ammonia in the purge stream 12 are recovered via either direct or indirect steam stripping. The overhead condensate stream 13 from the ammonia stripper 216, containing the recovered nitrated aromatics and ammonia, is returned to the ammonia washing stage 102. The carbon dioxide in carbonate form remains in the stripped caustic effluent 14, which can now be conveyed to biological treatment. The ammonia stripper 216 may or may not be required depending on the economics of recovered chemicals and/or maximum ammonia nitrogen limits acceptable to the biological treatment plant.

[0027] The purification method of the invention can be used to purify many nitroaromatic products, including nitrobenzenes, nitrotoluenes and nitroxylenes, removing by-products comprising nitrophenols, nitrocresols and nitroxylenols, respectively.

Example 1

[0028] The washing process of the invention was carried out on a laboratory scale. The composition for the crude mononitrobenzene (MNB) (equivalent to stream 1 in the description above) used in the experiment was analyzed to be: [0029] Mono-nitrophenols: 362 ppmw [0030] Di-nitrophenols: 1,122 ppmw [0031] Picric acid: 97 ppmw

[0032] The remainder was MNB, with some excess benzene from the nitration reaction, dissolved water and other minor impurities.

[0033] Following an ammonia washing stage, analysis of the ammonia-washed MNB (equivalent to stream 5) yielded the following composition: [0034] Mono-nitrophenols: 213 ppmw [0035] Di-nitrophenols: <5 ppmw [0036] Picric acid: 13 ppmw

[0037] The remainder was MNB, with some excess benzene from the nitration reaction, dissolved water and other minor impurities.

[0038] These results show that the ammonia washing stage was able to remove essentially all of the di-nitrophenols which make up the majority of the impurities in the nitrobenzene; however, a significant portion of the mono-nitrophenols remained, as they have a relatively higher pKa than the other forms. Some picric acid also remained in the ammonia washed MNB; this was surprising, as it was believed that it would be more easily removed due to its low pKa value.

[0039] Upon subsequent Caustic Washing of the ammonia-washed MNB, analysis showed that the remainder of the nitrophenols were removed from the caustic washed MNB (equivalent to stream 9).

[0040] This caustic-washed MNB stream can then be sent to stripping or distillation to remove the benzene, DNB and other non-acid impurities.

Example 2

[0041] The following stream table presents the operating data for an industrial mononitrobenzene purification process, which was modelled after the embodiment of FIG. 2. The stream numbers set forth in Table 1 correspond to the stream numbers of FIG. 2.

TABLE-US-00001 TABLE 1 Stream No. 1 2 3 4 5 6 7 Total Flow kg/h 35,962.5 54,000.0 78.0 5,193.0 36,072.7 54,000.0 45.3 Temperature C. 55 68 17 65 61 60 54 Nitrobenzene 1 33,550.7 166.1 0.0 16.0 33,556.9 412.4 0.0 Benzene 2 1,921.6 0.0 0.0 0.0 1,950.1 14.4 0.0 Nitrophenols 3 63.3 0.0 0.0 0.0 5.0 0.0 0.0 Other Organic 4 167.7 0.0 0.0 0.0 169.1 1.2 0.0 Impurities Sulfuric Acid 5 1.4 2.2 0.0 0.2 0.0 0.0 0.0 Water 6 249.1 52,604.8 71.7 5,058.9 382.8 51,929.6 38.5 Ammonia 7 0.0 499.8 6.2 48.1 1.9 1,240.3 0.0 Ammonium 8 0.0 660.8 0.0 63.6 0.1 2.2 0.0 Nitrophenolates Ammonium 9 0.0 20.9 0.0 2.0 0.0 0.1 0.0 Sulphate Ammonium 10 0.0 45.4 0.0 4.4 0.0 0.0 0.0 Carbonate Sodium 11 0.0 0.0 0.0 0.0 0.0 134.2 6.8 Hydroxide Sodium 12 0.0 0.0 0.0 0.0 0.0 145.0 0.0 Nitrophenolates Sodium 13 0.0 0.0 0.0 0.0 0.0 120.6 0.0 Carbonate Dissolved 14 8.7 0.0 0.0 0.0 6.8 0.0 0.0 Gases (CO.sub.2/NOx) Stream No. 8 9 10 11 12 13 14 Total Flow kg/h 2,156.4 39,552.8 5,439.7 687.4 687.4 370.3 2,237.8 Temperature C. 60 61 50 45 45 45 35 Nitrobenzene 1 16.5 37,026.3 0.1 15.9 15.9 16.4 0.0 Benzene 2 0.6 2,020.0 0.0 0.0 0.0 0.6 0.0 Nitrophenols 3 0.0 0.0 0.0 0.0 0.0 0.0 0.0 Other Organic 4 0.0 170.8 0.0 0.0 0.0 0.0 0.0 Impurities Sulfuric Acid 5 0.0 0.0 0.2 0.0 0.0 0.0 0.0 Water 6 2,073.7 328.9 5,373.6 619.3 619.3 303.9 2,221.6 Ammonia 7 49.5 0.2 0.3 47.8 47.8 49.4 0.1 Ammonium 8 0.1 0.0 63.6 0.0 0.0 0.0 0.1 Nitrophenolates Ammonium 9 0.0 0.0 2.0 0.0 0.0 0.0 0.0 Sulphate Ammonium 10 0.0 0.0 0.0 4.4 4.4 0.0 0.0 Carbonate Sodium 11 5.4 0.0 0.0 0.0 0.0 0.0 5.4 Hydroxide Sodium 12 5.8 0.0 0.0 0.0 0.0 0.0 5.8 Nitrophenolates Sodium 13 4.8 0.0 0.0 0.0 0.0 0.0 4.8 Carbonate Dissolved 14 0.0 6.7 0.0 0.0 0.0 0.0 0.0 Gases (CO.sub.2/NOx)

[0042] In this example, the strong effluent stream 10 was sent to a coal gasification process, where this effluent stream was used to off-set water used in creating the slurry sent to gasification. This allowed the strong effluent stream to be thermally oxidized for essentially zero energy cost as the water was already required to create the slurry.

[0043] The caustic effluent stream 14 was diluted, with the nitration reaction water generated in the process, by approximately 10:1 before being sent outside battery limits and directly to biological treatment.

[0044] Throughout the foregoing description and the drawings, specific details have been set forth in order to provide a more thorough understanding to persons skilled in the art. However, well known elements may not have been shown or described in detail to avoid unnecessarily obscuring the disclosure. For example, various conduits and pumps which provide means to convey streams of reactants and products, and some unit operations commonly used in nitration purification processes, may not have been shown. Accordingly, the description and drawings are to be regarded in an illustrative, rather than a restrictive, sense.

[0045] As will be apparent to those skilled in the art in the light of the foregoing disclosure, many alterations and modifications are possible in the practice of this invention without departing from the scope thereof. Accordingly, the scope of the invention is to be construed in accordance with the following claims.