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    • 专利摘要:
    Passive colorimetric sensor for the detection and/or determination of ammonia or aliphatic amines in gases, method of manufacture and use. The sensor is capable of determining ammonium and aliphatic amines with high precision in gases, particularly in large volumes of gases such as those found in premises dedicated to livestock or other breeding. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2619356A1
    申请号:ES201600032
    申请日:2015-12-23
    公开日:2017-06-26
    发明作者:Pilar CAMPINS FALCÓ；Yolanda MOLINER MARTÍNEZ；Rosa HERRÁEZ HERNÁNDEZ；Carmen MOLINS LEGUA；Jorge VERDU ANDRÉS；Neus JORNET MARTÍNEZ
    申请人:Universitat de Valencia；
    IPC主号:
    专利说明:

    DESCRIPTION

    Passive device for the detection and / or determination in situ of ammonia in gases.

    Field of the invention 5

    The invention falls within the field of detection and / or in situ determination of ammonia in gases and gas mixtures, in particular of large volumes such as those found in the atmospheres of bulky rooms, in particular those dedicated to breeding of cattle and other animals. 10

    Summary

    The present specification describes the extension of the device developed in patent application P201300436, published as ES2519891 82, for the determination of ammonia in gases and gas mixtures such as those present in the atmospheres of premises, in particular premises , generally bulky, for the storage and breeding of animals and livestock, in which it is very important to have their ammonia content under control. To this end, polymeric membranes of polydimethylsiloxane (PDMS) doped with 1,2-naphthoquinone 4-20 sulphonate have been developed (NQS) for use as passive colorimetric devices in the determination of NH3 in gases. In addition to PDMS, polymeric membranes have been synthesized with an amount of tetraortoethylsilicate (TEOS) and silicon nanoparticles (SiO2 NPs).
     25
    State of the art

    Ammonia is a naturally occurring micro-constituent in the environment and therefore its deposition contributes to the acidification of water and soil. The increase in nitrogen in terrestrial and aquatic ecosystems can contribute to eutrophication. 30 Ammonia has a short life in the atmosphere, however it can be a risk to ecosystems. In fact, in 1999, ammonia was included as an air pollutant in the Gothenburg protocol. In the case of livestock industries, nitrogen is acquired from food intake, one part is retained and the rest is excreted. The excreted nitrogen is usually bound to organic compounds, and it is estimated that ammonia volatilization from urine nitrogen is 5 to 6 times higher than in feces. Therefore, in this case the main source of ammonia is the urine of animals where nitrogen is found as urea (CO (NH2)), which is rapidly hydrolyzed to give ammonium ions that volatilize to form NH3.
     40
    The amount of ammonia that volatilizes depends on factors such as the amount of nitrogen in the food source, the measure, animal species, living conditions of the animals, humidity, temperature and treatment of animal waste.

    The determination of atmospheric pollutants is carried out by techniques such as gas chromatography (GC) or liquid chromatography (HPLC). However, for the determination of ammonia in atmospheres there are calorimetric devices (Rakow NA; Suslick KS .; Artificial nose or tongue for detecting metal ligating vapors comprising an array comprising two chemoresponsive dyes deposited directly on a single support in a predetermined pattern combination, Nature , 406 (2000) 710-713), which allow the reduction of analysis time and cost. However, these devices do not allow monitoring in large areas and therefore the modeling of the distribution of substances cannot be carried out.

    Brief description of the figures

    Figure 1. Mold plate for sensor design.

    Figure 2. Diffuse reflectance spectra obtained for the targets with the sensors 5 developed in this study. Abs: absorbance, λ: wavelength (nm).

    Figure 3. Diffuse reflectance spectra obtained for a blank and an NH3 atmosphere of 5 mg / m3. Abs: absorbance, λ: wavelength (nm).
     10
    Figure 4. Variation of the sensor response as a function of exposure time for NH3 atmospheres of a) 5 mg / m3, b) 20 mg / m3 and c) 40 mg / m3. Abs: absorbance, T: exposure time.

    Figure 5. Variation of the sensor response as a function of the concentration in time of 15 exposure of 3, 6 and 9 days. Abs: absorbance, Cc: concentration (ppmv).

    Figure 6. Diffuse reflectance spectra obtained for a blank and an NH3 atmosphere of 5 mg / m3. Abs: absorbance. λ: wavelength (nm).
     twenty
    Figure 7. Variation of the response of the PDMS-TEOS-SiO2, NPs-NQS sensor with the exposure time. A) 5 mg / m3, B) 20 mg / m3 and C) 40mg / m3. Abs: absorbance, T: exposure time.

    Figure 8. Variation of the sensor response as a function of the concentration at different exposure times. Abs: absorbance, Cc: concentration (ppmv).

    Figure 9. Colorimetric panel in ppmv-hr for the estimation of the concentration of NH3 in atmospheres with the proposed sensor. The detection limit is 2.4 ppm (8 hours). Abs: absorbance. 30

    Description of the invention

    The present invention relates to passive colorimetric devices for the determination of ammonia in improved gases to those already described in ES2519891. 35

    The present invention relates to a simple, fast and low cost method for the estimation and sampling of ammonia by means of the NQS (1,2-naphthoquinone-4-sulfonate) as a derivatization agent. By means of active sampling it is usually achieved that the detection takes place in a short time; However, the dependence of an external source 40 that enables such sampling implies an energy cost to be taken into account and the need for specific sampling equipment. In addition, the same conditions that the determination cannot be in situ and in real time. On the other hand, passive sampling, although it may require longer exposure times, however it does not need an external source, so that the energy cost is zero and in addition, it is possible to make determinations in situ.

    This description describes the development of a passive sensor for the detection of ammonia in gases under the aforementioned conditions that overcome the disadvantages found in other systems. For this, polydimethylsiloxane 50 (PDMS) modified with tetraortoethylsilicate (TEOS) and nanoparticles of SiO2 (SiO2 NPs) and doped with 1,2-naphthoquinone 4-sulphonate (NQS) is used, which allows obtaining a colored derivative in the presence of ammonia . The polydimethylsiloxane that is preferably used in the present invention is Sylgard 184, a product of the Dow Corning Corporation,
    which is a silicone elastomer kit. The kit contains two chemicals: the base (component A) and the curing agent (component B), which are mixed in a 10: 1 mass ratio. Sylgard PDMS is one of the most elastic and active polymers. In addition, its easy preparation, zero toxicity, malleability and thermal and electrical stability are also advantageous features. The characteristics of this material 5 allow the rapid diffusion of ammonia through the described sensor.

    On the other hand, the presence of TEOS facilitates the dispersion of NQS in the polymer matrix and reduces gelation time, while the addition of SiO2 NPs improves the mechanical properties of the polymer matrix, increases the roughness of the sensor, and therefore , increases the sensor response. The presence of these nanoparticles produces an increase in pore in the polymer matrix, reducing the pressure in the gelation process. This increase in pore improves the diffusion of ammonia and therefore improves the response.
     fifteen
    One of the studies carried out in the present specification is the one related to the optimization of the composition of the sensor to evaluate the response of ammonia. Once the composition of the sensor is optimized, the responses of the sensors have been studied according to the exposure time and concentration. It has been shown that. Under optimal conditions, the device is able to determine NH3 at 20 concentrations of 2.4 mg / m3 (exposure time 8 h). The results show that the determination of NH3 can be carried out semiquantitatively by visual inspection, since the presence of NH3 produces a color change in the sensor that is proportional to the concentration. In addition, quantitative determination can be carried out by diffuse reflectance measurements or digital image analysis. The 25 results show that these devices are reproducible, cost efficient and stable over time, so that they can be stored for long periods of time. Another feature to highlight is its simplicity, since sampling and detection are carried out in situ and also does not require reagent preparation.
     30
    In a particular embodiment, the SiO2 nanoparticles have a size between 5 and 20 nm and are added in a concentration of up to 0.1% by weight. In another particular embodiment, the TEOS is added to the sensor in a concentration between 40% and 80% by weight, preferably about 60% by weight.
     35
    Example

    1. Experimental procedure

    eleven. Reagents 40

    Base Elastomer (PDMS) (Sylgard 184); 1,2-naphthoquinone-4-sulfonate (NQS) (Sigma Aldrich); tetraethylorthosilicate (TEOS) (Sigma Aldrich); SiO2 nanoparticles (Sigma Aldrich); ammonium chloride (NH4CI) (Probus); 2M NaOH solution (J.T Baker); NH4 standard + 1000 ppm; methylamine (Sigma); dimethylamine (Sigma). Four. Five

    1.2. Instrumentation

    Cary 60 UV-Vis spectrophotometer, with VideoBarrelino video accessory: reflectance spectral registers in the 200-1000 nm range. fifty




    1.3. Sensor design

    A mixture of TEOS (3.06 g) and NQS (6.65 mg) was prepared. Then, he underwent ultrasound for 15 min. The resulting mixture was added to the elastomer base (component A, 2.04 g) and kept under stirring for 15 min. The Sylgard 184 curing agent (component B, 0.18 g) was then added and kept under stirring for 15 min. Finally, the resulting mixture was placed on a mold plate (200 μL / mold) and left in the oven for 24 h at 30 ° C. Figure 1 shows the image of a plate with the corresponding sensors.
     10
    For the synthesis of the sensors with SiO2 NPs, the same procedure explained above was followed, but adding SiO2 NPs (5.1 mg) in the mixture of TEOS and NQS.

    1.4 Generation of ammonia patterns
     fifteen
    For the preparation of ammonia standards a static dilution bottle was used. A known concentration of ammonium solution was added and then a volume of NaOH (100 µL) to achieve complete volatilization of ammonia to ammonia.
     twenty
    1.5. Sensor response

    The measurement of the response was carried out by introducing in the static dilution bottle, where a sensor, a solution of NH4 + had previously been suspended to generate the atmosphere of NH3 as described in the previous section. The 25 concentrations of NH3 studied were 5, 10, 20, 30 and 40 mg / m3.

    1.6. Example of application to real atmosphere

    As an example of application, the sensors were used for the determination of NH3 in 30 a family farm of hens, which were in a 6 m2 enclosure. The exposure time was 3 days.

    2. Results
     35
    In this example, the use of polymer membranes doped with NQS for the estimation of NH3 in atmospheres was evaluated. The polymer matrix is composed of PDMS, TEOS and SiO2 NPs where the derivatizing reagent is embedded.

    2.1. Sensor characterization 40

    In this example PDMS-TEOS sensors (40:60) and 0.1% of SiO2 NPs by weight over the total mixture were used. This composition was selected considering gelation time, embedded reagent stability and good diffusion of ammonia.
     Four. Five
    As indicated, the presence of TEOS facilitates the dispersion of NQS in the polymer matrix and reduces gelation time. The addition of SiO2 NPs improves the mechanical properties of the polymer matrix, increases the roughness of the sensor and therefore increases the response of the sensor.
     fifty
    Figure 2 shows the reflectance spectra of the sensors with and without SiO2 NPs synthesized and evaluated in this study.


    2.2. PDMS-TEOS-NQS sensor response study

    Figure 3 shows the reflectance spectra obtained by a blank and a concentration of NH3 (5 mg / m3). As can be seen, the presence of ammonia in the atmosphere causes a color change in the polymeric membrane. 5

    2.2.1. Study of the response of the sensor as a function of time

    Figure 4 shows the variation of the signal at ammonia concentrations of 5, 20 and 40 mg / m3 as a function of exposure time. At low concentrations of NH3 in the atmosphere, the response time is longer than for high concentrations. Figure 4 shows that at 5 mg / m3 concentrations the response time is 3 days, while at concentrations of 40 mg / m3, the response time is hours.

    2.2.2. Study of the sensor response as a function of concentration 15

    Figure 5 shows the variation of the sensor response for a given exposure time as a function of the NH3 concentration at 597 nm. As can be seen, using a 3, 6 and 9 day exposure time, a linear relationship between concentration and absorbance was obtained. The response of the sensor depends on the concentration of 20 NH3 in the atmosphere, therefore the exposure time will depend on the expected concentration of NH3.

    2.3. Study of the response of the PDMS-TEOS-SiO2 NPs-NQS sensor
     25
    The addition of nanoparticles to the sensor has first of all the function of improving the mechanical properties. The presence of these nanoparticles produces an increase in pore in the polymer matrix, reducing the pressure in the gelation process. This increase in pore improves the diffusion of ammonia and therefore improves the response.
     30
    Figure 6 shows the reflectance spectra for a target and for the exposure of the sensor to an atmosphere of 5 mg / m3 of ammonia for an exposure time of 1 day.

    2.3.1. Study of the response of the sensor as a function of time
     35
    The response of the sensors as a function of time was carried out at three levels of concentration. Figure 7 shows the answers obtained. The results show that the presence of nanoparticles in the polymer matrix provides an increase in response compared to sensors that do not have SiO2 NPs in their composition, and consequently the exposure time is considerably reduced. 40

    2.3.2. Study of the sensor response as a function of concentration

    Figure 8 shows the variation of the sensor response as a function of the concentration at different exposure times, 6 hours and 2 days. It should be noted that this study was not carried out at longer exposure times; however, in cases of very low levels of NH3, the exposure time could be increased in order to achieve adequate sensitivity.

     fifty




    2.4. Analytical parameters

    2.4.1. Precision

    Accuracy was studied for both sensors at different concentration levels and at 5 different exposure times

    Table 1. Relative standard deviations for PDMS-TEOS-NQS sensors.

     10


    Table 2. Relative standard deviations for the PDMS-TEOS-SiO2 NPs-NQS sensors.
     fifteen


    The results show that the accuracy for both types of sensors is comparable and adequate for the determination of ammonia in atmospheres.
     twenty
    2.4.2. Sensitivity

    The calibration equations for the two types of sensors as a function of exposure time as well as the limits of detection (LD) and quantification (LC) are shown in Table 3 25




     30
    Table 3. Analytical parameters for the determination of NH3 with the different sensors and at different exposure times.


     5
    It should be noted that the detection limit for 8 hours of exposure was 2.4 mg / m3.

    2.5 Estimation of the concentration in real samples

    To estimate the concentration of NH3 in real atmospheres, calibration 10 was carried out based on the sampling time (mg / m3 per h). The results are shown in Figure 9. As can be seen, it is possible to carry out the semi-quantitative estimation using a colorimetric panel.

    2.6. Application to real samples 15

    As an example of an application, an atmosphere in a family farm was analyzed using PDMS-TEOS-SiO2 NPs-NQS sensors. The sampling time was 3 days. The results show that the measured concentration was 3.3 ± 0.1 mg / m3. twenty
    权利要求:
    Claims (18)
    [1]

    1. Passive calorimetric sensor for the detection and / or determination of ammonia or aliphatic amines in gases comprising a matrix of polydimethylsiloxane (PDMS) having embedded 1,2-naphthoquinone-4-sulphonate (NQS) and tetraethylorthosilicate (TEOS). 5

    [2]
    2. Sensor according to claim 1, further comprising SiO2 nanoparticles.

    [3]
    3. Sensor according to claims 1 or 2, wherein the PDMS is polydimethylsiloxane.

    [4]
    4. Sensor according to any one of the preceding claims, wherein the NQS is embedded in the PDMS at a concentration between 0.43 and 0.46 mg NQS / g PDMS. fifteen

    [5]
    5. Sensor according to any one of the preceding claims, wherein the TEOS is in a concentration between 40% and 80% by weight over the total mixture.

    [6]
    6. A sensor according to claim 5, wherein the TEOS is in a concentration of 60% by weight over the total mixture.

    [7]
    7. Sensor according to any one of the preceding claims 2 to 6, wherein the SiO2 nanoparticles have a size between 5 and 20 nm.
     25
    [8]
    8. Sensor according to claim 7, wherein the SiO2 nanoparticles are in a concentration of up to 0.1% by weight over the total mixture.

    [9]
    9. Sensor according to any one of the preceding claims, wherein the PDMS matrix is a sheet with a thickness between 1.0 and 1.5 cm. 30

    [10]
    10. Sensor according to claim 9, wherein the sheet has a surface between 1.0 and 3.0 cm2.

    [11]
    11. Method of manufacturing a passive colorimetric sensor of ammonia or aliphatic amines in gases comprising the steps of:
    a) mix TEOS and NQS in certain quantities;
    b) add the PDMS to the mixture in section a), stirring if necessary until obtaining a homogeneous mixture;
    c) pour the solution obtained in section b) into a mold; Y
    d) once the solution of section e) has solidified, remove the resulting sheet 45, which is the sensor, from the mold.

    [12]
    12. Method according to claim 11, wherein, in step a), SiO2 nanoparticles are further added.
     fifty
    [13]
    13. Method according to claim 12, wherein the SiO2 nanoparticles have a size between 5 and 20 nm and are added in a concentration of up to 0.1% by weight over the total mixture.

    [14]
    14. Method according to any one of claims 11 to 13, wherein the TEOS is added in a concentration between 40% and 80% by weight over the total mixture.
     5
    [15]
    15. A method according to claim 14, wherein the TEOS is added in a concentration of 60% by weight over the total mixture.

    [16]
    16. A method according to any one of claims 11 to 15, wherein the NQS is added to the PDMS at a concentration between 0.43 and 0.46 mg NQS / g PDMS. 10

    [17]
    17. Method of manufacturing a calorimetric sensor according to any one of claims 11 to 16, wherein the PDMS is a two component silicone elastomer.
     fifteen
    [18]
    18. Use of the sensor according to any one of claims 1 to 10 in the measurement of ammonium or aliphatic amines in atmospheres of habitats dedicated to the breeding of cattle and other animals.
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    同族专利:
    公开号 | 公开日
    ES2619356B1|2018-01-15|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    ES2339368T3|2004-10-07|2010-05-19|Commissariat A L'energie Atomique|CHEMICAL SENSORS UNDERSTANDING POLYLILOXANES WITH ANILINE AS SENSITIVE MATERIALS AND THEIR USE FOR DETECTION OR ASSESSMENT OF NITRATED COMPOUNDS.|
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