CN107561109A - Fresh peanut moisture content detecting method based on nuclear magnetic resonance transverse relaxation spectral technology - Google Patents
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- 241001553178 Arachis glabrata Species 0.000 title claims abstract description 46
- 235000020232 peanut Nutrition 0.000 title claims abstract description 46
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- 235000019483 Peanut oil Nutrition 0.000 description 7
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- 239000000312 peanut oil Substances 0.000 description 7
- 239000013505 freshwater Substances 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 235000019198 oils Nutrition 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 235000014633 carbohydrates Nutrition 0.000 description 3
- 150000001720 carbohydrates Chemical class 0.000 description 3
- 235000018102 proteins Nutrition 0.000 description 3
- 102000004169 proteins and genes Human genes 0.000 description 3
- 108090000623 proteins and genes Proteins 0.000 description 3
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- 230000005684 electric field Effects 0.000 description 2
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- 238000004497 NIR spectroscopy Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000009795 derivation Methods 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005290 field theory Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
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- 239000004615 ingredient Substances 0.000 description 1
- 238000012966 insertion method Methods 0.000 description 1
- 235000021084 monounsaturated fats Nutrition 0.000 description 1
- 238000001225 nuclear magnetic resonance method Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
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Abstract
本发明涉及一种基于核磁共振横向弛豫谱技术的鲜花生含水率检测方法,通过鲜花生的烘干前后的质量变化率与烘干前后的横向弛豫谱总面积变化率的正比关系,来获得鲜花生含水率与其烘干前后的横向弛豫谱总面积变化率的正比关系并建立标准曲线,从而得到待测鲜花生含水率。本发明为核磁共振技术进行高含水率检测开拓了一个新思路,即不使用油水峰的区别,而使用横向弛豫谱总面积的变化关系得到含水率的变化。该方法对于水分含量高的新鲜作物的含水率测量与分析具有广泛的意义及实用价值。
The invention relates to a method for detecting the moisture content of fresh peanuts based on nuclear magnetic resonance transverse relaxation spectrum technology, which is obtained through the direct proportional relationship between the mass change rate of fresh peanuts before and after drying and the total area change rate of the transverse relaxation spectrum before and after drying. Obtain the proportional relationship between the moisture content of fresh peanuts and the total area change rate of the transverse relaxation spectrum before and after drying, and establish a standard curve, so as to obtain the moisture content of fresh peanuts to be tested. The invention develops a new idea for the detection of high water content by nuclear magnetic resonance technology, that is, the change of water content is obtained by using the change relationship of the total area of the transverse relaxation spectrum instead of using the difference between oil and water peaks. This method has extensive significance and practical value for the measurement and analysis of moisture content of fresh crops with high moisture content.
Description
技术领域technical field
本发明涉及一种鲜花生含水率检测方法,具体涉及一种基于核磁共振横向弛豫谱技术的鲜花生含水率检测方法。The invention relates to a method for detecting the moisture content of fresh peanuts, in particular to a method for detecting the moisture content of fresh peanuts based on nuclear magnetic resonance transverse relaxation spectrum technology.
背景技术Background technique
鲜花生含水率比较高,一般在25%到50%之间,该参数是其加工工艺选择和技术参数配置的依据,也是指导包装和安全贮藏的重要措施。目前测定鲜花生含水率的方法主要有传统的烘箱法和基于电磁场理论的插针式水分检测法。烘箱法的新型仪器有红外水分测定仪,如冠亚/SFY-60,其环状的卤素加热器确保样品在高温测试过程中均匀受热,使样品表面不易受损,快速干燥,在干燥过程中,水分仪持续测量并即时显示样品丢失的水分含量百分率,干燥程序完成后,最终测定的水分含量值被锁定显示。插针法的花生水分测定仪,如深圳艾格瑞生产的SH系列插针式水分检测仪,在使用过程中仪器能在测试探头周围产生对水分子敏感的电磁场,利用水分子吸收能量的特性产生固定的电场能与失去的电场能进行比较得出准确的水分值。针对含水量不同的被测物,仪器根据其吸收的能量不同从而得出不同的水分值来。The moisture content of peanuts is relatively high, generally between 25% and 50%. This parameter is the basis for its processing technology selection and technical parameter configuration, and is also an important measure to guide packaging and safe storage. At present, the methods for measuring the moisture content of fresh peanuts mainly include the traditional oven method and the pin-type moisture detection method based on electromagnetic field theory. The new instruments for the oven method include infrared moisture analyzers, such as Guanya/SFY-60, whose ring-shaped halogen heater ensures that the sample is evenly heated during the high-temperature test, so that the surface of the sample is not easily damaged, and it dries quickly. , the moisture meter continuously measures and instantly displays the percentage of moisture content lost in the sample. After the drying process is completed, the final measured moisture content value is locked and displayed. The peanut moisture analyzer with pin insertion method, such as the SH series pin moisture analyzer produced by Shenzhen Aigerui, can generate an electromagnetic field sensitive to water molecules around the test probe during use, and use the characteristics of water molecules to absorb energy to generate The fixed electric field energy is compared with the lost electric field energy to obtain an accurate moisture value. For the measured objects with different moisture content, the instrument can obtain different moisture values according to the energy absorbed by them.
烘箱法的优点是操作简单,测量准确,缺点是需要将样品的水分全部烘干才能得到含水率数据;插针法不需要将水分烘干,可以实时获得样品含水率,但需要将测试探头插入样品中,对样品造成损害。The advantage of the oven method is that it is easy to operate and the measurement is accurate. The disadvantage is that all the moisture in the sample needs to be dried to obtain the moisture content data; in the sample, causing damage to the sample.
近年来兴起的近红外光谱检测法是一种无损、快速检测方法,但其算法复杂,且受样品厚度、大小、颜色等性状影响大,不够通用。The near-infrared spectroscopy detection method that has emerged in recent years is a non-destructive and rapid detection method, but its algorithm is complex, and it is greatly affected by sample thickness, size, color and other properties, so it is not universal enough.
低场核磁共振(NMR)弛豫谱技术能够快速、无损地测定食品水分,研究食品中水分的动态信息的变化。目前已有针对花生含油率和低含水率核磁共振测试的方法。但对于含水率高的鲜花生,由于其弛豫谱中的油、水峰产生部分交迭,因此还没有基于核磁共振技术的检测方法。Low-field nuclear magnetic resonance (NMR) relaxation spectroscopy technology can quickly and non-destructively measure food moisture, and study the change of dynamic information of moisture in food. At present, there are methods for NMR testing of peanut oil content and low moisture content. However, for peanuts with high water content, there is no detection method based on NMR technology because the oil and water peaks in the relaxation spectrum partially overlap.
发明内容Contents of the invention
针对上述问题,本发明提供一种不使用油水峰的区别,而使用横向弛豫谱总面积的变化关系得到含水率的基于核磁共振横向弛豫谱技术的鲜花生含水率检测方法。In view of the above problems, the present invention provides a water content detection method based on nuclear magnetic resonance transverse relaxation spectrum technology, which does not use the difference between oil and water peaks, but uses the change relationship of the total area of the transverse relaxation spectrum to obtain the water content.
针对上述问题,本发明采取的技术方案为:基于核磁共振横向弛豫谱技术的鲜花生含水率检测方法,包括如下步骤:In view of the problems referred to above, the technical solution adopted by the present invention is: the method for detecting the moisture content of fresh flowers based on nuclear magnetic resonance transverse relaxation spectroscopy technology, comprising the steps of:
步骤一、随机选取鲜花生样品,并用天平分别称量各样品的初始质量,即m0;Step 1. Randomly select peanut samples, and use a balance to weigh the initial mass of each sample, i.e. m 0 ;
步骤二、使用CPMG脉冲序列分别测量各样品的一维横向弛豫谱,得到横向弛豫谱的初始面积,即s0;Step 2, using the CPMG pulse sequence to measure the one-dimensional transverse relaxation spectrum of each sample respectively, to obtain the initial area of the transverse relaxation spectrum, namely s 0 ;
步骤三、使用恒温设备将各样品低恒温烘干后,使用天平称量各样品烘干后的质量,即m1;Step 3, after drying each sample at a low and constant temperature with constant temperature equipment, use a balance to weigh the quality of each sample after drying, i.e. m 1 ;
步骤四、使用CPMG脉冲序列分别测量各样品烘干后的一维横向弛豫谱,得到烘干后的横向弛豫谱的面积,即s1;Step 4, use the CPMG pulse sequence to measure the one-dimensional transverse relaxation spectrum of each sample after drying, and obtain the area of the transverse relaxation spectrum after drying, ie s 1 ;
步骤五、获得鲜花生的烘干前后的质量变化率与烘干前后的横向弛豫谱总面积变化率的正比关系:Step 5. Obtain the proportional relationship between the mass change rate before and after drying of fresh flowers and the total area change rate of the transverse relaxation spectrum before and after drying:
Δm为鲜花生烘干前后的质量差,Δs为鲜花生烘干前后的横向弛豫谱总面积差;Δm is the quality difference before and after drying of fresh flowers, and Δs is the total area difference of transverse relaxation spectrum before and after drying of fresh flowers;
低温烘干的条件下,失去的质量完全是各种形态的水,因此设失水率另设弛豫谱总面积的变化率即η′=a×K+b (2)Under the condition of low-temperature drying, the mass lost is completely water in various forms, so the water loss rate is set Also set the rate of change of the total area of the relaxation spectrum That is, η'=a×K+b (2)
(1)式、(2)式中的a、b均为常数;(1) formula, a, b in (2) formula are all constants;
步骤六、获得鲜花生含水率与其烘干前后的横向弛豫谱总面积变化率的正比关系并建立标准曲线:Step 6. Obtain the direct proportional relationship between the moisture content of the fresh peanuts and the total area change rate of the transverse relaxation spectrum before and after drying and establish a standard curve:
由实验可证低温烘干状态下花生含水率η与失水率η’成正比关系即It can be verified by experiments that the moisture content η of peanuts in the low-temperature drying state is proportional to the water loss rate η', that is,
η=c×η’+d 式(3)η=c×η'+d formula (3)
(3)式中的c、d均为常数;(3) c and d in the formula are constants;
a,b,c,d都是常数,为公式导出的过程中的中间变量;a, b, c, and d are all constants, which are intermediate variables in the process of formula derivation;
将(2)式代入(3)式得到鲜花生含水率η与其烘干前后的横向弛豫谱总面积变化率K的正比关系Substituting formula (2) into formula (3) to obtain the direct proportional relationship between the moisture content η of fresh freshwater freshmen and the total area change rate K of the transverse relaxation spectrum before and after drying
η=e×K+f (4)η=e×K+f (4)
(4)式中的e、f均为常数;(4) e and f in the formula are constants;
根据前述步骤求出各样品对应的几个含水率变化值与烘干前后的横向弛豫谱总面积变化率的平均值,即Δη与ΔK的平均值,建立标准曲线;Obtain the average value of several water content change values corresponding to each sample and the total area change rate of the transverse relaxation spectrum before and after drying according to the foregoing steps, that is, the average value of Δη and ΔK, and establish a standard curve;
其中,各样品的含水率是根据质量变化计算获得的,因为花生油的沸点在335度左右,而低温烘干时的温度为103度,所以花生失去的质量可判断为完全为水分,因此标准曲线中,花生的含水率η是已知的,而由于核磁共振方法,烘干前后的横向弛豫谱总面积变化率k值也是已知的,因此,同做几个点,可以拟合出e和f的值。Among them, the moisture content of each sample is calculated according to the mass change, because the boiling point of peanut oil is about 335 degrees, and the temperature during low-temperature drying is 103 degrees, so the mass lost by peanuts can be judged to be completely water, so the standard curve Among them, the moisture content η of peanuts is known, and due to the nuclear magnetic resonance method, the value of the total area change rate k of the transverse relaxation spectrum before and after drying is also known. Therefore, by doing several points at the same time, we can fit e and the value of f.
步骤七、取一待测鲜花生,使用CPMG脉冲序列分别测量其烘干前横向弛豫谱的初始面积以及烘干后横向弛豫谱的面积;进而求出横向弛豫谱总面积变化率K,根据标准曲线,求出鲜花生含水率η。Step 7. Take a fresh flower to be tested, and use CPMG pulse sequence to measure the initial area of the transverse relaxation spectrum before drying and the area of the transverse relaxation spectrum after drying; then calculate the total area change rate K of the transverse relaxation spectrum , according to the standard curve, find the moisture content η of peanuts.
CPMG脉冲序列测量花生的一维横向弛豫谱,其主要参数包括:弛豫峰个数、各峰起止时间、峰顶点时间和峰面积等参数。其中,弛豫峰个数表征样品中含1H原子核的不同物质成分,峰顶点时间表征该物质的弛豫时间,峰面积表征1H原子核平均质子信号幅度。The CPMG pulse sequence measures the one-dimensional transverse relaxation spectrum of peanut, and its main parameters include: the number of relaxation peaks, the start and end time of each peak, the peak apex time and the peak area and other parameters. Among them, the number of relaxation peaks represents the different substance components containing 1 H nuclei in the sample, the peak apex time represents the relaxation time of the substance, and the peak area represents the average proton signal amplitude of 1 H nuclei.
步骤三中,当样品烘干前后的质量变化率小于0.2%,则认定质量恒定,烘干结束;否则,继续烘干直至样品烘干前后的质量变化率小于0.2%,质量恒定为止。In step 3, when the mass change rate of the sample before and after drying is less than 0.2%, the mass is determined to be constant, and the drying is completed; otherwise, continue drying until the mass change rate of the sample before and after drying is less than 0.2%, and the mass is constant.
本发明为核磁共振技术进行高含水率检测开拓了一个新思路,即不使用油水峰的区别,而使用横向弛豫谱总面积的变化关系得到含水率的变化。该方法对于水分含量高的新鲜作物的含水率测量与分析具有广泛的意义及实用价值。The invention develops a new idea for the detection of high water content by nuclear magnetic resonance technology, that is, the change of water content is obtained by using the change relationship of the total area of the transverse relaxation spectrum instead of using the difference between oil and water peaks. This method has extensive significance and practical value for the measurement and analysis of moisture content of fresh crops with high moisture content.
说明书附图Instructions attached
图1为鲜花生及花生油核磁共振横向弛豫谱;Fig. 1 is peanut and peanut oil nuclear magnetic resonance transverse relaxation spectrum;
图2为鲜花生含水率与横向弛豫谱总面积变化率标准曲线的建立流程图;Fig. 2 is the flow chart of establishing the standard curve of the moisture content and the total area change rate of the transverse relaxation spectrum of fresh peanuts;
图3为根据标准曲线测量鲜花生含水率的流程图;Fig. 3 is the flow chart of measuring fresh fresh peanut moisture content according to standard curve;
图4为鲜花生含水率与横向弛豫谱总面积变化率的关系曲线图;Fig. 4 is the relational curve diagram of the water content of fresh freshwater peanuts and the total area change rate of the transverse relaxation spectrum;
图5为标准曲线验证结果图。Figure 5 is a graph of the verification results of the standard curve.
具体实施方式detailed description
图1为鲜花生及花生油核磁共振横向弛豫谱。鲜花生中的有效成分为:鲜花生主要功能成分为脂肪、蛋白质、碳水化合物和水分,因此1H核主要来自脂肪、结合水(蛋白质紧密结合的水)、半自由水(碳水化合物)和自由水。花生油成分标示为:蛋白质、碳水化合物含量为0%,脂肪含量为99.9%。其中脂肪各成分含量:饱和脂肪17.8%;单不饱和脂43.9%;多不饱和脂肪38.2%。因此花生油的核磁共振弛豫峰完全是脂肪。以此峰为鲜花生中的脂肪成分定标。结合鲜花生的功能成分以及花生油的弛豫谱曲线,可得到鲜花生弛豫谱解释,峰1为结合水,峰2半自由水;峰3为自由水,峰4为脂肪峰1,峰5为脂肪峰2,由于峰3与峰4部分相互重叠,因此油、水峰不能完全分开,不能直接根据水峰峰面积的大小推测鲜花生的含水情况。Fig. 1 is the nuclear magnetic resonance transverse relaxation spectrum of peanut and peanut oil. The effective components in peanuts are: the main functional components of peanuts are fat, protein, carbohydrates and water, so the 1 H nucleus mainly comes from fat, bound water (water tightly bound by protein), semi-free water (carbohydrate) and free water. The ingredients of peanut oil are marked as: protein and carbohydrate content are 0%, and fat content is 99.9%. Among them, the content of each component of fat: saturated fat 17.8%; monounsaturated fat 43.9%; polyunsaturated fat 38.2%. Therefore the NMR relaxation peak of peanut oil is entirely fat. This peak was used as the calibration for the fat components in fresh peanuts. Combining the functional components of fresh peanuts and the relaxation spectrum curve of peanut oil, the interpretation of the relaxation spectrum of fresh peanuts can be obtained, peak 1 is bound water, peak 2 is semi-free water; peak 3 is free water, peak 4 is fat peak 1, peak 5 It is fat peak 2, because peak 3 and peak 4 partially overlap each other, so the oil and water peaks cannot be completely separated, and the water content of peanuts cannot be directly estimated based on the size of the water peak.
据此,本发明提供一种基于核磁共振横向弛豫谱技术的鲜花生含水率检测方法,如图2、图3所示,包括如下步骤:Accordingly, the present invention provides a freshwater freshwater detection method based on nuclear magnetic resonance transverse relaxation spectroscopy technology, as shown in Figure 2 and Figure 3, comprising the following steps:
步骤一、随机选取鲜花生样品,并用天平分别称量各样品的初始质量,即m0;Step 1. Randomly select peanut samples, and use a balance to weigh the initial mass of each sample, i.e. m 0 ;
步骤二、使用CPMG脉冲序列分别测量各样品的一维横向弛豫谱,得到横向弛豫谱的初始面积,即s0;Step 2, using the CPMG pulse sequence to measure the one-dimensional transverse relaxation spectrum of each sample respectively, to obtain the initial area of the transverse relaxation spectrum, namely s 0 ;
步骤三、使用恒温设备将各样品低恒温烘干,当样品烘干前后的质量变化率小于0.2%,则认定质量恒定,烘干结束;否则,继续烘干直至样品烘干前后的质量变化率小于0.2%,质量恒定为止;使用天平称量各样品烘干后的质量,即m1;Step 3. Use constant temperature equipment to dry each sample at a low and constant temperature. When the mass change rate of the sample before and after drying is less than 0.2%, it is determined that the quality is constant and the drying is over; otherwise, continue drying until the mass change rate of the sample before and after drying Less than 0.2%, until the mass is constant; use a balance to weigh the mass of each sample after drying, that is, m 1 ;
步骤四、使用CPMG脉冲序列分别测量各样品烘干后的一维横向弛豫谱,得到烘干后的横向弛豫谱的面积,即s1;Step 4, use the CPMG pulse sequence to measure the one-dimensional transverse relaxation spectrum of each sample after drying, and obtain the area of the transverse relaxation spectrum after drying, ie s 1 ;
步骤五、获得鲜花生的烘干前后的质量变化率与烘干前后的横向弛豫谱总面积变化率的正比关系:Step 5. Obtain the proportional relationship between the mass change rate before and after drying of fresh flowers and the total area change rate of the transverse relaxation spectrum before and after drying:
Δm为鲜花生烘干前后的质量差,Δs为鲜花生烘干前后的横向弛豫谱总面积差;Δm is the quality difference before and after drying of fresh flowers, and Δs is the total area difference of transverse relaxation spectrum before and after drying of fresh flowers;
低温烘干的条件下,失去的质量完全是各种形态的水,因此Under the condition of low-temperature drying, the lost quality is completely water in various forms, so
设失水率另设弛豫谱总面积的变化率 Set water loss rate Also set the rate of change of the total area of the relaxation spectrum
即η′=a×K+b (2)That is, η'=a×K+b (2)
(1)式、(2)式中的a、b均为常数;(1) formula, a, b in (2) formula are all constants;
步骤六、获得鲜花生含水率与其烘干前后的横向弛豫谱总面积变化率的正比关系并建立标准曲线:Step 6. Obtain the direct proportional relationship between the moisture content of the fresh peanuts and the total area change rate of the transverse relaxation spectrum before and after drying and establish a standard curve:
由实验可证低温烘干状态下花生含水率η与失水率η’成正比关系即It can be verified by experiments that the moisture content η of peanuts in the low-temperature drying state is proportional to the water loss rate η', that is,
η=c×η’+d 式(3)η=c×η'+d formula (3)
(3)式中的c、d均为常数;(3) c and d in the formula are constants;
将(2)式代入(3)式得到鲜花生含水率η与其烘干前后的横Substitute formula (2) into formula (3) to get the moisture content η of fresh flowers and its transverse value before and after drying.
向弛豫谱总面积变化率K的正比关系Proportional relationship to the total area change rate K of the relaxation spectrum
η=e×K+f (4)η=e×K+f (4)
(4)式中的e、f均为常数;(4) e and f in the formula are constants;
根据前述步骤求出各样品对应的几个含水率变化值与烘干前后的横向弛豫谱总面积变化率的平均值,即Δη与ΔK的平均值,建立标准曲线;Obtain the average value of several water content change values corresponding to each sample and the total area change rate of the transverse relaxation spectrum before and after drying according to the foregoing steps, that is, the average value of Δη and ΔK, and establish a standard curve;
步骤七、取一待测鲜花生,使用CPMG脉冲序列分别测量其烘干前横向弛豫谱的初始面积以及烘干后横向弛豫谱的面积;进而求出横向弛豫谱总面积变化率K,根据标准曲线,求出鲜花生含水率η。随机选择鲜花生样品两个,低温(103℃)烘干8小时,期间每隔1小时,测量其质量以及横向弛豫谱,根据质量变化率η’得到鲜花生含水率η,根据横向弛豫谱峰总面积变化率得到K,含水率η与K的关系曲线如图4,图中的y、X分别对应η、K。Step 7. Take a fresh flower to be tested, and use the CPMG pulse sequence to measure the initial area of the transverse relaxation spectrum before drying and the area of the transverse relaxation spectrum after drying; and then calculate the total area change rate of the transverse relaxation spectrum K , according to the standard curve, find the moisture content η of peanuts. Randomly select two peanut samples, dry them at low temperature (103°C) for 8 hours, measure their mass and transverse relaxation spectrum every 1 hour during this period, and obtain the moisture content η of fresh peanuts according to the mass change rate η', and according to the transverse relaxation K is obtained by the rate of change of the total area of the spectral peak, and the relationship curve between water content η and K is shown in Figure 4, and y and X in the figure correspond to η and K respectively.
图中η=1.0859K-0.0089In the figure η=1.0859K-0.0089
即(4)式中的e为1.0859,f为-0.0089,R^2为相关系数的平方,表明拟合图线性度的好坏。That is, e in formula (4) is 1.0859, f is -0.0089, and R^2 is the square of the correlation coefficient, indicating the linearity of the fitting graph.
以图4的关系曲线作为标准曲线,随机选择5个样品低温烘干1小时进行含水率检测验证,结果如图5所示。Using the relationship curve in Figure 4 as the standard curve, 5 samples were randomly selected and dried at low temperature for 1 hour to test and verify the moisture content, and the results are shown in Figure 5.
图5中圆点为采用烘箱法测得的各样品实际的含水率,两者测量的相对误差在10%之间,说明该方法可以对鲜花生的含水率进行估测。The dots in Figure 5 are the actual moisture content of each sample measured by the oven method, and the relative error between the two measurements is between 10%, indicating that this method can estimate the moisture content of fresh flowers.
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