WO2019242430A1 - Procédé de détermination de la teneur en formaldéhyde dans un adjuvant du béton - Google Patents

Procédé de détermination de la teneur en formaldéhyde dans un adjuvant du béton Download PDF

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Publication number
WO2019242430A1
WO2019242430A1 PCT/CN2019/086849 CN2019086849W WO2019242430A1 WO 2019242430 A1 WO2019242430 A1 WO 2019242430A1 CN 2019086849 W CN2019086849 W CN 2019086849W WO 2019242430 A1 WO2019242430 A1 WO 2019242430A1
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Prior art keywords
sample
solution
ionic liquid
concrete admixture
sodium
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PCT/CN2019/086849
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English (en)
Chinese (zh)
Inventor
李格丽
方云辉
钟丽娜
郭元强
林添兴
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科之杰新材料集团有限公司
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Publication of WO2019242430A1 publication Critical patent/WO2019242430A1/fr

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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/04—Preparation or injection of sample to be analysed
    • G01N30/06—Preparation
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/96—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation using ion-exchange
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/04—Preparation or injection of sample to be analysed
    • G01N30/06—Preparation
    • G01N2030/062—Preparation extracting sample from raw material

Definitions

  • the invention belongs to the technical field of building material detection, and particularly relates to a method for testing the formaldehyde content in a concrete admixture.
  • Formaldehyde is a colorless, strongly irritating gas at room temperature, and is easily soluble in water, alcohol and ether. Formaldehyde is highly toxic to humans and animals, and has been identified by the World Health Organization as a carcinogen and teratogenic substance, and it is also one of the potentially strong mutagenic substances.
  • formaldehyde is widely used in the production of resins, plastics, rubbers, interior wall coatings, concrete admixtures, plywood and adhesives because of its ease of preparation, wide use, and low price.
  • concrete admixtures have been widely used in construction projects to improve the workability of concrete. With the widespread use of additives, some harmful substances in the additives will also be released, formaldehyde is one of them.
  • the release of formaldehyde in concrete admixtures mainly comes from polycyclic aromatic group sulfonates, water-soluble resin sulfonates, and aliphatic water reducing agents.
  • the amount of formaldehyde used tends to increase, which makes the free formaldehyde contained in the admixture and the formaldehyde generated during degradation will be released during use. It will cause formaldehyde pollution in buildings.
  • the state has imposed a compulsory limit on the limits of harmful substances in interior decoration and decoration, and has also limited the formaldehyde limit in concrete admixtures.
  • gas chromatography The most commonly used method in gas chromatography is gas chromatography, which is generally tested after derivatization with derivatizing reagents, but the problem of the separation of derivative isomers is difficult to solve, which limits its application; the instrument detection method is convenient to carry, the reading is intuitive, and the determination It is fast, but the detection of the instrument is severe and the price is high, which limits its general use; spectrophotometry is more commonly used, including acetylacetone spectrophotometry, phenol reagent method, 4-amino-3-hydrazine-5-thio- 1,2,4-triazacene spectrophotometry (AHMT method), chromic acid method, sulfurous acid fuchsin method, etc.
  • AHMT method 4-amino-3-hydrazine-5-thio- 1,2,4-triazacene spectrophotometry
  • the test method also has certain disadvantages, such as the need for distillation, and to prevent the distilled formaldehyde from volatilizing at high temperatures, Ice cube cooling is required at the distillate outlet, which is cumbersome and time-consuming, which brings great inconvenience to the operator; the formation of complexes needs to be held at 60 ° C for 30 minutes, and under normal temperature conditions, it takes longer and cannot be achieved Its rapid determination and testing in an environment containing SO 2 will also have a certain impact on the measurement results.
  • the purpose of the present invention is to overcome the defects of the prior art and provide a method for testing the formaldehyde content in concrete admixtures.
  • a method for testing the formaldehyde content in a concrete admixture includes the following steps:
  • Pretreatment of concrete admixture samples Single-drop liquid phase microextraction of ionic liquid headspace is used to process concrete admixture samples to obtain an extracted sample solution.
  • the first treatment solution and the first extraction solution are added to the extracted sample solution.
  • the second treatment liquid is extracted for 30 to 60 minutes. After the extraction, it is left to stand to obtain the working liquid of the sample to be tested, which is used.
  • the first treatment liquid is a strong alkali solution with a concentration of 0.1 to 0.5% by weight
  • the second treatment liquid is strong. Oxidant solution with a concentration of 0.1 to 0.5 wt%;
  • the above-mentioned single-drop liquid-phase microextraction of the ionic liquid headspace is: accurately weighing an appropriate amount of a concrete admixture sample into a headspace bottle, adding 1 to 2 mL of a surfactant, sealingly soaking for 10 to 20 minutes, and then extracting 2.5 to 3.5 ⁇ L
  • the extraction solution is inserted into the space above the sample to be measured in the headspace bottle, and the headspace extraction is performed for 5 to 10 minutes.
  • the resulting droplets are pumped back to the micro syringe, and the operation is repeated until the extraction is completed to obtain the extracted sample solution.
  • the above ion chromatograph uses IonPac AS18 anion analysis column, 4 ⁇ 250mm, IonPac AG18 guard column, 4 ⁇ 50mm, AERS500 4mm anion suppressor, suppressor current is 50mA, conductivity detector, and column temperature is 30 °C ⁇ 50 °C.
  • the injection volume is 10 ⁇ L to 30 ⁇ L, and the flow rate is 0.5 mL / min to 1.0 mL / min.
  • the eluent contains 15 mmol / L sodium hydroxide, 3 mmol / L sodium tetraborate, and 1.2 mmol / L sodium gluconate.
  • the solvent of the liquid is water.
  • the eluent is a mixed eluent (sodium (potassium) hydroxide eluent) composed of 15mmol / L sodium hydroxide-3mmol / L sodium tetraborate-1.2mmol / L sodium gluconate. Weak ability, requires higher concentration.
  • Sodium gluconate-sodium borate is an eluent with strong leaching ability, suitable for the determination of weak acid anions.
  • Sodium hydroxide is added to the sodium gluconate-sodium borate eluent. In the case of ensuring the leaching ability, it has a certain alkalinity, which is suitable for the determination of the weak acid anion formate).
  • the surfactant is Tween 20, polyoxyethylene octyl phenol ether-10 (OP-10), cocoic acid monoethanolamide sulfosuccinic acid monoester Disodium (DMSS) or potassium monododecyl phosphate (MAPK).
  • the extract is 1-hexyl-2,3-dimethylimidazole hexafluorophosphate ion liquid, 1-dodecyl-3-methylimidazole hexafluorophosphate ion Liquid, 1-butyl-2,3-dimethylimidazole tetrafluoroborate ionic liquid or 1-octyl-3-methylimidazole bis (trifluoromethylalkanesulfonyl) imide salt ionic liquid.
  • the strong base in the strong base solution is one of choline, guanidine, quaternary amine base, sodium methoxide, sodium ethoxide, potassium ethoxide, and sodium tert-butoxide.
  • the strong oxidant is one of hydrogen peroxide, sodium peroxide, and potassium peroxide.
  • the method of extraction in step (1) is ultrasound, shaking, constant temperature water bath or cold dipping.
  • the temperature of the constant temperature water bath is 40 to 60 ° C, and the temperature of the cold immersion is 0 to 10 ° C. Furthermore, the temperature of the constant temperature water bath is 50 ° C, and the temperature of the cold immersion is 5 ° C.
  • the temperature of the chromatographic column is 40 ° C.
  • the injection volume is 25 ⁇ L
  • the flow rate is 0.8 mL / min.
  • the present invention adopts the method of single-drop liquid phase microextraction combined with ionic liquid headspace to pretreat the concrete admixture, so as to separate the residual formaldehyde in the concrete admixture without going through the distillation step to avoid the target in the distillation process.
  • Overflow of objects reduces measurement errors, simple operation steps, time saving, convenient use of instruments, and strong operability.
  • the present invention uses an oxidant to oxidize the separated formaldehyde into formic acid under alkaline conditions, and then tests the formic acid by ion chromatography to indirectly test the content of formaldehyde.
  • the test has high sensitivity, effectively shortens the test time, and improves the test. effectiveness.
  • the present invention uses a mixed eluent to elute and analyze the sample, which has strong eluent ability and better separation effect. It can effectively separate weak acid anions from other ions, improve the resolution, and make the results of quantitative analysis more Accurate and reliable.
  • the present invention applies ion chromatography to the measurement of formaldehyde content in concrete admixtures, broadens the test method for formaldehyde content in concrete admixtures, and provides a new test method for the test of formaldehyde content in concrete admixtures.
  • Figure 1 is a liquid chromatogram of formic acid.
  • FIG. 2 is a liquid chromatogram of the working solution of the sample to be measured in Example 1 of the present invention.
  • the solvent peak is at a retention time near 3.40 min, and the peak is formic acid at a retention time near 8.30 min.
  • Metrohm China Ltd. Metrohm 883 ion chromatography system; IonPac AS18 anion analysis column; IonPac AG18 guard column; AERS500 4mm anion suppressor; METTLER TOLEDO Instrument (Shanghai) Co., Ltd.
  • the chromatographic conditions are: IonPac AS18 anion analysis column, 4 ⁇ 250mm, IonPac AG18 guard column, 4 ⁇ 50mm, AERS500 4mm anion suppressor, suppressor current is 50mA, conductivity detector, column temperature is 30 ° C, injection volume is 10 ⁇ L, the flow rate is 0.5 mL / min, the eluent contains 15 mmol / L sodium hydroxide, 3 mmol / L sodium tetraborate and 1.2 mmol / L sodium gluconate, and the solvent of the eluent is water. Take the working solution of the sample to be tested and pass it through a 0.45 ⁇ m microporous membrane to test it in an ion chromatograph.
  • Chromatographic conditions are: IonPac AS18 anion analysis column, 4 ⁇ 250mm, IonPac AG18 guard column, 4 ⁇ 50mm, AERS500 4mm anion suppressor, suppressor current is 50mA, conductivity detector, column temperature is 35 ° C, injection volume is 15 ⁇ L, the flow rate is 0.6 mL / min, the eluent contains 15 mmol / L sodium hydroxide, 3 mmol / L sodium tetraborate and 1.2 mmol / L sodium gluconate, and the solvent of the eluent is water.
  • Example 1 1.1 and 1.3 are the same as in Example 1.
  • the chromatographic conditions are: IonPac AS18 anion analysis column, 4 ⁇ 250mm, IonPac AG18 guard column, 4 ⁇ 50mm, AERS500 4mm anion suppressor, suppressor current is 50mA, conductivity detector, column temperature is 40 ° C, injection volume is 20 ⁇ L, with a flow rate of 0.7 mL / min, the eluent contains 15 mmol / L sodium hydroxide, 3 mmol / L sodium tetraborate, and 1.2 mmol / L sodium gluconate.
  • the solvent of the eluent is water.
  • Example 1 1.1 and 1.3 are the same as in Example 1.
  • sample 1 # 6.000g in the headspace bottle add 5mL of MAPK, and soak it for 20min in a sealed manner. Then use a 10 ⁇ L micro-syringe to extract 3 ⁇ L of 1-octyl-3-methylimidazole bis (trifluoromethylalkanesulfonyl) imide salt ionic liquid, insert it into the headspace of the sample to be measured, and extract it for 10min in the headspace. The liquid droplet is pumped back to the micro-syringe, and the operation is repeated, and the extraction is completed to obtain an extracted sample solution. Then, 4 mL of 0.4% sodium methoxide solution and 0.6 mL of 0.3% hydrogen peroxide solution were added, and cold immersion extraction was performed at 5 ° C for 40 minutes to obtain a working solution of the sample to be tested.
  • the chromatographic conditions are: IonPac AS18 anion analysis column, 4 ⁇ 250mm, IonPac AG18 guard column, 4 ⁇ 50mm, AERS500 4mm anion suppressor, suppressor current is 50mA, conductivity detector, column temperature is 40 ° C, injection volume is 25 ⁇ L, the flow rate is 0.8 mL / min, the eluent contains 15 mmol / L sodium hydroxide, 3 mmol / L sodium tetraborate and 1.2 mmol / L sodium gluconate, and the solvent of the eluent is water.
  • Example 1 1.1 and 1.3 are the same as in Example 1.
  • the chromatographic conditions are: IonPac AS18 anion analysis column, 4 ⁇ 250mm, IonPac AG18 guard column, 4 ⁇ 50mm, AERS500 4mm anion suppressor, suppressor current is 50mA, conductivity detector, column temperature is 50 ° C, injection volume is 30 ⁇ L with a flow rate of 1.0 mL / min.
  • the eluent contains 15 mmol / L sodium hydroxide, 3 mmol / L sodium tetraborate and 1.2 mmol / L sodium gluconate.
  • the solvent of the eluent is water.
  • Example 1 1.1 and 1.3 are the same as in Example 1.

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  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Sampling And Sample Adjustment (AREA)
  • Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)

Abstract

L'invention concerne un procédé de détermination de la teneur en formaldéhyde dans un adjuvant du béton, qui consiste à : 1) prétraiter un échantillon de l'adjuvant du béton; 2) tracer une courbe de travail standard; et 3) calculer la concentration de formaldéhyde. Le procédé de détermination consiste à prétraiter un adjuvant du béton par combinaison d'une microextraction par simple goutte en espace de tête et d'une microextraction en phase liquide de liquides ioniques, de sorte que le formaldéhyde résiduel soit séparé de l'adjuvant du béton sans nécessité de distillation, ce qui évite le débordement d'un objet cible au cours d'un processus de distillation, et réduit les erreurs de mesure. Les étapes d'exécution sont simples et économes en temps, l'utilisation d'équipement est pratique et l'efficacité d'exploitation élevée.
PCT/CN2019/086849 2018-06-22 2019-05-14 Procédé de détermination de la teneur en formaldéhyde dans un adjuvant du béton WO2019242430A1 (fr)

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CN201810650460.7A CN110632242B (zh) 2018-06-22 2018-06-22 一种混凝土外加剂中甲醛含量的测试方法
CN201810650460.7 2018-06-22

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001113180A (ja) * 1999-10-20 2001-04-24 Sumika Chemical Analysis Service Ltd カルボニル化合物捕集管の製造方法
CN101793777A (zh) * 2009-02-04 2010-08-04 苏州艾杰生物科技有限公司 甲醛测定试剂(盒)及甲醛浓度测定方法
CN102435698A (zh) * 2011-09-12 2012-05-02 红云红河烟草(集团)有限责任公司 一种同时测定烟用纸张中甲醛和乙醛含量的方法
CN104502486A (zh) * 2014-12-31 2015-04-08 广东出入境检验检疫局检验检疫技术中心 一种应用顶空-固相微萃取技术测定奶粉中甲基香兰素和乙基香兰素的方法

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102719844A (zh) * 2012-07-03 2012-10-10 北京化工大学 一种苯甲醇氧化制苯甲醛的方法
CN103399106B (zh) * 2013-08-08 2014-12-10 四川出入境检验检疫局检验检疫技术中心 同时检测皮革中各种醛分别含量的低压离子色谱法
CN104597186A (zh) * 2014-12-30 2015-05-06 广西中烟工业有限责任公司 一种水基胶中甲醛的气相色谱/质谱联用检测方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001113180A (ja) * 1999-10-20 2001-04-24 Sumika Chemical Analysis Service Ltd カルボニル化合物捕集管の製造方法
CN101793777A (zh) * 2009-02-04 2010-08-04 苏州艾杰生物科技有限公司 甲醛测定试剂(盒)及甲醛浓度测定方法
CN102435698A (zh) * 2011-09-12 2012-05-02 红云红河烟草(集团)有限责任公司 一种同时测定烟用纸张中甲醛和乙醛含量的方法
CN104502486A (zh) * 2014-12-31 2015-04-08 广东出入境检验检疫局检验检疫技术中心 一种应用顶空-固相微萃取技术测定奶粉中甲基香兰素和乙基香兰素的方法

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
WANG, YONGMEI ET AL.: "Determination of Formaldehyde and Glyoxal in Cigarette Paper by Ion Chromatography", JOURNAL OF ANALYTICAL SCIENCE, vol. 30, no. 6, 31 December 2014 (2014-12-31), pages 915; 916, ISSN: 1006-6144 *
WEN, LICHAO: "Experimental Analysis of Determination of Formaldehyde Content in Ambient Air by Chromatography", SCIENCE AND TECHNOLOGY & INNOVATION, 31 December 2016 (2016-12-31), pages 101, ISSN: 2095-6835 *

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