Composition for removing chemical residues and use thereof
阅读说明：本技术 用于去除化学残留物的组合物及其用途 (Composition for removing chemical residues and use thereof ) 是由 A·杜瓦尔 J·布洛梅 于 2020-02-20 设计创作，主要内容包括：本发明涉及用于去除化学残留物的组合物,使用所述组合物的方法,以及所述组合物用于去除被任何类型的化学品污染的材料、机器和设备上的残留物的用途。(The present invention relates to a composition for removing chemical residues, a method for using said composition, and the use of said composition for removing residues on materials, machines and equipment contaminated with any type of chemical.)
1. A stain removal composition comprising:
-at least one first neutralizing agent (a) which is an aluminium and ethylenediaminetetraacetic acid based complex and has a pKa >4,
-at least one second neutralizing agent (b) selected from amphoteric agents, agents having at least one pKa of 7 to 11 and mixtures thereof, the two pKa values of said amphoteric agents satisfying the following condition:
(pKa1+pKa2)/2>5
7>pKa1>4
11>pKa2>7，
-water, which is water,
optionally a colour indicator or a mixture of colour indicators (c), and
optionally, at least one additive (d),
characterized in that the composition is free of salt HaXbWherein H is an alkali metal or an alkaline earth metal, X is a halogen atom, a is an integer of 1 to 2, and b is an integer of 1 to 4.
2. The composition according to claim 1, characterized in that the first neutralizing agent is present in an amount ranging from 0.1% to 25% by weight, preferably from 10% to 20% by weight and more preferably from 15% to 18% by weight relative to the total weight of the composition.
3. The composition of claim 1 or 2, wherein the second neutralizing agent is selected from the group consisting of ascorbic acid and salts thereof; bicarbonate salts and salts thereof; creatinine; glutathione; isoguanine; adenine; amino acids and salts thereof, such as glutamic acid, aspartic acid, arginine, lysine, ornithine, cysteine; and mixtures thereof.
4. The composition of claim 3, wherein the second neutralizing agent is selected from the group consisting of sodium glutamate, lysine, ornithine, cysteine and L-arginine.
5. The composition according to any one of the preceding claims, characterized in that the second neutralizing agent is present in an amount ranging from 0.1% to 50% by weight, preferably from 1% to 20% by weight and more preferably from 5% to 15% by weight relative to the total weight of the composition.
6. The composition according to any one of the preceding claims, wherein the color indicator or the mixture of color indicators has a color change zone at a pH of 1 to 7, preferably 2 to 6, more preferably 2.5 to 5, and a color change zone at a pH of 8 to 13, preferably 8.5 to 11, more preferably 9 to 10.
7. The composition of claim 6 wherein the color indicator is selected from the group consisting of methyl red, thymol blue, ethyl orange, methyl orange, diphenylamine orange, bromophenol blue, and mixtures thereof.
8. The composition according to claim 6 or 7, characterized in that the color indicator or the mixture of color indicators is present in an amount of 0% to 5% by weight, preferably 0.001% to 1% by weight, more preferably 0.002% to 0.5% by weight, relative to the total weight of the composition.
9. The composition of any one of the preceding claims, wherein the salt H isaXbIs at least one compound selected from the salt NaCl, the salt KCl, the salt NaF and the salt NaBr.
10. The composition of any one of the preceding claims, wherein the composition comprises:
(a) from 5% to 25%, preferably from 8% to 20%, more preferably from 10% to 17% of a first neutralising agent,
(b) from 1% to 50%, preferably from 5% to 15%, more preferably from 8% to 13% of a second neutralising agent,
(c) 0% to 5%, preferably 0.001% to 1%, more preferably 0.002% to 0.5% of a color indicator or a mixture of color indicators,
(d) the amount of water is controlled by the amount of water,
the percentages are weight percentages relative to the total weight of the composition.
11. A method of decontamination using a composition as defined in any one of claims 1 to 10, characterized in that it comprises the following steps:
(1) dispersing the composition on a surface contaminated with a chemical,
(2) repeating step (1) until a neutral pH is obtained, preferably until a pH of 5.5-9 is obtained, and
(3) optionally, rinsing with water to prevent the appearance of colored crystals during drying of the decontaminated surface.
12. Use of a composition as defined in any one of claims 1 to 10 for decontaminating materials, machines and equipment contaminated with any type of chemical.
Technical Field
The present invention relates to a composition for removing chemical residues, a method for using said composition, and the use of said composition for removing residues on materials, machines and equipment contaminated with any type of chemical.
Background
In industry, there has heretofore been no effective solution for decontaminating materials, machines and/or equipment contaminated with chemical contaminants. If a chemical accident occurs during a maintenance operation or operation, splashing of liquid, solids or gas may occur, resulting in contamination of the working area and/or the protective equipment. The materials and surfaces in the working area are then contaminated with chemicals, which are not necessarily visible, and therefore not only risk chemical injury to workers (skin contact with chemicals or inhalation), but also risk corrosion of the material, resulting in a shortened service life thereof.
Using absorptive minerals (such as diatomaceous earth or sepiolite) or special absorbents (such asOr UNISAFE PH) So that spatter on the floor can be neutralized. However, these absorbents cannot be used when the contaminated surface is not horizontal but vertical or uneven (walls, ceilings, machines and protective equipment).
None of the existing solutions available to the person skilled in the art is effective in decontaminating said surfaces.
The person skilled in the art can:
-rinsing the contaminated surface with water. All this is done simply to dilute the chemicals, for which a large amount of water must be used, resulting in a large amount of hazardous chemical waste.
Use of detergents (such as soaps) and water, surfactants and water, or solvents (such as acetone or ethanol) to carry away hydrophobic products. Thus, there is no neutralizing chemical activity and the surface is only rinsed.
The use of chemical detergents, but the latter have the disadvantage of being specific for one type of chemical and corrosive or irritating. Mention may in particular be made of the products consisting of sodium hydroxide for neutralizing acidic descaling solutionsAlkaline solution for cleaning laboratory glassware, capable of removing only alkaline solid residues (alkaline solution)>pH 12) cleaning agentOr other detergents(detergents specific for acids, which belong to the carcinogenic-mutagenic-reproductive toxicity (CMR) category).
Use of detergents in the NRBCE (nuclear, radiological, biological, chemical and explosive) military environment for the contamination of equipment or toxic products (such as DES 'of Ouvry Co.) used in war'Solution R2D2/R2D4 or Easydecon DF) And (4) decontaminating. However, such detergents are only sold in the military field and are not effective for the decontamination of corrosive chemicals (such as acids or bases) that are ubiquitous in the industry.
-using chemical detergents on the material: LeVert. This allows the acid and base to be neutralized. Neutralization of acids and bases is understood to mean ensuring that the contaminated surface is restored to a pH value of 5.5-9, i.e. a pH value at which the acidity or alkalinity is not harmful to the organism. However, this product has the disadvantage of containing salts which can lead to corrosion of certain surfaces or certain metals, such as crude steel. In addition, the product requires the use of an external device to monitor the pH to check the neutralization process (pH paper, pH meter).
The problem faced by those skilled in the art is even greater when fluorine-based compounds (such as hydrofluoric acid) spill or splash into hard-to-reach areas. This is because, in addition to eliminating the hazards associated with the corrosive nature of chemicals, toxicity must also be prevented. Fluoride poisoning may occur following skin exposure, gastrointestinal exposure, and/or exposure by inhalation. It can lead to bone, respiratory and cardiac disease that can lead to death. The potentially lethal dose is 5mg/kg body weight.
None of these solutions described above reduces the toxicity of the fluoride ions.
The chemical decontaminant for the particular material hydrofluoric acid and its derivatives is LeVert HF. The latter makes it possible to decontaminate the surface of the contaminating material by restoring the pH of the contaminating chemical to 5.5-9 and by binding fluoride ions. Decontamination is considered effective when the fluoride ion concentration in the detergent-fluoride mixture reaches a harmless 1.5mg/L threshold. The person skilled in the art must use an external device (test paper for measuring fluoride ions, ion meter) to check whether the limit of 1.5mg fluoride ions per litre of waste has been reached. However, the effect of the chemical detergent LeVert HF is limited to hydrofluoric acid and other fluoride ion-containing compounds, and thus cannot effectively neutralize the basic chemicals. Thus, such compositions are not versatile and do not indicate when the decontamination operation is complete. In addition, this composition contains high concentrations of NaCl salts, which can corrode metals.
Thus, to date there is no composition:
(1) by binding free fluoride ions, any type of chemical, including hydrofluoric acid and its derivatives,
(2) when the acid/alkaline decontamination operation is complete, no external indicating device is required,
(3) is harmless to human body or environment (nontoxic, noncorrosive, nonflammable and nonirritating), and
(4) does not contain salts which can cause metal corrosion.
However, the present inventors have found a detergent composition which exhibits an excellent compromise between these different criteria (1) to (4).
Disclosure of Invention
Accordingly, the present invention relates to a stain removal composition comprising:
-at least one first neutralizing agent (a) which is an aluminium and ethylenediaminetetraacetic acid based complex and has a pKa >4,
-at least one second neutralizing agent (b) selected from amphoteric agents, agents having at least one pKa of 7 to 11 and mixtures thereof, the two pKa values of said amphoteric agents satisfying the following condition:
(pKa1+pKa2)/2>5
7>pKa1>4
11>pKa2>7，
-water, which is water,
optionally a colour indicator or a mixture of colour indicators (c), and
optionally, at least one additive (d),
characterized in that the composition is free of salt HaXbWherein H is an alkali metal or an alkaline earth metal, X is a halogen atom, a is an integer of 1 to 2, and b is an integer of 1 to 4.
The invention also relates to a method of decontaminating using the composition of the invention, characterized in that it comprises the following steps:
(1) dispersing the composition on a surface contaminated with a chemical,
(2) repeating step (1) until a pH of 5.5-9 is obtained, and
(3) optionally, rinsing with water to prevent the appearance of colored crystals during drying of the decontaminated surface.
The invention also relates to the use of the composition according to the invention for decontaminating materials, machines and equipment contaminated with any type of chemical.
Drawings
FIG. 1 shows a schematic view of a
Figure 1 shows a diagram depicting neutralization of 1M NaOH and 1M HCl with the solution from example 1.
FIG. 2
[ FIG. 2]]The delineation present in 5mL of 1M NH4Graph of fluoride in F combined with solution from example 1.
FIG. 3
Figure 3 shows a graph depicting neutralization of 1M NaOH and 1M HCl with the solution from example 2.
FIG. 4
[ FIG. 4]]The delineation present in 5mL of 1M NH4Graph of fluoride in F combined with the solution from example 2.
FIG. 5
Figure 5 shows a diagram depicting neutralization of 1M NaOH and 1M HCl with the solution from example 3.
FIG. 6
[ FIG. 6]]The delineation present in 5mL of 1M NH4Graph of fluoride in F combined with the solution from example 3.
Examples
In the following examples, the following commercial products were used:
-sodium L-glutamate monohydrate sold by MB Biomedicals, LLC,
methyl Red sold by EMD Millipore Corporation,
thymol blue sold by Alfa Aesar,
l-arginine monohydrochloride sold by Alfa Aesar,
l-lysine hydrochloride sold by ThermoFisher (Kandel) GmbH,
ethyl orange sold by Alfa Aesar,
bromophenol blue sold by EMD Millipore Corporation,
sodium hydroxide sold by VWR Chemicals,
-sodium aluminate sold by Sigma Aldrich,
ethylenediaminetetraacetic acid (EDTA) sold by Merck Millipore.
Example 1
Preparing a stain removal composition 1 comprising:
[ Table 1]
Stain removal composition 1 does not contain salt H as defined according to the inventionaXb。
Neutralization test
Using the composition prepared in example 1, neutralization tests were performed with the following liquids according to the following procedure: 1M sodium hydroxide (NaOH) and 1M hydrochloric acid (HCl):
to 1mL of 1M sodium hydroxide (NaOH) or 1mL of 1M hydrochloric acid (HCl) were added in the order:
1mL, 2mL, 3mL, 4mL, 5mL, 10mL, 20mL, 30mL, 40mL, and/or 50mL of the solution from example 1, waiting up to 1 minute between each addition, and measuring the pH after each addition.
The results are listed in table 2 and depicted in fig. 1.
[ Table 2]
Color testing
Using the composition prepared in example 1, a color test was performed with the following liquids according to the following procedure: 1M sodium hydroxide (NaOH) and 1M hydrochloric acid (HCl):
to a beaker containing 20mL of the solution from example 1 was added 10mL of 1M sodium hydroxide (NaOH) or 1M hydrochloric acid (HCl). The color was observed with the naked eye.
The color of the solution from example 1 was observed to change with changes in pH. The results are shown in Table 3 below.
[ Table 3]
pH
Observed color
3
Red colour
7
Yellow colour
12
Blue color
Fluoride ion binding assay
Using the composition prepared in example 1, 1M ammonium fluoride (NH) was used according to the following procedure4F) The solution was subjected to a fluoride ion binding test:
to 5mL of 1M ammonium fluoride (NH)4F) 1mL or 5mL of the solution from example 1 was added continuously to the solution, waiting a maximum of 1 minute between each addition, and the concentration of free fluoride ion was measured continuously.
Having a fluoride ion counter with PHM240 ionization gauge sold by Radiometer and p-fluoride ion sold by Thermo ScientificSpecific OrionTMBrand electrodes to measure the fluoride ion concentration.
The results are depicted in fig. 2.
Example 2
Preparing a stain removal composition 2 comprising:
[ Table 4]
Stain removal composition 2 does not contain salt H as defined according to the inventionaXb。
Neutralization test
Neutralization tests were performed according to the procedure from example 1 using the composition from example 2.
The results are listed in table 5 and depicted in fig. 3.
[ Table 5]
Color testing
Color testing was performed according to the procedure from example 1 using the composition from example 2.
The color of the solution from example 2 was observed to change with changes in pH. The results are shown in table 6 below.
[ Table 6]
pH
Observed color
1
Red colour
7
Orange colour
12
Blue color
Fluoride ion binding assay
The fluoride ion binding test was performed according to the procedure from example 1 using the composition from example 2.
The results are depicted in fig. 4.
Example 3
Preparing a stain removal composition 3 comprising:
[ Table 7]
Stain removal composition 3 does not contain salt H as defined according to the inventionaXb。
Neutralization test
Neutralization tests were performed according to the procedure from example 1 using the composition from example 3.
The results are listed in table 8 and depicted in fig. 5.
[ Table 8]
Color testing
Color testing was performed according to the procedure from example 1 using the composition from example 3.
The color of the solution from example 3 was observed to change with changes in pH. The results are shown in table 9 below.
[ Table 9]
pH
Observed color
3
Orange colour
7
Purple color
12
Grey colour
Fluoride ion binding assay
The fluoride ion binding test was performed according to the procedure from example 1 using the composition from example 3.
The results are depicted in fig. 6.
In summary, the stain removal compositions 1-3 neutralized 1M sodium hydroxide and 1M hydrochloric acid by returning the pH to 5.5-9. This change in pH is accompanied by a change in color.
The stain removal compositions 1-3 may also bind fluoride ions by restoring the concentration of free fluoride to acceptable values, i.e. values below 1.5 mg/L.
Detailed Description
The present invention relates to a stain removal composition comprising:
-at least one first neutralizing agent (a) which is an aluminium and ethylenediaminetetraacetic acid based complex and has a pKa >4,
-at least one second neutralizing agent (b) selected from amphoteric agents, agents having at least one pKa of 7 to 11 and mixtures thereof, the two pKa values of said amphoteric agents satisfying the following condition:
(pKa1+pKa2)/2>5
7>pKa1>4
11>pKa2>7，
-water, which is water,
optionally a colour indicator or a mixture of colour indicators (c), and
optionally, at least one additive (d),
characterized in that the composition is free of salt HaXbWherein H is an alkali metal or an alkaline earth metal, X is a halogen atom, a is an integer of 1 to 2, and b is an integer of 1 to 4.
"salt HaXb"is understood to mean not only the salts in molecular form but also the salts H which are aggregated and are insoluble in solutionaXbAnd (3) forming granules.
The first neutralizing agent may be complex AlNa2EDTAOH。
The first neutralizing agent may be present in an amount of 0.1 wt% to 25 wt%, preferably 10 wt% to 20 wt%, more preferably 15 wt% to 18 wt%, relative to the total weight of the composition.
The second neutralizing agent may be selected from ascorbic acid and salts thereof; bicarbonate salts and salts thereof; creatinine; glutathione; isoguanine; adenine; amino acids and salts thereof, such as glutamic acid, aspartic acid, arginine, lysine, ornithine, cysteine; and mixtures thereof.
The bicarbonate salt and its salt can be sodium bicarbonate, potassium bicarbonate, ammonium bicarbonate and mixtures thereof.
The glutamic acid and its salt may be glutamate in the form of sodium glutamate, sodium L-glutamate hydrate and mixtures thereof.
The salt of aspartic acid may be an aspartate salt.
The salt of arginine may be L-arginine monohydrochloride.
The salt of ornithine may be L-ornithine monohydrochloride.
The salt of lysine may be L-lysine hydrochloride.
In a specific embodiment, the second neutralizing agent is selected from the group consisting of sodium glutamate, lysine, ornithine, cysteine and L-arginine.
The second neutralizing agent may be present in an amount ranging from 0.1% to 50% by weight, preferably from 1% to 20% by weight, more preferably from 5% to 15% by weight, relative to the total weight of the composition.
Examples of additives which may be mentioned are dyes, fragrances, viscosity regulators and mixtures thereof.
In a particular embodiment, the color indicator or the mixture of color indicators has a color change zone at a pH of 1 to 7, preferably 2 to 6, more preferably 2.5 to 5, and a color change zone at a pH of 8 to 13, preferably 8.5 to 11, more preferably 9 to 10.
Color indicators which may be mentioned are methyl red, thymol blue, ethyl orange, methyl orange, diphenylamine orange, bromophenol blue and mixtures thereof.
The color indicator may be present in an amount of 0 wt% to 5 wt%, preferably 0.001 wt% to 1 wt%, more preferably 0.002 wt% to 0.5 wt%, relative to the total weight of the composition.
The compositions of the invention are free of salt HaXbThis means that it causes little or no corrosion or degradation of the surface (plastic, metal, glass, etc.) to which it is applied, especially of metal surfaces which are susceptible to corrosion.
In particular, the composition of the invention does not contain at least one compound selected from the salt NaCl, the salt KCl, the salt NaF and the salt NaBr.
The compositions of the invention advantageously comprise:
(a) from 5% to 25%, preferably from 8% to 20%, more preferably from 10% to 17% of a first neutralising agent,
(b) from 1% to 50%, preferably from 5% to 15%, more preferably from 8% to 13% of a second neutralising agent,
(c) 0% to 5%, preferably 0.001% to 1%, more preferably 0.002% to 0.5% of a color indicator or a mixture of color indicators,
(d) the amount of water is controlled by the amount of water,
the percentages are weight percentages relative to the total weight of the composition.
The invention also relates to a method of decontaminating using the composition of the invention, characterized in that it comprises the following steps:
(1) dispersing the composition on a surface contaminated with a chemical,
(2) repeating step (1) until a neutral pH is obtained, preferably until a pH of 5.5-9 is obtained, and
(3) optionally, rinsing with water to prevent the appearance of colored crystals during drying of the decontaminated surface.
In case the composition comprises a color indicator, step (1) is repeated until a visually neutral pH is obtained, preferably until a pH of 5.5-9 is obtained.
The invention also relates to the use of the composition of the invention or the composition obtained by the process of the invention for decontaminating materials, machines and equipment contaminated with any type of chemical.
"decontamination" is understood to mean not only the mechanical removal of the contaminating chemicals but also the neutralization, i.e.:
-returning the pH of the chemical contaminant-chemical detergent mixture to 5.5-9, and
-when the contaminating chemical is hydrofluoric acid or a derivative thereof, restoring the level of free fluoride ions in the chemical contaminant-detergent mixture to below 1.5 mg/L.
The contaminating chemical may be a strong base or a strong acid, preferably sodium hydroxide, hydrochloric acid, hydrofluoric acid or derivatives thereof (such as ammonium fluoride or sodium fluoride), or mixtures thereof.
The stain removal status may be monitored by the presence of a color indicator or a mixture of color indicators. Thus, no external means of checking for acid/alkaline decontamination may be required.
The composition according to the invention can be used for decontamination of materials, machines and equipment contaminated with hydrofluoric acid and derivatives thereof, such as ammonium fluoride or sodium fluoride.
Without being bound by any theory, the first neutralizing agent allows for neutralization of the fluoride ion.
"neutralizing fluoride ions" is understood to mean preventing their accessibility and their harmful effects and thus their toxicity.
The composition of the invention advantageously makes it possible to restore the concentration of free fluoride to an acceptable value, i.e. a value lower than 1.5 mg/L.
This threshold corresponds to the maximum allowable fluoride concentration in human consumption water (WHO, 2004). The individual can consume (by drinking) 2L of water at a concentration of 1.5mg/L per day without developing dental fluorosis. Similarly, individuals whose skin is exposed to a liquid having a fluoride concentration of 1.5mg/L will not exhibit deleterious effects.
The fluoride ion concentration may be measured with an ionization gauge or with an electrode specific for fluoride ions.
The electrode specific for fluorine ions may be an electrode having a membrane permeable only to fluorine ions. Examples of films permeable only to fluoride ions include, but are not limited to, europium-doped lanthanum fluoride films.
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