CN102680561A - Method for measuring boric acid content in water-based adhesive for cigarettes - Google Patents

Method for measuring boric acid content in water-based adhesive for cigarettes Download PDF

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CN102680561A
CN102680561A CN2012101189030A CN201210118903A CN102680561A CN 102680561 A CN102680561 A CN 102680561A CN 2012101189030 A CN2012101189030 A CN 2012101189030A CN 201210118903 A CN201210118903 A CN 201210118903A CN 102680561 A CN102680561 A CN 102680561A
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water
tobacco
boric acid
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王文元
者为
段焰青
夏建军
蒋举兴
刘亚
杨丽萍
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Hongyunhonghe Tobacco Group Co Ltd
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Hongyunhonghe Tobacco Group Co Ltd
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Abstract

The invention discloses a method for measuring boric acid content in water-based adhesive for cigarettes. Accurately weighing a certain amount of water-based adhesive sample for tobacco, placing the sample in a microwave digestion tank, and adding nitric acid (HNO)3) And hydrogen peroxide (H)2O2) After pre-digestion, screwing and sealing the mixture, placing the mixture into a microwave digestion instrument for digestion to obtain a water-based adhesive sample solution for cigarettes, and introducing the sample solution into an inductively coupled plasma emission spectrum mass spectrometer for detection: detecting the characteristic ionic strength of boron (B) element and online internal standard germanium (Ge) element in the sample solution, quantitatively determining by adopting an internal standard calibration curve method, calculating the content of the B element in the water-based adhesive for cigarettes, and obtaining HBO (hydrogen bromide oxide) through the conversion coefficient3The content of (a). The method has the advantages of accurate test, simple operation, high sensitivity and good repeatability. Is suitable for technical personnel in tobacco industry and tobacco adhesive production enterprises to carry out HBO treatment on water-based adhesive for tobacco3The quantitative determination is carried out, and the blank of the technical field is filled.

Description

一种烟用水基胶中硼酸含量的测定方法A kind of determination method of boric acid content in water-based glue for tobacco

技术领域 technical field

本发明属于卷烟材料理化检验技术领域,具体涉及一种烟用水基胶中硼酸含量的测定方法。The invention belongs to the technical field of physical and chemical testing of cigarette materials, and in particular relates to a method for measuring boric acid content in water-based glue for cigarettes.

背景技术 Background technique

随着世界范围内对“吸烟与健康”的广泛关注和FCTC协议正式签署,对卷烟产品中有害人体健康的元素的控制成为了烟草行业关注的重点。烟用水基胶是卷烟生产过程中不可缺少的物质,也是体现卷烟工艺特色的关键材料,因而,水基胶的质量控制一直是烟草企业非常关注的问题。目前国内卷烟生产中使用的胶黏剂大多是化学合成的水基胶,针对目前烟用水基胶出台的相关检测标准,粘度测定是一项重要的指标,有些商家为了使烟用水基胶的粘度值达到相应的技术标准,会加入硼酸来调节其粘度,从而提高水基胶的粘合性能,但在卷烟生产过程中,过量的硼酸会产生强烈的刺激性,引起皮肤刺激、结膜炎、支气管炎,同时若人体摄入过量的硼酸则会对人的生命造成一定的威胁。因而,无论是从卷烟产品感官质量方面还是从卷烟吸食安全性考虑,烟用水基胶中硼酸的残留分析和监控都具有重要的意义。With the widespread concern on "smoking and health" worldwide and the official signing of the FCTC agreement, the control of elements harmful to human health in cigarette products has become the focus of the tobacco industry. Tobacco water-based glue is an indispensable substance in the cigarette production process, and it is also a key material that reflects the characteristics of cigarette technology. Therefore, the quality control of water-based glue has always been a matter of great concern to tobacco companies. At present, most of the adhesives used in domestic cigarette production are chemically synthesized water-based adhesives. According to the relevant testing standards for tobacco water-based adhesives, viscosity measurement is an important indicator. When the value reaches the corresponding technical standard, boric acid will be added to adjust its viscosity, thereby improving the adhesive performance of the water-based adhesive. However, in the process of cigarette production, excessive boric acid will produce strong irritation, causing skin irritation, conjunctivitis, bronchial Inflammation, and at the same time, if the human body ingests excessive boric acid, it will pose a certain threat to human life. Therefore, the analysis and monitoring of boric acid residues in tobacco water-based adhesives are of great significance, both in terms of the sensory quality of cigarette products and the safety of cigarette smoking.

目前,国内外硼酸测定方法主要有甲亚胺-H法、3-甲氧基甲亚胺-H法和姜黄素法,前两种方法分析时间长,后者需在非水条件下测定,使其应用受到限制;这些方法的测定对象多为环境样品、食品中硼酸的检测。也有报道采用薄层色谱法和单极扫描极谱法测定粮食和矿泉水中的硼酸,但操作麻烦,干扰多,可检测的样品品种少。有关烟用水基胶中硼酸的测定方法及其专利未见报道。因而,开发一种稳定性好、选择性高、快速准确、无需有机试剂的测定方法,对提升卷烟产品质量安全、进一步探讨卷烟减害具有重要的意义。At present, domestic and foreign methods for the determination of boric acid mainly include methylimine-H method, 3-methoxymethylimine-H method and curcumin method. Its application is limited; the determination objects of these methods are mostly the detection of boric acid in environmental samples and food. It is also reported to use thin layer chromatography and monopolar scanning polarography to determine boric acid in grain and mineral water, but the operation is troublesome, there are many interferences, and the number of detectable samples is small. There is no report on the determination method and patent of boric acid in the tobacco water-based glue. Therefore, it is of great significance to develop an assay method with good stability, high selectivity, fast accuracy, and no need for organic reagents to improve the quality and safety of cigarette products and further explore the harm reduction of cigarettes.

发明内容 Contents of the invention

本发明的目的在于针对现有方法存在的样品前处理繁琐、灵敏度较低、重现性较差等技术不足,提供一种烟用水基胶中硼酸含量的测定方法,为烟草行业和烟用胶粘剂生产企业烟用水基胶的选择和监控提供数据支撑,进而为更加科学的评估吸烟对健康的危害,为卷烟产品研发中的辅料选择以及减害降焦等给予技术支撑。The purpose of the present invention is to provide a method for determining the content of boric acid in tobacco water-based adhesives for the technical deficiencies of existing methods such as cumbersome sample pretreatment, low sensitivity, and poor reproducibility. Production enterprises provide data support for the selection and monitoring of tobacco water-based adhesives, and then provide technical support for a more scientific assessment of the health hazards of smoking, as well as for the selection of auxiliary materials and harm reduction and coke reduction in cigarette product research and development.

本发明的目的通过以下技术方案予以实现。The purpose of the present invention is achieved through the following technical solutions.

除非另有说明,本发明所采用的百分数均为重量百分数。Unless otherwise stated, the percentages used in the present invention are all percentages by weight.

一种烟用水基胶中硼酸含量的测定方法,包括以下步骤:A method for assaying boric acid content in water-based glue for tobacco, comprising the following steps:

(1)称取0.2g~0.6g试样,精确至0.1mg,置于微波消解罐中,加入5mLHNO3和2mLH2O2消解12~16h;(1) Weigh 0.2g~0.6g sample, accurate to 0.1mg, put it in a microwave digestion tank, add 5mLHNO 3 and 2mLH 2 O 2 to digest for 12~16h;

(2)将步骤(1)所述微波消解罐旋紧密封置于微波消解仪中进行消解,同时做未加试样的空白溶液;(2) Tighten and seal the microwave digestion tank described in step (1) and place it in a microwave digestion instrument for digestion, while making a blank solution without adding a sample;

(3)消解完毕,待温度降至室温后取出消解罐,直接将试样溶液转移至50mLPET容量瓶中,用纯水冲洗消解罐,清洗液一并转移至容量瓶中,然后用纯水定容,摇匀后得试样溶液;(3) After the digestion is completed, take out the digestion tank after the temperature drops to room temperature, transfer the sample solution directly to a 50mL PET volumetric flask, rinse the digestion tank with pure water, transfer the cleaning solution to the volumetric flask, and then set the solution with pure water. volume, shake well to get the sample solution;

(4)制备标准溶液:使用B标准储备溶液,用5%的HNO3逐级稀释成浓度为0μg/L,1μg/L,2μg/L,5μg/L,10μg/L,20μg/L的B标准溶液;(4) Preparation of standard solution: use B standard stock solution, dilute it step by step with 5% HNO3 to B standard solution;

(5)绘制校准曲线:采用Ge标准溶液在线内标加入,内标Ge使用浓度为15μg/L,分别吸取标准空白溶液和不同浓度B的标准溶液,注入电感耦合等离子体质谱仪中,以待测元素B含量与对应内标元素Ge含量的比值为横坐标,待测元素B质荷比强度与对应内标元素Ge质荷比强度的比值为纵坐标,建立B的校准曲线;对校正数据进行线性回归,求得B的回归方程,R应不小于0.999;(5) Draw the calibration curve: adopt Ge standard solution online internal standard to add, internal standard Ge use concentration is 15 μ g/L, draw the standard blank solution and the standard solution of different concentration B respectively, inject in the inductively coupled plasma mass spectrometer, wait for The ratio of the measured element B content to the corresponding internal standard element Ge content is the abscissa, the ratio of the mass-to-charge ratio intensity of the element to be measured to the corresponding internal standard element Ge mass-to-charge ratio is the ordinate, and the calibration curve of B is established; Carry out linear regression to obtain the regression equation of B, and R should not be less than 0.999;

(6)按步骤(5)方法测定步骤(3)样品溶液中B元素和内标Ge元素的离子强度,使用所得的校准曲线计算获得烟用水基胶样品溶液中B元素浓度;计算公式如下:(6) Measure the ionic strength of the B element and the internal standard Ge element in the step (3) sample solution according to the method of step (5), and use the obtained calibration curve to calculate and obtain the B element concentration in the tobacco water-based glue sample solution; the calculation formula is as follows:

烟用水基胶中硼酸的含量以X表示,按式(I)进行计算:The content of boric acid in the tobacco water-based glue is represented by X, and is calculated according to formula (I):

Xx == (( CC -- CC 00 )) ×× VV 10001000 ×× mm ×× Ff .. .. .. (( II ))

式中:In the formula:

X——烟用水基胶中硼酸的含量,单位为微克每克(μg/g);X——the content of boric acid in the tobacco water-based adhesive, in micrograms per gram (μg/g);

C——烟用水基胶样品溶液中被测元素的浓度,单位为微克每升(μg/L);C—concentration of the measured element in the sample solution of the tobacco water-based adhesive, in micrograms per liter (μg/L);

C0——空白溶液中被测元素的浓度,单位为微克每升(μg/L);C 0 —concentration of the measured element in the blank solution, in micrograms per liter (μg/L);

V——烟用水基胶样品溶液中定容体积,单位为毫升(mL);V——the constant volume in the tobacco water-based adhesive sample solution, in milliliters (mL);

m——烟用水基胶样品质量,单位为克(g);m - the mass of the tobacco water-based adhesive sample, in grams (g);

F——硼换算为硼酸的系数,硼酸系数为5.72。F——The coefficient of converting boron into boric acid, and the coefficient of boric acid is 5.72.

作为优选的技术方案,所述步骤(2)中微波消解系统消解程序由以下四个步骤构成:As a preferred technical solution, the digestion program of the microwave digestion system in the step (2) is composed of the following four steps:

(1)由室温升至100℃升温时间为5min,保持时间为5min。(1) The heating time from room temperature to 100°C is 5 minutes, and the holding time is 5 minutes.

(2)由100℃升至135℃升温时间为5min,保持时间为5min。(2) The heating time from 100°C to 135°C is 5 minutes, and the holding time is 5 minutes.

(3)由135℃升至165℃升温时间为5min,保持时间为5min。(3) The heating time from 135°C to 165°C is 5 minutes, and the holding time is 5 minutes.

(4)由165℃升至185℃升温时间为10min,保持时间为25min。(4) The heating time from 165°C to 185°C is 10 minutes, and the holding time is 25 minutes.

作为优先的技术方案,所述步骤(4)中制备标准溶液的具体步骤:准确吸取1mL硼标准储备溶液到100mL的容量瓶中,用1%HNO3溶液稀释定容至刻度,获得1μg/mL的标准溶液;分别移取硼标准溶液0,0.1,0.2,0.5,1.0,2.0mL于100mL塑料容量瓶中,用5%HNO3溶液定容至刻度,容量瓶中溶液浓度为0μg/L,1μg/L,2μg/L,5μg/L,10μg/L,20μg/L的B标准溶液。As a preferred technical scheme, the specific steps for preparing the standard solution in the step (4): accurately draw 1mL of the boron standard stock solution into a 100mL volumetric flask, dilute with 1% HNO3 solution to the mark, and obtain 1 μg/mL standard solution; respectively pipette boron standard solution 0, 0.1, 0.2, 0.5, 1.0, 2.0mL in a 100mL plastic volumetric flask, and use 5% HNO3 solution to set the volume to the mark, the solution concentration in the volumetric flask is 0 μg/L, 1μg/L, 2μg/L, 5μg/L, 10μg/L, 20μg/L B standard solution.

作为优选的技术方案,所述步骤(5)中电感耦合等离子体质谱仪的工作条件为:真空度(Torr)、雾化器流量(L/min)、辅助气流量(L/min)、等离子体气体流量(Ar)(L/min)、射频功率(W)、扫描模式、扫描次数、离子透镜电压(V)、脉冲电压(V)、重复次数、清洗时间(s)、CeO氧化物、双电荷(Ba++)分别为≤1.2×10-6、0.66~0.68、1.2、15、1300、Peak Jumping、20、6.0~6.4、950、4、20、≤0.03、≤0.03;同时,为了有效地减少信号漂移和基体效应对测定的影响,在线加入Ge作为内标。As a preferred technical solution, the working conditions of the inductively coupled plasma mass spectrometer in the step (5) are: vacuum degree (Torr), atomizer flow rate (L/min), auxiliary gas flow rate (L/min), plasma Bulk gas flow (Ar) (L/min), RF power (W), scan mode, scan times, ion lens voltage (V), pulse voltage (V), repetition times, cleaning time (s), CeO oxide, Double charges (Ba++) are ≤1.2×10 -6 , 0.66~0.68, 1.2, 15, 1300, Peak Jumping, 20, 6.0~6.4, 950, 4, 20, ≤0.03, ≤0.03; at the same time, in order to effectively To reduce the influence of signal drift and matrix effect on the determination, Ge was added online as an internal standard.

作为优选的技术方案,所述的测定方法中器皿均为塑料容器,并经25%HNO3溶液浸泡12~16h后,用纯水洗涤干净后备用;由于玻璃器皿中易引入硼污染,同时硼容易在仪器的雾化器和锥口聚集,产生记忆效应,因而,在测定硼含量较高的溶液后,采用5%硝酸冲洗进样系统以消除硼的记忆效应。As a preferred technical solution, the vessels in the measurement method are all plastic containers, and after being soaked in 25% HNO3 solution for 12-16 hours, they are washed with pure water for later use; since boron pollution is easily introduced into glassware, boron It is easy to accumulate in the atomizer and cone of the instrument, resulting in memory effect. Therefore, after measuring the solution with high boron content, use 5% nitric acid to flush the sampling system to eliminate the memory effect of boron.

本发明克服了现有方法的缺陷,建立了一种高效、灵敏度高、准确度高,采用ICP-MS检测技术测定烟用水基胶中硼酸含量的方法,使前处理更为简单、高效、完全、回收率高,待测元素不易受外源性污染、损失,并且ICP-MS操作简便、精密度高、稳定性好、检出限低,回收率、相对标准偏差、检出限分别为105.59%、4.52%、0.12μg/L,适用于烟草行业和烟用胶粘剂生产企业技术人员对烟用水基胶中HBO3进行定量测定。The invention overcomes the defects of the existing methods, establishes a method with high efficiency, high sensitivity and high accuracy, and uses ICP-MS detection technology to measure the content of boric acid in the tobacco water-based glue, making the pretreatment simpler, more efficient and more complete , high recovery rate, the elements to be measured are not easily affected by exogenous pollution and loss, and ICP-MS is easy to operate, high precision, good stability, and low detection limit. The recovery rate, relative standard deviation, and detection limit are 105.59 %, 4.52%, 0.12μg/L, suitable for the technical personnel of the tobacco industry and tobacco adhesive manufacturers to quantitatively determine HBO 3 in the water-based adhesive for tobacco.

本发明填补了国内ICP-MS法在烟用水基胶中硼酸检测这一技术领域的空白,对于制定烟用水基胶中有害限用物质检测技术新标准具有重要的意义,同时对保护人类身体健康,促进我国烟草行业中的卷烟产品和烟用水基胶产业健康发展和促进对外贸易具有非常现实的意义。The invention fills up the gap in the domestic ICP-MS method in the technical field of boric acid detection in tobacco water-based glue, and has important significance for formulating new standards for the detection of harmful and restricted substances in tobacco water-based glue, and at the same time protects human health , to promote the healthy development of cigarette products and tobacco water-based rubber industry in my country's tobacco industry and to promote foreign trade has very practical significance.

具体实施方式 Detailed ways

下面通过实施例对本发明作进一步地详细说明,但实施例并不是对本发明技术方案的限定。所有基于本发明教导所作的变换,均应属于本发明的保护范围。The present invention will be further described in detail through the examples below, but the examples are not intended to limit the technical solution of the present invention. All transformations made based on the teaching of the present invention shall belong to the protection scope of the present invention.

实施例1Example 1

1.使用仪器及仪器工作条件1. The use of instruments and instrument working conditions

1.1使用仪器:电感耦合等离子体质谱仪(ICP-MS),型号:PE Elan DRC-e1.1 Instrument used: Inductively coupled plasma mass spectrometer (ICP-MS), model: PE Elan DRC-e

1.2仪器工作条件,见表11.2 Instrument working conditions, see Table 1

表1ICP-MS的工作条件参数Table 1 The working condition parameters of ICP-MS

  工作条件参数Parameters Working condition parameters Parameters   设定值Value Set value Value   真空度(Torr) Vacuum (Torr)   ≤1.2×10-6 ≤1.2×10 -6   雾化器流量(L·min-1)Atomizer flow(L·min -1 )   0.68 0.68   辅助气流量(L·min-1)Auxiliary gas flow(L·min -1 )   1.2 1.2   等离子体气体流量(Ar)(L·min-1)Plasma gas flow(Ar)(L·min -1 )   15 15   射频功率(W) RF power (W)   1300 1300   扫描模式 scan mode   Peak Jumping Peak Jumping   扫描次数 Number of scans   20 20   离子透镜电压(volts) Ion lens voltage (volts)   6.3 6.3   脉冲电压(volts) Pulse voltage (volts)   950 950   重复次数 repeat times   4 4   清洗时间/s Cleaning time/s   20 20   CeO氧化物 CeO oxide   ≤0.03 ≤0.03   双电荷(Ba++) double charge (Ba++)   ≤0.03 ≤0.03

2.使用试剂2. Using Reagents

2.1实验用水为GB6682规定的二级水,化学试剂均为优级纯以上。2.1 The experimental water is the second-grade water specified in GB6682, and the chemical reagents are all above-grade pure.

2.2硼(B)标准储备溶液为100μg/mL(国家标准试剂,GBW)。2.2 Boron (B) standard stock solution is 100μg/mL (national standard reagent, GBW).

2.3B标准系列溶液,使用2.2标准储备溶液(GBW),用5%的HNO3逐级稀释成B元素浓度为0,1,2,5,10,20μg/L的标准系列溶液。2.3B standard series solution, using 2.2 standard stock solution (GBW), diluted step by step with 5% HNO3 to form a standard series solution with B element concentrations of 0, 1, 2, 5, 10, 20 μg/L.

2.465%(质量分数,下同)HNO3和30%H2O22.465% (mass fraction, the same below) HNO 3 and 30% H 2 O 2 .

2.510μg/mL Ge内标溶液(使用前用5%HNO3,稀释成15ng/mL)。2.510μg/mL Ge internal standard solution (diluted to 15ng/mL with 5% HNO3 before use).

2.6仪器调谐液(美国PE公司,含Be、Ce、Co、In、Pb、Mg、Rh、U1μg/L,Ba 10μg/L介质0.5%HNO3)。2.6 Instrument tuning solution (US PE company, containing Be, Ce, Co, In, Pb, Mg, Rh, U 1 μg/L, Ba 10 μg/L medium 0.5% HNO 3 ).

3.样品消解3. Sample Digestion

称取0.2g试样,精确至0.1mg,置于微波消解罐中,加入5mL HNO3和2mL H2O2消解12h后,将微波消解罐旋紧密封置于微波消解仪中进行消解,消解程序步骤如下,同时做未加样品溶液的空白溶液。Weigh 0.2g sample, accurate to 0.1mg, put it in a microwave digestion tank, add 5mL HNO 3 and 2mL H 2 O 2 to digest for 12h, then screw the microwave digestion tank tightly and place it in a microwave digestion instrument for digestion. The program steps are as follows, and a blank solution without sample solution is made at the same time.

(1)由室温升至100℃升温时间为5min,保持时间为5min。(1) The heating time from room temperature to 100°C is 5 minutes, and the holding time is 5 minutes.

(2)由100℃升至135℃升温时间为5min,保持时间为5min。(2) The heating time from 100°C to 135°C is 5 minutes, and the holding time is 5 minutes.

(3)由135℃升至165℃升温时间为5min,保持时间为5min。(3) The heating time from 135°C to 165°C is 5 minutes, and the holding time is 5 minutes.

(4)由165℃升至185℃升温时间为10min,保持时间为25min。(4) The heating time from 165°C to 185°C is 10 minutes, and the holding time is 25 minutes.

消解完毕,待温度降至室温后取出消解罐,直接将试样溶液转移至50mLPET容量瓶中,用纯水冲洗消解罐,清洗液一并转移至容量瓶中,然后用纯水定容至刻度,混匀。After the digestion is completed, take out the digestion tank after the temperature drops to room temperature, transfer the sample solution directly to a 50mL PET volumetric flask, rinse the digestion tank with pure water, transfer the cleaning solution to the volumetric flask, and then dilute to the mark with pure water , mix well.

4.校准曲线和样品测定4. Calibration Curve and Sample Determination

在表1.条件下,在线加入内标溶液(2.5),将B标准空白溶液、B标准系列溶液、烟用水基胶样品溶液和试剂空白液注入电感耦合等离子体质谱中,以待测元素B的含量与内标Ge元素含量的比值为横坐标,待测元素B质荷比强度与内标Ge元素质荷比强度的比值为纵坐标,建立硼的工作曲线。对校正数据进行线性回归,求得硼的回归方程:Y=0.054411X+0.000002,相关系数R、检出限分别为0.999976、0.12μg/L。Under the conditions of Table 1., add the internal standard solution (2.5) online, inject the B standard blank solution, the B standard series solution, the tobacco water-based glue sample solution and the reagent blank solution into the inductively coupled plasma mass spectrometer, and use the analyte B The ratio of the content of B to the content of the internal standard Ge element is the abscissa, the ratio of the mass-to-charge ratio of the element B to be measured to the mass-to-charge ratio of the internal standard Ge element is the ordinate, and the working curve of boron is established. Linear regression was performed on the calibration data to obtain the regression equation of boron: Y=0.054411X+0.000002, the correlation coefficient R and the detection limit were 0.999976 and 0.12 μg/L, respectively.

将测得的样品溶液中B元素和内标Ge元素的离子强度,使用所得的校准曲线计算获得烟用水基胶样品溶液中B元素浓度,再通过结果计算公式换算出烟用水基胶中硼酸的含量,结果见表3。The measured ionic strength of the B element in the sample solution and the internal standard Ge element is calculated using the obtained calibration curve to obtain the B element concentration in the tobacco water-based glue sample solution, and then the result calculation formula is used to calculate the concentration of boric acid in the tobacco water-based glue. Content, the results are shown in Table 3.

计算公式如下:Calculated as follows:

烟用水基胶中硼酸的含量以X表示,按式(I)进行计算:The content of boric acid in the tobacco water-based glue is represented by X, and is calculated according to formula (I):

Xx == (( CC -- CC 00 )) ×× VV 10001000 ×× mm ×× Ff .. .. .. (( II ))

式中:In the formula:

X——烟用水基胶中硼酸的含量,单位为微克每克(μg/g);X——the content of boric acid in the tobacco water-based adhesive, in micrograms per gram (μg/g);

C——烟用水基胶样品溶液中被测元素的浓度,单位为微克每升(μg/L);C—concentration of the measured element in the sample solution of the tobacco water-based adhesive, in micrograms per liter (μg/L);

C0——空白溶液中被测元素的浓度,单位为微克每升(μg/L);C 0 —concentration of the measured element in the blank solution, in micrograms per liter (μg/L);

V——烟用水基胶样品溶液中定容体积,单位为毫升(mL);V——the constant volume in the tobacco water-based adhesive sample solution, in milliliters (mL);

m——烟用水基胶样品质量,单位为克(g);m - the mass of the tobacco water-based adhesive sample, in grams (g);

F——硼换算为硼酸的系数,硼酸系数为5.72。F——The coefficient of converting boron into boric acid, and the coefficient of boric acid is 5.72.

计算结果保留三位有效数字。The calculation result retains three significant figures.

测得烟用水基胶样品1中的硼酸结果详见表2。The results of the measured boric acid in the tobacco water-based adhesive sample 1 are shown in Table 2.

表2烟用水基胶中硼酸含量的检测结果Table 2 Detection results of boric acid content in water-based adhesive for tobacco

  样品编号 Sample serial number   化合物 compound   含量(μg/g) Content (μg/g)   1 1   HBO3 HBO 3   2.851 2.851

实施例2Example 2

与实施例1的不同之处在于:The difference with Example 1 is:

1.测定方法仪器工作条件项下:雾化器流量0.67L/min,离子透镜电压6.4v。1. Measuring method Under the working conditions of the instrument: the nebulizer flow rate is 0.67L/min, and the ion lens voltage is 6.4v.

2.样品溶液的制备项下:称取烟用水基胶样品0.4g,精确至0.1mg,预消解14h。2. Under the preparation of the sample solution: weigh 0.4g of the tobacco water-based adhesive sample, accurate to 0.1mg, and pre-digest for 14h.

3.其它均同实施例1。3. Others are the same as in Example 1.

4.按照本实施例“测定方法”项的仪器工作条件对硼的标准空白溶液、硼标准系列溶液、空白样品溶液、烟用水基胶样品溶液进行测定,得到校准曲线回归方程:Y=0.010934X-0.000001,相关系数R:0.999991通过结果计算公式换算出烟用水基胶中硼酸的含量,测定10个不同品牌烟用水基胶中硼酸的含量,结果见表4。4. Measure the boron standard blank solution, boron standard series solution, blank sample solution, and tobacco water-based glue sample solution according to the instrument working conditions of the "measurement method" item of this embodiment, and obtain the calibration curve regression equation: Y=0.010934X -0.000001, correlation coefficient R: 0.999991 The content of boric acid in the tobacco water-based adhesive was converted by the result calculation formula, and the content of boric acid in the tobacco water-based adhesive of 10 different brands was measured. The results are shown in Table 4.

表4烟用水基胶样品中B和HBO3的分析结果(μg/g)Analysis results of B and HBO 3 in table 4 tobacco water-based adhesive samples (μg/g)

Figure BDA0000155920480000071
Figure BDA0000155920480000071

注:N.D.表示未检出。Note: N.D. means not detected.

实施例3Example 3

与实施例1的不同之处在于:The difference with Example 1 is:

1.测定方法仪器工作条件项下:雾化器流量0.66L/min,离子透镜电压6.0v。1. Measuring method Under the working conditions of the instrument: the nebulizer flow rate is 0.66L/min, and the ion lens voltage is 6.0v.

2.样品溶液的制备项下:称取烟用水基胶样品0.6g,精确至0.1mg,预消解16h。2. Under the item of sample solution preparation: weigh 0.6g of tobacco water-based glue sample, accurate to 0.1mg, and pre-digest for 16h.

3.其它均同实施例1。3. Others are the same as in Example 1.

4.按照本实施例“测定方法”项的仪器工作条件对硼的标准空白溶液、硼标准系列溶液、空白样品溶液、烟用水基胶样品溶液进行测定,得到校准曲线回归方程:Y=0.065521X+0.000003,R:0.999983,通过结果计算公式换算出烟用水基胶中硼酸的含量,测定编号12的烟用水基胶样品中硼酸的含量为1.790μg/g。4. Measure the boron standard blank solution, boron standard series solution, blank sample solution, and tobacco water-based glue sample solution according to the instrument working conditions of the "measurement method" item of this embodiment, and obtain the calibration curve regression equation: Y=0.065521X +0.000003, R: 0.999983, the content of boric acid in the tobacco water-based adhesive was converted by the result calculation formula, and the content of boric acid in the tobacco water-based adhesive sample No. 12 was measured to be 1.790 μg/g.

5.精密度试验:5. Precision test:

称取10号烟用水基胶样品6个0.5g的平行样,精确至0.1mg,按照本实施例3“样品溶液的制备”和测定方法仪器工作条件参数项进行测试,结果见表5。Weigh six 0.5g parallel samples of the No. 10 tobacco water-based adhesive sample, accurate to 0.1mg, and test according to this Example 3 "Preparation of sample solution" and the determination method instrument working condition parameters, and the results are shown in Table 5.

表5方法的精密度试验结果和茶叶标准物质的测定值The precision test result of table 5 method and the determined value of tea standard substance

Figure BDA0000155920480000081
Figure BDA0000155920480000081

6.稳定性试验6. Stability test

选用12号烟用水基胶样品,称取0.5g,精确至0.1mg,按照本实施例3“样品溶液的制备”和测定方法仪器工作条件参数项进行测试,在48h内对同一样品进行重复检测,结果见表6。Select No. 12 cigarette water-based glue sample, weigh 0.5g, accurate to 0.1mg, and test according to the "preparation of sample solution" in this example 3 and the parameters of the instrument's working conditions in the determination method, and repeat the test on the same sample within 48 hours , the results are shown in Table 6.

表6烟用水基胶中硼酸含量的稳定性试验结果Table 6 Stability test results of boric acid content in water-based adhesive for tobacco

Figure BDA0000155920480000082
Figure BDA0000155920480000082

Figure BDA0000155920480000091
Figure BDA0000155920480000091

6.回收率试验6. Recovery test

方法的回收率实验采用基质加标法,取三份12号烟用水基胶样品,分别添加高中低三个不同浓度的B标准溶液,按照本实施例3“样品溶液的制备”和测定方法仪器工作条件参数项进行测试,结果如下表7。The recovery rate experiment of the method adopts the matrix addition method. Take three samples of No. 12 cigarette water-based glue, and add B standard solutions with three different concentrations of high, medium and low respectively. The working condition parameter items are tested, and the results are shown in Table 7.

表7回收率试验结果Table 7 recovery rate test result

实施例1、2、3试验结果显示:采用本发明方法对烟用水基胶中硼酸含量进行定量测定,分析准确、灵敏度高、精密度高、且操作简便。The test results of Examples 1, 2, and 3 show that the quantitative determination of the boric acid content in the tobacco water-based glue by the method of the present invention is accurate, sensitive, precise, and easy to operate.

Claims (5)

1.一种烟用水基胶中硼酸含量的测定方法,包括以下步骤:1. a method for assaying boric acid content in water-based glue for tobacco, comprising the following steps: (1)称取0.2g~0.6g试样,精确至0.1mg,置于微波消解罐中,加入5mLHNO3和2mLH2O2消解12~16h;(1) Weigh 0.2g~0.6g sample, accurate to 0.1mg, put it in a microwave digestion tank, add 5mLHNO 3 and 2mLH 2 O 2 to digest for 12~16h; (2)将步骤(1)所述微波消解罐旋紧密封置于微波消解仪中进行消解,同时做未加试样的空白溶液;(2) Tighten and seal the microwave digestion tank described in step (1) and place it in a microwave digestion instrument for digestion, while making a blank solution without adding a sample; (3)消解完毕,待温度降至室温后取出消解罐,直接将试样溶液转移至50mLPET容量瓶中,用纯水冲洗消解罐,清洗液一并转移至容量瓶中,然后用纯水定容,摇匀后得试样溶液;(3) After the digestion is completed, take out the digestion tank after the temperature drops to room temperature, transfer the sample solution directly to a 50mL PET volumetric flask, rinse the digestion tank with pure water, transfer the cleaning solution to the volumetric flask, and then set the solution with pure water. volume, shake well to get the sample solution; (4)制备标准溶液:使用B标准储备溶液,用5%的HNO3逐级稀释成浓度为0μg/L,1μg/L,2μg/L,5μg/L,10μg/L,20μg/L的B标准溶液;(4) Preparation of standard solution: use B standard stock solution, dilute it step by step with 5% HNO3 to B standard solution; (5)绘制校准曲线:采用Ge标准溶液在线内标加入,内标Ge使用浓度为15μg/L,分别吸取标准空白溶液和不同浓度B的标准溶液,注入电感耦合等离子体质谱仪中,以待测元素B含量与对应内标元素Ge含量的比值为横坐标,待测元素B质荷比强度与对应内标元素Ge质荷比强度的比值为纵坐标,建立B的校准曲线;对校正数据进行线性回归,求得B的回归方程,R应不小于0.999;(5) Draw the calibration curve: adopt Ge standard solution online internal standard to add, internal standard Ge use concentration is 15 μ g/L, draw the standard blank solution and the standard solution of different concentration B respectively, inject in the inductively coupled plasma mass spectrometer, wait for The ratio of the measured element B content to the corresponding internal standard element Ge content is the abscissa, the ratio of the mass-to-charge ratio intensity of the element to be measured to the corresponding internal standard element Ge mass-to-charge ratio is the ordinate, and the calibration curve of B is established; Carry out linear regression to obtain the regression equation of B, and R should not be less than 0.999; (6)按步骤(5)方法测定步骤(3)样品溶液中B元素和内标Ge元素的离子强度,使用所得的校准曲线计算获得烟用水基胶样品溶液中B元素浓度;计算公式如下:(6) Measure the ionic strength of the B element and the internal standard Ge element in the step (3) sample solution according to the method of step (5), and use the obtained calibration curve to calculate and obtain the B element concentration in the tobacco water-based glue sample solution; the calculation formula is as follows: 烟用水基胶中硼酸的含量以X表示,按式(I)进行计算:The content of boric acid in the tobacco water-based glue is represented by X, and is calculated according to formula (I): Xx == (( CC -- CC 00 )) ×× VV 10001000 ×× mm ×× Ff .. .. .. (( II )) 式中:In the formula: X——烟用水基胶中硼酸的含量,单位为微克每克(μg/g);X——the content of boric acid in the tobacco water-based adhesive, in micrograms per gram (μg/g); C——烟用水基胶样品溶液中被测元素的浓度,单位为微克每升(μg/L);C—concentration of the measured element in the sample solution of the tobacco water-based adhesive, in micrograms per liter (μg/L); C0——空白溶液中被测元素的浓度,单位为微克每升(μg/L);C 0 —concentration of the measured element in the blank solution, in micrograms per liter (μg/L); V——烟用水基胶样品溶液中定容体积,单位为毫升(mL);V——the constant volume in the tobacco water-based adhesive sample solution, in milliliters (mL); m——烟用水基胶样品质量,单位为克(g);m - the mass of the tobacco water-based adhesive sample, in grams (g); F——硼换算为硼酸的系数,硼酸系数为5.72。F——The coefficient of converting boron into boric acid, and the coefficient of boric acid is 5.72. 2.根据权利要求1所述的烟用水基胶中硼酸含量的测定方法,其特征在于:所述步骤(2)中微波消解系统消解程序由以下四个步骤构成:2. the assay method of boric acid content in the tobacco water-based glue according to claim 1, is characterized in that: in described step (2), microwave digestion system digestion procedure is made of following four steps: (1)由室温升至100℃升温时间为5min,保持时间为5min;(1) The heating time from room temperature to 100°C is 5 minutes, and the holding time is 5 minutes; (2)由100℃升至135℃升温时间为5min,保持时间为5min;(2) The heating time from 100°C to 135°C is 5 minutes, and the holding time is 5 minutes; (3)由135℃升至165℃升温时间为5min,保持时间为5min;(3) The heating time from 135°C to 165°C is 5 minutes, and the holding time is 5 minutes; (4)由165℃升至185℃升温时间为10min,保持时间为25min。(4) The heating time from 165°C to 185°C is 10 minutes, and the holding time is 25 minutes. 3.根据权利要求1所述的烟用水基胶中硼酸含量的测定方法,其特征在于:所述步骤(4)中制备标准溶液的具体步骤:准确吸取1mL硼标准储备溶液到100mL的容量瓶中,用1%HNO3溶液稀释定容至刻度,获得1μg/mL的标准溶液;分别移取硼标准溶液0,0.1,0.2,0.5,1.0,2.0mL于100mL塑料容量瓶中,用5%HNO3溶液定容至刻度,容量瓶中溶液浓度为0μg/L,1μg/L,2μg/L,5μg/L,10μg/L,20μg/L的B标准溶液。3. the assay method of boric acid content in the tobacco water-based glue according to claim 1, is characterized in that: the concrete step of preparing standard solution in described step (4): accurately draw 1mL boron standard stock solution to the volumetric flask of 100mL , dilute with 1% HNO 3 solution to the mark to obtain a standard solution of 1 μg/mL; pipette boron standard solutions 0, 0.1, 0.2, 0.5, 1.0, 2.0mL into 100mL plastic volumetric flasks, and use 5% The HNO 3 solution was adjusted to the mark, and the solution concentration in the volumetric flask was 0μg/L, 1μg/L, 2μg/L, 5μg/L, 10μg/L, 20μg/L B standard solution. 4.根据权利要求1所述的烟用水基胶中硼酸含量的测定方法,其特征在于:所述步骤(5)中电感耦合等离子体质谱仪的工作条件为:真空度、雾化器流量、辅助气流量、等离子体气体流量、射频功率、扫描模式、扫描次数、离子透镜电压、脉冲电压、重复次数、清洗时间、CeO氧化物、双电荷分别为≤1.2×10-6、0.66~0.68、1.2、15、1300、Peak Jumping、20、6.0~6.4、950、4、20、≤0.03、≤0.03;同时,为了有效地减少信号漂移和基体效应对测定的影响,在线加入Ge作为内标。4. the assay method of boric acid content in the water-based glue for tobacco according to claim 1, is characterized in that: the operating condition of inductively coupled plasma mass spectrometer in described step (5) is: degree of vacuum, atomizer flow rate, Auxiliary gas flow, plasma gas flow, RF power, scan mode, scan times, ion lens voltage, pulse voltage, repetition times, cleaning time, CeO oxide, double charge ≤1.2×10 -6 , 0.66~0.68, 1.2, 15, 1300, Peak Jumping, 20, 6.0~6.4, 950, 4, 20, ≤0.03, ≤0.03; at the same time, in order to effectively reduce the influence of signal drift and matrix effect on the determination, Ge was added online as an internal standard. 5.根据权利要求1所述的烟用水基胶中硼酸含量的测定方法,其特征在于:所述的测定方法中器皿均为塑料容器,并经25%HNO3溶液浸泡12~16h后,用纯水洗涤干净后备用;在测定硼含量较高的溶液后,采用5%硝酸冲洗进样系统以消除硼的记忆效应。5. the assay method of boric acid content in the water-based glue for tobacco according to claim 1 is characterized in that: in the described assay method, utensils are all plastic containers, and through 25% HNO After solution soaking 12~16h, use Wash it with pure water and use it for later use; after measuring the solution with high boron content, use 5% nitric acid to flush the sampling system to eliminate the memory effect of boron.
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CN103399079A (en) * 2013-08-02 2013-11-20 广西中烟工业有限责任公司 Applications of inductively coupled plasma mass spectrometry in boron detection of water-based gel
CN103399079B (en) * 2013-08-02 2015-04-29 广西中烟工业有限责任公司 Applications of inductively coupled plasma mass spectrometry in boron detection of water-based gel
CN108414675A (en) * 2018-01-25 2018-08-17 中国科学院青岛生物能源与过程研究所 A method of quickly measuring low concentration boric acid in aqueous solution using pH meter
CN108414675B (en) * 2018-01-25 2020-11-03 中国科学院青岛生物能源与过程研究所 A kind of method that utilizes pH meter to quickly measure low concentration boric acid in aqueous solution
CN109342538A (en) * 2018-12-17 2019-02-15 南通新宙邦电子材料有限公司 A kind of quality detecting method of aluminum capacitor electrolyte boric acid
CN109342538B (en) * 2018-12-17 2021-02-12 南通新宙邦电子材料有限公司 Quality detection method of boric acid for aluminum capacitor electrolyte
CN110988098A (en) * 2019-11-19 2020-04-10 甘肃烟草工业有限责任公司 Method for measuring various heavy metals in water-based adhesive for cigarettes after direct dilution
CN112986481A (en) * 2021-02-25 2021-06-18 中国原子能科学研究院 Method and equipment for measuring boron content in nuclear power station loop
CN113155940A (en) * 2021-04-20 2021-07-23 云南省烟草质量监督检测站 Method for determining heavy metal elements in cigarette blasting beads by inductively coupled plasma mass spectrometer

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Application publication date: 20120919