WO2021036570A1 - 一种确定海砂中氯离子含量的检测方法 - Google Patents

一种确定海砂中氯离子含量的检测方法 Download PDF

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WO2021036570A1
WO2021036570A1 PCT/CN2020/102548 CN2020102548W WO2021036570A1 WO 2021036570 A1 WO2021036570 A1 WO 2021036570A1 CN 2020102548 W CN2020102548 W CN 2020102548W WO 2021036570 A1 WO2021036570 A1 WO 2021036570A1
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filtrate
sea sand
powder
chloride ion
washed
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French (fr)
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杨政险
洪荣灿
卢林
蔡水坤
邓长泰
林晓晖
林修清
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福州大学
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Priority to US17/290,784 priority Critical patent/US11940431B2/en
Publication of WO2021036570A1 publication Critical patent/WO2021036570A1/zh

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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00—Sampling; Preparing specimens for investigation
    • G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
    • G01N31/16—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using titration
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00—Sampling; Preparing specimens for investigation
    • G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
    • G01N1/34—Purifying; Cleaning
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00—Sampling; Preparing specimens for investigation
    • G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
    • G01N1/38—Diluting, dispersing or mixing samples
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00—Sampling; Preparing specimens for investigation
    • G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
    • G01N1/40—Concentrating samples
    • G01N1/4077—Concentrating samples by other techniques involving separation of suspended solids
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/24—Earth materials
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00—Sampling; Preparing specimens for investigation
    • G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
    • G01N1/38—Diluting, dispersing or mixing samples
    • G01N2001/386—Other diluting or mixing processes
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00—Sampling; Preparing specimens for investigation
    • G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
    • G01N1/40—Concentrating samples
    • G01N1/4077—Concentrating samples by other techniques involving separation of suspended solids
    • G01N2001/4088—Concentrating samples by other techniques involving separation of suspended solids filtration

Definitions

  • the invention belongs to the technical field of chloride ion content detection, and specifically relates to a detection method for determining the chloride ion content in sea sand.
  • sea sand is a better substitute for river sand, with good grain shape, low cost, low mud content and abundant reserves.
  • the rational use of sea sand is of great significance to the construction of infrastructure and the sustainable development of society.
  • chloride salts in sea sand which can accelerate the corrosion of steel bars and greatly reduce the durability of concrete structures.
  • the country allows the use of purified sea sand that meets the requirements of the standard, actual engineering investigations have found that the phenomenon of concrete structure damage caused by chloride ions is still widespread. This is mainly because the purified sea sand has many problems in the detection of chloride ion content. The problems are summarized as follows:
  • the preparation method of the filtrate to be tested is not targeted: the filtrate to be tested for chloride ions can be obtained from sea sand regardless of fresh water purification or grinding and filtration, but the sea sand before and after grinding and crushing has a larger particle size and chloride ion concentration. The difference; if the same method is used to prepare the test solution, it is easy to cause the chloride ion to be incompletely dissolved, and ultimately affect the detection result of the chloride ion content.
  • test result lacks reference and is difficult to correct: In the current chloride ion content test, the same solution is often tested one or more times. Even if the test results are multiple times, the arithmetic average is simply calculated, and the test results often vary. The inability to refer to and compare each other makes it difficult to correct the detection error.
  • the present invention provides a detection method that can accurately measure the chloride ion content in sea sand. It processes sea sand samples in steps, and then detects different filtrates of the same sea sand sample. The quality of chloride ions, and the comparison, analysis and correction of the detection results have significantly improved the accuracy of the detection results of the chloride ion content.
  • a detection method for determining the chloride ion content in sea sand is carried out as follows:
  • Step 1 Prepare water-washed filtrate
  • step 2 After drying the washed sea sand obtained in step 1 until the surface is dry, grind the washed sea sand into a sea sand powder with a fineness of not less than 100 mesh, and then add the sea sand powder to deionized water and fully stir for 5-10 minutes, then Filtering to obtain a powder filtrate; wherein the mass ratio of the dried washed sea sand to the deionized water is 1:1.5 ⁇ 2.5;
  • Step 4 Determine the quality of chloride ions in different filtrates
  • Step 5 Determine the content of chloride ions in sea sand
  • the a is the sum of the chloride ion mass H 1 in the other water-washed filtrate measured in step 4 and the chloride ion mass H 2 in the other powder filtrate measured in step 4
  • the ratio of chloride ion mass H 3 in the mixed filtrate measured in step 4, namely a (H 1 +H 2 )/H 3 ;
  • the remaining water-washed filtrate and another powder filtrate are placed in the same thermostat. (Ensure that the mixed filtrate, water-washed filtrate and powder filtrate have the same temperature during testing). So as to ensure the consistency of the test results of each filtrate.
  • step 4 when the quality of chloride ions in different filtrates is determined by silver nitrate titration, a potassium chromate aqueous solution with a mass fraction of 5% is used as an indicator, and the dropping volume of the potassium chromate aqueous solution is compared with the amount used in the titration.
  • the ratio of the volume of the mixed filtrate, the volume of the other water-washed filtrate to the volume of the other powder filtrate is 1:50.
  • a drying oven with a temperature of 100-110°C is used for drying in the first and second steps; the temperature of the thermostat in the third step is controlled to be 25-35°C.
  • the stirring in step 1 and step 2 adopts a magnetic stirrer
  • the rotation speed of the magnetic stirrer is 800-1500 r/min
  • the maximum heating temperature during the stirring process of the magnetic stirrer is 120°C.
  • the present invention first washes and filters the sea sand to avoid the loss of chloride ions on the surface of the sea sand caused by direct crushing, and then crushes the washed sea sand to promote the sea sand surface to be tightly coated with the film and the chloride ions in the cracks to a greater extent Released from the ground; targeted treatment of sea sand step by step provides a scientific guarantee for the authenticity of the test results of chloride ion content in sea sand.
  • the present invention adopts different methods to prepare the filtrate to be tested before and after the sea sand grinding, which realizes the dissolution of chloride ions to a greater extent, while also greatly shortening the detection time and reducing the detection error of the chloride ion content.
  • the invention provides a detection method for determining the chloride ion content in sea sand.
  • the present invention will be described in detail below in conjunction with specific embodiments.
  • a detection method for determining the chloride ion content in sea sand is carried out as follows:
  • Step 1 Prepare water-washed filtrate
  • step 2 After drying the washed sea sand obtained in step 1 until the surface is dry, grind the washed sea sand into a sea sand powder with a fineness of not less than 100 mesh, and then add the sea sand powder to deionized water and fully stir for 5-10 minutes, then Filtering to obtain a powder filtrate; wherein the mass ratio of the dried washed sea sand to the deionized water is 1:1.5 ⁇ 2.5;
  • Step 4 Determine the quality of chloride ions in different filtrates
  • Step 5 Determine the content of chloride ions in sea sand
  • the a is the sum of the chloride ion mass H 1 in the other water-washed filtrate measured in step 4 and the chloride ion mass H 2 in the other powder filtrate measured in step 4
  • the ratio of chloride ion mass H 3 in the mixed filtrate measured in step 4, namely a (H 1 +H 2 )/H 3 ;
  • the remaining water-washed filtrate and another powder filtrate are placed in the same thermostat. (Ensure that the mixed filtrate, water-washed filtrate and powder filtrate have the same temperature during testing). So as to ensure the consistency of the test results of each filtrate.
  • step 4 when the quality of chloride ions in different filtrates is determined by silver nitrate titration, a potassium chromate aqueous solution with a mass fraction of 5% is used as an indicator, and the dropping volume of the potassium chromate aqueous solution is compared with the amount used in the titration.
  • the ratio of the volume of the mixed filtrate, the volume of the other water-washed filtrate to the volume of the other powder filtrate is 1:50.
  • a drying oven with a temperature of 100-110°C is used for drying in the first and second steps; the temperature of the thermostat in the third step is controlled to be 25-35°C.
  • the stirring in step 1 and step 2 adopts a magnetic stirrer
  • the rotation speed of the magnetic stirrer is 800-1500 r/min
  • the maximum heating temperature during the stirring process of the magnetic stirrer is 120°C.
  • the formula for calculating chloride ion content in sea sand using silver nitrate titration method is:
  • Q is the chloride ion content percentage (%) in the sea sand sample to be tested
  • C is the concentration of silver nitrate standard solution (mol/L)
  • V is the volume of silver nitrate standard solution consumed during titration (mL)
  • D It is the volume (mL) of the silver nitrate standard solution consumed in the blank test
  • 0.03545 is the millimolar mass of chloride ion (g/mmol)
  • ⁇ is the ratio of the total volume of the solution to be tested to the volume of the solution taken during the silver nitrate titration.
  • the chloride ion content in the sea sand sample to be tested is:
  • V 1 is the volume of silver nitrate standard solution consumed during the titration of the sample of the water-washed filtrate (mL)
  • V 2 is the volume of silver nitrate standard solution consumed during the titration of the powder filtrate sample (mL)
  • V 3 is the mixed filtrate
  • ⁇ 1 is the ratio of the total volume of the washing solution to the volume of the washing solution taken during the silver nitrate titration
  • ⁇ 2 is the total volume of the powder solution and the silver nitrate titration
  • ⁇ 3 is the ratio of the total volume of the mixed solution to the volume of the mixed solution taken during the titration of silver nitrate.
  • the test method in GB/T 14684-2011 "Sand for Construction" is used to calculate the chloride ion content in sea sand. Take 1000g of the sea sand sample from the same source as in the application example 1 above and place it in a drying oven to dry to a constant weight, and then cool it for later use; weigh 500g of dry sand into a ground-mouth flask, and pour 500mL of distilled water into the ground-mouth flask.
  • the test method in GB/T 14684-2011 "Sand for Construction" is used to calculate the chloride ion content in sea sand. Take 1000g of the sea sand sample from the same source as in the application example 2 above and place it in a drying oven to dry it to a constant weight, and then cool it for later use; weigh 500g of dry sand into a ground-mouth flask, and pour 500mL of distilled water into the ground-mouth flask.
  • the test method in GB/T14684-2011 "Sand for Construction” is used to calculate the chloride ion content in sea sand. Take 1000g of the sea sand sample from the same source as in Application Example 3 above and place it in a drying oven to dry to constant weight, and then cool it for later use; weigh 500g of dry sand into a ground-mouth flask, and pour 500mL of distilled water into the ground-mouth flask.
  • breaking the sea sand can promote the release of chloride ions in the tight coating film on the surface of the sea sand and the release of chloride ions in the cracks; at the same time, different methods are used to prepare the filtrate to be tested before and after the sea sand grinding, which can achieve the dissolution of chloride ions to a greater extent. At the same time, it greatly shortens the detection time and reduces the detection error of the chloride ion content.

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Abstract

本发明涉及一种确定海砂中氯离子含量的检测方法，按如下步骤进行：将烘干至恒重的海砂加入煮沸的去离子水中充分搅拌、静置和过滤，得到水洗海砂和水洗滤液；将水洗海砂研磨为海砂粉末，将海砂粉末加入去离子水中充分搅拌过滤得到粉末滤液；量取一半水洗滤液和一半粉末滤液进行混合搅拌制取混合滤液；采用硝酸银滴定法分别测定水洗滤液、粉末滤液和混合滤液的氯离子含量，并对检测结果进行分析和修正，得到海砂中的氯离子含量。本发明促使海砂表面紧密包覆膜及裂缝中的氯离子较大程度地释放出来，为海砂中氯离子含量检测结果的真实性提供了科学的保障；快速地实现氯离子的溶解，极大地缩短了检测时间，显著地提高了氯离子含量检测结果的准确度。

Description

一种确定海砂中氯离子含量的检测方法 技术领域
本发明属于氯离子含量检测技术领域，具体涉及一种确定海砂中氯离子含量的检测方法。
背景技术
目前，我国砂石资源呈现逐渐减少甚至枯竭的趋势，海砂是一种较好的河砂替代品，其粒形好、成本低、含泥量少以及储量十分丰富。合理利用海砂对基础设施建设和社会的可持续发展具有重大的意义。但是海砂中存在着氯盐杂质，氯盐能加速钢筋的锈蚀，极大的降低了混凝土结构的耐久性。虽然国家允许使用净化处理且符合标准要求的海砂，但实际工程调查发现：由氯离子导致混凝土结构破坏的现象依然普遍存在。这主要是由于经过净化处理的海砂在氯离子含量检测时存在着诸多问题，问题汇总如下：
(1)待测海砂处理不当：现有的氯离子含量检测方法对海砂的处理往往不够彻底，这主要是由于海砂裂缝和孔隙中的氯离子被海洋中的有机物质紧密包裹处于一种稳定状态，而采用常温浸泡或振荡的方法均无法将残留在海砂裂缝和孔隙中的氯离子释放出来，从而使得海砂中氯离子含量的测量值比实际值明显偏低；此类海砂应用到建筑工程中将会导致危害建筑物结构安全问题的发生。
(2)待测滤液的制取方法没有针对性：海砂无论经过淡水净化还是研磨过滤均可得到氯离子待测滤液，但是研磨破碎前后海砂在粒径大小和氯离子浓度上存在较大差别；若采用同种方法制取待测液，容易导致氯离子溶解不彻底，最终影响氯离子含量的检测结果。
(3)检测结果缺乏参照难以修正：现有氯离子含量检测时，往往是对同一溶液进行一次或多次检测，即使是多次检测也只是简单的求取算术平均值，检测结果之间往往不能相互参照和对比，使得检测误差难以修正。
(4)常见的氯离子检测方法花费时间较长，长时间的实验极易让操作人员产生疲劳感，从而增加了出现实验误差的概率。
因此，根据实际需要对确定海砂中氯离子含量的检测方法进行优化具有重要的意义。
发明内容
为了解决现有技术存在的问题，本发明提供了一种能准确测量海砂中氯离子含量的检测方法，它分步骤处理海砂样品，然后分别进行检测同一海砂样品的不同待测滤液的氯离子质量，并对检测结果进行对比、分析及修正，显著地提高了氯离子含量检测结果的准确度。
为了实现上述目的，本发明是通过如下的技术方案来实现：一种确定海砂中氯离子含量的检测方法，按如下步骤进行：
步骤一：制取水洗滤液；
取海砂待测样品烘干至恒重，然后称取质量为G 0的烘干海砂待测样品，之后加入煮沸的去离子水中充分搅拌3～6min，然后静置10～15min，之后过滤得到水洗海砂和水洗滤液；在搅拌过程中通过加热保持去离子水的温度不低于90℃；其中用来混合搅拌的烘干海砂待测样品与所述的去离子水的质量比为1:1.5～2.5；
步骤二：制取粉末滤液；
将步骤一得到的水洗海砂烘干至表面无水后，将水洗海砂研磨为细度不小于100目的海砂粉末，然后将所述海砂粉末加入去离子水中充分搅拌5～10min，之后过滤得到粉末滤液；其中烘干后的水洗海砂与所述的去离子水的质量比为1:1.5～2.5；
步骤三：制取混合滤液；
先将步骤一制得的水洗滤液和步骤二制得的粉末滤液放置于恒温箱中静置15～20min，然后分别将静置后的水洗滤液和静置后的粉末滤液分别平均分成2份，之后将其中一份水洗滤液和其中一份粉末滤液混合得到混合滤液，剩下的另一份水洗滤液和另一份粉末滤液分别单独待用；
步骤四：测定不同滤液中氯离子质量；
取相同体积的步骤三中混合滤液、另一份水洗滤液和另一份粉末滤液，采用硝酸银滴定法分别测定得到另一份水洗滤液中的氯离子质量H 1、另一份粉末滤液中的氯离子质量H 2和混合滤液中氯离子质量H 3；
步骤五：确定海砂中氯离子的含量；
首先，计算a值：所述a为步骤四所测得的另一份水洗滤液中的氯离子质量H 1和步骤四所测得的另一份粉末滤液中的氯离子质量H 2之和与步骤四所测得的混合滤液中氯离子质量H 3的比值，即a＝(H 1+H 2)/H 3；
之后，当0.850≤a≤1.150时，直接按以下三种状况确定海砂中氯离子含量Q；当a值小于0.850或a值大于1.150时，重复步骤四并重新计算a值直到0.850≤a≤1.150时，再按以下三种状况确定海砂中氯离子含量Q：
状况一：当0.850≤a＜0.975时，海砂中氯离子总质量H为：H＝m(H 1+H 2)+H 3；则海砂中氯离子含量Q为：
Figure PCTCN2020102548-appb-000001
状况二：当0.975≤a≤1.025时，海砂中氯离子总质量H为：H＝H 1+H 2+H 3；则海砂中氯离子含量Q为：
Figure PCTCN2020102548-appb-000002
状况三：当1.025＜a≤1.150时，海砂中氯离子总质量H为：H＝H 1+H 2+nH 3；则海砂中氯离子含量Q为：
Figure PCTCN2020102548-appb-000003
其中：m、n为系数，m＝1+(1-a)＝2-a；n＝1+(a-1)＝a。
进一步地，步骤三制备完成混合滤液后，将剩下的另一份水洗滤液和另一份粉末滤液放置于同一个恒温箱中。(保证混合滤液、水洗滤液和粉末滤液在检测时温度相同)。从而能保证各个滤液检测结果的一致性。
进一步地，步骤四采用硝酸银滴定法测定不同滤液中氯离子质量时，采用质量分数为5％的铬酸钾水溶液作为指示剂，所述铬酸钾水溶液的滴入体积与滴定时所使用的混合滤液的体积、另一份水洗滤液的体积和另一份粉末滤液的体积之比均为1:50。
进一步地，所述步骤一和步骤二烘干时采用温度为100～110℃的干燥箱；步骤三所述的恒温箱的温度控制为25～35℃。
进一步地，步骤一和步骤二所述搅拌采用磁力搅拌机，所述磁力搅拌机的转速为800～1500r/min，所述磁力搅拌机搅拌过程中加热的最大温度为120℃。
本发明的有益效果为：
1、本发明先将海砂水洗过滤，避免了直接破碎导致海砂表面氯离子的损失，再将水洗后的海砂破碎，促使海砂表面紧密包覆膜及裂缝中的氯离子较大程度地释放出来；分步骤对海砂进行针对性处理，为海砂中氯离子含量检测结果的真实性提供了科学的保障。
2、本发明在海砂研磨前后采用不同的方法制取待测滤液，较大程度上实现氯离子溶解的同时，还极大地缩短了检测时间，降低了氯离子含量的检测误差。
3、本发明对同一海砂样品得到的不同待测滤液，分别进行检测得到氯离子质量，并对检测结果进行对比、分析及修正，显著地提高了氯离子含量检测结果的准确度。
具体实施方式
本发明提供的是一种确定海砂中氯离子含量的检测方法。为更进一步阐述本发明所采用的技术手段及功效，下面结合具体实施方式，对本发明进行详细的说明。
一)具体实施方式
实施例中一种确定海砂中氯离子含量的检测方法，按如下步骤进行：
步骤一：制取水洗滤液；
取海砂待测样品烘干至恒重，然后称取质量为G 0的烘干海砂待测样品，之后加入煮沸的去离子水中充分搅拌3～6min，然后静置10～15min，之后过滤得到水洗海砂和水洗滤液；在搅拌过程中通过加热保持去离子水的温度不低于90℃；其中用来混合搅拌的烘干海砂待测样品与所述的去离子水的质量比为1:1.5～2.5；
步骤二：制取粉末滤液；
将步骤一得到的水洗海砂烘干至表面无水后，将水洗海砂研磨为细度不小于100目的海砂粉末，然后将所述海砂粉末加入去离子水中充分搅拌5～10min，之后过滤得到粉末滤液；其中烘干后的水洗海砂与所述的去离子水的质量比为1:1.5～2.5；
步骤三：制取混合滤液；
先将步骤一制得的水洗滤液和步骤二制得的粉末滤液放置于恒温箱中静置15～20min，然后分别将静置后的水洗滤液和静置后的粉末滤液分别平均分成2份，之后将其中一份水洗滤液和其中一份粉末滤液混合得到混合滤液，剩下的另一份水洗滤液和另一份粉末滤液分别单独待用；
步骤四：测定不同滤液中氯离子质量；
取相同体积的步骤三中混合滤液、另一份水洗滤液和另一份粉末滤液，采用硝酸银滴定法分别测定得到另一份水洗滤液中的氯离子质量H 1、另一份粉末滤液中的氯离子质量H 2和混合滤液中氯离子质量H 3；
步骤五：确定海砂中氯离子的含量；
首先，计算a值：所述a为步骤四所测得的另一份水洗滤液中的氯离子质量H 1和步骤四所测得的另一份粉末滤液中的氯离子质量H 2之和与步骤四所测得的混合滤液中氯离子质量H 3的比值，即a＝(H 1+H 2)/H 3；
之后，当0.850≤a≤1.150时，直接按以下三种状况确定海砂中氯离子含量Q；当a值小于0.850或a值大于1.150时，重复步骤四并重新计算a值直到0.850≤a≤1.150时，再按以下三种状况确定海砂中氯离子含量Q：
状况一：当0.850≤a＜0.975时，海砂中氯离子总质量H为：H＝m(H 1+H 2)+H 3；则海砂中氯离子含量Q为：
Figure PCTCN2020102548-appb-000004
状况二：当0.975≤a≤1.025时，海砂中氯离子总质量H为：H＝H 1+H 2+H 3；则海砂中氯离子含量Q为：
Figure PCTCN2020102548-appb-000005
状况三：当1.025＜a≤1.150时，海砂中氯离子总质量H为：H＝H 1+H 2+nH 3；则海砂中氯离子含量Q为：
Figure PCTCN2020102548-appb-000006
其中：m、n为系数，m＝1+(1-a)＝2-a；n＝1+(a-1)＝a。
进一步地，步骤三制备完成混合滤液后，将剩下的另一份水洗滤液和另一份粉末滤液放置于同一个恒温箱中。(保证混合滤液、水洗滤液和粉末滤液在检测时温度相同)。从而能保证各个滤液检测结果的一致性。
进一步地，步骤四采用硝酸银滴定法测定不同滤液中氯离子质量时，采用质量分数为5％的铬酸钾水溶液作为指示剂，所述铬酸钾水溶液的滴入体积与滴定时所使用的混合滤液的体积、另一份水洗滤液的体积和另一份粉末滤液的体积之比均为1:50。
进一步地，所述步骤一和步骤二烘干时采用温度为100～110℃的干燥箱；步骤三所述的恒温箱的温度控制为25～35℃。
进一步地，步骤一和步骤二所述搅拌采用磁力搅拌机，所述磁力搅拌机的转速为800～1500r/min，所述磁力搅拌机搅拌过程中加热的最大温度为120℃。
相关理论依据：
采用硝酸银滴定法计算海砂中氯离子含量的公式为：
Figure PCTCN2020102548-appb-000007
式中：Q为海砂待测样品中氯离子含量百分比(％)，C为硝酸银标准溶液的浓度(mol/L)，V为滴定时消耗的硝酸银标准溶液的体积(mL)，D为空白试验时消耗的硝酸银标准溶液的体积(mL)，0.03545为氯离子的毫摩尔质量(g/mmol)，η为待测溶液总体积与硝酸银滴定时所取溶液的体积之比。
则有海砂中氯离子的总质量H＝C×(V-D)×0.03545×η；则海砂待测样品中氯离子含量为：
Figure PCTCN2020102548-appb-000008
利用海砂待测样品制取得到水洗滤液、粉末滤液和混合滤液后，采用硝酸银滴定法分别计算得到水洗滤液、粉末滤液和混合滤液中氯离子质量，其中：水洗滤液中 氯离子质量H 1＝C×(V 1-D)×0.03545×η 1；粉末滤液中氯离子质量H 2＝C×(V 2-D)×0.03545×η 2；混合滤液中氯离子质量H 3＝C×(V 3-D)×0.03545×η 3。
式中：V 1为水洗滤液的样品滴定时消耗的硝酸银标准溶液的体积(mL)，V 2为粉末滤液的样品滴定时消耗的硝酸银标准溶液的体积(mL)，V 3为混合滤液的样品滴定时消耗的硝酸银标准溶液的体积(mL)，η 1为水洗溶液总体积与硝酸银滴定时所取水洗溶液的体积之比，η 2为粉末溶液总体积与硝酸银滴定时所取粉末溶液的体积之比，η 3为混合溶液总体积与硝酸银滴定时所取混合溶液的体积之比。
二)实施例
实施例1
将烘干至恒重的400g海砂待测样品倒入800ml煮沸的去离子水中，采用转速为1000r/min的磁力搅拌机充分搅拌5min，在搅拌过程中不断加热保持去离子水的温度为92℃，搅拌完成，静置12min后进行过滤，得到水洗海砂和580ml水洗滤液。将水洗海砂在干燥箱内烘干至表面无水后，采用球磨机将水洗海砂研磨为细度为100目的海砂粉末，将海砂粉末倒入800ml去离子水中充分搅拌10min后过滤得到520ml粉末滤液。将水洗滤液和粉末滤液放置于30℃恒温箱中20min后，分别量取290ml水洗滤液和260ml粉末滤液混合搅拌得到550ml混合滤液；将混合滤液与水洗滤液和粉末滤液放置于同一个恒温箱中，在30℃条件下保温15min。
用移液管分别取50ml的水洗滤液、50ml的粉末滤液和50ml的混合滤液注入三个不同的三角瓶中，在盛有水洗滤液、粉末滤液和混合滤液的三个三角瓶中均滴入质量分数为5％的铬酸钾溶液1.0ml；采用硝酸银滴定法分别得到水洗滤液中氯离子质量为0.264g、粉末滤液中氯离子质量为0.240g和混合滤液中氯离子质量为0.526g；则a值为0.958，利用本发明中状况一的方法计算得到海砂中氯离子含量为0.263％。
对照实例1：
采用GB/T 14684-2011《建设用砂》中的测试方法计算海砂中的氯离子含量。取与上述应用实例1中来源相同的海砂样品1000g置于干燥箱烘干至恒重后，冷却备用；称取500g干砂倒入磨口瓶中，向磨口瓶中注入500mL的蒸馏水，盖上塞子，摇动一次后放置2h，然后每隔5min摇动一次，共摇动3次；将溶液过滤后进行两次硝酸银滴定法测量氯离子含量，计算两次试验结果的算术平均值得到氯离子含量为0.135％。
实施例2
将烘干至恒重的400g海砂倒入600ml煮沸的去离子水中，采用转速为1200r/min的磁力 搅拌机充分搅拌4min，在搅拌过程中不断加热保持去离子水的温度为90℃，搅拌完成，静置10min后进行过滤，得到水洗海砂和380ml水洗滤液。将水洗海砂在干燥箱内烘干至表面无水后，采用球磨机将水洗海砂研磨为细度为120目的海砂粉末，将海砂粉末倒入600ml去离子水中充分搅拌10min后过滤得到350ml粉末滤液。将水洗滤液和粉末滤液放置于30℃恒温箱中20min后，分别量取190ml水洗滤液和175ml粉末滤液混合搅拌得到365ml混合滤液；将混合滤液与水洗滤液和粉末滤液放置于同一个恒温箱中，在30℃条件下保温16min。
用移液管分别取50ml的水洗滤液、50ml的粉末滤液和50ml的混合滤液注入三个不同的三角瓶中，在盛有水洗滤液、粉末滤液和混合滤液的三个三角瓶中均滴入质量分数为5％的铬酸钾溶液1.0ml；采用硝酸银滴定法分别得到水洗滤液中氯离子质量为0.256g、粉末滤液中氯离子质量为0.230g和混合滤液中氯离子质量为0.496g；则a值为0.980，利用本发明中状况二的方法计算得到海砂中氯离子含量为0.246％。
对照实例2：
采用GB/T 14684-2011《建设用砂》中的测试方法计算海砂中的氯离子含量。取与上述应用实例2中来源相同的海砂样品1000g置于干燥箱烘干至恒重后，冷却备用；称取500g干砂倒入磨口瓶中，向磨口瓶中注入500mL的蒸馏水，盖上塞子，摇动一次后放置2h，然后每隔5min摇动一次，共摇动3次；将溶液过滤后进行两次硝酸银滴定法测量氯离子含量，计算两次试验结果的算术平均值得到氯离子含量为0.132％。
实施例3
将烘干至恒重的200g海砂倒入500ml煮沸的去离子水中，采用转速为1000r/min的磁力搅拌机充分搅拌6min，在搅拌过程中不断加热保持去离子水的温度为95℃，搅拌完成，静置15min后进行过滤，得到水洗海砂和370ml水洗滤液。将水洗海砂在干燥箱内烘干至表面无水后，采用球磨机将水洗海砂研磨为细度为120目的海砂粉末，将海砂粉末倒入500ml去离子水中充分搅拌6min后过滤得到340ml粉末滤液。将水洗滤液和粉末滤液放置于30℃恒温箱中20min后，分别量取185ml水洗滤液和170ml粉末滤液混合搅拌得到355ml混合滤液；将混合滤液与水洗滤液和粉末滤液放置于同一个恒温箱中，在30℃条件下保温15min。
用移液管分别取50ml的水洗滤液、50ml的粉末滤液和50ml的混合滤液注入三个不同的三角瓶中，在盛有水洗滤液、粉末滤液和混合滤液的三个三角瓶中均滴入质量分数为5％的铬酸钾溶液1.0ml；采用硝酸银滴定法分别得到水洗滤液的氯离子质量为0.158g、粉末滤液的氯离子质量为0.126g和混合滤液的氯离子质量为0.255g；则a值为1.114，利用本发明中状况三的方法计算得到海砂中氯离子含量为0.284％。
对照实例3：
采用GB/T14684-2011《建设用砂》中的测试方法计算海砂中的氯离子含量。取与上述应用实例3中来源相同的海砂样品1000g置于干燥箱烘干至恒重后，冷却备用；称取500g干砂倒入磨口瓶中，向磨口瓶中注入500mL的蒸馏水，盖上塞子，摇动一次后放置2h，然后每隔5min摇动一次，共摇动3次；将溶液过滤后进行两次硝酸银滴定法测量氯离子含量，计算两次试验结果的算术平均值得到氯离子含量为0.154％。
由此可见，将海砂破碎可以促进海砂表面紧密包覆膜及裂缝中氯离子的释放；同时，在海砂研磨前后采用不同的方法制取待测滤液，较大程度上实现氯离子溶解的同时，还极大地缩短了检测时间，降低了氯离子含量的检测误差。
以上所述，仅为本发明的较佳实施例，但本发明的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明揭露的技术范围内，凡依本发明申请专利范围所做的均等变化与修饰，皆应属本发明的涵盖范围。

Claims (5)

  1. 一种确定海砂中氯离子含量的检测方法，其特征在于：按如下步骤进行：
    步骤一：制取水洗滤液；
    取海砂待测样品烘干至恒重，然后称取质量为G 0的烘干海砂待测样品，之后加入煮沸的去离子水中充分搅拌3～6min，然后静置10～15min，之后过滤得到水洗海砂和水洗滤液；在搅拌过程中通过加热保持去离子水的温度不低于90℃；其中用来混合搅拌的烘干海砂待测样品与所述的去离子水的质量比为1:1.5～2.5；
    步骤二：制取粉末滤液；
    将步骤一得到的水洗海砂烘干至表面无水后，将水洗海砂研磨为细度不小于100目的海砂粉末，然后将所述海砂粉末加入去离子水中充分搅拌5～10min，之后过滤得到粉末滤液；其中烘干后的水洗海砂与所述的去离子水的质量比为1:1.5～2.5；
    步骤三：制取混合滤液；
    先将步骤一制得的水洗滤液和步骤二制得的粉末滤液放置于恒温箱中静置15～20min，然后分别将静置后的水洗滤液和静置后的粉末滤液分别平均分成2份，之后将其中一份水洗滤液和其中一份粉末滤液混合得到混合滤液，剩下的另一份水洗滤液和另一份粉末滤液分别单独待用；
    步骤四：测定不同滤液中氯离子质量；
    取相同体积的步骤三中混合滤液、另一份水洗滤液和另一份粉末滤液，采用硝酸银滴定法分别测定得到另一份水洗滤液中的氯离子质量H 1、另一份粉末滤液中的氯离子质量H 2和混合滤液中氯离子质量H 3；
    步骤五：确定海砂中氯离子的含量；
    首先，计算a值：所述a为步骤四所测得的另一份水洗滤液中的氯离子质量 H 1和步骤四所测得的另一份粉末滤液中的氯离子质量H 2之和与步骤四所测得的混合滤液中氯离子质量H 3的比值，即a＝(H 1+H 2)/H 3；
    之后，当0.850≤a≤1.150时，直接按以下三种状况确定海砂中氯离子含量Q；当a值小于0.850或a值大于1.150时，重复步骤四并重新计算a值直到0.850≤a≤1.150时，再按以下三种状况确定海砂中氯离子含量Q：
    状况一：当0.850≤a＜0.975时，海砂中氯离子总质量H为：H＝m(H 1+H 2)+H 3；则海砂中氯离子含量Q为：
    Figure PCTCN2020102548-appb-100001
    状况二：当0.975≤a≤1.025时，海砂中氯离子总质量H为：H＝H 1+H 2+H 3；则海砂中氯离子含量Q为：
    Figure PCTCN2020102548-appb-100002
    状况三：当1.025＜a≤1.150时，海砂中氯离子总质量H为：H＝H 1+H 2+nH 3；则海砂中氯离子含量Q为：
    Figure PCTCN2020102548-appb-100003
    其中：m、n为系数，m＝1+(1-a)＝2-a；n＝1+(a-1)＝a。
  2. 根据权利要求1所述的一种确定海砂中氯离子含量的检测方法，其特征在于：步骤三制备完成混合滤液后，将剩下的另一份水洗滤液和另一份粉末滤液放置于同一个恒温箱中。
  3. 根据权利要求1所述的一种确定海砂中氯离子含量的检测方法，其特征在于：步骤四采用硝酸银滴定法测定不同滤液中氯离子质量时，采用质量分数为5％的铬酸钾水溶液作为指示剂，所述铬酸钾水溶液的滴入体积与滴定时所使用的混合滤液的体积、另一份水洗滤液的体积和另一份粉末滤液的体积之比均为1:50。
  4. 根据权利要求1所述的一种确定海砂中氯离子含量的检测方法，其特征在于：所述步骤一和步骤二烘干时采用温度为100～110℃的干燥箱；步骤三所述的 恒温箱的温度控制为25～35℃。
  5. 根据权利要求1所述的一种确定海砂中氯离子含量的检测方法，其特征在于：步骤一和步骤二所述搅拌采用磁力搅拌机，所述磁力搅拌机的转速为800～1500r/min，所述磁力搅拌机搅拌过程中加热的最大温度为120℃。
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