PROCESS FOR THE PRODUCTION OF AN AQUEOUS SOLUTION OF A TERTIARY AMINE-OXIDE
The present invention is concerned with a process for the production of an aqueous amine-oxide solution used in the amine-oxide process for the production of a mouldable cellulose solution, wherein aqueous, amine-oxide containing solutions produced in the amine-oxide process particularly as precipitation baths are purified and concentrated.
For some decades there has been searched for processes for the production of cellulose moulded bodies able to substitute the 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 amine-oxide, primarily N-methylmorpholine-N-oxide. (NMMO) is used. Other amine-oxides are described 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 others a suspension of cellulose in liquid, aqueous N-methylmorpholine-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 into filaments by a forming tool such as a spinneret and the filaments are passed through a precipitation bath.
In the precipitation bath the cellulose is precipitated. The tertiary amine-oxide is accumulated in the precipitation bath. The precipitation bath may contain up to 30% by 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.
In addition to these substances, in the amine-oxide process also substances in a colloidal state may occur. Moreover, coatings may form at the walls of pipes and the like which may impair the flow and may even lead to an obstruction of the pipe.
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. In the residue of this evaporation, highly concentrated aqueous amine-oxide is produced which is recycled again into the amine-oxide process.
In the state of the art, no step is known whereby the above formation of coatings at walls of pipes can be effectively prevented. It is the object of the present invention to carry out the amine-oxide process such that the formation of these coatings is prevented.
The process according to the invention for the production of an aqueous amine-oxide solution used in the amine-oxide process for the production of a mouldable cellulose solution, wherein aqueous, amine-oxide containing solutions produced in the amine-oxide process particularly as precipitation baths are purified and concentrated, is characterized in that a microbicide agent is added to the aqueous, amine-oxide containing solutions before, during or after purification.
The invention is based on the finding that the formation of

coatings is caused by microorganisms and consists substantially of biological substances. As microorganisms, particularly bacteria, yeasts, fungi and algae have been found. This is surprising since for some decades it was considered that tertiary amine-oxides generally have a microbicide effect (Stupavska, S., Acta Fac. Rer. Nat. Univ. Comen, 1980, pages 85ff) and that they are not biodegradable, only recently it has been found out that NMMO can be degraded in a biological sewage plant (H. Firgo, M. Eibl, W. Kalt, G. Meister: Kritische Fragen zur Zukunft der NMMO-Technologie", Lenzinger Berichte 9/94, pages 81ff). Therefore it is all the more surprising for those skilled in the art that microorganisms are capable of surviving in a variety of NMMO solutions of the amine-oxide process wherein NMMO is present in a much higher concentration than in a sewage plant, may even propagate and thus cause the formation of coatings.
When a microbicide agent acting on these microorganisms is added to the amine-oxide process, the formation of the unwanted biological substances and thus the formation of wall coatings may be effectively prevented.
As microbicide agents, preferably fungicides, algicides and bactericides are used.
As microbicide agents, the following agents have shown particularly good results: agents of the aliphatic aldehyde group, aromatic aldehydes, thiadiazin derivatives, tetramethylolacetylen urea, hydroxy ethylphenyl ethers, organobromine compounds, polyhexamethylene-biguanide-hydrochloride, sodium azide, hydrogen peroxide and peracetic acid, ortho-phthalaldehyde or glutaraldehyde being particularly preferred.
It is evident to those skilled in the art that the type and concentration of the microbicide agents will vary for each individual case. The effective dosage for each individual case however may be easily determined by testing. It has been shown that the effective amount generally lies in the range of from 10 to 500 ppm.
The invention is further concerned with a process for the production of cellulose moulded bodies according to the amine-oxide process, wherein a cellulose suspension and finally a mouldable solution are produced from an aqueous solution of an amine-oxide and shredded cellulose, which solution is moulded and passed into a precipitation bath, a spent precipitation bath and cellulose moulded bodies being produced, said spent precipitation bath being purified and repassed to an aqueous solution of the amine-oxide which is repassed to the amine-oxide process, characterized in that the process is carried out at least partially in the presence of a microbicide agent.
By means of the following Examples, the invention will be described in more detail.
Example l (Control)
A spent precipitation bath of the NMMO process containing 20% by weight of NMMO was lightly shaken for 24 hours at 25'c. Afterwards, the germination index/ml was determined by means of the test described below.
Determination of the germination index/ml
To determine the germination index/ml, 1 ml of each of the solutions was pipetted into a sterile Petri dish and carefully mixed with agar medium. Afterwards the samples were incubated for 3 days at 37°C. After incubation, the entire surface of the Petri dish was counted for germs with the naked eye, and the number obtained was based on 1 ml of sample.
Dishes exhibiting 20 to 300 germs may be evaluated. When more germs were present, the determination was repeated in an appropriate dilution.
A germination index/ml of 2,200,000 was determined.
To determine the effect of microbicide agents, Example 1 was repeated with the substances indicated in the Table using the indicated concentrations. The germination indices obtained in each case are also shown in the Table.
Table Example Substance Concentration (ppm) Germination index/ml
(Table Removed)
A = ortho-phthalaldehyde;
B = glutaraldehyde;
C = 3,5-dimethylperhydro-l,3,5-thiadiazine-2-thion;
D = tetramethylolacetylendiurea
F = 2,2-dibromo-3-nitrilo-propionamide.
Similarly good results could be obtained with polyhexamethylenbiguanid-hydrochloride and sodium azide.

WE CLAIM:
1. A process for the production of cellulose moulded bodies according to the amine-oxide process, wherein a cellulose suspension and finally a mouldable solution are produced from an aqueous solution of an amine-oxide by the process as claimed in claim 1 and shredded cellulose, said solution being moulded and passed into a precipitation bath, a spent precipitation bath and cellulose moulded bodies being produced, said spent precipitation bath being purified and regenerated to an aqueous solution of said amine-oxide which is repassed to said amine-oxide process, characterized in that said process is carried out at least partially in the presence of a microbicide agent.