AU699419B2 - Process for regeneration of an aqueous process liquid of the amine-oxide process - Google Patents

Abstract

The invention relates to a process for producing a solution of N-methyl morpholine-N-oxide in water, in which (a) an aqueous solution is used which contains N-methyl morpholine and morpholine and has a pH between 6.0 and 9.0, whereafter (b) said aqueous solution is treated with a peroxidic oxidising agent in order to oxidise N-morpholine to N-methyl morpholine-N-oxide.

Description

-1 L~c- I- Ph -I.1 WO 97/07138 PCT/AT96/00150 PROCESS FOR THE REGENERATION OF AN AQUEOUS PROCESS LIQUID OF THE AMINE-OXIDE PROCESS The present invention is concerned with a process for the regeneration of an aqueous process liquid of the amine-oxide process containing N-methylmorpholine and morpholine.

For some decades there has been searched for processes for the production of cellulose moulded bodies able to substitute tie viscose process, today widely employed. As an alternative which is interesting for its reduced environmental impact among other reasons, it has been found to dissolve cellulose without derivatisation in an organic solvent and extrude from this solution moulded bodies, e.g. fibres, films and other moulded bodies. Fibres thus extruded have received by BISFA (The International Bureau for the Standardization of man made fibers) the generic name Lyocell. By an organic solvent, BISFA understands a mixture of an organic chemical and water.

It has turned out that as an organic solvent, a mixture of a tertiary amine-oxide and water is particularly appropriate for the production of cellulose moulded bodies. As the amineoxide, primarily N-methylmorpholine-N-oxide (NMMO) is used.

Other amine-oxides are dercribed e.g. in EP-A 0 553 070. A process for the production of mouldable cellulose solutions is known e.g. from EP-A 0 356 419. For the purposes of the present specification and the present claims, the production of cellulose moulded bodies using tertiary amine-oxides generally is referred to as amine-oxide process.

In EP-A 0 356 419, an amine-oxide process for the production of spinnable cellulose solutions is described, wherein as a starting material among other substances a suspension of cellulose in liquid, aqueous Nmethylmorpholine-N-oxide (NMMO) is used. This process consists in transforming the suspension in a thin-film treatment apparatus in one single step and continuously into a mouldable solution. Finally, the mouldable solution is spun

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WO 97/07138 PCT/AT96/00150 S-2into filaments by a forming tool such as a spinneret and the filaments are passed through a precipitation bath.

In the precipitation bath cellulose is precipitated. The tertiary amine-oxide is accumulated in the precipitation bath. The precipitation bath may contain up to 30 weight% of amine-oxide. For the economy of the amine-oxide process it is of vital importance to recover the amine-oxide as completely as possible and reuse it for the production of a mouldable cellulose solution. Thus it is necessary to recover NMMO from the precipitation bath.

In addition to the amine-oxide however, degradation products of the amine-oxide are also accumulated in the precipitation bath. These degradation products may be intensively coloured, thus deteriorating the quality of the cellulose moulded bodies produced. On the other hand, other substances may represent an additional safety risk, since under certain conditions the amine-oxide tends to show highly exothermic decomposition reactions and these decomposition reactions may be induced or accelerated by certain substances. These substances have to be removed from the precipitation bath which is to be regenerated before the NMMO is concentrated and separated.

After removing these unwanted substances, water is withdrawn from the purified precipitation bath which optionally is combined with other process liquids of the amine-oxide process such as vapour condensates formed during the production of the cellulose solution. This may be carried out for instance by means of evaporation. The residue of this evaporation contains highly concentrated aqueous amine-oxide which is recycled again into the amine-oxide process. The vapours of the evaporation consist mainly of water, wherein significant amounts of N-methylmorpholine, the main degradation product of NMMO, are also dissolved. Moreover, the vapours contain also NMMO and morpholine. Typically, the vapours contain up to 100 mg of NMMO, 240 mg of Nr I O"A~g 0,11 P-MRM -MR."W"11 WO 97/07138 PCT/AT96/00150 -3methylmorpholine and 30 mg of morpholine per litre.

Conveniently, these vapours are concentrated, e.g. by means of reverse osmosis. The aqueous solution obtained contains typically up to 4 g of NMMO, up to 10 g of N-methylmorpholine and up to approximately 1 g of morpholine.

To keep the NMMO losses as low as possible, it is tried to reoxidize the N-methylmorpholine to NMMO. This may be achieved for instance by means of a peroxidic oxidant.

A process for the preparative production of tertiary amineoxides by means of oxidation of tertiary amines is known e.g.

from EP-A 0 092 862. According to this process, the amineoxide is oxidized under pressure with molecular oxigen in an aqueous solvent, said solvent having a pH value approximately equal or higher than the pKa value of the tertiary amine.

DD-A 259 863 is concerned with the production of aqueous NMMO solutions by means of oxidation of N-methylmorpholine with H 2 0 2 and by passing the reaction solution over one or more exchanger columns filled with styrene/divinylbenzene copolymer containing sulphonate groups, as well as by adjusting a pH value of the solution to values ranging from 8 to 5 by addition of phosphoric acid.

In an oxidation it is disadvantageous that morpholine present in the process liquid introduced as a contamination together with the tertiary amines is partially transformed into toxic N-nitrosomorpholine, which is accumulated unwantedly in the NMMO cycle. Additionally, other nitrosoamines are also formed in the oxidation reactions.

Oxidation of N-methylmorpholine with H 2 0 2 to NMMO is known e.g. from EP-A 0 254 803. From DE-A 4 140 259, the production of NMMO by a process is known wherein the formation of nitrosoamines is restricted by scavenging primary and secondary amines, for instance by means of acid halides. EP-A 0 320 690 describes the production of amine- J C- ~L C WO 97/07138 PCT/AT96/00150 -4oxides substantially free from nitrosoamines by oxidation with peroxides in the presence of a combination of

CO

2 /ascorbic acid acting as a nitrosoamine inhibitor. From EP-A 0 401 503, oxidation with H 2 0 2 in water and a cosolvent, preferably a carboxylic acid ester, is known.

According to FR-A 8 808 039, oxidation is carried out while adding CO 2 and according to US-A 5,216,154, oxidation to NMMO is carried out in a pure CO 2 atmosphere.

In the state of the art, the forming of nitrosoamine either is not prohibited, or it is achieved by removing the starting products of the N-nitrosomorpholine or by employing additives to slow down the formation rate of the N-nitrosomorpholine.

Particularly in an amine-oxide process comprising a closed cycle, the addition of various chemicals such as acid halides or ascorbic acid or CO 2 to the process causes problems in the purification of the process liquids, since the degradation products introduced together with the added chemicals have to be removed from the process. For many chemicals, it is also necessary to consider safety aspects such as the risk of exothermic reactions. Thus, neither of the described processes is appropriate for the regeneration of process liquids of the amine-oxide process.

Thus is is the objective of the present invention to provide a process for the regeneration of process liquids, wherein Nmethylmorpholine is oxidized to NMMO in a simple way, restricting the formation of the toxic N-nitrosomorpholine.

This is to be achieved without chemical additives scavenging e.g. morpholine, the starting product for the formation of the N-nitrosomorpholine, for instance by means of derivatisation. Further it is the object of the present invention to carry out this process in such a way that even the reduced amounts of N-nitrosomorpholine formed during oxidation are destroyed to a great extent without chemical additives.

WO 97/07138 PCT/AT96/00150 i SThe object to provide a process for the regeneration of d process liquids wherein N-methylmorpholine is oxidized to NMMO, the formation of the toxic N-nitrosomorpholine being restricted, is attained by means of a process wherein an aqueous solution containing N-methylmorpholine and morpholine and having a pH value of from 6,0 to 9,0 is provided, whereafter said aqueous solution is treated with a peroxidic i oxidant to oxidize N-methylmorpholine to Nmethylmorpholine-N-oxide.

It has been shown that by simply adjusting the pH of the oxidation mixture within the indicated range it is possible to restrict the formation of the toxic N-nitrosomorpholine and simultaneously attain a maximum oxidation of Nmethylmorpholine to NMMO. The pH dependence of these two reaction modes is to be seen from the attached Figures.

Figure 1 shows the yield of NMMO produced of theory) depending on the pH value of the solution, a maximum being reached in the range of from 6,0 to 9,0 which in the present Example is approximately 50%. Figure 2 shows the Nnitrosomorpholine concentration (in ppb) in the solution after oxidation depending on the pH value. It can be seen that from a pH value of 8-9 on, the formation of Nnitrosomorpholine increases, reaching a maximum from pH on. By adjusting a pH value according to the invention in the range of from 6,0 to 9,0 in the solution to be oxidized, the yield of NMMO can be maximized and at the same time the formation of the toxic N-nitrosomorpholine can be minimized.

It has proven highly advantageous to adjust the pH value of the aqueous solution within the desired range by passing the solution to be regenerated over a cation exchanger capable of absorbing morpholine. This step provides two important effects regarding the reduction of nitrosoamines. By means of the cation exchanger, morpholine is selectively removed from

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LU-l-- LLI* rL WO 97/07138 PCT/AT96/00150 -6the solution, thus being actually no morpholine available for the new formation of nitrosoamines. Additionally, by separating the morpholine exhibiting the strongest basicity compared to the other components, the pH value of the solution is lowered precisely into the range wherein the production of NMMO reaches high levels and the formation of nitrosoamines is further inhibited.

Conveniently, the cation exchanger comprises carboxyl groups or sulphonic acid groups.

The object to carry out the process according to the invention such that even the reduced amounts of Nnitrosomorpholine formed during oxidation are destroyed to a great extent without chemical additives may be attained by exposing the aqueous solution during or subsequently to treatment with the peroxidic oxidant to ultraviolet light having substantially a wavelength of 254 nm.

It has been shown that in the preferred embodiment of the process according to the invention to adjust the pH value by means of a cation exchanger, a new formation of Nnitrosomorpholine in the subsequent oxidation actually will not occur, since the pH adjustment is based on the selective removal of morpholine. In this case, the exposure according to the invention fulfils the purpose to destroy a certain basic level of N-nitrosomorpholine present in the process.

Furthermore it has been shown that exposure according to the invention allows a highly efficient destruction of the Nnitrosomorpholine and that the presence of the peroxidic oxidant will not impede that destruction.

The exposure rate may range e.g. from 200 to 500 mJ/cm 2 depending on the design of the lamp and the process conditions, particularly the temperature. This embodiment of the process according to the invention does not involve any additional chemicals either.

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~~~r~~rv*yr3-~~~s;uirsmmarr;rrwrrr ~~pU WO 97/07138 PCT/AT96/00150 -7- General methods for the quantitative analysis of nitrosoamines which use a UV exposure and a subsequent determination of the nitrites formed are known (D.E.G.

Shuker, S.R. Tannenbaum, Anal. Chem., 1983, 55, 2152-2155; M.

Rhighezza, M.H. Murello, A.M. Siouffi, J. Chromat., 1987, 410, 145-155; J.J. Conboy, J.H. Hotchkiss, Analyst, 1989, 114, 155-159; B. BUchele, L. Hoffmann, J. Lang, Fresen.J.Anal.Chem., 1990, 336, 328-333). These analytic methods however do not deal with the destruction of Nnitrosomorpholine.

As the peroxidic oxidant, in the process according to the invention preferably H 2 0 2 is used. The H202 is employed preferably as an aqueous solution having 30-50 weight% of H202. The H 2 0 2 is best employed in an amount of from 0,8 to 2 mole per mole of N-methylmorpholine.

The ultraviolet light to which the aqueous solution is exposed is best emitted from a mercury low-pressure lamp.

These low-pressure lamps have an intensity maximum at 254 nm.

For exposure according to the invention using a low-pressure lamp, the lamp may be hung into a container containing the process liquid which is to be treated. However the lamp may also be arranged in another way. Moreover, exposure may be carried out for instance during a continuous recycling of the solution to be exposed in a thin-film UV-reactor.

Another preferred embodiment of the process according to the invention comprises the following steps: passing the above vapours concentrated for instance by means of reverse osmosis over a cation exchanger capable of selectively adsorbing morpholine and safeguarding that the pH value is in the range of from 6,0 to thereafter f WO 97/07138 PCT/AT96/00150 -8combining the eluate obtained from the cation exchanger with purified precipitation bath of the amine-oxide process, said precipitation bath containing 10-30 weight% of NMMO, and treating the eluate combined with the precipitation bath with the peroxidic oxidant in an evaporation reactor to oxidize N-methylmorpholine and concentrate, obtaining concentrated, aqueous NMMO which is recycled again into the amine-oxide process and vapours which are condensed and employed in step By means of the following Examples, the invention will be explained in more detail. The abbreviations NMOR, NMMO, NMM and M used in the following denote N-nitrosomorpholine, Nmethylmorpholine-N-oxide, N-methylmorpholine and morpholine respectively.

Example 1 7 aqueous solutions (50 ml) having 284 ppb of NMOR, containing 6097 mg of NMM, 272 mg of M and 1085 mg of NMMO per litre, were adjusted with HCl/NaOH to the pH values of 4, 6, 7, 8, 10, 12 and 14. Afterwards aqueous hydrogen peroxide having 30 weight% of H202 was added in such an amount as to reach a surplus of 1,3 mole, based on NMM, and heated for 4 hours to 50°C. Subsequently, the yield of newly produced NMMO and the concentration of NMOR was determined by means of HPLC (see Example The results are shown graphically in Figures 1 and 2.

In Figure 1, the pH value is shown as abscissa and the yield of NMMO produced of the theory) as ordinate. It can be clearly seen that in the range of from 6,0 to 9,0 there is a maximum of approximately 50%. In Figure 2, the pH value is also shown as abscissa and the NMOR concentration (in ppb) in the solution after oxidation as ordinate. It can be seen that only from a pH value of from 8-9 formation of N- )R nitrosomorpholine will considerably increase. Thus in the 7r tij WO 97/07138 PCT/AT96/00150 -9range of from 6,0 to 9,0 the production of NMMO is maximized and simultaneously the formation of the toxic Nnitrosomorpholine is minimized. This applies particularly to the pH range of between 7,0 and Example 2 An aqueous solution containing 25 gg of NMOR, 2530 mg of NMMO, 3923 mg of NMM and 30 mg of M per litre was mixed with

H

2 0 2 (mole of NMM/mole of H 2 0 2 1/1,2) to oxidize NMM to NMMO and exposed to radiation in a UV reactor by means of a mercury low-pressure lamp (of the Katadyn UV projector EK-36, no. 79000 type, made by Katadyn) (wavelength: 254 nm). The temperature of the process liquid was The NMOR concentration was determined by means of HPLC (column: Hypersil ODS 250 x 4 mm; 50'C; eluant: A 0,6% of acetonitrile; B 49,7% of H 2 0; gradient 1 ml/min., 10 min. 100% A; 7 min. 100% B; detector: UV 238 nm).

Within the first 90 minutes, the NMOR concentration increased to 45 gg/l, which is due to a fast reaction of the M present in the solution. Afterwards however, the NMOR concentration decreased again rapidly. After 6 hours, there was no evidence of NMOR.

After a total oxidation time of 20 hours, the solution contained 5386 mg of NMMO/litre. This amounts to a yield of 62% of theory.

Claims (7)

1. A process for the production of a solution of N- methylmorpholine-N-oxide in water, characterized by the following steps: providing an aqueous solution containing N- methylmorpholine and morpholine and having a pH value of from 6,0 to 9,0, thereafter treating said aqueous solution with a peroxidic oxidant to oxidize N-methylmorpholine to N- methylmorpholine-N-oxide.

2. A process according to Claim 1, characterized in that in step an aqueous solution which has been passed over a cation exchanger capable of absorbing morpholine to adjust the pH value is employed.

3. A process according to sim 2, characterized in that said cation exchanger comprises carbo:yl groups.

4. A process according to Claim 2, characterized in that said cation exchanger comprises sulphonic acid groups.

A process according to one of the Claims 1 to 4, characterized in that said aqueous solution is exposed to ultraviolet light having substantially a wavelength of 254 nm during or subsequently to treatment with the peroxidic oxidant.

6. A process according to Claim 5, characterized in that said ultraviolet light is emitted from a mercury low- pressure lamp.

7. A process according to one of the Claims 1 to 6, characterized in that as said aqueous solution containing morpholine and N-methylmorpholine process Sliquids from the amine-oxide process are employed. WO 97/07138 PCT/AT96/00150 -11- Abstract The invention is concerned with a process for the production of a solution of N-methylmorpholine-N-oxide in water, characterized by the following steps: providing an aqueous solution containing N- methylmorpholine and morpholine and exhibiting a pH value of from 6,0 to 9,0, thereafter treating said aqueous solution with a peroxidic oxidant to oxidize N-methylmorpholine to N-methylmorpholine-N- oxide. (Fig.) I ST fO