Aqueous Chlorine Dioxide Solution, its Preparation Process and its Uses, Provision, and Reservoir

专利摘要:
aqueous chlorine dioxide solution, its preparation process and its uses, apparatus, and reservoir. "The present invention relates to a process for the preparation of a very pure, aqueous, long-term stable solution and storage in this manner. , transportable chlorine dioxide, comprising the stages of chlorite preparation, peroxodisulfate preparation and the combination of chlorite and peroxodisulfate in an aqueous system and at a peroxodisulfate to chlorite [s2o810 2 -] / [clo2-] molar ratio greater than 1 forming the aqueous chlorine dioxide solution, and for the preparation of the aqueous chlorine dioxide solution no additional buffer is added, furthermore the present invention relates to a corresponding chlorine dioxide solution to the use of these chlorine dioxide solutions as well as a device for the preparation of chlorine dioxide solutions and a reservoir comprising a chlorine dioxide solution chlorine oxide.
公开号:BR112013015732B1
申请号:R112013015732-1
申请日:2011-12-22
公开日:2019-02-12
发明作者:Helmut Uhlmann
申请人:A.P.F. Aqua System Ag；
IPC主号:

专利说明:

Descriptive Report of the Invention Patent for AQUEOUS CHLORINE DIOXIDE SOLUTION, ITS PREPARATION PROCESS AND ITS USES, DEVICE, AND RESERVOIR.
The present invention relates to a process for the preparation of a very pure, aqueous, long-term stable solution and the storage, in this way, transportable of chlorine dioxide, comprising the stages of the preparation of chlorite, the preparation of peroxodisulfate and the combination of chlorite and peroxodisulfate in an aqueous system and a molar ratio of peroxodisulfate to chlorite [S2O8 ² ·] / [CIO2 '] greater than 1 forming the aqueous solution of chlorine dioxide, and for the preparation of the dioxide solution of aqueous chlorine no additional buffer is added. In addition, the present invention relates to the corresponding chlorine dioxide solutions, to the use of such chlorine dioxide solutions, as well as to a device for the preparation of chlorine dioxide solutions.
Aqueous solutions of chlorine dioxide (CIO2), due to their high oxidation strength of chlorine dioxide, find use for bleaching, disinfecting and deodorizing, in particular, in water treatment technology. Chlorine dioxide solutions, however, are generally considered to be difficult to handle, since chlorine dioxide gas easily detaches from solutions and in higher concentrations it is explosive. Therefore, chlorine dioxide solutions for the applications mentioned above, are usually not marketed as ready-made solutions, but only on demand, that is, they are freshly prepared on the spot and applied.
In that case, several processes are known for the preparation of aqueous chlorine dioxide solutions.
Thus, an aqueous chlorine dioxide solution can be prepared, for example, by reacting a sodium chlorite solution with a hydrochloric acid solution (this is called the hydrochloric acid-chlorite process). This process has, among others, the disadvantage, that chlorine dioxide is not stable in such a solution and soon decomposes to chlorate and chloride. Therefore, solutions prepared from that
2/45 way cannot be stored, but must be used directly.
In the so-called chloro-chlorite process, a solution of sodium chlorite is reacted with either chlorine or hypochlorous acid. However, this process has the disadvantage that chlorine gas and hypochlorous acid are difficult to handle. In addition, this process results in a considerable portion of chlorate as an unwanted by-product, which reduces the chlorine dioxide yield and, thus, the oxidizing power of the solution.
As an alternative to the two processes above, it has been proposed to prepare a chlorine dioxide solution by oxidizing chlorite with peroxodisulfate. WO-A-96/33947 describes, for example, a process for the preparation of an aqueous chlorine dioxide solution, in which a chlorite solution is reacted with a halogen-free oxidizing agent at a pH value in the range from 5.5 to 9.5 at room temperature for so long, until the chlorite is essentially completely reacted to chlorine dioxide. As an oxidizing agent, peroxodisulfate is preferably used, and in this document - as in the state of the art - the following sum equation (1) is described for the reaction of chlorite with peroxodisulfate:
CIO ₂ '+ S ₂ O ₈ ² · 2 CIO ₂ · + 2 SO ₄ ² ' (1)
From this summation equation, it is generally assumed that one equivalent of peroxodisulfate oxidizes two equivalents of chlorite. Consequently, WO-A-96/33947 proposes to use peroxodisulfate in an amount, which is between the amount one or two times greater than the stoichiometrically necessary for the oxidation of the chlorite. In this way, WO-A-96/33947 describes a molar ratio of peroxodisulfate to chlorite [S ₂ O ₈ ² '] / [CIO ₂ ] in the range of 0.5 to 1.0.
A corresponding process is also described in U.S. Patent 2,323,593, in which examples of that patent describe molar ratios of peroxodisulfate to chlorite [S2O ₈ ² '] / [CIO2'] of 0.57 or 0.78. Furthermore, in the US patent 2,323,593 it is stated that peroxodisulfate to chlorite [S2O8 ² '] / [CIO2'] ratios of <0.5 are disadvantageous,
3/45 as these slow the reaction.
Similarly, EP-A-1,787,953 describes a process for the preparation of chlorine dioxide solutions through the reaction of chlorite with peroxodisulfate, in which chlorine dioxide solutions are provided for the disinfection of the skin and solid surfaces. Therefore, the focus of EP-A-1,787,953 is focused on the rapid supply of extremely diluted chlorine dioxide solutions (2 to 300 ppm) at the respective place of use (“point of use” preparation). For this, a molar ratio of peroxodisulfate to chlorite [S ₂ O8 ² '] / [CIO2'] greater than 2 is used, with the peroxodisulfate solution as well as the chlorite solution being buffered.
However, the processes described above have a number of disadvantages, which make it difficult to apply these processes.
In particular, the solutions are limited in their stability to storage only for a short period, at most a few weeks, so that the application of aged solutions is problematic with respect to their active substances and decomposition products. In addition, a distribution of the finished solution, in most cases, is not possible. Therefore, a point of use preparation is usually recommended (compare, for example, EP-A-1,787,953). In this case, the preparation of the corresponding chlorine dioxide solution is reserved for the user, who must prepare the chlorine dioxide solution himself by mixing the corresponding pre-solutions. But this referred to the expertise in determining the degree of conversion and the formation of by-products.
In addition, the processes known in the art have the disadvantage that for the controlled reaction temperatures above room temperature or alternatively long reaction periods are required. In addition, the systematically fluctuating reaction periods, which are highly dependent on temperature and yields, as well as the resulting different degrees of purity, are other problems in the common processes so far. In addition, stabilization of the pH value is most often required through various buffer systems, as well as
4/45 as the addition of reaction accelerators (silver and copper salts, Carosche acid), which further reduce the purity of the chlorine dioxide solution to be used.
Thus, the present invention is based on the objective of providing a chlorine dioxide solution, which has a high stability to storage and, therefore, does not necessarily need to be prepared on site, but which can also be sold as a ready-made solution. . In addition, the present invention is based on the objective of providing a process for the preparation of that chlorine dioxide solution, which in a simple way and manner, allows the preparation of a stable chlorine dioxide solution under moderate reaction conditions.
This objective is solved by the embodiments characterized in the claims.
In particular, a process is made available for the preparation of an aqueous chlorine dioxide solution, which comprises the following stages:
(a) preparation of chlorite, (b) preparation of peroxodisulfate, (c) combination of chlorite and peroxodisulfate in an aqueous system and a molar ratio of peroxodisulfate to chlorite [S2O8 ² '] / [CIO ₂ ] greater than 1 forming the aqueous chlorine dioxide solution, and for the preparation of the aqueous chlorine dioxide solution no additional buffer is added.
In this case, stages (a) and (b) can be carried out in any desired order.
In stage (a) of the process according to the invention, chlorite (CIO ₂ ') is prepared. The chlorite can be used according to the invention in the form of the HCIO ₂ chlorous acid or as a suitable salt. Preferably, the chlorites are selected from the group, consisting of alkali metal chlorites, in particular, lithium chlorite, sodium chlorite and potassium chlorite, alkaline earth metal chlorites, in particular, magnesium chlorite and calcium chlorite, chlorites ammonium, in particular ammonium chlorite (NH ₄ CIO ₂ ) and
5/45 tetraalkylammonium chlorites, such as tetramethylammonium chlorite, tetraethylammonium chlorite and tetrabutylammonium chlorite, as well as mixtures thereof. Particularly preferred, the chlorite is selected from the group, consisting of sodium chlorite, potassium chlorite and mixtures thereof.
The chlorite can be used either as a solid or in the form of a solution, in particular, in the form of an aqueous solution. Preferably, the chlorite is used in the purest form possible, as impurities can generally disturb the reaction of chlorite with peroxodisulfate to chlorine dioxide and can reduce the stability of the chlorine dioxide obtained. However, for example, solid sodium chlorite, which is commercially available and in addition to sodium chlorite, can also contain up to about 25% by weight of sodium chloride, preferably up to about 20% by weight, of sodium chloride, particularly preferably up to about 10% by weight, of sodium chloride, since sodium chloride neither disturbs the reaction for chlorine dioxide nor impairs the stability of chlorine dioxide. In a preferred embodiment of the process according to the invention, the chlorite is available in solid form as a molded, compressed, capsule or pellet.
In stage (b) of the process according to the invention, peroxodisulfate (S ₂ O ₈ ² ') is prepared. Peroxodisulfate can be used according to the invention in the form of peroxodisulfuric acid H2S2O8 or as a suitable salt. Preferably, peroxodisulphates are selected from the group, consisting of alkali metal peroxodisulphates, in particular, lithium peroxodisulphate, sodium peroxodisulphate and potassium peroxodisulphate, alkaline earth metal peroxodisulphates, in particular, magnesium peroxysulfate peroxodisulphate and peroxodisulphate, peroxodisulphate ammonium, in particular, ammonium peroxodisulfate (NH4) 2S ₂ O ₈ ) and tetraalkylammonium peroxodisulfates, such as tetramethylammonium peroxodisulfate, tetraethylammonium peroxodisulfate and tetrabutylammonium peroxodisulfate, as well as mixtures thereof. Most preferably, the peroxodisulfate is selected from the group consisting of sodium peroxodisulfate, potassium peroxodisulfate and mixtures thereof.
6/45
Peroxodisulfate can be used either as a solid or in the form of a solution, in particular, in the form of an aqueous solution. Preferably, peroxodisulfate is used in the purest form possible, as impurities can disturb the reaction of chlorite with peroxodisulfate to chlorine dioxide and can reduce the stability of the chlorine dioxide obtained. In a preferred embodiment of the process according to the invention, peroxodisulfate is available in solid form as a molded, compressed, capsule or pellet.
In addition, it is also possible to prepare the chlorite and the peroxodisulfate together, for example, as a biphasic binary solid mixture or as a molded body, tablet, capsule or pellet, in which / in which the two components are contained separately from each other and dissolve late.
If chlorite and / or peroxodisulfate are prepared in the form of a solution, then this is preferably carried out in the form of an aqueous solution. In that case, any suitable water, such as piped water, can be used as a solvent. Preferably, however, demineralized or distilled water is used. However, the aqueous solutions may also contain other suitable co-solvents, such as, for example, halogenated or non-halogenated organic solvents. In a preferred embodiment, the other solvent is a suitable water-soluble solvent, inert to the reaction, preferably selected from the group consisting of methanol, ethanol, n-propanol, iso-propanol, butanol and mixtures thereof. It is particularly preferable to use a water-miscible solvent. The other solvent can be used, for example, in an amount of up to 80% by volume, preferably up to 50% by volume, particularly preferably up to 10% by volume, most particularly preferably up to 5% by volume. volume.
Stage (c) of the process according to the invention, comprises the purification of chlorite and peroxodisulfate in an aqueous system forming the aqueous chlorine dioxide solution. This purification can be carried out through all the appropriate processes, which are known in the
7/45 state of the art. Preferably, the purification of the two components is carried out with mixing. Mixing can also be carried out using all suitable processes, known to the skilled person. For example, mixing can be done on a laboratory scale with a laboratory stirrer. On an industrial scale, for example, mixing can be carried out in a tank with agitator. Preferably, the purification is carried out in such a way that a homogeneous solution of the two components results, which essentially no longer contains any solids. Mixing using a mixing device offers the advantage that the reaction of chlorite and peroxodisulfate to chlorine dioxide is accelerated.
In a preferred embodiment of the process according to the invention, chlorite and peroxodisulfate in stages (a) and (b) are prepared in solid form or in the form of an aqueous solution, whereas in stage (c) (c1 ) the two components are dissolved before combining in water, if the two components are prepared in solid form or (c2) the two components are introduced in solid form simultaneously or successively in an aqueous solvent or (c3) the two solutions are combined, if the two components are prepared in the form of aqueous solutions or (c4) the two components are prepared in aqueous solution and simultaneously or successively are introduced in an aqueous solvent, to prepare the aqueous chlorine dioxide solution.
Preferably, the combination in stage (c1) is carried out in which the two components together, simultaneously or successively, are dissolved in water, when the two components are prepared in solid form. If chlorite and peroxodisulfate are prepared, for example, as a binary solid mixture or as a molded body, then that solid mixture or molded body can simply be dissolved in water and, soon after, the two solutions thus obtained in the molar ratio of according to the invention, they can be essentially combined simultaneously or also successively.
8/45
In stage (c2), the two components, preferably in solid form, are successively introduced in an aqueous solvent. In particular, it is preferable, in that case, to first introduce the peroxodisulfate in aqueous solution first and then to add chlorite, either in solid form or in aqueous solution.
In stage (c3), preferably the two solutions are simultaneously combined in the molar ratio according to the invention. However, it is also possible to first introduce the aqueous solution with peroxodisulfate and then add the chlorite solution.
In stage (c4), the two components are preferably prepared in an aqueous solution and successively introduced in an aqueous solvent. In that case, the order of addition is indifferent and either the aqueous peroxodisulfate solution or the chlorite solution can be previously introduced and the respective other solution added thereafter.
The preferred process, in this case, is the process according to (c3), in which two components are initially separately dissolved in an aqueous solvent and then the two solutions are combined and mixed.
It is particularly preferable to pre-introduce an aqueous solvent, particularly preferably demineralized or distilled water, in the desired quantity and, immediately thereafter, to separate the desired quantities to prepare the aqueous solutions of the two components, prepare the solutions and add them back to the aqueous solvent.
In all cases (c1) to (c4), the aqueous solutions may contain chlorite in any suitable concentration up to the saturation concentration of the corresponding chlorite salt. In that case, the respective saturation concentration does not represent any solid value, but depends, for example, on the temperature used and on the nature of the concrete chlorite salt. Sodium chlorite has, for example, a saturation concentration of about 64.5% by weight, at 20 ° C. But it is also preferable to adjust the concentration of the aqueous chlorite solutions to no more than approximately 5% by weight, preferably no more than 2% by weight and, in
9/45 particular, not more than 1% by weight. The concentration of peroxodisulfate in the aqueous solution can be up to its saturation concentration. In that case, the respective saturation concentration does not represent a solid value, but depends, for example, on the temperature used and the nature of the concrete peroxodisulfate salt. Sodium peroxodisulfate has, for example, a saturation concentration of approximately 54.5% by weight, at 20 ° C.
The water used to prepare the chlorine dioxide solution according to the invention can be any suitable water, such as, for example, tap water. Preferably, however, demineralized or distilled water is used, since, in this way, the solution contains less impurities, which is advantageous with respect to a better reaction of chlorite and peroxodisulfate to chlorine dioxide and to a greater stability of carbon dioxide. chlorine obtained in this way. In addition, one of the co-solvents described above can be used in the preferred amounts described above.
After the purification of chlorite and peroxodisulfate, chlorine dioxide is formed. Since this reaction is carried out in an aqueous system, the chlorine dioxide formed is present in the form of an aqueous solution.
Following the preparation of chlorine dioxide in aqueous solution, it is also possible to add non-water miscible solvents, such as organic solvents, in particular, dichloromethane, chloroform and / or tetrachloromethane and convert the chlorine dioxide into the organic phase. With this, stable solutions of chlorine dioxide in organic solvents are obtained.
It was found to be surprising, that in this reaction, contrary to the sum equation (1) described above to keep the molar ratios according to the peroxodisulfate to chlorite invention greater than 1, a peroxodisulfate equivalent reacts with a chlorite equivalent forming a stable chlorine dioxide solution. It is assumed, without linking to a theory, that in this reaction a radical of hydrogen sulfate is formed, which has a stabilizing effect on the chlorine dioxide formed. This reaction is represented by the following sum equation (2):
CIO ₂ - + HS ₂ O ₈ - [CIO ₂ ·. HSO ₄ ·] + SO4 ² · (2).
10/45
In this case, ο HS ₂ O ₈ 'is formed autocatalytically from S ₂ O ₈ ² . In the reaction of a chlorite equivalent with a peroxodisulfate equivalent, consequently, in addition to a chlorine dioxide radical CIO ₂ *, a radical of hydrogen sulfate HSO ₄ * also forms. These two radicals stabilize reciprocally in an associative way, represented by the pair of radicals [CIO ₂ * * HSO ₄ ']. This representation is only exemplary. Likewise, it is conceivable that such a pair of radicals forms an association with water of the form [CIO ₂ * * H ₂ O * HSO ₄ ']. The hydrogen sulfate radical itself has not been considered as stable until now.
Furthermore, it is assumed, without linking to a theory, that the stabilization of the radical complex [CIO ₂ '* HSO ₄ “] can be supported by the following observations:
1) The chlorine dioxide solution has, based on the proton of the hydrogen sulfate radical, an acidic pH value (preferably in the pH range of 2.5 to 3). As a result, each chlorine dioxide radical is found in the weakly acidic environment and it is assumed that it contributes to the stabilization of the chlorine dioxide radical.
2) Through the association with the hydrogen sulfate radical, an increase in hydrate formation could be carried out, which would increase water solubility. In addition, through the association, the vapor pressure of the radical could be reduced.
3) Through the association, possibly the tendency to recover the radical from chlorine dioxide to chlorite decreases.
4) It is assumed that, due to the uncharged character of the two radicals in the member, there is no effect on their mobility or permeability through salt-impermeable membranes, such as inversion osmosis (RO) membranes, nanofiltration and so on.
5) In addition, it is assumed that the hydrogen sulfate radical has the possibility to react with water for hydrogen monopersulfate or for id or sulfate sulfate. In this reaction, chlorine dioxide reacts to form chloride or chlorate. Thus, the decomposition of the radical complex
11/45 [CIO ₂ * * HSO / J roughly leads to decomposition products. In oxidation reactions, the radical complex reacts to form chloride and sulfate anions that are not relevant to the environment. Conversely, conventional, that is, unstabilized chlorine dioxide solutions tend to decompose in a tendency to explode due to the formation of chlorine and oxygen.
6) The concentration of the chlorine dioxide radical is the determining size for the formation of the radical pair.
The formation of the associate of a pair of radicals described above, is confirmed through experimental analyzes that show, that this associate of a pair of radicals is distilled as a whole and, in this way, it can pass to the gas phase and is also membrane permeable. In addition, the associate of a pair of [CIO ₂ * * HSO ₄ * J radicals has modified physical properties in comparison to the chlorine dioxide radical, such as, for example, a modified vapor pressure and a modified solubility. The oxidation potential of the hydrogen sulphate radical is fully available as an oxidation potential with another electron equivalent and therefore, there is no loss of oxidation potential. This was confirmed through photometry and titration. In total, there are six electron equivalents available, five for reducing chlorine dioxide to chloride, as well as one for reducing the radical from hydrogen sulfate to sulfate. Research has shown that the chlorine dioxide radical initially reacts in water, only then the hydrogen sulfate radical.
With respect to the above knowledge, the process according to the invention is characterized by the fact that in comparison with the processes known in the art, another stoichiometry is used for the reaction of chlorite and peroxodisulfate to chlorine dioxide.
Therefore, in stage (c) of the process according to the invention, chlorite and peroxodisulfate are used in a molar ratio of peroxodisulfate to chlorite [S ₂ Os ² ] / [CIO ₂ ] greater than 1. Therefore, an equivalent chlorite is reacted with a molar excess of peroxodisulfate, en
12/45 as in conventional processes, normally for one equivalent of chlorite, only about 0.5 equivalent of peroxodisulfate was used.
In a preferred embodiment of the present invention, the starting materials are used in a molar ratio of peroxodisulfate to chlorite between 1 and 2 (1 <[S ₂ O ₈ ² '] / [CIO2'] <2). In this case, peroxodisulfate is used merely in a slight excess in relation to chlorite, which means that in the complete reaction of the chlorite, less than one equivalent of unreacted peroxodisulfate (in relation to the chlorine dioxide formed) remains in the chlorine. Since the stability of chlorine dioxide in the solution is generally reduced by the presence of other components (even if only through low-grade peroxodisulfate), a chlorine dioxide solution is obtained through the molar ratio between 1 and 2 described above, which presents greater stability.
In another preferred embodiment of the present invention, the starting materials are used in a molar ratio of peroxodisulfate to chlorite greater than 2, particularly preferably, greater than 4, even more preferably, greater than 10. In addition , it is possible to use a peroxodisulfate to chlorite ratio of up to approximately 100. In this embodiment, peroxodisulfate is used in a greater excess than chlorite, in order to obtain a faster or more complete reaction of the chlorite used for chlorine dioxide .
By maintaining the molar ratio according to the invention, the reaction proceeds in an accelerated and almost quantitative manner. In particular, in the process according to the invention, a yield of more than about 80% is preferred, in particular, more than about 90%, particularly preferably, more than 95% based on the quantity of chlorite used. In the reaction conditions according to the invention, there are also no side reactions.
In addition, it was found that for an effective reaction of chlorite and peroxodisulfate to chlorine dioxide, it is not necessary to adjust the reaction solution to a certain pH value by adding a buffer. Much more, it was verified that by adding the buffer other im
13/45 purities are introduced into the aqueous solution, which reduce the reaction rate for chlorine dioxide and the stability of chlorine dioxide in the solution. Consequently, according to the invention, to prepare the chlorine dioxide solution no buffer is added. Therefore, no additional buffer is added to the preparation. But that does not mean, that the obtained solution does not contain buffer. Thus, for example, during the reaction, a hydrogen sulfate / sulfate buffer can be formed from the sulfate formed during the reaction.
A commonly applied buffer to stabilize chlorine dioxide is a mixture of substances from at least one weak acid and its conjugated base. As weak acids in the sense of the present invention are considered acidic, having a pK value in the range of about -2 to about 12 in water. By adding a buffer, the pH value of an aqueous solution is kept substantially constant within a pH range. In this way, each buffer system has a pH range, within which the pH value when adding a strong acid, does not essentially change. Strong acids are those acids, which are present completely dissociated in the aqueous solution.
In particular, according to the invention, no buffer selected from the group is used, consisting of an acetate buffer, a phosphate buffer, a borate buffer, a citrate buffer and a carbonate buffer. In particular, according to the invention, no bicarbonate or carbonate is used.
In a particularly preferred way, to an aqueous chlorite solution prepared in stage (a) no buffer is added, which buffers the solution in a pH range of 9 to 12. Preferably also, to an aqueous solution of peroxodisulfate prepared in stage ( b) no buffer is added, buffering the solution in a pH range of 3 to 9.
In a preferred embodiment of the present invention, the chlorine dioxide solution is prepared, in which a chlorite solution is combined with a peroxodisulfate solution. Preferably, in this
14/45 case, the peroxodisulfate solution is used in such a concentrated way that it has a pH value in the range of about 4 to about 8. In a preferred embodiment, the pH value of the pero solution matters at about 4 to about 6, in another preferred embodiment, the pH value matters at about 6 to about 8. In addition, the chlorite solution is preferably used so concentrated that it has a value of pH in the range of about 10 to about 12. Preferably, the peroxodisulfate solution has a pH value of about 5 and the chlorite solution, a pH value of about 11.
If the aqueous solutions of chlorite and peroxodisulfate described above are combined, then the pH value of the solution during the reaction of chlorite with peroxodisulfate for chlorine dioxide is preferably adjusted to a value of about 2 to about 4, that is, the pH value of the aqueous solution stabilizes with the increasing complementation of the chlorite reaction with peroxodisulfate to chlorine dioxide in the range of about 2 to about 4. It is particularly preferable if the pH value is adjusted to a range from about 2.5 to about 3. Even more preferably, the chlorite and peroxodisulfate are used in such an amount and concentration that the pH of the combined solution during the reaction stabilizes to a value of about 2 , 5.
To the chlorine dioxide solutions obtained, a buffer can be added after preparation, preferably a buffer, which buffers in a pH range of about 2 to 4.
The process according to the invention can be carried out at any suitable temperature. But it is advantageous if the reaction of chlorite and peroxodisulfate is carried out at comparatively low temperatures in the range of about 0 ° C to about 25 ° C. Conversely, in conventional processes, higher temperatures above 25 ° C are generally required to obtain an accelerated reaction of chlorite with peroxodisulfate to chlorine dioxide. In a preferred embodiment of the present invention, the combination of peroxodisulfate and chlorite is carried out at a temperature in the range of about 0 ° C to about 25 ° C, particularly
15/45 is preferred over a range of about 2 ° C to about 20 ° C. Most preferably, stage (c) of the combination is carried out at a temperature in the range of about 5 ° C to about 15 ° C. It has been found that at higher temperatures (therefore greater than about 25 ° C) side reactions occur, which lead to unwanted side products. The formation of by-products is disadvantageous, since they reduce the stability of the chlorine dioxide solution according to the invention.
In this case, moreover, it is advantageous that this temperature range is maintained not only during the combination of the chlorite component with the peroxodisulfate component, but for so long, until the reaction of chlorite with peroxodisulfate for chlorine dioxide essentially completed. For this purpose, preferably the aqueous solutions used are brought to the corresponding temperature before the combination and, then, they are kept for that long in this temperature range, until the reaction for chlorine dioxide is essentially completed. In addition to the hardening of the solutions used, it is also advantageous, in addition, to temper the medium during the combination and even complete the reaction to the preferred ranges described above. This tempering can be carried out, for example, in a refrigerator, refrigerator or cooling tank. In a particularly preferred embodiment of the process according to the invention, a solution of chlorite and a solution of peroxodisulfate is combined under refrigeration at a temperature in the range of about 5 ° C to about 15 ° C and is then left react in this temperature range until the complete reaction for chlorine dioxide.
In another preferred embodiment, the chlorine dioxide solution obtained by the process according to the invention is also maintained or stored in that temperature range after the reaction is complete. Pure chlorine dioxide has a boiling point of 11 ° C to 101.3 KPa (1013 mbar). Preferably, therefore, the aqueous chlorine dioxide solution obtained by the process according to the invention, is stored below about 11 ° C, in particular, at a temperature in the range of about 0 ° C to about 11 ° Ç.
16/45
If the combination of chlorite and peroxodisulfate is carried out in the preferred temperature range of about 0 ° C to about 25 ° C, more preferably above 0 ° C to about 11 ° C, then the appearance of side reactions and, with this, from unwanted by-products, such as chlorine, hypochlorite and chlorate, during the formation of chlorine dioxide, can be essentially avoided. Therefore, the chlorine dioxide solution prepared with the process according to the invention contains less impurities, which further increases the stability of the chlorine dioxide solution according to the invention.
Preferably, the process according to the invention is carried out under the exclusion of light. Thus, it was verified that in the presence of UV radiation or sunlight, the formation of by-products is possible. The formation of by-products is disadvantageous, since it has been found that by-products or impurities destabilize the chlorine dioxide solution according to the invention. The fewer by-products are in the reaction mixture, the more the solution obtained is stable in the long run.
Through the combination of chlorite and peroxodisulfate in stage (c) of the process according to the invention, the reaction occurs between these two components, forming chlorine dioxide (compare the sum equation above (2)). With the process according to the invention, it is possible, within about 72 hours, to achieve an almost quantitative conversion (i.e., greater than 95% conversion) from chlorite to chlorine dioxide. Preferably, an almost quantitative conversion is obtained after 48 hours, particularly preferably after 24 hours. In particular, for solutions of 0.3 to 0.6% by weight, an almost quantitative conversion is obtained after 48 hours, preferably after 24 hours. For more concentrated concentrations (for example, for concentrations of 1% by weight or more), the reaction time until a quantitative conversion can be reduced to a few minutes, preferably to 30 minutes or less, particularly preferably to 15 minutes or less. At constant temperature and constant peroxodisulfate-chlorite ratio, the
17/45 is faster, the higher the chlorite concentration. In constant concentration of chlorite and peroxodisulfate, the reaction is carried out the faster, the higher the temperature. Finally, an increase in the ratio of peroxodisulfate to chlorite at constant temperature also leads to a faster reaction.
Conversely, in the state of the art (compare, for example, WO-A-96/33947), for the preparation of more concentrated chlorine dioxide solutions, reaction times up to the quantitative reaction of about 12 days have been described.
Preferably, the process according to the invention contains, after stage (c), the other stage of letting the chlorite react with peroxodisulfate, until the chlorite is completely reacted (that is, more than 95% of the chlorite used) to dioxide chlorine. In a particularly preferred embodiment, the process according to the invention contains, after stage (c), the other stage of letting the chlorite react with peroxodisulfate for a period of at least 12 hours, preferably for a period of at least 24 hours, even more preferably, over a period of at least 36 hours. In another particularly preferred embodiment, the process according to the invention contains, after stage (c), the other stage of letting the chlorite react with peroxodisulfate for a period of 12 to 48 hours and preferably for a period of 24 to 36 hours.
With the process according to the invention, chlorine dioxide solutions can be prepared at any desired or suitable concentration. Preferably, with the process according to the invention, aqueous solutions of about 2% by weight, preferably about 1% by weight, of chlorine dioxide can be prepared. More concentrated solutions of chlorine dioxide are obtained, in fact, with greater difficulty due to the limited solubility of chlorine dioxide in water, but, however, they can be carried out. When using higher concentrations of chlorite for the preparation of chlorine dioxide solutions according to the invention, in particular, when using concentrations of chlorite in the range of saturation solubility
18/45 ration of the corresponding chlorite salt, aqueous solutions of chlorine dioxide with a concentration of up to approximately 4.5% by weight can be prepared. The value of about 4.5% by weight, in this case, represents the practically determined saturation limit of chlorine dioxide in water at 5 ° C and normal pressure. Under high pressure, even the free chlorine dioxide phases can be produced in water. Such mixtures typically contain more than about 4.5 to about 12% by weight of chlorine dioxide, based on the total amount of chlorine dioxide and water. The solubility of chlorine dioxide in water is even decisively influenced by impurities dissolved in water, which decrease the solubility of chlorine dioxide. This means that the solubility of chlorine dioxide in water is greater, the less impurities are contained in the solution. Since with the process according to the invention chlorine dioxide solutions are obtained with a smaller portion of impurities, the solubility of chlorine dioxide in the solutions according to the invention is also greater than in conventional chlorine dioxide solutions.
In addition, the chlorine dioxide solutions according to the invention can be handled well even with comparatively high concentrations of up to approximately 12% by weight and preferably up to approximately 2% by weight, of chlorine dioxide and show no tendency to explosion through spontaneous decomposition. However, for safety reasons, as a precaution, chlorine dioxide solutions with a concentration of up to approximately 2.5% by weight, preferably up to approximately 1% by weight, are preferably prepared with the process according to the invention. , and, in particular, about 0.6% by weight of chlorine dioxide. On the contrary, in the state of the art it is described that chlorine dioxide solutions are more stable, the more diluted they are. Therefore, in the state of the art, concentrations of not more than 0.3% by weight are described in the majority. But with the process according to the invention, it is naturally also possible to prepare less concentrated solutions of chlorine dioxide, if desired. This preparation can also be carried out, for example,
19/45 where initially more concentrated solutions of chlorine dioxide with concentrations preferably in the range of about 0.5 to 4.5% by weight, are prepared by the process and these are then diluted to lower concentrations desired, for example, in the range of about 0.003 to about 1% by weight.
In the context of the present invention, therefore, solutions with a chlorine dioxide concentration in the range of about 0.003% by weight to about 4.5% by weight, more preferably in the range of about 0.03%, are preferably prepared. by weight, to about 2.5% by weight, more preferably, in the range of about 0.1% by weight to 1% by weight, most particularly preferably, in the range of more than about 0.3% by weight, at about 0.6% by weight and, in particular, from about 0.5% by weight, at about 0.6% by weight. Corresponding solutions with a chlorine dioxide concentration of more than about 0.3% by weight to about 0.6% by weight, are especially advantageous, since these are clearly more concentrated chlorine dioxide solutions than conventional ones and yet, they are storage-stable as well as well-manageable. The appropriate concentration, in this case, depends essentially on the intended use and can be selected accordingly by a specialist. Less concentrated solutions can be obtained - as already described above - without further ado, from more concentrated chlorine dioxide solutions by corresponding dilution.
With the process according to the invention, chlorine dioxide can be prepared either continuously in the passing process or, alternatively, in batches, in the batch process. If the process according to the invention is carried out in the passage process, then this is particularly advantageous for preparing chlorite, as well as peroxodisulfate in the form of aqueous solutions.
In another preferred embodiment of the present invention, the solution obtained after the combination in stage (c) is filled into a container, in which the solution can be stored and / or transported. When the solution is filled in the container, the reaction for chlorine dioxide
20/45 is not yet complete. In particular, it is also possible that the completion of the chlorite and peroxodisulfate reaction is carried out only after the solution has been transferred to the containers intended for storage or transportation of the solution. Therefore, the filling stage can be carried out before or after the other optional stage of the reaction of chlorite with peroxodisulfate. In another preferred embodiment, the combination is carried out in stage (c) already in the container provided for storage or transportation of the solution. This variant is particularly advantageous since, in this case, it is not necessary to transfer the finished chlorine dioxide solution again. Suitable containers are described below.
The process according to the invention for the preparation of a chlorine dioxide solution and the resulting chlorine dioxide solutions have numerous advantages compared to the state of the art. Thus, the process according to the invention makes it possible to prepare a chlorine dioxide solution under extremely moderate reaction conditions (in particular, at a low temperature) using only two components. In addition, it requires a low industrial cost, since, for example, no heating of the reaction mixture is necessary. In addition, with the process according to the invention in comparatively short reaction periods, an almost quantitative reaction of the chlorine component can be obtained, without the need to add an activator or catalyst (mostly heavy metal salts) or use a defined buffer system .
Based on the simple and complete reaction, the resulting solution contains almost no other components or impurities (such as, for example, unreacted starting materials, unwanted by-products, buffers, activators or catalysts), but almost exclusively chlorine dioxide . Now, it has been surprisingly found that this lack of impurities in the chlorine dioxide solution significantly improves the stability of the chlorine dioxide solution. Thus, it was verified that the stability of the chlorine dioxide solution is both greater and the tendency to decompose
The smaller the chlorine dioxide solution, the greater the purity of the chlorine dioxide solution. As a result, a greater stability of a chlorine dioxide solution is obtained, when chlorine dioxide is prepared with the least possible use of chemicals, which is possible by the process according to the invention. It was verified that additives obviously lead to the destabilization of the solution.
In the chlorine dioxide solution according to the invention, based on the extremely selective reaction, if all in all, there are only small amounts of hypochlorite, chlorine and chlorate as impurities. Therefore, the risk of chlorine dioxide decomposition through possible redox reactions with these components is considerably reduced. Based on this, the chlorine dioxide solution according to the invention can be stored permanently, in particular, for at least one year, without observing a significant decomposition of chlorine dioxide. Therefore, the addition of a stabilizer to the chlorine dioxide solution according to the invention is also not necessary.
To ensure greater purity of the chlorine dioxide solution, no buffer is used in the process according to the invention for the preparation of the chlorine dioxide solution. In a preferred embodiment, the process according to the invention, moreover, is limited to the use of the chlorite component, as well as the peroxodisulfate component, with no other components selected from the group being used, consisting of activators, catalysts and stabilizers for the preparation of the chlorine dioxide solution, that is, added to the starting materials or the resulting chlorine dioxide solution. Activators can be, for example, radical initiators. In a particularly preferred embodiment, no catalysts are used in the process according to the invention. The catalysts can be, in particular, transition metal salts, such as, for example, silver, manganese, copper and iron salts or alkali and alkaline earth metal halides. It was verified, in particular, that the addition of alkali and alkaline earth metal bromides and iodides is disadvantageous, since they lead to the destruction of the dioxide
22/45 of chlorine through the formation of bromine and iodine. Stabilizers can be, for example, EDTA salts. In another preferred embodiment, in the process according to the invention, no coadjuvants are used, such as, for example, sorbitol, starch, polyethylene glycol, sodium benzoate or perfumes. In a particularly preferred embodiment of the process according to the invention, the process is furthermore limited to the use of the chlorite component, as well as the peroxodisulfate component, with no other component being used for the preparation of the carbon dioxide solution. chlorine.
In the state of the art, on the contrary, it is described that high concentrations of chlorine dioxide in themselves accelerate decomposition and that buffer additives or stabilizers are necessary to increase stability. This prejudice has already been refuted.
Due to this increased stability, the chlorine dioxide solutions according to the invention can not only be permanently stored, but also offer a transportable solution. In comparison with the state of the art, with the process according to the invention, it is now no longer necessary to prepare the chlorine dioxide solution just directly on site before the planned application. On the contrary, a chlorine dioxide solution can now be prepared and packaged in larger quantities and only then transported to the intended application site.
In addition, an application of the process according to the invention in any order of magnitude is possible without problems and danger, namely from quantities in the milligram range to large scale applications in the range of several thousand cubic meters.
After completing the preparation process according to the invention, the solution is directly ready for use, further processing, for example, by means of absorption columns, desalination, mixtures with other solutions and so on, it is not necessary .
The present invention also relates to an aqueous solution of chlorine dioxide, which is prepared using the process described above.
23/45
The present invention also relates to an aqueous solution of chlorine dioxide, which contains chlorine dioxide in an amount of approximately 0.1% by weight to approximately 12% by weight and preferably approximately 0.3% by weight. weight to approximately 4.5% by weight, the pH of the aqueous solution is in the range of approximately 2 to approximately 4 and the solution does not contain any buffer. In a particularly preferred embodiment, the aqueous solution contains chlorine dioxide in an amount of approximately 0.3 to approximately 1% by weight, the pH of the solution being in the range of approximately 2 to approximately 4 and the solution does not contain any buffer. Even more preferred is a chlorine dioxide solution with a chlorine dioxide concentration in the range of more than approximately 0.3 to approximately 0.6% by weight. The solution according to the invention is advantageous, in particular, since it is markedly more concentrated than conventional chlorine dioxide solutions and, however, it is stable to storage, as well as being well manageable.
The present invention also relates to an aqueous solution of chlorine dioxide, which contains chlorine dioxide together with the hydrogen sulfate radical in the form of an associate of a radical pair, the solution containing no buffer. In a preferred embodiment, this chlorine dioxide solution according to the invention does not contain any other components, selected from the group, consisting of activators, catalysts and stabilizers.
These chlorine dioxide solutions have the advantages described above of high stability even at high concentrations and of prolonged storage capacity, as well as associated transport capacity.
In addition, the chlorine dioxide solutions according to the invention, due to their only weakly acidic pH value, are of low corrosion and have, in addition, compared to conventional chlorine dioxide solutions, for the protection of the solution, an oxidizing potential
24/45 addition due to the hydrogen sulphate radical contained additionally in the solutions (compare the sum equation (2) above) or a resulting by-product.
The chlorine dioxide solutions according to the invention are permanent, however, they are storable or durable for at least one year, that is, within that period, there is no noticeable decomposition of chlorine dioxide. Preferably, the chlorine dioxide solutions according to the invention are unlimited storage. In order to increase the stability of the chlorine dioxide solutions according to the invention to storage, they are preferably stored chilled, preferably at a temperature in the range above 0 ° C to approximately 25 ° C, particularly preferably, in the range of approximately 2 ° C to approximately 20 ° C, even more preferably, in the range of approximately 5 ° C to approximately 15 ° C.
In addition, it is advantageous that the chlorine dioxide solutions according to the invention are kept under exclusion of air. But since it has surprisingly been found that chlorine dioxide in aqueous solution is clearly more stable against UV radiation or sunlight than in the gas phase, according to a preferred embodiment, it is sufficient to protect the gas phase that is on the solution, inside the container, in which the solutions are kept, against the incidence of light. For this purpose, for example, a light-impermeable film or a light-impermeable container or a light-impermeable structure can be used.
The aqueous solutions according to the invention of chlorine dioxide are real solutions of chlorine dioxide in water, whereas chlorine dioxide does not hydrolyze. The vapor pressure of the solutions varies according to Henry's law, that is, the sum of the partial pressures provides the total pressure. The vapor pressure of chlorine dioxide depends on the temperature and increases with increasing temperature. Chlorine dioxide in pure, non-aqueous form, has a boiling point of 11 ° C at 101.3 KPa (1013 mbar). In water, chlorine dioxide in surprisingly high concentrations is soluble, without it reacting with water. With increasing temperature am
25/45 environment, water solubility drops and chlorine dioxide behaves in the gas phase just like an ideal gas, whereas chlorine dioxide in the gas phase behaves so much more real than the aqueous chlorine dioxide solution , as for the ambient temperature it approaches the boiling point or does not even reach it.
But for various reasons it is desirable to keep the vapor pressure of the chlorine dioxide solutions according to the invention as low as possible. Thus, a high vapor pressure of chlorine dioxide causes some of the chlorine dioxide to come off the solution, which reduces the usable chlorine dioxide concentration. This can lead, in particular, then to significant losses of chlorine dioxide, if the storage container for the chlorine dioxide solution according to the invention, for example, is ventilated or opened. In this way, the chlorine dioxide can gradually pass from the solution to the gas phase and then detach from the container. In addition, chlorine dioxide is less stable in the gas phase against UV radiation or sunlight than in dissolved form. Consequently, with the increase in the fraction of chlorine dioxide in the gas phase, multiple decomposition reactions can occur, which reduces the concentration and purity of chlorine dioxide in the solution according to the invention. In addition, chlorine dioxide is clearly more dangerous in the gas phase due to its tendency to explode and, therefore, more complicated to handle.
Therefore, it is advantageous to store the aqueous chlorine dioxide solutions according to the invention below their boiling temperature of 110 ° C, in particular, at a temperature in the range from 0 ° C to 11 ° C, particularly preferred, at a temperature in the range of 5 ° C to 11 ° C.
But the use of a superpressure is also advantageous with respect to reducing the vapor pressure of chlorine dioxide. For example, the chlorine dioxide solutions according to the invention can be ordered with an overpressure of approximately 1 KPa to approximately 1000 KPa (0.01 to approximately 10 bar), optionally under inert gas,
26/45 such as nitrogen or the like, preferably in the range of approximately 10 KPa to approximately 100 KPa (0.1 to approximately 1 bar), whereby the vapor pressure of chlorine dioxide decreases further. But overpressures at temperatures above the boiling point also lead to a similar result. In this way, the solutions according to the invention can also be stored at temperatures up to 40 ° C, as long as the solutions are simultaneously ordered with an adequate overpressure, to reduce the amount of chlorine dioxide in the gas phase.
In this way, it has been found in accordance with the invention, that chlorine dioxide solutions, both in accordance with the invention, as well as conventional ones, can be advantageously stored in a pressure vessel. The pressure is preferably 1 KPa to approximately 1000 KPa (0.01 to approximately 10 bar), preferably in the range of approximately 10 KPa to approximately 100 KPa (0.1 to approximately 1 bar).
In a particularly preferred embodiment of the chlorine dioxide solutions according to the invention, they are stored at a temperature in the range above 0 ° C to approximately 15 ° C with simultaneous pressure demand, in the range of approximately 10 KPa at approximately 100 KPa (0.1 bar to approximately 1 bar).
In another preferred embodiment of the present invention, chlorine dioxide solutions can also be stored under an atmosphere of inert gas.
Suitable containers include, for example, conventional plastic or metal containers, snap-on bottles, barrels, glass bottles and the like. With respect to the material, there are no restrictions, as long as it remains inert in relation to chlorine dioxide and is the most widely resistant to corrosion. Preferably, glass, metal or synthetic material containers are used, in particular, HDPE, LDPE, PVC, PTFE or mixed polymers. In a preferred embodiment of the present invention, the container intended for mixing, transporting and / or storing the solutions is impermeable to light.
With respect to the container for storing chlorine dioxide solutions according to the invention, Henry's law, which describes the temperature dependent proportions of chlorine dioxide solubilities in the gas phase and in the liquid after adjusting the balance. In particular, in a purely mathematical form, at lower filling levels, for example, after the partial consumption of the chlorine dioxide solutions according to the invention, there is more chlorine dioxide in the gas phase in the gas than in the liquid. This also explains, as a rule, the main losses of active substance in chlorine dioxide solutions. Leaks in the supply containers lead to constant post-regulation of balance and, thus, complete loss of the active substance. The speed of adjusting the balance also varies according to the surface present, the passage of chlorine dioxide from the liquid to the gas phase depends on the surface of the solution and, in particular, on the free gaseous space above. If the surface of a container, moreover, closed, is covered, for example, by a floating body overlying more or less narrowly, then the speed of the adjustment of the balance of chlorine dioxide in the gas phase to the liquid decreases considerably. Accordingly, the container provided for storing and / or transporting the solution according to the invention preferably comprises a floating body. In this way, it is possible to reduce the surface of the chlorine dioxide solution with low filling levels in such a way that the vapor pressure of the chlorine dioxide remains low and the remaining fillers can also be used safely.
In one embodiment, the pH value of the chlorine dioxide solutions according to the invention is in the range of approximately 2 to approximately 4 and preferably in the range of approximately 2.5 to 3. This pH range is advantageous , in particular, with respect to the stability of the solution according to the invention. In contrast, conventional chlorine dioxide solutions typically have a
28/45 pH value greater than 4, this pH value is obtained by a suitable buffer system. According to an embodiment of the present invention, that chlorine dioxide solution does not contain any buffer. In a preferred embodiment, the chlorine dioxide solution according to the invention contains no other components, selected from the group, consisting of activators, catalysts and stabilizers.
In another embodiment of the chlorine dioxide solution according to the invention, it contains, in addition to chlorine dioxide, at least one other radical. Preferably, this chlorine dioxide solution according to the invention was prepared by the process described above. From the sum equation (2) it is evident, in this case, that it is presumed that through the reaction of a chlorite equivalent with a peroxodisulfate equivalent, in addition to a chlorine dioxide equivalent, a radical equivalent is also formed. hydrogen sulfate as described above. In this regard, according to the present invention, the other radical is preferably a hydrogen sulfate radical or a by-product thereof, which was obtained by reacting with the hydrogen sulfate radical.
Due to the other radical present in the solution, that chlorine dioxide solution according to the invention comprises another strong oxidizing agent and therefore has an additional oxidizing effect, whereby the autocatalytic decomposition is suppressed or reduced. Based on this, this chlorine dioxide solution according to the invention is advantageous in comparison with conventional chlorine dioxide solutions.
The present invention also relates to a kit, which in addition to the chlorine dioxide solution according to the invention, comprises a suitable separate reducing agent, such as a separate solution of sulfite, disulfite, thiosulfate, sulfide or nitrite . Preferably, the sulfite solution is a sodium sulfite solution. Alternatively, a solid sulfite can also be used. The chlorine dioxide solutions according to the invention can be exterminated simply and safely in a short time by adding sufficient amounts of sulfite. The addition of
29/45 an aqueous solution of sodium sulfite to the chlorine dioxide solution according to the invention, immediately exterminates the chlorine dioxide contained in the aqueous phase and in the air. The use of the kit according to the invention simplifies the transport, handling, as well as the extermination of chlorine dioxide and allows risk-free handling of the chlorine dioxide solution according to the invention. The exterminator kit also allows, during use, the application of solutions with higher concentrations of chlorine dioxide with subsequent defined detoxification. The extermination of chlorine dioxide has the other advantage, that it forms merely non-poisonous chloride and, if sulfite is used, non-poisonous sulfate.
The present invention further relates to the use of the aqueous chlorine dioxide solution described above as a disinfectant, as an oxidizing or bleaching agent and / or as a deodorant. In that case, the chlorine dioxide solutions according to the invention can be used, for example, for the disinfection of air, soil and water, such as drinking water, bath water, waste water, industrial water and so on, in medicine, in filters or biofilms. In addition, the chlorine dioxide solutions according to the invention can be used as oxidizing or bleaching agents, for example, in various technological processes, such as for paper production, food production and so on, in beneficiation waste and clarifying iodines or purifying agents. The chlorine dioxide solutions according to the invention can also be used as deodorants, for example, in combating odors, such as in a waste water channel, in industrial processes, in the home and so on, in solids, suspensions and purifying agents. The applications mentioned above, however, should not represent any definitive listing. On the contrary, the chlorine dioxide solutions according to the invention can be applied in all suitable areas, in which their disinfectant, oxidizing and deodorizing effect is useful.
The chlorine dioxide solution according to the invention can also be used to convert chlorine dioxide from that solution by extraction with organic solvents, such as ethers, hydrocarbons
30/45 and so on, quantitatively in organic solvents. Thus, chlorine dioxide is accessible for other reactions limited to suitable organic solvents. With this, it can be used in work areas, where water is preventive or counterproductive (for example, due to corrosion based on the humidity of the air and so on).
The present invention also relates to the use of an aqueous solution of chlorine dioxide for the disinfection of drinking water and for bathing or for the treatment of industrial and waste water, the chlorine dioxide solution being obtainable through of a process, which comprises the stages of the preparation of chlorite, the preparation of peroxodisulfate and the combination of chlorite and peroxodisulfate in an aqueous system and in a molar ratio of peroxodisulfate to chloride of [S ₂ O8 ² ] / [CIO2] greater 1, with the formation of the aqueous chlorine dioxide solution.
The present invention also relates to the use of an aqueous chlorine dioxide solution for the disinfection of drinking water and for bathing or for the effective combat of biofilms, the solution comprising chlorine dioxide together with the sulfate radical. hydrocarbon in the form of an associate of a pair of radicals.
In the following, particularly preferred uses of the chlorine dioxide solutions according to the invention or chlorine dioxide solutions prepared by the process according to the invention are exposed again. Thus, the chlorine dioxide solutions according to the invention can be used in technical processes.
Exemplary technical processes include non-destructive cleaning (disinfection) of membrane systems, for example, RO systems, also in the medical field; the removal of moss in all types of materials; the removal of coating, for example, on vehicles, ships, airplanes; combating odor in production processes; the treatment of industrial wastewater through disinfection of wastewater, physical-chemical separation of water and reuse of waste materials; corrosion protection in wastewater conducting systems; surface protection of lacquers, coatings of all types, synthetic materials
31/45 cos, wood, metal, ceramic, stone; the removal of germs with a long-term effect; the detoxification of areas and environments (gas phase); conservation of air purity; cosmetic or medicinal applications, for example, as a mouthwash, for the treatment of warts, for the elimination of mites, for the specific destruction of cells, for external and internal application or for application against pathogenic germs; the oxidation of waste materials (medicines, X-ray contrasts, oxidation products, cyanides and so on), in waste water (AOP) behind clarification systems; the oxidation of gaseous products (H ₂ S, NO, NO _2> as well as organic materials); as well as low temperature sterilization, for example, OP material. The chlorine dioxide solutions according to the invention can also be used for the treatment of oxidative heavy metals.
In addition, the chlorine dioxide solutions according to the invention can be used for the treatment of drinking water, for example, in hydraulic systems for the permanent disinfection of drinking water, for the degradation of biofilm in water pipes in the form of daily disinfection or in the form of permanent disinfection. In addition, chlorine dioxide solutions can be used for emergency chlorination or disinfection of drinking water, for example, after heavy rain, after a contamination attack (for example, after bacterial infestation of a water container drinking groundwater, surface or brackish water and for the elimination of pathogenic germs, eg anthrax, cholera and so on) or after natural disasters, to thereby provide disinfected drinking water or to maintain a potable water supply also of poor quality surface water. Finally, chlorine dioxide solutions can be used in buildings (for example, clinics, hospitals, geriatric clinics, administrative buildings, office buildings, residential buildings), swimming pools, vehicles (for example, automobiles, trains, ships, airplanes) for disinfection and piping of warm and cold water, air conditioning systems, water treatment systems, heaters, wastewater or bath water systems in
32/45 pools, in order to remove, in particular, legionella and other germs, as well as biofilms or to suppress the formation of biofilms. Preferably, the chlorine dioxide solution according to the invention is used in the form of a daily disinfection or in the form of a permanent disinfection to remove biofilms, legionella or other germs in drinking water pipes, air conditioning systems, treatment systems water, heaters or pools.
Other suitable applications in this area are represented by the substitution for emergency disinfections, the disinfection of underground and tall tanks, the disinfection of equipment and plumbing, the disinfection after the rupture of the pipe, the emergency disinfection after new contamination, the fight against biofilm and the prophylaxis of biofilm, the treatment of wastewater from medicinal residues, as well as the elimination of multi-resistant germs.
In air conditioning systems and cooling towers, the chlorine dioxide solutions according to the invention can be used for the elimination of biofilm from heat exchangers and pipes, for the elimination of contamination, such as, for example, legionella, for daily, permanent or intermittent disinfection and for corrosion protection.
In food production, the chlorine dioxide solutions according to the invention can be used for the treatment of production and washing water, for the conservation of hygiene in the production process, for the disinfection of transport vehicles, for the creation of animals, for the elimination, combat and prophylaxis of infection colonies and for the conservation of hygiene in the slaughter area, for example, during processing, packaging or cleaning.
In the case of fruits, fruits and seeds, the chlorine dioxide solutions according to the invention can be used for the conservation of hygiene during the growth phase, during and after harvest, for the conservation of hygiene in processing, during the packaging to prolong durability, to preserve hygiene in the storage of
33/45 seed, for preventing the germination of the seed, for disinfection or for sterilization with long lasting effect.
In the case of trains, airplanes or ships, the chlorine dioxide solutions according to the invention can be used to conserve the hygiene of sanitary areas, air conditioning systems, to combat odor, to eliminate ecological vegetation from long-lasting, for example, in the area of rails, signs and so on, for the disinfection of ships, for the treatment of waste water, for the treatment of gray, yellow or black water, for the disinfection of drinking water and for obtaining drinking water from sea water.
The chlorine dioxide solutions according to the invention can be applied in a particularly good way to eliminate odor, for example, in wastewater conducting systems, also channels. In these wastewater conducting systems, these also serve as protection against corrosion, because they permanently interrupt the putrefaction process. The elimination of biofilm with this solution can be applied very well as surface protection for lacquers, coatings of all types, synthetic materials, wood, metal, ceramic, stone. In this case, the applied solution is particularly effective with a lasting effect. The lasting effect is the result of the complete elimination of the biofilm from the surface. Likewise, the solution can be used to detoxify areas and environments (gas phase), also to keep the air fresh. The chlorine dioxide solution can be used for lasting purification, disinfection, as well as membrane sterilization. Stable radicals also allow use in medicinal applications, for example, as a mouthwash, for the treatment of warts, for the elimination of mites, for the specific destruction of cells, moreover, in general for external disinfection and for the destruction of pathogens.
The present invention further relates to a device for preparing the chlorine dioxide solution described above. This device for preparing the chlorine dioxide solution according to the invention is based on the idea that the process for preparing a chlorine dioxide solution
34/45 chlorine dioxide according to the invention cannot be carried out only on an industrial scale, but also for application on smaller scales. Therefore, a corresponding device for carrying out the process according to the invention can be present, for example, also in single-family or multi-family buildings, for example, to continuously make necessary quantities of chlorine dioxide available for the disinfection of drinking water and bathing.
Against this background, the device (1) according to the invention for preparing the chlorine dioxide solution according to the invention, comprises (a) at least one reservoir for a chlorite component (2), (b) at least at least one reservoir for a peroxodisulfate component (3), (c) at least one mixing container (4), which is connected or can be connected via a supply pipe to the chlorite component (5), with at least a reservoir for a chlorite component (2) and which is connected or can be connected via a supply pipe to the peroxodisulfate component (6), with at least one reservoir for a peroxodisulfate component (3), (d) at least a reservoir for the chlorine dioxide solution (7), which is connected or can be connected through at least one supply pipe for the chlorine dioxide solution (16), with the mixing container (4) and (e ) a device dosing device (18), which is installed in at least one reservoir for the chlorine dioxide solution (7).
The device according to the invention is described, for example, below, with reference to the attached drawing of a preferred embodiment, since the objectives, characteristics and advantages of the device according to the invention must be understood more simply based on the following detailed specification, as well as the attached drawing. In this case, the specification should be understood
35/45 such that the embodiment shown in the drawing is also shown with merely preferred characteristics, which need not necessarily be present.
Figure 1 shows a preferred embodiment of the device according to the invention for the preparation of a chlorine dioxide solution.
In this case, the device 1 comprises a reservoir for a chlorite component 2. This reservoir 2 is structured in such a way that it can store the chlorite component, for example, in solid form and as an aqueous solution. In a preferred embodiment of the device according to the invention, the reservoir 2 can comprise a mixing or stirring device 8, so that in the reservoir 2 an aqueous chlorite component can be produced by dissolving solid chlorite in water, this dissolution is facilitated by the mixing or stirring device 8. In another preferred embodiment, reservoir 2 contains one or more measuring cells 9, which are equipped to determine the amount or concentration of chlorite in reservoir 2. These can be, for example, measuring cells suitable for conductivity, pH value, redox value, amperometric measuring cells or combinations thereof.
The device 1 further comprises a reservoir for a peroxodisulfate component 3. That reservoir 3 is structured in such a way that it can store the peroxodisulfate component, for example, in solid form and as an aqueous solution. In a preferred embodiment of the device according to the invention, the reservoir 3 can comprise a mixing or stirring device 10, so that in the reservoir 3 an aqueous peroxodisulfate component can be produced by dissolving solid peroxodisulfate in water, this dissolution is facilitated by the mixing or stirring device 10. In another preferred embodiment, reservoir 3 contains one or more measuring cells 11, which are suitable for determining the amount or concentration of peroxodisulfate in the reservoir
36/45 rio 3. These can be, for example, measuring cells suitable for conductivity, pH value, redox value, amperometric measuring cells or combinations of these
The device 1 further comprises a mixing vessel 4, which is connected or can be connected via a supply pipe for the chlorite component 5, with at least one reservoir for the chlorite component 2 and which is connected or can be connected via a feed pipe to the peroxodisulfate component 6, with at least one reservoir for a peroxodisulfate component 3. Feed pipes 5 and 6 are equipped to carry the chlorite or peroxodisulfate component from reservoirs 2 and 3 to the mixing container. In a preferred embodiment, the feed lines 5 and 6 are provided with metering devices 12 and 13, which are equipped to regulate the amount of chlorite or peroxodisulfate to be fed and also to completely stop the chlorite or peroxodisulfate feed. In a particularly preferred embodiment, the supply lines 5 and 6 are provided with dosing devices 12 and 13, which are equipped to regulate the amount of chlorite and peroxodisulfate to be fed in such a way that the peroxodisulfate and chlorite are fed in a ratio of [S ₂ O ₈ ² '] / [CIO ₂ '] greater than 1 to the mixing vessel (4).
The mixing vessel 4 preferably comprises a mixing or stirring device 14, which is equipped to mix the fed chlorite and peroxodisulfate component with one another. In addition, the mixing vessel 4 preferably comprises one or more measuring cells 15, which are equipped to determine the amount or concentration of chlorine dioxide and / or chlorite and peroxodisulfate in the mixing vessel 4. Via the measuring cells 15 correspondents, it is possible to monitor the reaction of chlorite and peroxodisulfate to chlorine dioxide. In addition, the mixing vessel 4 is preferably equipped in such a way that it is possible to feed it water. This is particularly significant when the two components are fed to the mixing vessel 4 in a solid form.
In addition, the device 1 according to the invention comprises one or more reservoirs for the chlorine dioxide solution 7. In a preferred embodiment, the device 1 according to the invention comprises at least two reservoirs for the dioxide solution chlorine 7a and 7b. The at least one reservoir 4 is connected or can be connected via at least one supply pipe 16, with the mixing vessel 4. The at least one reservoir 7 is equipped to store the chlorine dioxide solution prepared by means of process according to the invention, until it is necessary for the concrete application. In a preferred embodiment of the device according to the invention, the at least one reservoir 4 is provided with a device for regulating pressure 17, which is equipped to measure the pressure in at least one reservoir 7, as well as to request hair least one reservoir 7 with pressure. This is advantageous with respect to reducing the vapor pressure of the chlorine dioxide solution. In a particularly preferred embodiment, the at least one reservoir 7 furthermore also comprises a floating body 20, which is equipped to cover the surface of the chlorine dioxide solution in reservoir 7. This is advantageous, in particular, at low reservoir filling levels with respect to a reduction in the vapor pressure of the chlorine dioxide solution.
In addition, the device 1 according to the invention comprises a metering device 18, which is installed in at least one reservoir for the chlorine dioxide solution 7. That metering device 18 is equipped to regulate the withdrawal of carbon dioxide solution chlorine from at least one reservoir 7. The metering device 18 can be, for example, a metering pump. If the device 1 comprises at least two reservoirs for the chlorine dioxide solution 7a and 7b, then it is advantageous that the dosing device 18 is structured in such a way, so that chlorine dioxide solution or the reservoir 7a or of reservoir 7b. In addition, reservoir 7 preferably comprises one or more measuring cells 19, which are equipped to determine the quantity or
38/45 concentration of chlorine dioxide and / or chlorite and peroxodisulfate in the reservoir 7. By this means it is possible to determine at any time the concentration of chlorine dioxide as well as its purity in the chlorine dioxide solution.
The device according to the invention makes it possible to prepare and make the chlorine dioxide solution available in varying amounts. Storage in at least two different reservoirs 7a and 7b also allows for the continuous withdrawal of ready chlorine dioxide solution. Thus, for example, during withdrawal of the solution from reservoir 7a, reservoir 7b can be completed again and vice versa.
In a preferred embodiment, the device according to the invention further comprises a ripening vessel, which is disposed between the mixing vessel 4, as well as the reservoir 7. That ripening vessel is advantageously equipped such that it absorbs the combined solutions in the mixing vessel 4 and receives them for so long, until the reaction of chlorite and peroxodisulfate to chlorine dioxide is completed. In a particularly preferred embodiment, the ripening vessel also comprises a device for regulating the pressure.
In addition, the device according to the invention preferably comprises an automated process control unit, which is connected or can be connected, for example, with measuring cells 9, 11, 15 and 19, with the devices for regulating the pressure 17, as well as dosing devices 12 and 13. Through this automated pressure control unit, for example, the amount and concentration of the chlorine dioxide solution to be prepared can be regulated by controlling the amounts of chlorite and peroxodisulfate to be fed.
In another preferred embodiment, the device 1 according to the invention is equipped in such a way that the preparation, as well as the storage of the chlorine dioxide solution, takes place under the exclusion of light. This can be done, for example, by the fact that the containers and supply pipes are structured in an im-
39/45 light permeable. But it is also possible that the device 1 is arranged in a box or a compartment, which is impermeable to light.
In another preferred embodiment, the device 1 according to the invention can be tempered. In that case, it is particularly preferable that the device 1 is equipped in such a way that, in particular, the mixing of the two starting products, as well as the storage of the ready chlorine dioxide solutions can be carried out at temperatures in the range of approximately 0 ° C to approximately 25 ° C. Storage can be carried out, for example, by means of suitable cooling devices, which cool the individual mixing vessel or reservoir. But it is also possible that the entire device 1 is arranged in a type of refrigerator.
In another preferred embodiment, the device 1 according to the invention is equipped to prepare the chlorine dioxide solution continuously in the flow operation. In another preferred embodiment, the device 1 according to the invention is equipped to prepare the chlorine dioxide solution at charges in the mixing operation.
In a preferred embodiment, the device according to the invention is equipped to be used as a small system in a single- or multi-family residence. This is advantageous, for example, for making available the amounts of chlorine dioxide necessary for disinfecting drinking water and for bathing continuously or for loads as needed. In another preferred embodiment, the device according to the invention for the preparation of a chlorine dioxide solution is transportably equipped, in which it is accommodated in a box. The box can be any box suitable for transportation, for example, a metal or synthetic material box. Preferably, the transportable device is a device weighing less than 500 kg, particularly preferably less than 100 kg. In this way, it is possible to transport the device according to the invention and, in this way, to apply the process according to the invention only at the place where the chlorine dioxide solution is used. This can be, for example, in the form of small pe40 / 45 systems in a single or multifamily residence.
In another preferred embodiment, the device according to the invention is equipped for use as a large-scale system, for example, as a tank system. This is advantageous, for example, for preparing the chlorine dioxide solution according to the invention in large quantities and then optionally filling in smaller containers and selling or transporting. This has the advantage that the chlorine dioxide solution according to the invention does not need to be prepared on the spot.
Finally, the present invention also relates to an associate of a radical pair, which comprises at least one chlorine dioxide radical, as well as a hydrogen sulfate radical. Preferably, this radical pair member also contains at least one water molecule and optionally other radical species. These other species of radicals can be, for example, intermediate intermediate stages, such as OH *, SO4 * ’or CIO *, which have been formed from chlorine dioxide or the hydrogen sulfate radical. In a preferred embodiment, the radical pair associate according to the invention is stable, that is, it is stable to storage for at least 1 hour. In a particularly preferred embodiment, it is stable for one day, even more preferably, for 1 year. In another preferred embodiment, the radical pair associate according to the invention is not present in the presence of a buffer.
The invention is elucidated in detail now, based on examples.
Examples
Analyze:
The concentration of chlorine dioxide in the chlorine dioxide solutions according to the invention can be determined by several measurement methods. In particular, the chlorine dioxide concentration can be determined amperometrically, photometrically, iodometrically, by titrating the chlorine dioxide solution with a sulfite solution
41/45 or ion chromatography.
The methods of analysis are described in detail in the spreadsheets of the German Gas and Water Association (Deutschen Vereins DES Gas-und Wasserfaches) (DVGW) W224 (February 2010), page 18 and following in relation to DIN 38408-5.
In the following examples, photometry was used, in particular, to determine the concentration of chlorine dioxide, as well as ion chromatography to determine the other fractions, such as chlorite, chlorate, perchlorate, hypochlorite and chlorine dioxide.
In photometry, Lambert-Beer's law is unlimited. To determine the concentration of chlorine dioxide with photometry, measure at a wavelength of 360 nm. The molar extinction coefficient is 1100 +/- 50 [1 / mol * cm],
With ion chromatography, the fractions of chlorite, chlorate, perchlorate, hypochlorite and chlorine dioxide are determined in a combinatorial manner. Conditions are known in the prior art and are described, for example, in Petra Hübenbecker, Dissertation Bonn, 2010: “Untersuchung zur Entstehung Von Desinfektionsnebenprodukten bei der Aufbereitung Von Trinkwasser an Bord schwimmender Marineeinheiten unter Anwendungsbeningen.
Example 1: Preparation of 60 liters of an aqueous solution of approximately 0.6% chlorine dioxide
56.530 g of demineralized water are weighed in a 60 liter container. Separately, 1970 g of a 24.5% technical solution of sodium chlorite and 1,500 g of sodium peroxodisulfate (99%) are weighed in separate containers. Peroxide and chlorite are dissolved separately in a sufficient amount of water from the vessel. After the introduction of the sodium chlorite solution, the sodium peroxodisulfate solution is poured and left to stand for 24 to 48 hours at 12 ° C. Chlorine dioxide yields matter and 88 to 98%, based on the use of sodium chlorite.
Example 2: Preparation of 50 bottles with 0.2 liter snap-on closure
42/45 each of approximately 0.6% chlorine dioxide solution
In a 10 liter bucket, 9.65 liters of demineralized water are weighed. Separately, 100 g of 80% sodium chlorite in powder form (containing 20% sodium chloride) and 250 g of sodium peroxodisulfate (99%) are weighed separately. The two solids are dissolved separately with sufficient water from the bucket. The sodium chlorite solution is placed in the residual water in the bucket and mixed with the peroxide solution under rapid stirring.
The finished mixture is filled in bottles and stored closed for 2 to 3 days in the refrigerator at 5 to 10 ° C. Chlorine dioxide yields matter 85 to 99%, based on the use of sodium chlorite. Example 3: Preparation of one liter of a 0.3% chlorine dioxide solution
500 mg of sodium chlorite (80%) are dissolved in 500 ml of demineralized water and mixed with a solution of 2500 mg of sodium peroxodisulfate in 497 ml of demineralized water. The bottle is closed and left to stand in a refrigerator for 24 hours. The yield is> 85%, based on the use of sodium chlorite.
Example 4: Preparation of one liter of a 0.6% chlorine dioxide solution
10.00 g of sodium chlorite (80%) are dissolved in 100 ml of demineralized water. 105.00 g of sodium peroxodisulfate (99%) are also dissolved in 100 ml of demineralized water. The two solutions are placed in 685 ml of demineralized water. The bottle is closed and left to stand in a refrigerator for 3 hours. The yield is> 95%, based on the use of sodium chlorite.
Example 5: Preparation of one liter of a 0.6% chlorine dioxide solution
10.00 g of sodium chlorite (80%) are dissolved in 40 ml of demineralized water. 330 g of sodium peroxodisulfate (99%) are also dissolved in 620 ml of demineralized water. The bottle is closed and left to stand in a refrigerator for 30 minutes. The ren
43/45 dances matter> 98%, based on the use of sodium chlorite.
It was found that all chlorine dioxide solutions prepared in examples 1 to 5 are storage-stable, that is, that after one year no significant decomposition (> 5%) of chlorine dioxide is observed. In addition, it has been shown that the solutions are all the more stable, the less by-products are found in the reaction mixture.
It was found that the finished product, as an associate of a pair of radicals, is a permeable membrane and that associate of a pair of radicals has modified physical properties (vapor pressure, so10 lubricity and so on).
For the vapor pressure of a chlorine dioxide solution to
0.6%, the following values were determined:
temperature [° C] actual gas concentration (Kg / CIO ₂ / m ³ ) [g / CIO ₂ / m ³ ] calculated CIO ₂ concentration (KPa) [mbar] total pressure including water vapor (KPa) [mbar] 10 0.096 [96] 3.3 [33] 0.5 [5] 20 0.114 [114] 4.1 [41] 6.7 [67] 30 0.147 [147] 5.4 [54] 14 [140] 40 0.171 [171] 6.5 [65] 18.5 [185] 50 0.209 [209] 8.2 [82] 30.1 [301]
According to the literature (DVGW W224 / 1986 S.5), from a CIO ₂ concentration of 10 KPa (100 mbar) (= 10% by volume, 300 g 15 CIO ₂ / m ³ ) it is warned due to a tendency for the solution to explode.
On the contrary, it has been found that the solutions according to the invention can be handled well and do not show any tendency to spontaneous decomposition or explosion. Even at elevated temperatures of 50 ° C, the product reacts only slowly to chlorate, at temperatures of 80 to 90 ° C, quickly. In this case, the solution is not flammable at any time. This has also been tested with chlorine dioxide concentrations of up to 4.5%. When chlorine dioxide solutions are prepared with concentrations greater than 2.5% by weight, this leads to an increase in pressure in the reaction vessel, which can be calculated approximately according to
44/45 with the ideal gas law. At concentrations greater than approximately 4.5% by weight, chlorine dioxide precipitates as an oily liquid.
If solutions with chlorine dioxide concentrations of 0.01 to 4.5% are brought into contact with objects in combustion / open fire, then those same objects are extinguished in solutions of 4.5% CIO ₂ ; however, in this case, the gas phase decomposes. In solutions with <1% CIO ₂ , the reaction with the gas phase is not noticeable.
List of references
Device for preparing the chlorine dioxide solution according to the invention
Reservoir for a chlorite component
Reservoir for a peroxodisulfate component
Mixing container
Supply pipe for the chlorite component
6Power line for the peroxodisulfate component
7, 7a, 7b Supply line for chlorine dioxide solution
Mixing or stirring device
Measuring cell in the reservoir for a chlorite component
Mixing or stirring device
Mixing cell in the reservoir for a peroxodisulfate component
Dosing devices for the chlorite component
Dosing devices for the peroxide component
Mixing or stirring device in the mixing vessel
Measuring cell in the mixing vessel
Supply pipe for at least one reservoir for the chlorine dioxide solution
Pressure regulating device
Dosing device
45/45
Measuring cell
Floating body

权利要求:
Claims (18)
[1]
1. Process for the preparation of an aqueous chlorine dioxide solution, characterized by the fact that it comprises the steps of:
(a) preparation of chlorite, (b) preparation of peroxodisulfate, (c) combination of chlorite and peroxodisulfate in an aqueous system and in a molar ratio of peroxodisulfate to chlorite [S2Oe ² '] / [CIO2'] greater than 1 forming the aqueous chlorine dioxide solution, and for the preparation of the aqueous chlorine dioxide solution, no additional buffer is added and no catalyst is used.
[2]
2. Process according to claim 1, characterized by the fact that the molar ratio between peroxodisulfate and chlorite [S2Oe ² '] / [CIO2'] is greater than 2.
[3]
3. Process according to claim 1, characterized by the fact that the molar ratio between peroxodisulfate and chlorite [S2Oe ² '] / [CIO2'] is between 1 and 2.
[4]
Process according to any one of claims 1 to 3, characterized in that the chlorite and peroxodisulfate, in stages (a) and (b), are prepared in solid form or in the form of an aqueous solution, and in stage (c) (c1) the two components are dissolved in water before combining, if the two components are prepared in solid form, or (c2) the two components are introduced into an aqueous solvent in solid form simultaneously or successively, or (c3) the two solutions are combined, if the two components are prepared in the form of aqueous solutions, or (c4) the two components are prepared in aqueous solution and are introduced in an aqueous solvent simultaneously or successively, to prepare the aqueous solution of Chlorine dioxide.
[5]
5. Process according to claim 4, characterized by the fact that both peroxodisulfate and chlorite are
2/4 prepared in the form of aqueous solutions, with the peroxodisulfate solution having a pH value in the range of about 4 to about 6, and the chlorite solution having a pH value in the range of about 10 to about 12.
[6]
Process according to any one of claims 1 to 5, characterized in that the combination of peroxodisulfate and chlorite is carried out at a temperature in the range of about 0 ° C to about 25 ° C.
[7]
7. Aqueous chlorine dioxide solution, characterized by the fact that it is prepared by the process as defined in any one of claims 1 to 6.
[8]
8. Aqueous chlorine dioxide solution, characterized by the fact that it contains chlorine dioxide in an amount of about 0.1 to about 1% by weight, preferably in the range of more than approximately 0.3 to about 0 , 6% by weight, with the pH value of the solution ranging from about 2.5 to about 3.
[9]
9. Aqueous chlorine dioxide solution according to claim 8, characterized in that the solution does not contain any buffer.
[10]
10. Aqueous chlorine dioxide solution, characterized by the fact that it contains chlorine dioxide in an amount of about 0.1 to about 12% by weight, preferably in the range of more than about 0.3 to about 4.5% by weight, with the pH value of the solution in the range of about 2.5 to about 3 and the solution containing no buffer.
[11]
11. Use of the aqueous chlorine dioxide solution, as defined in any one of claims 7 to 10, characterized by the fact that it is as a disinfectant, as an oxidizing or bleaching agent, and / or as a deodorant.
[12]
12. Use of an aqueous chlorine dioxide solution for the disinfection of drinking and bathing water or for the treatment of drinking and waste water, characterized by the fact that the chlorine dioxide solution can be obtained by a process, which understands the stages of
3/4 preparation of chlorite, preparation of peroxodisulfate and combination of chlorite and peroxodisulfate in an aqueous system and in a molar ratio of peroxodisulfate to chlorite [S2Oe ² '] / [CIO2'] greater than 1 forming the aqueous solution of chlorine dioxide, and for the preparation of the aqueous chlorine dioxide solution no additional buffer is added and no catalyst is used.
[13]
13. Use according to claim 11 or 12, characterized by the fact that the chlorine dioxide solution is used in the form of an instant disinfection or in the form of a permanent disinfection for the removal of biofilms, legionella or other grooves in plumbing drinking water, air conditioning systems, water treatment systems, heaters or swimming pools.
[14]
14. Device (1) for preparing chlorine dioxide solution, as defined in any one of claims 7 to 10, characterized by the fact that it comprises:
(a) at least one reservoir for a chlorite component (2), (b) at least one reservoir for a peroxodisulfate component (3), (c) at least one mixing reservoir (4), which is connected via a supply pipe for the chlorite component (5), with at least one reservoir for the chlorite component (2) and which is connected via a supply pipe for the peroxodisulfate component (6), with at least one reservoir for the peroxodisulfate component (3), (d) at least one reservoir for the chlorine dioxide solution (7), which is connected or can be connected via at least one supply pipe to the chlorine dioxide solution (16) , with the mixing tank (4), (e) a metering device (18), which is installed in at least one reservoir for the chlorine dioxide solution (7), and (f) a floating body (20) to cover the surface of the
4/4 chlorine dioxide in the reservoir (7).
[15]
15. Device (1) for the preparation of a chlorine dioxide solution according to claim 14, characterized by the fact that the device is equipped for use as a small system in a simple house or building or as a great industry.
[16]
16. Device (1) for the preparation of a chlorine dioxide solution, according to claim 14, characterized by the fact that the device is equipped to be transported, in which it is accommodated in a box.
[17]
17. Device (1) for the preparation of a chlorine dioxide solution according to any one of claims 14 to 16, characterized in that the supply lines (5) and (6) are provided with metering devices (12) and (13), which are equipped to regulate the amount of chlorite and peroxodisulfate to be fed in such a way that the peroxodisulfate and chlorite are fed in a ratio of [S ₂ O ₈ ² ] / [CIO ₂ ] greater than 1 to the mixing tank (4).
[18]
18. Reservoir, characterized by the fact that it comprises a chlorine dioxide solution, as defined in any of claims 7 to 10, said reservoir being under pressure from 1 KPa to about 1000 KPa (0.01 to about 10 bar).
1/1

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法律状态:
2018-12-11| B09A| Decision: intention to grant|

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2019-02-12| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 22/12/2011, OBSERVADAS AS CONDICOES LEGAIS. (CO) 20 (VINTE) ANOS CONTADOS A PARTIR DE 22/12/2011, OBSERVADAS AS CONDICOES LEGAIS |

优先权:

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申请号 | 申请日 | 专利标题

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DE102010055982.2|2010-12-23|

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DE201010055982|DE102010055982A1|2010-12-23|2010-12-23|Process for the preparation of an aqueous chlorine dioxide solution|

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PCT/EP2011/006510|WO2012084247A1|2010-12-23|2011-12-22|Method for producing an aqueous stable chlorine dioxide solution|

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