PROCESS FOR THE WORK-UP AND REUSE OF SALT-CONTAINING PROCESS WATER

Abstract

A process for the work-up of salt-containing process water which contains an alkali metal chloride as salt in a concentration of at least 4% by weight and organic or inorganic and organic impurities from chemical production processes and reuse of the salt by a combination of prepurification and concentration, crystallization and purification of the salt and optionally subsequently use of the salt in an electrolysis for producing basic chemicals are described.

Claims

1.-16. (canceled)

17. Process for the work-up and reuse of salt-containing process water from a production process, which contains an alkali metal chloride, as salt in a concentration of at least 4% by weight and organic or inorganic and organic impurities, wherein a) the process water is firstly subjected to oxidative and/or adsorptive purification to remove organic impurities, with one or more adsorbents of the group consisting of activated carbon, adsorbent resins and zeolites, b) a preconcentrated, purified process water is optionally produced from the purified process water by removal of water, to a concentration of not more than 26% by weight of alkali metal chloride in the process water, c) a partial amount of the purified process water from step a) or b) having a salt concentration of from 4% by weight to 26% by weight, is optionally introduced into the brine circuit of a chloralkali electrolysis, d) the process water from step a) or optionally from step b) or the residual amount of process water optionally remaining from step c) is concentrated further by removal of water e) and the alkali metal chloride is crystallized out and f) separated off as solid alkali metal chloride from the mother liquor and purified, so that the solid alkali metal chloride, analysed after dissolution in deionized pure water in a concentration of 300 g/l, has a TOC content of not more than 1 mg/l, g) the solid, purified alkali metal chloride from step f) is introduced into the brine stream of the chloralkali electrolysis, h) the products obtained from the alkali metal chloride electrolysis after step g) and optionally c): chlorine, alkali metal hydroxide, and optionally hydrogen are recirculated as desired to the production process.

18. Process according to claim 17, wherein the optional oxidative purification in step a) for the removal of organic impurities is carried out by treatment with ozone at an initial pH to be set in the process water of at least 1 and a temperature of at least 35° C.

19. Process according to claim 17, wherein the oxidative purification of organic impurities from the process water in step a) is carried out optionally in addition to another oxidative purification or solely by means of electrochemical reaction at a diamond electrode.

20. Process according to claim 17, wherein the purification of organic impurities in step a) is carried out down to a residual content of impurities of not more than 5 mg/l of TOC.

21. Process according to claim 17, wherein the concentration of salt, in the process water before step a) is at least 6% by weight.

22. Process according to claim 17, wherein the water obtained in the preconcentration in the optional step b) is reused for diluting alkali metal hydroxide solution (33; 34), for the production process.

23. Process according to claim 17, wherein the water obtained in the concentration and crystallization in the steps d) and e) is reused for diluting alkali metal hydroxide solution, for the production process.

24. Process according to claim 17, wherein the solid alkali metal chloride obtained in the crystallization in step f) is washed, by means of deionized water and/or by means of purified alkali metal chloride solution to effect purification before reuse.

25. Process according to claim 17, wherein the production process from which the process water is taken is a process for the preparation of polycarbonates or of polycarbonate precursors, or of isocyanates.

26. Process according to claim 17, wherein water which is removed and is obtained in the optional preconcentration according to step b) and/or the concentration according to step d) or e) is used for the optional washing of the solid salt in step f).

27. Process according to claim 17, wherein purified alkali metal chloride solution from a substream of the process water which has been purified in step a) or from a substream of the purified process water which has been concentrated in step b) is used for the wash in step f).

28. Process according to claim 17, wherein an alkali metal chloride solution for which purified alkali metal chloride salt is dissolved in water which is removed and obtained in the performance of step b) and/or d) is used for the wash in step f).

29. Process according to claim 17, wherein the mother liquor which has been separated off from the alkali metal chloride in step f) is divided into two streams, and the one larger stream is recirculated to the concentration according to step d) and the other smaller substream which amounts to not more than 5% by weight of the mother liquor separated off is disposed of.

30. Process according to claim 17, wherein, based on 100 parts by weight of alkali metal chloride separated off, from 5 to 20 parts by weight of washing liquid are used for the optional washing of the solid alkali metal chloride in step f).

31. Process according to claim 17, wherein the organic impurities are compounds selected from the group consisting of: aniline, MDA and the precursor compounds thereof: formaldehyde, methanol, phenol; or from the group consisting of bisphenol A, phenol and benzene derivatives having different alkyl substitutions and halogenated aromatics.

32. Process according to claim 17, wherein the inorganic impurities are compounds selected from the group consisting of salts of cations of the metals: Ca, Mg, Fe, Al, Si, B, Sc, Ba, Ti, Cr, Mn, Ni and Ru in combination with anions.

Description

[0065] The invention will be illustrated in more detail by way of example below with the aid of FIG. 1 without being restricted thereto.

[0066] FIG. 1 schematically shows the process of the invention with concentration of process water from different sources (MDA, SPC and DPC production) by evaporation and crystallization.

LIST OF REFERENCE NUMERALS

[0067] Ia SPC production [0068] Ib DPC production [0069] Ic MDA production [0070] IIa adsorptive prepurification [0071] IIb adsorptive prepurification [0072] IIc oxidative prepurification [0073] III preconcentration [0074] IV heat exchanger [0075] V evaporation stage [0076] VI crystallization [0077] VII liquid/solid separator and salt wash [0078] VIII chloralkali membrane electrolysis [0079] 1a SPC process water [0080] 1b DPC process water [0081] 1c MDA process water [0082] 2a, 2d prepurified SPC process water [0083] 2b prepurified DPC process water [0084] 2c prepurified MDA process water [0085] 3 deionized process water from preconcentration stage III [0086] 4 preconcentrated process water from preconcentration stage III [0087] 5 mixed process water from 2a, 2b, 2c, 2d and 4 [0088] 6 prepurified process water (substream) [0089] 7 prepurified process water (substream) [0090] 8 feed stream [0091] 9 preheated salt solution [0092] 10 evaporated salt solution [0093] 11 concentrated salt solution with salt [0094] 12 mother liquor (purge) [0095] 13 salt [0096] 14 mother liquor [0097] 15 loaded washing water [0098] 16 deionized water [0099] 17 distillate from crystallization VI [0100] 18 distillate from evaporation V [0101] 19 distillate (total stream from heat exchanger IV) [0102] 20 distillate (substream) used as washing water [0103] 21 distillate (substream) [0104] 22 distillate (residual stream) [0105] 23 distillate (substream) [0106] 24 solid additional salt [0107] 25 concentrated salt stream [0108] 26 water [0109] 27 salt solution [0110] 28 finished salt solution to electrolysis [0111] 29 dilute brine [0112] 30 chlorine [0113] 31 sodium hydroxide [0114] 32 sodium hydroxide (addition) [0115] 33 sodium hydroxide [0116] 34 diluted sodium hydroxide [0117] 35 diluted sodium hydroxide [0118] 36 a, b, c sodium hydroxide entry streams for SPC, DPC and MDA production [0119] 37 a, b, c chlorine entry streams for SPC, DPC and MDA production

EXAMPLES

[0120] General Description of the Work-Up and Concentration of Process Water from Various Sources

[0121] The work-up and concentration of process water can be carried out by evaporation and crystallization of the various prepurified process waters either separately or together according to the scheme as depicted in FIG. 1.

[0122] FIG. 1 schematically shows the process of the invention with concentration of process water from different sources (MDA, SPC and DPC production) by evaporation and crystallization.

[0123] In the case of SPC production (Ia), the process water 1a is formed and is firstly brought to a pH of less than 8 using hydrochloric acid (HCl) and then prepurified by means of activated carbon (IIa). The prepurified stream 2a can optionally be preconcentrated (III) to form a stream 4 and then be introduced in the mixed process water 5 or can be introduced directly (2d) into the mixed process water 5.

[0124] In the case of DPC production (Ib), the process water 1b is formed and is likewise brought to a pH of less than 8 using hydrochloric acid (HCl), then prepurified by means of activated carbon (11b) and introduced as stream 2b into the mixed process water 5.

[0125] In the case of MDA production (Ic), the process water 1c is formed and is also brought to a suitable pH value using hydrochloric acid (HCl), then oxidatively prepurified (IIc) and introduced as stream 2c into the mixed process water 5.

[0126] A substream 6 can be taken from the mixed process water 5 and fed into the brine circuit of the electrolysis VIII. A further substream 7 can optionally be fed to the solid/liquid separator VII for salt washing. The remaining mixed process water can then be introduced as feed stream 8 into the heat exchanger IV and be preheated therein.

[0127] The hot distillate 18 or 17 from the evaporation stage V (stream 18) or the crystallization VI (stream 17) is preferably used for this purpose. In the subsequent evaporation stage V and the crystallization stage VI, water is withdrawn as distillate 17 or 18 by evaporation to form the brine streams 9 and 10.

[0128] The amount of water evaporated depends on the concentration of impurities in the feed stream 8. In general, more than 95% of the water can be withdrawn from the feed stream 8. Depending on the size of the feed stream 8, it can also be useful to carry out evaporation and crystallization in a single apparatus (not shown).

[0129] The evaporated water is compressed by means of compressors and used for heating the evaporation (stage V) or the crystallization (stage VI) (mechanical vapour compression; not shown here). As an alternative, however, in the case of a multistage process procedure, it can be fed directly into the next stage of a multistage evaporation or crystallization plant to effect heating (not shown here). The condensate 17 or 18 (distillate) formed from the steam is used for preheating the feed stream 8 in the heat exchanger IV. Since the TOC content of the distillate 17 or 18 is below 5 mg/l due to the prepurification of the feed stream 8, it can, after feed preheating, be used in a process requiring a particular purity, e.g. a chloralkali membrane electrolysis VIII (stream 21).

[0130] The evaporation and crystallization VI forms a mixture 11 of solid salt and mother liquor saturated with NaCl. The mother liquor comprises a major part of the organic and inorganic impurities. For this reason, part of the mother liquor remaining after the crystallization (stream 12, purge) is discharged together with the major part of the impurities present therein from the crystallization stage VI and discarded.

[0131] Part of the mother liquor 14 is separated off from the mixture 11 in the separator VII and recirculated to the crystallization step VI.

[0132] The solid salt with residual adhering mother liquor is washed with distillate (substream 20) as washing water in stage VII and obtained as clean salt 13. It is particularly advantageous to carry out a countercurrent wash with the distillate (stream 20) in stage VII: the particularly pure stream 20 is used for the second washing step for the solid salt. In this second washing step in stage VII, the stream 20 takes up residual impurities from the surface of the solid salt. The loaded washing water is collected and used for the first washing step in stage VII. Here, it displaces the residual adhering mother liquor and takes up additional further impurities. Since the washing water also becomes loaded with salt, it is likewise recirculated as loaded washing water 15 after the wash in stage VII to the crystallization VI.

[0133] As an alternative, washing of the salt in stage VII or the countercurrent wash can also be carried out using fresh water, preferably demineralized or deionized water (stream 16) instead of the distillate 20.

[0134] Since the water becomes loaded with salt in the wash or countercurrent wash in stage VII, prepurified process water (stream 7) can optionally also be used, as shown in FIG. 1. Since this already contains salt, the loss of crystallized salt in the wash is lower.

[0135] The use of the salt solution having the electrolysis entry concentration (stream 27) is particularly advantageous since virtually no crystallized salt dissolves in this case.

[0136] Based on 100 parts by weight of alkali metal chloride which has been separated off, the amount of the washing liquid is 10 parts by weight.

[0137] As a result of the crystallization and the countercurrent wash, the salt obtained is provided in a purity required for the CA electrolysis VIII. The TOC value is preferably less than or equal to 5 mg/l in the saturated solution.

[0138] Since, inter alia, part of the salt is discharged together with the mother liquor (stream 12) and discarded, a partial amount of salt has to be added as supplement (stream 24) in order to provide a sufficient amount of chlorine for the processes Ia-Ic from the CA electrolysis (step VIII). The amount of salt originating from the evaporation/crystallization step (stream 13) and this supplement 24 are fed as stream 25 to the CA electrolysis VIII. Depending on the requirements of the electrolysis VIII, it can be necessary to introduce fresh water (stream 26) in order to produce the starting solution 28 for the electrolysis VIII.

[0139] In order to cover the water requirement of the CA electrolysis, part 6 of the prepurified process water can, as an alternative, be fed directly into the electrolysis VIII. The salt requirement is covered by the crystallized salt 13 and the salt 24 introduced from the outside. The streams are mixed with the dilute brine 29 so as to give a brine concentration of about 300 g/l of NaCl. The TOC content of the mixture must not exceed 5 mg/l.

[0140] The chlorine 30 formed in the electrolysis is used for the production processes SPC, DPC and MDI (chlorine entry streams 37a, 37b, 37c). The sodium hydroxide 31 formed is likewise used there. The requirement going beyond the sodium hydroxide formed is if necessary provided by introduction of external sodium hydroxide 32.

[0141] Since the total sodium hydroxide stream 33 is usually used as dilute feed streams 36a, 36b, 36c in the production processes Ia, Ib and Ic, a substream 23 of the distillate 19 and the permeate 3 from the preconcentration can be used for producing dilute alkali (streams 34, 35). The excess water 22 can be used for other purposes in production processes.

Example 1 (Comparative Example)

[0142] Crystallization without Prepurification, Salt Water from MDA Production:

[0143] A polluted sodium chloride solution (starting solution) which simulates a typical MDA process water and has the following composition: 135 g/l of NaCl, 132 mg/l of formate, 0.56 mg/l of aniline, 11.6 mg/l of MDA, 30 mg/l of phenol was used. About 1.155 l of water (distillate) were withdrawn from 1.5 litres of this solution at a vaporization rate of 12 ml/min while stirring continually. This corresponds to about 80% of the proportion of water in the starting solution. The remaining concentrate containing the solid was separated on a suction filter into the mother liquor and solid salt (wet). The solid salt separated off was subsequently washed with high-purity brine (pure washing brine) in the suction filter and collected (washing brine). The washed salt was dried at about 100° C. in a drying oven. For analytical purposes, 30 g of the dried salt were subsequently taken up in deionized pure water until a solution having the NaCl concentration of 300 g/l (brine) was formed. The measured values from the analyses carried out are summarized in Table 1. As can be seen from Table 1, although the TOC value was below the value of 5 mg/l required for the chloralkali electrolysis as a result of the crystallization and washing procedure, a yellowish discoloration of the salt obtained after the drying procedure was observed. The yellowish discoloration is attributable to the oxidation of the MDA. For use of the salt obtained in this way, this would mean that the CA electrolysis would be damaged over time by MDA oxidation products. Furthermore, part of the organic impurities goes into the distillate (TOC 13 mg/l), which would prohibit direct reuse of the distillate in production processes.

TABLE-US-00001 TABLE 1 MDA without NaCl TOC prepurification Amount [g/l] [mg/l] pH Starting solution 1.5 l 135 52 12 Distillate 1.155 l  0 13 6.1 Mother liquor 265 ml 310 131 10.4 Solid salt (wet) 121.5 g — — — Pure washing brine 48 ml 310 <1 — Washing brine 48 ml 310 91.5 — Brine for analysis 100 ml 300 3.5 8

Example 2

[0144] Example for Sole Crystallization and Wash without Prepurification with Countercurrent Washing of the Salt Produced, Salt Water from DPC Production (Comparison):

[0145] 3 litres of DPC process water after neutralization (pH 7.3) were used as initial charge (starting solution). About 2.679 l of water (distillate) were withdrawn from the initial charge (DPC process water) at an evaporation rate of 12 ml/min while stirring continually. This corresponds to about 95% of the proportion of water in the initial process water. The remaining concentrate was separated on a suction filter into the mother liquor and solid salt (wet). A two-stage countercurrent wash was then carried out using washing brine.

[0146] In the countercurrent wash, pure washing brine is brought into contact with the salt which has already been washed once, so that the salt is washed a second time. The filtrate then obtained from the pure washing brine is reused for the first washing of the salt.

[0147] This in-principle procedure can be approximated as follows:

[0148] The solid salt which had been separated off was divided into two approximately equal partial amounts (salt S1 and salt S2). Pure washing brine was likewise divided into two equal parts (pure washing brine RW1 and pure washing brine RW2). The salt S1 was subsequently washed with pure washing brine RW1 on the suction filter. The filtrate was collected as washing brine WS1.1. Washing brine WS1.1 thus represents an approximation of the filtrate which is reused for the first washing of the salt. For this reason, the salt S2 was subsequently washed with the washing brine WS1.1, resulting in the washing brine WS1.2 as filtrate. Finally, the pure washing brine RW2 was used for renewed washing of the salt S2, forming a washing brine WS2. The salt S1 which had been washed once and the twice-washed salt S2 were dried at about 100° C. in a drying oven. For analytical purposes, 30 g of the dried salt S1 and 30 g of the dried salt S2 were in each case subsequently taken up in deionized water to give 100 ml of solution, so that a brine containing 300 g of NaCl/L was formed. The measured values for the various fractions are summarized in Table 2. The quality of the brines Br1 and Br2 produced was found to be comparatively good. Nevertheless, a large amount of TOC was found in the distillate (about 80% of the TOC burden) in the experiment. This experiment showed that sole crystallization and washing of the salt formed is not sufficient to provide distillate having a quality sufficient to allow reuse, as in FIG. 1.

TABLE-US-00002 TABLE 2 DPC without NaCl TOC prepurification Amount [g/l] [mg/l] pH Starting solution 3 l 177 25 7.3 Distillate 2.679 l    1.5 22.5 6.8 Mother liquor 124 ml 300 99.8 9.7 Solid salt (wet) 535 g — — — Salt S1 (wet) 272 g — — — Salt S2 (wet) 263 g — — — Pure washing brine RW1 60 ml 310 <1 — Pure washing brine RW2 60 310 <1 — Washing brine WS1.1 64 ml — — — Washing brine WS1.2 70 310 51 9.6 Washing brine WS2 58 310 27 9.6 Brine Br1 100 ml 296 1.5 9.5 Brine Br2 100 ml 294 <1 9.4

[0149] The examples presented show that prepurification of the process water is necessary. Owing to the different chemical natures of the impurities, different purification methods have to be employed to remove organics from the process waters.

Example 3 (Process for Prepurification as Per Step a) (Stage IIc) According to the Invention)

Prepurification of MDA Process Water Using Ozone at Various pH Values:

[0150] Mixed MDA process water 1c (reaction and washing water) having a TOC content in the order of 70 mg/l (for values, see Table 3) was subjected to O.sub.3 oxidation IIc at various pH values. Firstly, the ozonolysis of original MDA process water having an initial pH of pH 13.1 was carried out. Two further samples were brought by means of HCl to a pH of 7 and 3.4 and ozonized. For the ozonolysis, 3.5 l in each case of process water were firstly brought to a temperature of 75° C. in a double-walled glass reactor with continual stirring. An ozone generator COM-AD-01 from Anseros was used for generation of the ozone. The ozone generator setting was kept constant in all tests: oxygen volume flow at inlet 100 l/h; generator power 80% (corresponds to about 3.5 g of ozone per hour). The ozone/oxygen mixture was fed into the glass reactor and mixed with process water. To monitor the experiment, samples were taken every 15 minutes and both TOC and pH were measured. The important parameters and results are summarized in Table 3.

TABLE-US-00003 TABLE 3 Initial pH 3 Initial pH 7 Initial pH 13 Time g of TOC TOC TOC [min] O.sub.3/l pH [mg/l] pH [mg/l] pH [mg/l] 0 0 3.4 73.5 7 68.4 13.1 69.7 15 0.25 3.5 62.9 7.8 35.4 13.1 37.9 30 0.50 3.9 43.8 8 18.8 13.1 21.3 45 0.75 6.9 23.7 8.3 10.1 13.1 14.4 60 1.00 7.5 14.6 8.4 7.3 13.1 11.5 75 1.25 7.9 8.2 8.5 5.7 13.1 10.6 90 1.50 8.1 5.7 8.5 5 13.1 10.4 105 1.75 8.3 3.2 8.6 2.8 13.1 10.1 120 2.00 8.3 1.9 8.7 3.15 13.1 10.5

Example 4 (Process for Prepurification; Stage IIc According to the Invention)

Prepurification of MDA Process Water Using 03 at Various Temperatures:

[0151] Mixed MDA process water (reaction and washing water) Ic was subjected to an O.sub.3 oxidation IIc at various temperatures (25° C., 50° C. and 75° C.). Ozonolysis was carried out at an initial pH of 7.7. The important parameters and results are summarized in Table 4. As can be seen from Table 4, the TOC degradation rate at 75° C. is better than that at 25° C. by a factor of about 2.

TABLE-US-00004 TABLE 4 25° C. 50° C. 75° C. Time g of TOC TOC TOC [min] O.sub.3/l pH [mg/l] pH [mg/l] pH [mg/l] 0 0 7.7 72 7.7 72 7.7 72 15 0.25 7.9 56 8.2 45 8.4 48 30 0.50 7.9 43 8.3 42 8.4 28 45 0.75 8.0 37 8.3 28 8.5 21 60 1.00 8.0 33 8.3 24 8.5 17 75 1.25 8.0 27 8.2 22 8.5 13 90 1.50 8.0 25 8.2 16 8.5 12 105 1.75 8.0 22 8.2 15 8.6 11 120 2.00 8.1 20 8.3 11 8.6 9

Example 5 (Stage VI According to the Invention)

[0152] Crystallization after the prepurification of MDA process water: MDA process water 2c (starting solution) after prepurification by means of the ozonolysis IIc (pH after ozonolysis 8.1) was used. 3 litres of MDA process water 2c were treated in a manner analogous to the procedure in Example 2 (crystallization without prepurification DPC). The measured values for the process materials are summarized in Table 5 below. In the experiment, a small amount of TOC was found in the distillate (about 7.9% TOC burden). The quality of the brines Br1 and Br2 produced was found to be excellent.

TABLE-US-00005 TABLE 5 MDA after NaCl TOC prepurification Amount [g/l] [mg/l] pH Starting solution 3 l 153 11.3 8.1 Distillate 2.693 l  1 1 4.9 Mother liquor 147 ml 310 161.8 9.6 Solid salt (wet) 433 g — — — Salt S1 (wet) 216 g — — — Salt S2 (wet) 217 g — — — Pure washing brine RW1 60 ml 310 <1 — Pure washing brine RW2 60 ml 310 <1 — Washing brine WS1.1 51 ml 310 — — Washing brine WS1.2 46 ml 310 72.7 — Washing brine WS2 59 ml 310 56.5 — Brine Br1: 30 g of salt 1 + 100 ml 296 <1 8.8 deionized water to 100 ml Brine Br2: 30 g of salt 2 + 100 ml 296 <1 8.8 deionized water to 100 ml

[0153] In addition, it was surprisingly found in the experiment that inorganic ions also mostly remain in the mother liquor or can be removed by salt washing (Table 6). Here, the masses of the ions in the 3 litres of the starting solution used were determined from the ion concentrations measured in the starting solution and entered in the table. The masses of the ions which would be present in salt S1 and salt S2 after corresponding double washing were calculated from the measured ion concentrations in brine Br2. For this purpose, the volume of the brine Br2 was converted according to the amounts of salt S1+salt S2: 100 ml/30 g*(216 g+217 g)=1.443 ml.

TABLE-US-00006 TABLE 6 Ion Sr Ni Ru Unit mg mg mg 3 l of starting solution 0.172 <0.03 <0.073 (153 g/l of NaCl) Brine 2 (296 g/l of NaCl), 0.075 <0.005 <0.016 converted to all of salt 1 and salt 2: 100 ml/30 g * (216 g + 217 g) = 1.443 ml

Example 7 (Stage VI According to the Invention)

[0154] Crystallization of Salt Water from DPC Production after Prepurification:

[0155] DPC process water 1b (starting solution) after the prepurification IIb by means of activated carbon (pH 7.5) was used. 3 litres of DPC process water 2b were treated in a manner analogous to the procedure in Example 2 (crystallization without prepurification of DPC). The measured values for the process materials are summarized in Table 7. No TOC (measurement limit less than 0.5 mg/l) was found in the distillate in the experiment. The quality of the brines Br1 and Br2 produced was found to be excellent.

TABLE-US-00007 TABLE 7 DPC after NaCl TOC prepurification Amount [g/l] [mg/l] pH Starting solution 3 l 169 ca. 1 7.5 Distillate 2.662 l    1.5 not 5.2 detectable Mother liquor 164 ml 310   12.1 8.9 Solid salt (wet) 473 g — — — Pure washing brine RW1 60 ml 310 <1 — Pure washing brine RW2 60 ml 310 <1 — Washing brine WS1.1 55 ml 310 — — Washing brine WS1.2 53 ml 310 27 — Washing brine WS2 59 ml 310  7 — Brine Br1 for analysis 100 ml 296 not 8.8 detectable Brine Br2 for analysis 100 ml 296 not 8.8 detectable

[0156] Here too, it was found in the experiment that inorganic ions mostly remain in the mother liquor or can be removed by salt washing. The measured values are summarized in Table 8. Here, the masses of the ions in the 3 litres of the starting solution used were determined from the ion concentrations measured in the starting solution as for Table 6 above and entered in the table. The masses of the ions which would be present in the solid salt after corresponding double washing were calculated from the measured ion concentrations in brine Br2. For this purpose, the volume of the brine Br2 was converted according to the amount of solid salt: 100 ml/30 g*473 g=1.577 ml.

TABLE-US-00008 TABLE 8 Ion Sr Ni Ru Unit mg mg mg 3 l of starting solution 0.17 <0.027 <0.073 (169 g/l of NaCl) Brine Br2 (296 g/l of NaCl), 0.124 <0.006 <0.017 converted to all the salt: 100 ml/30 g * 473 g = 1.577 ml

Example 8 (Stage VI According to the Invention)

[0157] Crystallization after the Prepurification of MDA Process Water, Washing with Deionized Water:

[0158] MDA process water 2c (starting solution) after prepurification by means of the ozonolysis IIc is used and treated in a manner analogous to the procedure in Example 2 (crystallization without prepurification of salt water from DPC production): about 94% of the water is withdrawn as distillate from the initial charge (MDA process water) with continual stirring. The remaining concentrate is separated on a suction filter into the mother liquor and solid salt (wet). A two-stage countercurrent wash using deionized water in the last washing stage is then carried out.

[0159] In the countercurrent wash, deionized water is brought into contact with the salt which has already been washed once, so that this salt is washed a second time. Here, part of the salt dissolves in the deionized water, which leads to a loss of solid salt. The salt-containing filtrate then formed from the deionized water is reused for the first washing of the salt. This in-principle procedure was approximated as follows:

[0160] The solid salt which had been separated off was divided into three approximately equal partial amounts (salt S1, salt S2 and salt S3). Salt S3 was washed with deionized water RW1 on the suction filter. The filtrate was collected as loaded washing water WW2. The loaded washing water WW2 thus represents an approximate of the filtrate which is reused for the first washing of the salt. However, this approximate is not very good since salt S3 had not yet been prewashed.

[0161] For this reason, salt S2 was then washed with the loaded washing water WW2 on the suction filter, resulting in loaded washing water WW3 as filtrate. The salt S2 which had been prewashed in this way was then washed with deionized water RW4 on the suction filter, giving loaded washing water WW5 as filtrate. This loaded washing water WW5 is then a significantly better approximate of a filtrate which is used for the first washing of the salt since it has been produced using prewashed salt S2.

[0162] Finally, salt S1 was washed with loaded washing water WW5 on the suction filter, giving loaded washing water WW6 as filtrate. The prewashed salt S1 was then washed with deionized water RW7 on the suction filter, giving loaded washing water WW8 as filtrate.

[0163] The washed salts S1, S2 and S3 were dried at about 100° C. in a drying oven. For analytical purposes, 30 g of each of the dried salts S1, S2 and S3 were subsequently in each case taken up in deionized water to give 100 ml of solution, so that the brines Br1, Br2 and Br3 containing 300 g of NaCl/l were formed. The measured values for the various fractions are summarized in Table 9. The quality of the brines Br1, Br2 and Br3 produced in this way was comparatively very good. Owing to the prepurification according to the invention, only a small amount of TOC was found in the distillate (about 15% of the TOC burden) in the experiment.

TABLE-US-00009 TABLE 9 MDA after NaCl TOC prepurification Amount [g/l] [mg/l] pH Starting solution 3 l 145 9.3 7.3 Distillate 2.674 l    1.5 1.6 6.1 Mother liquor 155 ml 314 91 9.6 Solid salt (wet) 406.5 g — — — Salt S1 (wet) 135.8 g — — — Salt S2 (wet) 135.2 g — — — Salt S3 (wet) 135.5 g — — — Deionized water RW1 45 ml — — — Washing water WW2 50 ml 258 — 9.3 Washing water WW3 51 ml 313 35.1 9.0 Deionized water RW4 45 ml — — — Washing water WW5 49 ml 304 — 9.1 Washing water WW6 51 ml 316 25 8.9 Deionized water RW7 45 ml — — — Washing water WW8 51 ml 304 13 8.8 Brine Br1: 30 g of salt 1 + 100 ml 299 <1 8.0 deionized water to 100 ml Brine Br2: 30 g of salt 2 + 100 ml 298 <1 8.1 deionized water to 100 ml Brine Br3: 30 g of salt 3 + 100 ml 299 2.2 8.5 deionized water to 100 ml

Example 9 (Stage VI According to the Invention)

[0164] Crystallization of a Mixture of Process Water from MDA and DPC Production:

[0165] A mixture of 80% of DPC process water 2b after prepurification by means of activated carbon and 20% MDA process water 2c after ozonolysis was used. 3 litres of the mixture were treated in a manner analogous to the procedure in Example 2 (crystallization without purification DPC). The measured values for the process materials are summarized in Table 9. As regards the removal of organic and inorganic impurities by crystallization and salt washing, the mixture behaves in a manner analogous to the behaviours of the individual process waters. 90% of the organic impurities are removed. Most impurities remain in the mother liquor; the remaining impurities are removed by the salt wash.

TABLE-US-00010 TABLE 9 Mixture: NaCl TOC DPC 80% MDA 20% Amount [g/l] [mg/l] pH Starting solution 3 l 177 4 7.9 Distillate 2.664 l    1.5 1.5 6.9 Mother liquor 129 ml 310 37 9.4 Solid salt (wet) 516 g — — — Pure washing brine RW1 60 ml 310 <1 — Pure washing brine RW2 60 ml 310 <1 — Washing brine WS1.1 62 ml 310 — — Washing brine WS1.2 60 ml 310 14 — Washing brine WS2 63 ml 310 6 — Brine Br1 100 ml 296 <1 9.3 Brine Br2 100 ml 296 <1 9.3