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    • 专利摘要:
    Method for detecting total nitrogen in the slurry of a dairy farm. The method comprises the following steps (1): preparing slurry samples (2): detecting a total nitrogen content in each sample (3): scanning attenuated total reflection (ATR) spectra in the mid-infrared of each sample in order to obtain an ATR spectral matrix of the samples; (4): establish a quantitative analysis model by adopting a partial least squares method based on the ATR spectral matrix of the samples and on the matrix of total nitrogen concentrations in the samples, and (5): scan ATR spectra in slurry samples unknown to the dairy farm to obtain an ATR spectral matrix of the unknown slurry samples and substitute the ATR spectral matrix of the unknown slurry samples in the quantitative analysis model established in step (4) to obtain the total nitrogen content in the unknown slurry samples.
    公开号:BE1026769B1
    申请号:E20195812
    申请日:2019-11-21
    公开日:2020-12-08
    发明作者:Run Zhao；Renjie Yang；Keqiang Zhang；Haixue Liu；Peng Wang；Meirui Mou
    申请人:Agro Environmental Prot Institute Ministry Of Agriculture And Rural Affairs；Univ Tianjin Agricultural；
    IPC主号:
    专利说明:

    Method for detecting total nitrogen in the slurry of a large-scale dairy farm based on mid-infrared spectroscopy Technical field The present invention relates to the field of large-scale livestock and poultry farming, and in particular to a method for detecting total nitrogen in the slurry of a large scale dairy farm based on mid-infrared spectroscopy.
    Background At present, the healthy return of slurry to the field after harmless treatment is an important means of solving the environmental problems of large-scale dairy farms in China.
    The lack of methods to quickly detect nitrogen and phosphorus is a key technical obstacle that makes it difficult to return slurry to the field.
    In recent years, intensive guidance documents issued by various functional ministries and commissions in China have clearly highlighted the need to improve a standard system of processes for returning manure to fields at the level of use and disposal. detection.
    Therefore, the establishment of rapid detection procedures is very important to guide the scientific return of manure to the field and to control manure pollution.
    Spectroscopy technology, as a fast and convenient method for realizing on-line detection, has been widely used to detect total nitrogen in soil and, in particular, near infrared spectroscopy technology has been used to detect total nitrogen in farm manure.
    Mid-infrared represents the fundamental frequency absorption of molecules, and is more sensitive than near-infrared.
    The absorption peaks in the mid-infrared are essentially sharper and have fewer overlapping peaks,
    which can provide more characteristic information about an object to be tested. However, due to high water absorption in a mid-infrared frequency band, a detachable sample cell with a very small optical path is required to achieve an ideal transmission spectrum, and the data obtained is mainly used. for quantitative analysis and cannot be analyzed accurately and qualitatively. The main component of slurry is water. To remedy the influence of water absorption, the present invention proposes to use the attenuated total reflection (ATR) spectra in the mid-infrared to detect the total nitrogen in the slurry of a dairy farm at large scale, and according to the state of research in domestic and foreign literature, no relevant report on the use of ATR spectra in the mid-infrared to detect total nitrogen in the slurry of a large-scale dairy farm. scales were not found.
    Summary The present invention provides a method for detecting total nitrogen in the slurry of a large scale dairy farm based on mid-infrared spectroscopy. The method is simple and scientific and exhibits high analytical efficiency and analytical precision.
    The present invention is implemented by the following technical solutions: A method for detecting total nitrogen in the slurry of a large-scale dairy farm based on mid-infrared spectroscopy comprises the following steps: (1) preparing slurry samples from a large-scale dairy farm showing different concentrations for experimental purposes;
    (2) detecting a total nitrogen content in each sample in order to obtain a matrix of total nitrogen concentrations in the large-scale dairy farm slurry samples for experimental purposes; (3) respectively scanning a mid-infrared ATR spectrum of each sample for the purpose of obtaining a mid-infrared ATR spectral matrix of the large-scale dairy farm slurry samples for experimental purposes; (4) Establish a quantitative analysis model by adopting partial least squares method based on mid-infrared attenuated total reflection spectral matrix (ATR) of large-scale dairy farm slurry samples for purposes experiments obtained in step (3) and on the matrix of total nitrogen concentrations in the slurry samples from the large-scale dairy farm for experimental purposes obtained in step (2); and (5) scanning mid-infrared ATR spectra of slurry samples unknown to the large-scale dairy farm to obtain a mid-infrared ATR spectral matrix of slurry samples unknown to the farm large-scale dairy farm, and substitute the ATR spectral matrix in the mid-infrared of the slurry samples unknown to the large-scale dairy farm in the quantitative analysis model established in step (4) in order to obtain the total nitrogen content in slurry samples unknown to the large-scale dairy farm.
    In addition, the preferred frequency band range for mid-infrared spectra is 800 cm ”! to 1800 cm ”. In step (2), the total nitrogen content in each sample is detected using a Kjeldahl nitrogenometer.
    The advantageous and beneficial effects of the present invention are as follows:
    1. Compared with a conventional detection method, the detection method of the present invention has the advantages of simple preprocessing of samples, low cost, speed, convenience, and the like.
    2. The detection method provided by the present invention is simple and scientific and has high analytical efficiency and analytical precision, and can be popularized to detect total nitrogen in the slurry of other animals. Brief Description of the Drawings Figure 1 shows a mid-infrared ATR spectrum of a slurry sample from a large-scale dairy farm which has a concentration of 789.5 mg / L for experimental purposes in the 800 range. cm “to 1800 cm! in one embodiment of the present invention; Figure 2 shows a curve of variation of the error of the cross-validation squared means (RMSECV) of partial least squares models with principal components; and Figure 3 is a linear representation diagram of the predicted and actual concentrations of total nitrogen in unknown samples in a mid-infrared ATR spectrum based prediction set and partial least squares model. detailed description
    > BE2019 / 5812 A detection method of the present invention is described in more detail below through embodiments. Note that the embodiments which follow are illustrative and not limiting, and the scope of protection of the present invention cannot be limited by the embodiments which follow.
    Embodiment 1 A method for detecting total nitrogen in slurry from a large-scale dairy farm based on mid-infrared spectroscopy comprises the following steps: (1) preparing slurry samples from a dairy farm large scale which have different concentrations for experimental purposes; (2) detecting a total nitrogen content in each sample using a Kjeldahl nitrogen meter in order to obtain a matrix of total nitrogen concentrations in the slurry samples from the large-scale dairy farm for experimental purposes; (3) respectively scanning a mid-infrared ATR spectrum of each sample for the purpose of obtaining a mid-infrared ATR spectral matrix of the large-scale dairy farm slurry samples for experimental purposes; (4) Establish a quantitative analysis model by adopting a partial least squares method based on the ATR spectral matrix in the mid-infrared of the slurry samples from the large-scale dairy farm for experimental purposes obtained in step (3) and on the matrix of total nitrogen concentrations in the slurry samples from the large-scale dairy farm for experimental purposes obtained in step (2); and
    (5) scan mid-infrared ATR spectra of slurry samples unknown to the large-scale dairy farm in order to obtain a mid-infrared ATR spectral matrix of slurry samples unknown to the dairy farm on a large scale, and substitute the ATR spectral matrix in the mid-infrared of the slurry samples unknown to the large-scale dairy farm in the quantitative analysis model established in step (4) in order to obtain the total nitrogen content in slurry samples unknown to large-scale dairy farming.
    In this embodiment, the slurry from the large-scale dairy farm was supplied from a pasture in Binhai New Area in Tianjin City. In the experiment, a FOSS 2300 Kjeldahl nitrogen meter was used to make nitrogenization measurements. The total nitrogen concentration range in the slurry was 116.5 mg / L to 1656.8 g / L. Spectral data acquisition in the present invention was performed based on a Fourier transform mid-infrared spectrometer of PerkinElmer Company of the United States. The spectrometer is equipped with ATR accessories, with a scanning range of 650 cm "to 4000 cmt, a resolution of 8 cm", a scan interval of 2 cm! And an average of 64 scans for signal / noise. The samples slurry from the large-scale dairy farm were placed in ATR crystal cells, and mid-infrared ATR spectra of all samples were acquired with water as a background. no characteristic information can be provided in the frequency range from 650 cm! to 800 cm ”and from 1800 cm“ to 4000 cm “in the mid-infrared region, the frequency range from 800 cm“ to 1800 cm ”is selected in the present invention to analyze total nitrogen in large scale dairy farm slurry samples. Figure 1 is a mid-infrared ATR spectrum of a slurry sample from a large scale. large-scale dairy farming (with a total nitrogen equal to 789, 5 mg / L) in the frequency range 800 cm! to 1800 cm ”. Mid-infrared ATR spectra (40 x 501) of 40 slurry samples acquired from the large-scale dairy farm were used to establish a quantitative model of total nitrogen in the slurry samples from the dairy farm. in large scale.
    A method for establishing a model for quantitative analysis of total nitrogen in slurry samples from a large-scale dairy farm is as follows: a concentration gradient method was used to select 26 samples from the 40 samples collected. from the slurry from the large-scale dairy farm as calibration sets, and the remaining 14 samples were used as independent prediction sets. The mid-infrared spectral matrix (40 x 501) of the slurry samples from the large-scale dairy farm was used as an independent variable, and the matrix of total nitrogen concentrations of the slurry samples obtained by the nitrogen meter of Kjeldahl was used as the dependent variable. The RMSECV was used to select an optimal number of major model components. Figure 2 is a diagram of a variation curve of the RMSECV of the models established with the numbers of principal components. It can be seen that when the number of main components is more than 13, the RMSECV is small and has little variation. Therefore, 13 major components are selected to establish a model of partial least squares quantitative analysis of total nitrogen in the slurry samples from the large-scale dairy farm, and the RMSECV is equal to 106.5 mg / L and the cross-validation correlation coefficient is 0.96, which indicates that the established model exhibits a good effect of stability and adaptation.
    Predicting total nitrogen content for unknown samples: by measuring mid-infrared ATR spectra of unknown slurry samples in the large-scale dairy farm, and using the quantitative partial least squares model established to predict externally the total nitrogen contents of the unknown samples in the prediction sets, the predicted values of the total nitrogen concentration variable that correspond to the mid-infrared spectral matrix of the unknown samples are calculated. The prediction results of the model established for the unknown samples in the prediction sets are shown in Table 1: Table 1: Comparison between the predicted and actual concentrations based on partial least squares and mid-infrared spectroscopy Concentration Concentration z LA True Sample error predicted relative (%) (mgL ”) (mgL”) # 1 1500.0 1519.9 1.3 # 2 893.0 939.5 5.2 # 3 1320.9 1283, 0 2.9 # 4 1335.0 1443.7 8.1
    # 5 1070.3 1038.4 3.0 # 6 1634.9 1561.2 4.5 # 7 975.9 970.1 0.6 # 8 1656.8 1746.4 5.4 # 9 1501.7 1416 , 3 5.7 # 10 1169.4 1321.1 13.0 # 11 1450.3 1496.4 3.2 # 12 1551.3 1532.1 1.2 # 13 1271.5 1344.2 5.7 # 14 789.5 743.8 5.8 It can be deduced from Table 1 that the maximum relative error between the predicted value and the actual value of this process is 13%, the minimum relative error is 0.6%, and the mean relative error is 4.7%.
    Figure 3 is a linear representation diagram of the predicted concentration and the actual concentration, with a correlation coefficient of 0.97 and a predicted root mean square prediction error (RMSEP) of 71.0 mg / L, which indicates that the partial least squares model established on the basis of the mid-infrared spectroscopy shows good prediction ability of total nitrogen in the slurry of the large-scale dairy farm. The method applied by the present invention can realize the detection and analysis of total nitrogen in slurry samples of the large-scale dairy farm can be carried out.
    The foregoing detailed description of the method for detecting total nitrogen in slurry of a large scale dairy farm based on mid-infrared spectroscopy with reference to the embodiments is illustrative rather than restrictive.
    Therefore, changes and modifications which are not outside the general concept of the present invention will fall within the scope of protection of the present invention.
    权利要求:
    Claims (3)
    [1]
    1. A method for detecting total nitrogen in slurry from a large-scale dairy farm based on mid-infrared spectroscopy, comprising the following steps: (1) preparing slurry samples from a large-scale dairy farm. scale that show different concentrations for experimental purposes; (2) detecting a total nitrogen content in each sample in order to obtain a matrix of total nitrogen concentrations in the large-scale dairy farm slurry samples for experimental purposes; (3) respectively scan mid-infrared total attenuated reflection (ATR) spectra of each sample in order to obtain a mid-infrared ATR spectral matrix of the large-scale dairy farm slurry samples at experimental purposes; (4) Establish a quantitative analysis model by adopting a partial least squares method based on the ATR spectral matrix in the mid-infrared of the slurry samples from the large-scale dairy farm for experimental purposes obtained in step (3) and the matrix of total nitrogen concentrations in the slurry samples from the large-scale dairy farm for experimental purposes obtained in step (2); and (5) scanning mid-infrared ATR spectra of slurry samples unknown to the large-scale dairy farm to obtain a mid-infrared ATR spectral matrix of slurry samples unknown to the farm large-scale dairy farm, and substitute the ATR spectral matrix in the mid-infrared of the slurry samples unknown to the large-scale dairy farm in the quantitative analysis model established in step (4) in order to obtain the total nitrogen content in slurry samples unknown to the large-scale dairy farm.
    [2]
    A detection method according to claim 1, wherein the frequency band range of the ATR spectrum in the mid-infrared is 800 cm ”to 1800 cm”.
    [3]
    3. The detection method according to claim 1 or 2, wherein, in step (2), the total nitrogen content in each sample is detected by a Kjeldahl nitrogenometer.
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    同族专利:
    公开号 | 公开日
    CN109632689B|2019-11-26|
    BE1026769A1|2020-06-05|
    CN109632689A|2019-04-16|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    CN2741042Y|2004-11-18|2005-11-16|复旦大学|On-line multi-channel near-infrared spectrograph for measuring total nitrogen and acid content in soy sauce|
    CN101762569A|2010-01-08|2010-06-30|中国农业大学|Non-destructive monitoring method of livestock excrement industrialized composting fermentation process|
    CN102455285A|2010-10-26|2012-05-16|中国科学院城市环境研究所|Method for determining precipitate composition in recycling nitrogen and phosphorus from wastewater by guanite precipitation method|
    CN103575680A|2013-11-22|2014-02-12|南京农业大学|Spectroscopic method for evaluating quality indexes of organic fertilizer|
    法律状态:
    2021-02-03| FG| Patent granted|Effective date: 20201208 |
    优先权:
    申请号 | 申请日 | 专利标题
    CN201811408694.7A|CN109632689B|2018-11-23|2018-11-23|A kind of detection method based on total nitrogen in middle infrared spectrum large-scale milch cow farms liquid manure|
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