CN109696339A - A kind of sample pretreating method that the heavy metal ion suitable for water quickly detects - Google Patents

A kind of sample pretreating method that the heavy metal ion suitable for water quickly detects Download PDF

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Publication number
CN109696339A
CN109696339A CN201811523851.9A CN201811523851A CN109696339A CN 109696339 A CN109696339 A CN 109696339A CN 201811523851 A CN201811523851 A CN 201811523851A CN 109696339 A CN109696339 A CN 109696339A
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China
Prior art keywords
heavy metal
ion
water
detection
solid
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CN201811523851.9A
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Chinese (zh)
Inventor
彭先佳
孔令昊
胡星云
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Research Center for Eco Environmental Sciences of CAS
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Research Center for Eco Environmental Sciences of CAS
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Priority to CN201811523851.9A priority Critical patent/CN109696339A/en
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00Sampling; Preparing specimens for investigation
    • G01N1/28Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00Sampling; Preparing specimens for investigation
    • G01N1/28Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
    • G01N1/286Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q involving mechanical work, e.g. chopping, disintegrating, compacting, homogenising

Abstract

The present invention relates to a kind of heavy metal quickly detects suitable for water sample pretreating method, include the following steps: that moderate amount of sulfuric acid is added into the solution containing heavy metal, add a certain amount of calcium sulfide, stirring is after a certain period of time, with alkali neutralization, it is separated by solid-liquid separation, obtained solid is dry, and the solid after drying detects after being directly compacted with solid Fast Detection Technique.Liquid is changed into the sample pretreating method of solid by the present invention, solves the problems, such as that heavy metal is difficult to directly quickly detect in fluid sample, is realized the enrichment detection of heavy metal in solution, is improved detection limit and accuracy, have the characteristics that easy to operate, expense is low.

Description

A kind of sample pretreating method that the heavy metal ion suitable for water quickly detects
Technical field
The present invention relates to a kind of heavy metal quickly detects suitable for water sample pretreating method more particularly to it is a kind of will Heavy metals immobilization is enriched with and is used for the sample pretreating method that solid detecting instrument quickly detects in water.
Background technique
The defects of detection of heavy metal is there are complex pretreatment in all kinds of water, and detection time is long, it is difficult to adapt to certain conditions Under (such as burst accident waste water) heavy metal quick detection demand.One of heavy metal fast qualitative and the effective ways of quantitative detection It is to be examined with the non-contact spectral technique such as Laser induced plasma spectroscopy (LIPS) and X-ray fluorescence spectra (XRF) The advantages that survey has analysis time short, and various heavy detects simultaneously, is suitable for on-line analysis.However, the skills such as LIPS and XRF There are some defects in solution example context of detection for art.If LIBS technology is there are liquid splash, signal strength is low, is easy quenching, The problems such as spectrum-stable degree is poor;In XRF analysis, the bubble disturbed test result of x-ray bombardment fluid sample generation;Analyze liquid Higher ray scattering background value is generated when body sample, leads to lower signal-to-noise ratio.Meanwhile LIBS and XRF are to fluid sample Detection limit is generally ppm grades, is difficult to meet the analysis demand of the fields such as environment and industry Heavy Metals in Waters element sometimes.In order to It solves the above problems, fluid sample can be prepared as to solid or preenrichment and detected on solid sample.Conventional solid preparation It include freezing, seasoning, substrate (filter paper, wooden etc.) concentration method, absorption method etc. with Preconcentration.However, these methods There are complex pretreatment, the disadvantages such as concentration coefficient is low.At present need research and development suitable for solution heavy metal quickly detect it is efficient It is enriched with preconditioning technique.
Summary of the invention
The purpose of the present invention is to provide an anticoagulant small molecule compound and its application and include its drug.
The technical scheme to solve the above technical problems is that
The present invention provides a kind of sample pretreating method of detection of heavy metal ion suitable for water, includes the following steps:
A) sulfuric acid is added in the solution of Xiang Hanyou heavy metal ion;
B) calcium sulfide is added into the solution of step a);
C) certain time is mixed, mixed solution is obtained;
D) using the mixed solution in alkali neutralization step c, suspension is obtained;
E) suspension in step d is separated by solid-liquid separation;
F) obtained solid is dried at a certain temperature;
G) solid after drying is directly compacted obtain sample to be tested.
Further, the solution containing heavy metal ion includes natural water body, industrial wastewater or agricultural water.
Further, the heavy metal ion includes copper ion, lead ion, titanium ion, vanadium ion, antimony ion, bismuth ion, silver One of ion, indium ion, mercury ion, platinum ion, zirconium ion and metalloid arsenic ion are a variety of.
Further, the concentration of the sulfuric acid in solution obtained in the step 1 is 0.001g/L~1000g/L.
Further, the calcium sulfide is powdered or emulsion form;The dosage of the calcium sulfide is 0.01g/L~1000g/ L。
Further, the hybrid mode is concussion, ultrasound or stirring;The incorporation time is 10s~6h.
Further, described with the pH range of alkali neutralization is between 4-9;The alkali be 0.001M-10M sodium hydroxide or Sodium carbonate liquor.
Further, the solid-liquid separating method is filtering or centrifugation.
Further, any of the solid drying means to air-dry, drying, in freeze-drying and organics dehydration drying Kind;The drying temperature is -100 DEG C~400 DEG C.
Further, the solid compaction method is hydraulic or piece pressure.
The principle of the present invention:
Calcium sulfide, which is put into acidic aqueous solution, can occur to react as follows:
CaS+2H+→Ca2++H2S
Wherein the sulfate ion in calcium ion and water forms CaSO4 precipitating:
Since the solubility product between heavy metal and hydrogen sulfide is very small, hydrogen sulfide reacts to be formed with the heavy metal ion in water Precipitating:
Since many heavy metal sulfides are dissolved in acid, pH value of solution need to be adjusted to weakly acidic pH with alkali again.Make in solution Heavy metal reacts completely with hydrogen sulfide.
Obtained solid is the mixture of CaSO4 and MSn/2.Wherein CaSO4 is substrate, and MSn/2 is the effective of detection Component.If the amount that calcium sulfide is added is constant, the yield of substrate CaSO4 is constant, and the yield of MSn/2 and waste water or The concentration of heavy metal in waste liquid is related.Utilize the weight in the content and water of heavy metal M in this patent preprocess method obtained solid Tenor has positive correlation.The content for measuring heavy metal in the solid made of known concentration heavy metal aqueous solution, draws Standard curve processed can calculate the content of beary metal in unknown concentration aqueous solution.
The beneficial effects of the present invention are: the detection of heavy metal in solution is transformed into solid by liquid, with solid analysis Technology is used for quickly detecting, and is solved heavy metal tradition in aqueous solution and is quickly detected problem;Meanwhile the invention can efficiently concentrating weight Metal improves the detection accuracy of heavy metal.
Detailed description of the invention
Fig. 1 is the flow diagram of the sample pretreating method of detection of heavy metal ion suitable for water of the invention.
Specific embodiment
The principle and features of the present invention will be described below with reference to the accompanying drawings, and the given examples are served only to explain the present invention, and It is non-to be used to limit the scope of the invention.
The present invention provides a kind of sample pretreating method of detection of heavy metal ion suitable for water, includes the following steps:
A) sulfuric acid is added in the solution of Xiang Hanyou heavy metal ion;
B) calcium sulfide is added into the solution of step a);
C) certain time is mixed, mixed solution is obtained;
D) using the mixed solution in alkali neutralization step c, suspension is obtained;
E) suspension in step d is separated by solid-liquid separation;
F) obtained solid is dried at a certain temperature;
G) solid after drying is directly compacted obtain sample to be tested.
The solution containing heavy metal ion includes natural water body, industrial wastewater or agricultural water.
The heavy metal ion includes copper ion, lead ion, titanium ion, vanadium ion, antimony ion, bismuth ion, silver ion, indium One of ion, mercury ion, platinum ion, zirconium ion and metalloid arsenic ion are a variety of.
The concentration of sulfuric acid in solution obtained in the step 1 is 0.001g/L~1000g/L.
The calcium sulfide is powdered or emulsion form;The dosage of the calcium sulfide is 0.01g/L~1000g/L.
The hybrid mode is concussion, ultrasound or stirring;The incorporation time is 10s~6h.
Described with the pH range of alkali neutralization is between 4-9;The alkali is the sodium hydroxide or sodium carbonate of 0.001M-10M Solution.
The solid-liquid separating method is filtering or centrifugation.
Any one of the solid drying means is to air-dry, dry, and freeze-drying and organics dehydration are dry.
The drying temperature is -100 DEG C~400 DEG C.
The solid compaction method is hydraulic or piece pressure.
It can occur to react as follows due to putting into calcium sulfide in acidic aqueous solution:
CaS+2H+→Ca2++H2S
Wherein the sulfate ion in calcium ion and water forms CaSO4 precipitating:
Since the solubility product between heavy metal and hydrogen sulfide is very small, hydrogen sulfide reacts to be formed with the heavy metal ion in water Precipitating:
Since many heavy metal sulfides are dissolved in acid, pH value of solution need to be adjusted to weakly acidic pH with alkali again.Make in solution Heavy metal reacts completely with hydrogen sulfide.
Obtained solid is the mixture of CaSO4 and MSn/2.Wherein CaSO4 is substrate, and MSn/2 is the effective of detection Component.If the amount that calcium sulfide is added is constant, the yield of substrate CaSO4 is constant, and the yield of MSn/2 and waste water or The concentration of heavy metal in waste liquid is related.Utilize the weight in the content and water of heavy metal M in this patent preprocess method obtained solid Tenor has positive correlation.The content for measuring heavy metal in the solid made of known concentration heavy metal aqueous solution, draws Standard curve processed can calculate the content of beary metal in unknown concentration aqueous solution.
The beneficial effects of the present invention are: the detection of heavy metal in solution is transformed into solid by liquid, with solid analysis Technology is used for quickly detecting, and is solved heavy metal tradition in aqueous solution and is quickly detected problem;Meanwhile the invention can efficiently concentrating weight Metal improves the detection accuracy of heavy metal.
Embodiment 1
(preparatory sulfuric acid acidification (3g/L is added in 100mL gas cleaning contained waste liquid in powdered calcium sulfide 1g H2SO4)), stir 15 minutes, centrifuge separation, oven drying is compacted with hydraulic press, with the heavy metal in LIBS measurement solid Content.The detection that liquid directly detects copper is limited to 0.4mg/L, and detection is limited to 6.5 μ g/L after calcium sulfide enrichment.Detection after enrichment Limit is than directly detecting low 62 times.
Embodiment 2
Powdered calcium sulfide 2g is added to the sulphur generated in advance with the 100mL smelting zinc industry of sulfuric acid acidification (2g/L H2SO4) It in sour zinc waste liquid, stirs 10 minutes, centrifuge separation, ethanol dehydration is dry, is compacted with hydraulic press, in XRF measurement solid Content of beary metal.The detection that liquid directly detects lead is limited to 0.7mg/L, and detection is limited to 3.5 μ g/L after calcium sulfide enrichment.After enrichment Detection limit than directly detecting low 200 times.
Embodiment 3
Calcium sulfide is configured to the lotion of 100g/L, 10mL calcium sulfide lotion is taken to be added to 100mL high organic heavy metal It in waste water (preparatory sulfuric acid is acidified (5g/L H2SO4)), stirs 10 minutes, is centrifugated, freeze-drying is compacted with hydraulic press, is transported With the content of beary metal in LIBS measurement solid.The detection that liquid directly detects cadmium is limited to 13.5mg/L, examines after calcium sulfide enrichment Rising limit is 13.5 μ g/L.Detection limit after enrichment is than directly detecting low 1000 times.
Embodiment 4
Powdered calcium sulfide 1g is added in 100mL highly acid high-concentration sulfuric acid zinc waste liquid, ultrasound 3 minutes, membrane filtration Separation, ethanol dehydration is dry, is prepared into gypsum solid after 1mL water is added in solid after drying, with the weight in XRF measurement solid Tenor.The detection that liquid directly detects cobalt is limited to 0.8mg/L, and detection is limited to 1.4 μ g/L after calcium sulfide enrichment.After enrichment Detection limit is than directly detecting low 571 times.
Embodiment 5
Calcium sulfide is configured to the lotion of 100g/L, takes 5mL calcium sulfide lotion that (preparatory sulfuric acid is added into 100mL river water It is acidified (5g/L H2SO4)), it shakes 30 minutes, membrane filtration separation, after being compacted with tablet press machine, in LIBS measurement solid Content of beary metal.The detection that liquid directly detects nickel is limited to 1.3mg/L, and detection is limited to 11 μ g/L after calcium sulfide enrichment.After enrichment Detection limit than directly detecting low 118 times.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all in spirit of the invention and Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.

Claims (10)

1. a kind of sample pretreating method of the detection of heavy metal ion suitable for water, which comprises the steps of:
A) sulfuric acid is added in the solution of Xiang Hanyou heavy metal ion;
B) calcium sulfide is added into the solution of step a);
C) after mixing, mixed solution is obtained;
D) using the mixed solution in alkali neutralization step c, suspension is obtained;
E) suspension in step d is separated by solid-liquid separation;
F) obtained solid is dried;
G) solid after drying is directly compacted obtain sample to be tested.
2. the sample pretreating method of the detection of heavy metal ion according to claim 1 suitable for water, which is characterized in that The solution containing heavy metal ion includes natural water body, industrial wastewater or agricultural water.
3. the sample pretreating method of the detection of heavy metal ion according to claim 1 suitable for water, which is characterized in that The heavy metal ion includes copper ion, lead ion, titanium ion, vanadium ion, antimony ion, bismuth ion, silver ion, indium ion, mercury One of ion, platinum ion, zirconium ion and metalloid arsenic ion are a variety of.
4. the sample pretreating method of the detection of heavy metal ion according to claim 1 suitable for water, which is characterized in that The concentration of sulfuric acid in solution obtained in the step 1 is 0.001g/L~1000g/L.
5. the sample pretreating method of the detection of heavy metal ion according to claim 1 suitable for water, which is characterized in that The calcium sulfide is powdered or emulsion form;The dosage of the calcium sulfide is 0.01g/L~1000g/L.
6. the sample pretreating method of the detection of heavy metal ion according to claim 1 suitable for water, which is characterized in that The hybrid mode is concussion, ultrasound or stirring;The incorporation time is 10s~6h.
7. the sample pretreating method of the detection of heavy metal ion according to claim 1 suitable for water, which is characterized in that Described with the pH range of alkali neutralization is between 4-9;The alkali is the sodium hydroxide or sodium carbonate liquor of 0.001M-10M.
8. the sample pretreating method of the detection of heavy metal ion according to claim 1 suitable for water, which is characterized in that The solid-liquid separating method is filtering or centrifugation.
9. the sample pretreating method of the detection of heavy metal ion according to claim 1 suitable for water, which is characterized in that The solid drying means be air-dry, drying, freeze-drying and organics dehydration it is any one of dry;The drying temperature It is -100 DEG C~400 DEG C.
10. the sample pretreating method of the detection of heavy metal ion according to claim 1 suitable for water, feature exist In the solid compaction method is hydraulic or piece pressure.
CN201811523851.9A 2018-12-13 2018-12-13 A kind of sample pretreating method that the heavy metal ion suitable for water quickly detects Pending CN109696339A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101948226A (en) * 2010-09-15 2011-01-19 长沙达华污泥处理科技有限公司 Method for removing heavy metal from sludge in sewage treatment plant
CN108314229A (en) * 2018-01-19 2018-07-24 东南大学 Heavy metal in water ion based on nanopore device gradually partition method
CN108467949A (en) * 2018-02-22 2018-08-31 中国恩菲工程技术有限公司 The method of Zn accumulation from zinc-containing solution

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101948226A (en) * 2010-09-15 2011-01-19 长沙达华污泥处理科技有限公司 Method for removing heavy metal from sludge in sewage treatment plant
CN108314229A (en) * 2018-01-19 2018-07-24 东南大学 Heavy metal in water ion based on nanopore device gradually partition method
CN108467949A (en) * 2018-02-22 2018-08-31 中国恩菲工程技术有限公司 The method of Zn accumulation from zinc-containing solution

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
廖润华等: "《普通高等院校环境科学与工程类系列规划教材 环境治理功能材料》", 30 April 2017, 中国建材工业出版社 *
张蕾: "《固体废物污染控制工程》", 31 August 2014, 中国矿业大学出版社 *
罗琳等: "《普通高等教育"十二五"规划教材 环境工程学》", 30 April 2014, 冶金工业出版社 *

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