CN114441524A - Water hardness determination reagent combined with continuous flow analyzer - Google Patents

Water hardness determination reagent combined with continuous flow analyzer Download PDF

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CN114441524A
CN114441524A CN202210133572.1A CN202210133572A CN114441524A CN 114441524 A CN114441524 A CN 114441524A CN 202210133572 A CN202210133572 A CN 202210133572A CN 114441524 A CN114441524 A CN 114441524A
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hardness
reagent
water
edta
continuous flow
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李庆铁
熊迎军
李靖
田军
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Shanghai Lanchang Automation Technology Co ltd
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    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/75Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
    • G01N21/77Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
    • G01N21/78Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N31/00Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
    • G01N31/22Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using chemical indicators

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Abstract

The invention discloses a water hardness determination reagent used with a continuous flow analyzer, which realizes the sharp color change of a water sample to be detected when the hardness determination analysis endpoint is determined by configuring a hardness determination reagent containing an organic pigment dye and an EDTA chelating agent 'single-liquid system'. The hardness determination reagent is a liquid reagent with good stability, and can be used together with a continuous flow analyzer for real-time online monitoring of water hardness; the hardness determination of water samples to be determined in different hardness management ranges can be realized by adjusting the weight percentage of the chelating agent; the diol compound as a non-aqueous solvent has a free radical cage effect and certain protection capability on the organic pigment dye, and can effectively inhibit the decomposition of the organic pigment dye; the pigment stabilizer can inhibit or slow down the photooxidation process of the organic pigment dye; the diol compound has a lower freezing point, and can also ensure that the hardness measuring reagent has a wide applicable temperature range.

Description

Water hardness determination reagent combined with continuous flow analyzer
Technical Field
The invention relates to the technical field of water quality detection reagents, in particular to a water quality hardness determination reagent used with a continuous flow analyzer.
Background
The total hardness of the water body mainly describes the total content of calcium ions and magnesium ions in the water body, and becomes one of the conventional important technical indexes for measuring the water quality standard and supervising water treatment. The accurate and continuous determination of the hardness of the domestic drinking water and the industrial water is a precondition for monitoring whether the water quality can meet the requirements of daily life and industrial production, for example, the domestic water with high hardness can cause the detergent to generate precipitation so as to reduce the cleaning effect; high water hardness in the textile industry can lead to coarse and difficult dyeing of textiles; the water for the boiler has high hardness, so that the pipeline is blocked easily to cause boiler explosion accidents; the drinking water with too high hardness can cause bitter taste and is easy to induce calculi after long-term drinking. Therefore, research on a method for measuring the total hardness of the water body, in particular to a method for detecting the hardness of the water body by using a continuous flow analyzer based on a colorimetric method, becomes a research hotspot. The continuous flow analyzer mainly comprises an automatic sample injector, a peristaltic pump, a chemical analysis module, a colorimetric determination module and a data processing system, and the work flow of the continuous flow analyzer is as follows: according to a preset sampling program of the continuous flow analyzer, an automatic sampler is used for regularly and accurately taking out a water sample to be analyzed, the water sample with definite volume and a detection reagent are sequentially and quantitatively injected into a chemical analysis module through a peristaltic pump, colorimetric analysis is realized through a colorimetric determination module, and then a detector transmits a signal into a data processing system for hardness analysis and data transmission.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a water hardness determination reagent used with a continuous flow analyzer, and the sharp color change of a water sample to be determined at the end point of hardness determination analysis is realized by configuring a hardness determination reagent containing an organic pigment dye and an EDTA chelating agent 'single-liquid system'. Different from the traditional powdery hardness determination reagent which needs to be dissolved on site and a water system hardness determination reagent with poor stability, the hardness determination reagent is a liquid reagent with good stability, and can be used together with a continuous flow analyzer for real-time online monitoring of water hardness; the hardness determination of the water samples to be detected in different hardness management ranges can be realized by adjusting the weight percentage of the chelating agent; by adding the diol compound as the non-aqueous organic solvent, the non-aqueous solvent with proper viscosity and flexible spatial configuration not only realizes stable color development of the organic pigment dye, but also embodies certain protection capability of free radical cage effect on solute molecules of the organic pigment dye, effectively prevents the organic pigment dye molecules from generating transient free radicals after being irradiated by ultraviolet light with high excitation energy under natural environment, diffusing out of a solvent cage and being decomposed after being captured by oxygen molecules, namely the non-aqueous solvent with proper viscosity such as the diol compound can effectively inhibit the decomposition of the organic pigment dye; the photooxidation process of the organic pigment dye is inhibited or slowed down by adding a pigment stabilizer, wherein the pigment stabilizer can be divided into an ultraviolet absorbent, a light shielding agent, an ultraviolet quencher, a free radical trapping agent and the like according to different stabilizing mechanisms of the pigment stabilizer; the glycol compound has a lower freezing point, so that the hardness determination reagent disclosed by the invention can still keep good liquid fluidity in a low-temperature environment, and the low-temperature freezing of the liquid hardness determination reagent is avoided, so that the water hardness determination reagent has a wide application temperature range.
In order to realize the aim, the technical scheme of the invention is to design a water hardness measuring reagent used together with a continuous flow analyzer, which comprises the following components in percentage by weight: 0.1-1 wt% of organic pigment dye, 10-20 wt% of masking agent, 40-79 wt% of glycol compound, 0.1-1 wt% of pigment stabilizer, 0.01-10 wt% of chelating agent, 0.01-1 wt% of hydroxide and 10-20 wt% of deionized water; the organic pigment dye is a mixture of acid chrome blue K and naphthol green B, and the mass ratio of the acid chrome blue K to the naphthol green B is 1: 1; the masking agent is triethanolamine. The triethanolamine is used as an additive and a masking agent, is used for maintaining the pH of the water hardness measuring reagent in a proper alkaline solvent environment, stabilizes the pigment, and can be used as a masking agent for inhibiting the interference of metal cations such as iron ions and aluminum ions on the measurement of the total hardness. When the hardness measuring reagent is placed in a high-temperature environment of more than 40 ℃, the pigment stabilizer can effectively prevent the decomposition of organic pigment dye caused by free radical cracking when being heated and photon irradiation.
The preferable technical scheme is that the diol compound is one or more of ethylene glycol, propylene glycol, diethylene glycol and triethylene glycol.
The preferable technical scheme is that the pigment stabilizer is one of potassium sorbate, 2-tert-butylphenol, 3-tert-butylphenol and 2, 6-di-tert-butyl-4-methylphenol.
Preferably, the chelating agent is one or more of organic amino carboxylic acid chelating agent and alkali metal salt derivative thereof with inorganic base, and EDTA chelating agent.
In a more preferred embodiment, the organic aminocarboxylic acid type chelating agent is one of trans-1, 2-cyclohexanediaminetetraacetic acid (CDTA), nitrilotriacetic acid (NTA), diethylenetriaminepentaacetic acid (DTPA) and ethyleneglycol diethylenetriaminetetraacetic acid (EGTA).
Further preferably, the EDTA chelating agent is one of EDTA-2Na, EDTA-3Na, EDTA-4Na, and EDTA-2K, EDTA-3K, EDTA-4K.
The invention discloses a determination principle of a water hardness determination reagent combined with a continuous flow analyzer, which comprises the following steps: and dropwise adding a hardness determination reagent equivalent to the management of the total hardness into a water sample to be detected in a certain volume through a continuous flow analysis instrument, wherein a chelating agent in the hardness determination reagent generates a chelate with hardness components (calcium ions and magnesium ions) in the water sample to be detected in preference to the organic pigment dye, the rest hardness components (calcium ions and magnesium ions) in the water sample to be detected form a red complex with the organic pigment dye until the chelating agent is titrated to an inflection point where the calcium ions and the magnesium ions in the complex are completely replaced, and the water sample shows a mutation from deep red to deep blue. And detecting the discoloration inflection point by using an optical sensor, and recording the volume of the hardness determination reagent added by the peristaltic pump, so that the total hardness of the water sample to be detected can be calculated.
The invention has the advantages and beneficial effects that:
1. the invention discloses a water hardness determination reagent combined with a continuous flow analyzer, which realizes the sharp color change of a water sample to be detected when the hardness determination analysis endpoint is determined by configuring a hardness determination reagent containing an organic pigment dye and an EDTA chelating agent 'single-liquid system'. Different from the traditional powdered hardness determination reagent which needs to be dissolved on site and a water system hardness determination reagent with poor stability, the hardness determination reagent is a liquid reagent with good stability, and can be used together with a continuous flow analyzer for real-time online monitoring of water hardness.
2. The water hardness determination reagent combined with the continuous flow analyzer disclosed by the invention can realize hardness determination of water samples to be determined in different hardness management ranges by adjusting the weight percentage of the chelating agent.
3. The invention discloses a water hardness measuring reagent used together with a continuous flow analyzer, which is prepared by adding a diol compound as a non-aqueous organic solvent. The non-aqueous solvent with proper viscosity and flexible spatial configuration not only realizes stable color development of the organic pigment dye, but also embodies certain protection capability of free radical cage effect on solute molecules of the organic pigment dye, effectively prevents the organic pigment dye molecules from generating transient free radicals after being irradiated by ultraviolet light with high excitation energy in natural environment, diffusing out of a solvent cage and being decomposed after being captured by oxygen molecules, namely, the non-aqueous solvent with proper viscosity such as diol compounds can effectively inhibit the decomposition of the organic pigment dye.
4. The invention discloses a water hardness measuring reagent combined with a continuous flow analyzer, which can inhibit or slow down the photo-oxidation process of organic pigment dyes by adding a pigment stabilizer, wherein the pigment stabilizer can be divided into an ultraviolet absorbent, a light shielding agent, an ultraviolet quencher, a free radical trapping agent and the like according to different stabilizing mechanisms of the pigment stabilizer.
5. The water hardness measuring reagent combined with the continuous flow analyzer disclosed by the invention has the advantages that the glycol compound has a lower freezing point, the hardness measuring reagent can be ensured to still keep good liquid fluidity in a low-temperature environment, the liquid hardness measuring reagent is prevented from being frozen at a low temperature, and the water hardness measuring reagent has a wide application temperature range.
Drawings
FIG. 1 is a graph of color change of a mixed solution monitored by UV-vis absorption spectroscopy during water hardness titration in example 1.
Detailed Description
The following description of the embodiments of the present invention will be made with reference to the accompanying drawings. The following examples are only for illustrating the technical solutions of the present invention more clearly, and the protection scope of the present invention is not limited thereby.
Aiming at different hardness management intervals of the water body, the content of the chelating agent in the total hardness determination reagent combined with the continuous flow analyzer is also different. The hardness calculation formula in the water sample to be detected is as follows:
Figure BDA0003503555860000041
the definitions and units of the parameters in the formula are shown in table 1:
TABLE 1 definition and Unit of each parameter of hardness calculation formula in water sample to be measured
Symbols of formula Chemical significance Unit of
Chardness Total hardness of calcium and magnesium ions in water sample to be detected ppm
Vsample Analysis sampling volume of water sample to be detected mL
CEDTA@reagent Content of chelating agent in total hardness determination reagent ppm
Vreagent Volume of the added total hardness measuring reagent to the inflection point mL
Generally, the analysis sampling volume V of a water sample to be measuredsample10mL, water hardness interval C to be managedhardnessHardness measuring reagents with different chelating agent concentration contents are respectively used at 1-10ppm (low hardness), 10-100ppm (medium hardness) and 100-1000ppm (high hardness). When the peristaltic liquid adding volume of the continuous flow analyzer is about 0.1-1 mL each time, the optimal balance between data repeatability and the volume consumption of the hardness determination reagent can be obtained, and V is selectedreagent1.0mL, the water hardness interval C to be managedEDTA@reagentThe mass fractions of the chelating agent corresponding to 10-100ppm (low hardness), 100-1000ppm (medium hardness), 1000-10000ppm (high hardness) are shown in Table 2:
TABLE 2 parameters of chelating agent corresponding to different water hardness intervals
Figure BDA0003503555860000051
Example 1
A water hardness determination reagent used with a continuous flow analyzer is suitable for water hardness determination in a high hardness management interval (100-:
TABLE 3 Water sample hardness determination reagent suitable for high hardness management interval
Reagent (analytically pure) Weight (wt%)
Acid chrome blue K 0.33%
Naphthol Green B 0.33%
Ethylenediaminetetraacetic acid disodium salt (EDTA-2Na) 3.72%
Sodium hydroxide 1%
3-tert-butylphenol 0.33%
Deionized water 14.29%
Triethanolamine 10%
Ethylene glycol 70%
10mL of water sample is extracted into a color development analysis tank by using a continuous flow analyzer, the water hardness determination reagent is gradually added into the color development analysis tank by using a peristaltic pump, and the mixture is stirred and fully mixed by using magnetons. After adding the water hardness measuring reagent, the mixed solution is red and gradually deepens. And (3) intermittently sampling the red solution into a quartz cuvette and placing the quartz cuvette in an ultraviolet-visible spectrophotometer to measure the absorption spectrum of the red solution when 50uL of the water hardness measuring reagent is dripped into the peristaltic pump. As shown In the UV-vis absorption spectrum data In the attached figure 1, the maximum absorption peak wavelength is located at 510nm and 540nm when the solution is red In the initial stage, and is the absorption spectrum of the complex M-In formed by the metal ions and the organic pigment dye; and then adding the hardness determination reagent into 10mL of water sample for multiple batches gradually, wherein the mixed solution is red and gradually deepens, and intermittently sampling and determining the absorption spectrum at intervals of 50uL addition. The maximum absorption peak intensity at 510nm and 540nm on the UV-vis absorption spectrum is increased; when the total addition amount of the hardness titration reagent is 242uL, the mixed solution is changed from red to blue to generate a titration inflection point, which is reflected in that the maximum absorption peak is suddenly increased to 610nm when the UV-vis absorption spectrum is intermittently sampled at 250uL, and the hardness of the water sample is
Figure BDA0003503555860000061
Example 2
A water hardness determination reagent used with a continuous flow analyzer is suitable for water hardness determination in a high hardness management interval (100-:
TABLE 4 Water sample hardness determination reagent suitable for high hardness management interval
Reagent (analytically pure) Weight (wt%)
Acid chrome blue K 0.5%
Naphthol Green B 0.5%
Ethylenediaminetetraacetic acid trisodium salt (EDTA-3Na) 10%
Potassium hydroxide 1%
2, 6-di-tert-butyl-4-methylphenol 1%
Deionized water 20%
Triethanolamine 20%
Diethylene glycol 47%
Example 3
A water hardness measuring reagent used together with a continuous flow analyzer is suitable for measuring the hardness of a water sample in a high hardness management interval (10-100ppm), and the components are shown in a table 5:
TABLE 5 Water sample hardness determination reagent suitable for medium hardness management interval
Reagent (analytically pure) Weight (wt%)
Acid chrome blue K 0.5%
Naphthol Green B 0.5%
Ethylenediaminetetraacetic acid disodium salt 0.372%
Sodium hydroxide 1%
2-tert-butylphenol 1%
Deionized water 18.628%
Triethanolamine 8%
Propylene glycol 70%
Example 4
A water hardness measuring reagent used together with a continuous flow analyzer is suitable for measuring the hardness of a water sample in a medium hardness management interval (10-100ppm), and the components are shown in a table 6:
TABLE 6 Water sample hardness determination reagent suitable for medium hardness management interval
Reagent (analytically pure) Weight (wt%)
Acid chrome blue K 0.5%
Naphthol Green B 0.5%
Ethylenediaminetetraacetic acid tetrasodium salt (EDTA-4Na) 0.372%
Ethylene glycol diethyl ether diamine tetraacetic acid 0.38%
Potassium hydroxide 0.5%
3-tert-butylphenol 1%
Deionized water 11.748%
Triethanolamine 15%
Triethylene glycol dimer 70%
Example 5
A water hardness measuring reagent used together with a continuous flow analyzer is suitable for measuring the hardness of a water sample in a low hardness management interval (1-10ppm), and the components are shown in a table 7:
TABLE 7 reagent for measuring water hardness in Low hardness control zone
Reagent (analytically pure) Weight (wt%)
Acid chrome blue K 0.5%
Naphthol Green B 0.5%
Trans-1, 2-cyclohexanediaminetetraacetic acid 0.0364%
Sodium hydroxide (NaOH) 0.01%
Potassium sorbate 1%
Deionized water 12.9536%
Triethanolamine 8%
Ethylene glycol 77%
Example 6
A water hardness measuring reagent used together with a continuous flow analyzer is suitable for measuring the hardness of a water sample in a low hardness management interval (1-10ppm), and the components are shown in a table 8:
TABLE 8 reagent for measuring water hardness in Low hardness control zone
Reagent (analytically pure) Weight (wt%)
Acid chrome blue K 0.1%
Naphthol Green B 0.1%
Trans-1, 2-cyclohexanediaminetetraacetic acid 0.0364%
Ethylenediaminetetraacetic acid disodium salt 0.0372%
Potassium hydroxide 0.01%
3-tert-butylphenol 0.1%
Deionized water 15%
Triethanolamine 8%
Triethylene glycol dimer 76.6164%
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the technical principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (6)

1. A water hardness determination reagent used with a continuous flow analyzer is characterized by comprising the following components in percentage by weight: 0.1-1 wt% of organic pigment dye, 10-20 wt% of masking agent, 40-79 wt% of glycol compound, 0.1-1 wt% of pigment stabilizer, 0.01-10 wt% of chelating agent, 0.01-1 wt% of hydroxide and 10-20 wt% of deionized water; the organic pigment dye is a mixture of acid chrome blue K and naphthol green B, and the mass ratio of the acid chrome blue K to the naphthol green B is 1: 1; the masking agent is triethanolamine.
2. The reagent for measuring water hardness used in combination with a continuous flow analyzer according to claim 1, wherein the glycol compound is one or more of ethylene glycol, propylene glycol, diethylene glycol, and triethylene glycol.
3. The reagent for measuring water hardness according to claim 1, wherein the pigment stabilizer is one of potassium sorbate, 2-t-butylphenol, 3-t-butylphenol, and 2, 6-di-t-butyl-4-methylphenol.
4. The reagent for measuring the hardness of water used in combination with a continuous flow analyzer according to claim 1, wherein the chelating agent is one or more of organic aminocarboxylic acid type chelating agents and their alkali metal salt derivatives with inorganic bases, EDTA type chelating agents.
5. The reagent for measuring water hardness in combination with continuous flow analyzer of claim 4, wherein the organic aminocarboxylic acid type chelating agent is one of trans-1, 2-cyclohexanediaminetetraacetic acid (CDTA), nitrilotriacetic acid (NTA), diethylenetriaminepentaacetic acid (DTPA), ethyleneglycoldiethylenediaminetetraacetic acid (EGTA).
6. The reagent for measuring the hardness of water according to claim 4, wherein the EDTA chelating agent is one of EDTA-2Na, EDTA-3Na, EDTA-4Na, and EDTA-2K, EDTA-3K, EDTA-4K.
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Publication number Priority date Publication date Assignee Title
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CN101750469A (en) * 2009-12-17 2010-06-23 河北省科学院能源研究所 Indicator capable of rapidly determining hot water boiler feedwater hardness
CN101750468A (en) * 2009-12-17 2010-06-23 河北省科学院能源研究所 Indicator capable of rapidly determining steam boiler feedwater hardness
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