CN109187155A - The effective test method of the method for extraction and purification of boron and a kind of boron istope composition in a kind of water sample - Google Patents
The effective test method of the method for extraction and purification of boron and a kind of boron istope composition in a kind of water sample Download PDFInfo
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- CN109187155A CN109187155A CN201810841628.2A CN201810841628A CN109187155A CN 109187155 A CN109187155 A CN 109187155A CN 201810841628 A CN201810841628 A CN 201810841628A CN 109187155 A CN109187155 A CN 109187155A
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Abstract
The present invention provides the test method that a kind of method for extraction and purification of boron effective in water sample and boron istope form, it is 6~7 that the present invention adjusts water sample pH value first, and the water sample after adjusting pH value is placed in the nut cap of centrifuge tube；Sodium hydroxide solution is placed in the bottom of the centrifuge tube；Neutral water sample in nut cap is heated, obtains dobell's solution in centrifugation bottom of the tube；Then dobell's solution is successively carried out to effects of boron resin adsorption treatment, hydrochloric acid elution, leacheate evaporation process, zwitterion hybrid resin adsorption treatment, realize the extraction purification of effective boron in water sample.The boron istope in effective boron prepare liquid that the present invention obtains extraction purification by PTIMS method method is tested, and can test to obtain the composition of boron istope in water sample.Test method accuracy provided by the invention is higher, and as shown in the embodiment of the invention, test method 2SD (‰) value provided by the invention is lower than 0.1 ‰.
Description
Technical field
The present invention relates to the method for extraction and purification and boron of boron effective in boron istope research field more particularly to a kind of water sample
The test method of isotopics.
Background technique
Boron istope10B and11Biggish relative mass official post boron element has apparent Fractionation of boron isotope phenomenon between B,
In addition boron is soluble easily in water and chemical property is active, boron istope is made to become one of the best tracer of research water body feature.
The method of purification of boron is effects of boron resin absorption method in general water sample, but effects of boron resin absorption method is used to purify
Still there is a large amount of organic matter to remain in obtained sample, the measurement of boron istope composition can not be carried out.The extraction purification technology of boron
Limit application of the boron istope in water body example.
Summary of the invention
The present invention provides the test methods that a kind of method for extraction and purification of boron effective in water sample and boron istope form, originally
The method for extraction and purification that invention provides can extract to obtain effective boron of purity is high, so that extraction purification of the present invention obtained
Effective boron can be directly used for test boron istope composition, it is made to go on smoothly the measurement of boron istope.
The present invention provides a kind of method for extraction and purification of boron effective in water sample, comprising the following steps:
(1) adjusting water sample pH value is 6~7, obtains neutral water sample；
(2) the neutral water sample that the step (1) obtains is placed in the nut cap of centrifuge tube；Sodium hydroxide solution is placed in institute
State the bottom of centrifuge tube；The volume ratio of the sodium hydroxide solution and centrifuge tube is 1:10~20；Neutral water sample and sodium hydroxide
The volume ratio of solution is 1:0.8~1.2；
(3) the neutral water sample in the step (2) nut cap is heated, the boric acid molecule in neutral water sample is waved
Hair reacts to obtain dobell's solution with the sodium hydroxide solution of centrifugation bottom of the tube；
(4) adsorption treatment is carried out to the dobell's solution that the step (3) obtains using effects of boron resin, is adsorbed with
The resin column of borate ion；Then the resin column is eluted with hydrochloric acid, collects eluent；
(5) after mixing the eluent that the step (4) obtains with mannitol, it is evaporated processing, obtains concentrate；
(6) concentrate that the step (5) obtains is mixed with water, obtains dilution；Using zwitterion hybrid resin
Ion-exchange treatment is carried out to the dilution, obtains leacheate；
(7) after mixing the leacheate that the step (6) obtains with mannitol, it is evaporated processing.
Preferably, in the step (1) water sample be one of river water, well water, tap water, underground water and industrial wastewater or
It is a variety of.
Preferably, the temperature heated in the step (3) is 65~75 DEG C, and the time of heat treatment is 13~15h.
Preferably, the volume ratio of hydrochloric acid and resin column is 1:1 in the step (4), the concentration of the hydrochloric acid is 0.05~
0.15mol/L。
Preferably, the molar ratio of boron and mannitol is 1:1~1.2 in eluent in the step (5)；The step (7)
The molar ratio of boron and mannitol is 1:1~1.2 in middle leacheate；The mass concentration of mannitol in the step (5) and step (7)
It independently is 0.5~1.5%.
Preferably, the temperature of evaporation process independently is 55~65 DEG C in the step (5) and step (7)；The step
(5) and in step (7) degree of evaporation process independently by evaporation surplus solution fixing fabric structure, when the evaporation residue is molten
When the volume of liquid is 0.5~1.5% of liquor capacity before evaporating, stop evaporation process.
Preferably, zwitterion hybrid resin is strongly acidic cation-exchange and weak base type yin in the step (6)
Ion exchange resin；The mass ratio of the strongly acidic cation-exchange and weak base type anion exchange resin be 1:0.8~
1.2。
Preferably, the eluent of step (6) the intermediate ion exchange processing includes ultrapure water.
The present invention also provides a kind of test methods of the boron istope of boron effective in water sample composition, comprising: using above-mentioned
Method for extraction and purification described in technical solution extracts effective boron in water sample, obtains prepare liquid；Using the positive thermal ionization matter
Spectrometry tests boron istope composition in the prepare liquid.
The present invention provides a kind of method for extraction and purification of boron effective in water sample, comprising the following steps: adjusts water sample pH value
It is 6~7, obtains neutral water sample；Neutral water sample is placed in the nut cap of centrifuge tube；Sodium hydroxide solution is placed in the centrifuge tube
Bottom, obtain centrifuge tube to be processed；The volume ratio of the sodium hydroxide solution and centrifuge tube is 1:10~20；Neutral water sample with
The volume ratio of sodium hydroxide solution is 1:0.8~1.2；Neutral water sample in nut cap is heated, in neutral water sample
The volatilization of boric acid molecule reacts to obtain dobell's solution with the sodium hydroxide solution of centrifugation bottom of the tube；Using effects of boron resin to boron
Acid sodium solution carries out adsorption treatment, obtains the resin column for being adsorbed with borate ion；Then the resin column is carried out with hydrochloric acid
Eluent is collected in elution；After eluent is mixed with mannitol, it is evaporated processing, obtains concentrate；Concentrate and water are mixed
It closes, obtains dilution；Ion-exchange treatment is carried out to the dilution using zwitterion hybrid resin, obtains leacheate；It will
After leacheate is mixed with mannitol, it is evaporated processing.
Water sample pH value is adjusted to 6~7 by the present invention, and boron exists in the form of boric acid molecule in the neutral water sample made；
Then neutral water sample is placed in the nut cap of centrifuge tube, sodium hydroxide solution is placed in the bottom of the centrifuge tube, pass through control
The dosage of neutral water sample and sodium hydroxide solution, in conjunction with neutral water sample is adsorbed in nut cap, sodium hydroxide is molten
Liquid is adsorbed on the bottom of centrifuge tube；Then by being heated to the neutral water sample in centrifuge tube nut cap, make in neutral water sample
Water and boric acid volatilization, then the sodium hydroxide solution with centrifugation bottom of the tube reacts, and generates dobell's solution；By testing boron
The content of boron in acid sodium solution, it can be deduced that the content of effective boron in water sample.Then dobell's solution is subjected to effects of boron resin
Adsorption treatment enables borate ion to be adsorbed on effects of boron resin, is eluted by hydrochloric acid, borate ion can be dissolved
In hydrochloric acid eluant, eluent, then through evaporation process, achievees the purpose that for borate ion to be enriched with, then be mixed by zwitterion
Resin handles dilution, removes the hydrochloric acid in dilution, realizes the extraction purification of effective boron in water sample.
It is higher to obtain effective boron content in solution for the method extraction purification through the invention, so that mentioning through of the present invention
Take purification process treated that sample can be used for measuring boron istope composition.Extraction purification of the present invention obtains the presence of boron in solution
Form is H3BO3。
The test method that boron istope forms in the prepare liquid obtained the present invention also provides extraction purification, passes through positive thermoelectricity
From mass spectrography test boron istope composition.Effective boron purity is higher in the prepare liquid obtained due to extraction purification of the present invention, so that
The boron istope method accuracy that the present invention tests is higher, as shown in the embodiment of the invention, test side provided by the invention
Method 2SD (‰) value is lower than 0.1 ‰.
Specific embodiment
The present invention provides a kind of method for extraction and purification of boron effective in water sample, comprising the following steps:
(1) adjusting water sample pH value is 6~7, obtains neutral water sample；
(2) the neutral water sample that the step (1) obtains is placed in the nut cap of centrifuge tube；Sodium hydroxide solution is placed in institute
The bottom for stating centrifuge tube obtains centrifuge tube to be processed；The volume ratio of the sodium hydroxide solution and centrifuge tube is 1:10~20；In
Property water sample and sodium hydroxide solution volume ratio be 1:0.8~1.2；
(3) the neutral water sample in the step (2) nut cap is heated, the boric acid molecule in neutral water sample is waved
Hair reacts to obtain dobell's solution with the sodium hydroxide solution of centrifugation bottom of the tube；
(4) adsorption treatment is carried out to the dobell's solution that the step (3) obtains using effects of boron resin, is adsorbed with
The resin column of borate ion；Then the resin column is eluted with hydrochloric acid, collects eluent；
(5) after mixing the eluent that the step (4) obtains with mannitol, it is evaporated processing, obtains concentrate；
(6) concentrate that the step (5) obtains is mixed with water, obtains dilution；Using zwitterion hybrid resin
Ion-exchange treatment is carried out to the dilution, obtains leacheate；
(7) after mixing the leacheate that the step (6) obtains with mannitol, it is evaporated processing.
It is 6~7 that the present invention, which adjusts water sample pH value, obtains neutral water sample.
Water sample is not particularly limited in the present invention, using any water sample for needing to test effective boron content, preferably wraps
Include one of river water, well water, tap water, underground water and industrial wastewater or a variety of.
In the present invention, the regulator for adjusting water sample pH value is preferably hydrochloric acid, and the concentration of the hydrochloric acid is preferably
0.05~0.15mol/L, further preferably 0.01mol/L.The pH value of the water sample is adjusted to 6~7 by the present invention, preferably
6.2~6.8, further preferably 6.5.The pH value of the water sample is preferably adjusted to above range by the present invention, is conducive to make water
Boron element in sample exists in the form of boric acid molecule, and then in subsequent heat treatment process, is conducive to the volatilization of boric acid molecule.
After the pH value of water sample is adjusted to above range by the present invention, the water sample after adjusting pH value is preferably filtered place
Reason, obtains pure neutral water sample.In the present invention, the filtering is preferably 0.40~0.50 μm with filter paper aperture, further
Preferably 0.45 μm；The filtering is preferably water system syringe filter with device.The present invention does not have the specific embodiment of filtering
It is particularly limited to, using filter type well-known to those skilled in the art.
After obtaining neutral water sample, neutral water sample is placed in the nut cap of centrifuge tube by the present invention；Sodium hydroxide solution is placed in
The bottom of the centrifuge tube.
In the present invention, the volume of the centrifuge tube is preferably 1~2mL, further preferably 1.5mL；The hydroxide
The volume ratio of sodium solution and centrifuge tube is 1:10~20, preferably 1:12~18, further preferably 1:14~16；The neutrality
The volume ratio of water sample and sodium hydroxide solution is 1:0.8~1.2, preferably 1:1.The present invention is preferably by the volume control of neutral water sample
System within the above range, advantageously ensures that neutral water sample stays in nut cap, will not flow to centrifugation bottom of the tube.The present invention is preferably by hydrogen
The fixing fabric structure of the volume of sodium hydroxide solution and centrifuge tube within the above range, be conducive to even if it is subsequent centrifuge tube is inverted when,
Sodium hydroxide solution remains in the bottom of centrifuge tube, will not flow down.In the present invention, the concentration of the sodium hydroxide solution is excellent
It is selected as 0.05~0.15mol/L, further preferably 0.01mol/L.
The present invention heats the neutral water sample in nut cap, the boric acid molecule volatilization in neutral water sample, with centrifugation
The sodium hydroxide solution of bottom of the tube reacts to obtain dobell's solution.
In the present invention, the temperature of the heat treatment is preferably 65~75 DEG C, and further preferably 70 DEG C；The heating
The time of processing is preferably 13~15h, further preferably 12~14h.In the present invention, the mode of the heating is preferred are as follows:
Centrifuge tube is inverted in heating plate, the nut cap of centrifuge tube is heated.The present invention in particular during a heating process, it is described neutrality water sample in
Water and boric acid molecule volatilize, form gaseous vapor and boric acid steam in centrifuge tube, while gaseous boric acid point
Son and the sodium hydroxide solution of centrifugation bottom of the tube react, and generate dobell's solution.The present invention is by neutral water sample and hydroxide
Sodium solution, which is respectively placed in centrifuge tube nut cap, and centrifugation bottom of the tube is by heating neutral water sample makes neutral water sample
Middle boric acid volatilization, is dissolved in centrifugation bottom of the tube sodium hydroxide solution.The present invention is using the above method effectively by the boron in water sample
Element is transferred in sodium hydroxide solution, has achieved the purpose that boron element in the neutral water sample of preliminary extraction.In the present invention, above-mentioned
Method is known as: head space liquid phase microsublimation.
After obtaining dobell's solution, the present invention preferably tests effective boron content in the dobell's solution.In the present invention,
The obtained effective boron content that measures is for subsequent determining boron istope composition.
Present invention preferably employs effective boron contents in ICP-OES method test dobell's solution.The present invention is to ICP-OES method
Specific operation process is not particularly limited, using method well-known to those skilled in the art.
After obtaining dobell's solution, the present invention carries out adsorption treatment to the dobell's solution using effects of boron resin, obtains
To the resin column for being adsorbed with borate ion.
In the present invention, the effects of boron resin is preferably 743 resin of Amberlite IRA.Present invention preferably employs
743 resin of Amberlite IRA carries out adsorption treatment to dobell's solution, and 743 resin of Amberlite IRA is to boric acid
Radical ion has specificity, can borate ion in selective absorption dobell's solution, and then can be by dobell's solution
In borate ion enrichment, be conducive to subsequent to test to obtain boron istope composition.
The embodiment of the adsorption treatment is not particularly limited in the present invention, and use is well-known to those skilled in the art
The method that adsorbing separation is carried out using resin column.
After the adsorption treatment, the present invention is preferably using distilled water as eluant, eluent, to the resin column for being adsorbed with borate ion
It is eluted, what is cleaned is adsorbed with the resin column of borate ion.Present invention preferably employs distilled water to being adsorbed with boric acid
The resin column of radical ion is eluted, and is conducive to remove metal ion and anionic impurity.Time and side of the present invention to elution
Formula is not particularly limited, using those skilled in the art frequently with the elution time and mode.
It obtains after being adsorbed with the resin column of borate ion, the present invention is using hydrochloric acid to the borate ion that is adsorbed with
Resin column is eluted, and eluent is collected.
In the present invention, the volume ratio of the hydrochloric acid and resin column is preferably 1:1~1.2, further preferably 1:1.1；
The concentration of the hydrochloric acid is preferably 0.05~0.15mol/L, further preferably 0.1mol/L.The present invention preferably passes through above-mentioned item
The hydrochloric acid of part elutes resin column, is conducive to that the borate ion of Amberlite IRA743 resin adsorption is made to be dissolved into salt
In acid, and then be conducive to be enriched to borate ion in eluent.In the present invention, boric acid is preferably included in the eluent
Radical ion and hydrochloric acid.
After obtaining eluent, the present invention mixes the eluent with mannitol, is then evaporated processing, is concentrated
Liquid.
The present invention mixes eluent with mannitol, obtains mixed solution.
In the present invention, the mass concentration of the mannitol is preferably 0.5%~1.5%, and further preferably 1.0%.
In the present invention, the molar ratio of boron and mannitol is 1:1~1.2 in the eluent.
After the present invention mixes eluent with mannitol, boric acid or borate ion in the mannitol and eluent are sent out
Raw chelation, avoid it is subsequent processing is evaporated to mixed solution when, boron element loses.Due to eluent and sweet dew
Chelatropic reaction, which occurs, for alcohol will not lead to the loss of boron even if mixed solution is evaporated in a short time.
After obtaining mixed solution, the present invention is evaporated processing to the mixed solution, obtains concentrate.
In the present invention, the temperature of the evaporation process is preferably 55~65 DEG C, and further preferably 60 DEG C；The evaporation
The degree of processing preferably passes through the fixing fabric structure of evaporation surplus solution, solution before being to evaporate when the volume of the evaporation surplus solution
Volume 0.5~1.5% when, stop evaporation process, when preferably 1%, stop evaporation process.The present invention is to the evaporation process
Specific embodiment there is no particular/special requirement, using well-known to those skilled in the art；In an embodiment of the present invention,
The evaporation process carries out preferably in air dry oven.
The volume of eluent is concentrated by evaporation process, obtains concentrate by the present invention, is conducive to improve the dense of boron
Degree meets the needs of its isotope mass spectrometry measurement.
After obtaining concentrate, the present invention mixes the concentrate with water, obtains dilution.
In the present invention, the water is preferably ultrapure water, the volume ratio of the concentrate and water be preferably (0.05~
0.15): (0.45~0.55), further preferably 0.1:0.5.
After obtaining dilution, the present invention carries out ion-exchange treatment to the dilution using zwitterion hybrid resin,
Obtain leacheate.
In the present invention, the zwitterion hybrid resin be preferably strongly acidic cation-exchange and weak base type yin from
The hybrid resin of sub-exchange resin.In the present invention, the strongly acidic cation-exchange and weak base type anion exchange tree
The mass ratio of rouge is preferably 1:0.5~1.5, further preferably 1:1.
In the present invention, the eluent of the ion-exchange treatment preferably includes ultrapure water.
The specific embodiment of ion-exchange treatment is not particularly limited in the present invention, ripe using those skilled in the art institute
The method that ion-exchange treatment is carried out using resin column known.
The present invention carries out ion-exchange treatment to dilution using anion-cation exchange resin, is conducive to remove in dilution
Hydrochloric acid, improve dilution in boric acid purity.
After obtaining leacheate, the present invention mixes the leacheate with mannitol, is then evaporated processing.
The present invention mixes leacheate with mannitol, obtains the second mixed solution.
In the present invention, the mass concentration of the mannitol is preferably 0.5%~1.5%, and further preferably 1.0%.
In the present invention, the molar ratio of boron and mannitol is 1:1~1.2 in the leacheate.
After the present invention mixes leacheate with mannitol, chela occurs for boric acid or borate in the mannitol and leacheate
Cooperation use, avoid it is subsequent processing is evaporated to the second mixed solution when, boron element loses.Due to boric acid in leacheate
Or borate ion can occur chelatropic reaction with mannitol and will not lead even if the second mixed solution is evaporated in a short time
Cause the loss of boron element.
After obtaining the second mixed solution, the present invention is evaporated processing to second mixed solution, obtains prepare liquid.
In the present invention, the evaporation process carries out preferably in air dry oven；The temperature of the evaporation process is preferred
It is 55~65 DEG C, further preferably 60 DEG C；The degree of the evaporation process preferably passes through the fixing fabric structure of evaporation surplus solution,
When the volume of the evaporation surplus solution is to evaporate the 0.5~1.5% of preceding liquor capacity, stopping evaporation process, preferably 1%
When, stop evaporation process.
The volume of leacheate is concentrated by evaporation process, obtains prepare liquid by the present invention, is conducive to improve prepare liquid
The content of middle boron, and then be conducive to test and obtain the content of boron istope.
The present invention also provides a kind of test methods of the boron istope of boron effective in water sample composition, comprising: using above-mentioned
Method for extraction and purification described in technical solution extracts effective boron in water sample, obtains prepare liquid；Using PTIMS method
Boron istope composition in the prepare liquid obtained described in method test.
The method for extraction and purification extracts effective boron in water sample to the present invention by adopting the above technical scheme, obtain to
After surveying liquid, the present invention tests the composition of the boron istope in the prepare liquid using PTIMS method method.
In the present invention, the PTIMS method method is preferably based on Cs2BO2 +The PTIMS method method of ion.This
The method for using boron istope composition in PTIMS method method test prepare liquid is not particularly limited in invention, using this field
Method known to technical staff.
In the present invention, aforementioned that boron effective in water sample is extracted in the technical solution of purifying and to effective in water sample
In the technical solution of the isotopics test of boron, the beaker used is both preferably polytetrafluoroethylene beaker, and the crucible used is equal
Preferably polytetrafluoroethylene (PTFE) crucible.Present invention preferably uses polytetrafluoroethylene beaker and polytetrafluoroethylene (PTFE) crucible, be conducive to avoid
The dissolution of impurity component in the materials such as glass or ceramics, and be conducive to avoid the suction-operated to substance is contained, tie test
Fruit is more accurate.
Below in conjunction with the embodiment in the present invention, the technical solution in the present invention is clearly and completely described.
Embodiment 1:
The extraction purification of effective boron in water sample:
(1) it with tap water for water sample to be measured, after the tap water of acquisition is filtered with 0.45 μm of water system syringe filter, will filter
Liquid is collected in 10mL polytetrafluoroethylene (PTFE) material small beaker, is adjusted aqueous solution pH to 6.5 with 0.1mol/L HCl, is obtained neutral water
Sample；
(2) 1.5mL tool plug centrifuge tube is taken, 0.1mL neutrality water sample is added in nut cap, is added in centrifugation bottom of the tube
0.1mL 0.1mol/LNaOH solution, covers nut cap, is carefully inverted centrifuge tube, and nut cap end is placed in temperature automatically controlled electric boiling plate
On；
(3) electric plate temperature is adjusted to 70 DEG C, automatic temperature control heating first heats 3.5h, and the moisture in nut cap slowly steams
It is sent to the headspace of centrifuge tube, other components remain in nut cap；10h is reheated, boron sublimes up into head space sky in the form of boric acid
Between, and absorbed by the NaOH solution of centrifugation bottom of the tube, dobell's solution is formed, inverted centrifuge tube is removed, it is normal to place.
(4) dobell's solution of centrifugation bottom of the tube is sucked out, then uses 0.5mL high purity water washing centrifuge tube 5 times, collects and merges
All liquid measures the content of total boron after constant volume using ICP-OES method.
The measurement of boron istope composition in effective boron:
After dobell's solution is first passed through effects of boron resin, with high-purity water washing resin 3 times, 10mL 0.1mol/ is then used
L HCl solution washs resin, collects eluent, the mannitol solution that 2 drop mass fractions are 1% is added into eluent, then
0.1mL or so is evaporated at 60 DEG C；0.5mL high purity water is added, by it by zwitterion hybrid resin, with 1mL high purity water
Residual solution and resin column 5 times are washed, all solution is collected, obtains leacheate；2 drop mass fractions are added into leacheate is
Then 1% mannitol solution is evaporated to solution about 0.1mL at 60 DEG C, obtains prepare liquid.Using Cs2BO2 +The thermoelectricity of ion
Composition from mass spectrometric determination boron istope.
Embodiment 2
The extraction purification of effective boron in water sample:
(1) with river water for water sample to be measured, after the river water of acquisition is filtered with 0.45 μm of water system syringe filter, filtrate is received
Collection adjusts aqueous solution pH to 6 in 10mL polytetrafluoroethylene (PTFE) material small beaker, with 0.05mol/L HCl, obtains neutral water sample；
(2) 1.5mL tool plug centrifuge tube is taken, 0.1mL neutrality water sample is added in nut cap, is added in centrifugation bottom of the tube
0.1mL 0.1mol/LNaOH solution, covers nut cap, is carefully inverted centrifuge tube, and nut cap end is placed in temperature automatically controlled electric boiling plate
On；
(3) electric plate temperature is adjusted to 75 DEG C, automatic temperature control heating first heats 4h, and the moisture in nut cap slowly evaporates
To the headspace of centrifuge tube, other components remain in nut cap；10h is reheated, boron sublimes up into headspace in the form of boric acid,
And absorbed by the NaOH solution of centrifugation bottom of the tube, dobell's solution is formed, inverted centrifuge tube is removed, it is normal to place.
(4) dobell's solution of centrifugation bottom of the tube is sucked out, then uses 0.5mL high purity water washing centrifuge tube 5 times, collects and merges
All liquid measures the content of total boron after constant volume using ICP-OES method.
The measurement of boron istope composition in effective boron:
After dobell's solution is first passed through effects of boron resin, with high-purity water washing resin 3 times, 10mL 0.1mol/ is then used
L HCl solution washs resin, collects eluent, the mannitol solution that 2 drop mass fractions are 1% is added into eluent, then
0.1mL or so is evaporated at 60 DEG C；0.5mL high purity water is added, by it by zwitterion hybrid resin, with 1mL high purity water
Residual solution and resin column 5 times are washed, all solution is collected, obtains leacheate；2 drop mass fractions are added into leacheate is
Then 1% mannitol solution is evaporated to solution about 0.1mL at 60 DEG C, obtains prepare liquid.Using Cs2BO2 +The thermoelectricity of ion
Composition from mass spectrometric determination boron istope.
Embodiment 3
The extraction purification of effective boron in water sample:
(1) it with underground water for water sample to be measured, after the tap water of acquisition is filtered with 0.45 μm of water system syringe filter, will filter
Liquid is collected in 10mL polytetrafluoroethylene (PTFE) material small beaker, is adjusted aqueous solution pH to 7 with 0.15mol/L HCl, is obtained neutral water
Sample；
(2) 1.5mL tool plug centrifuge tube is taken, 0.1mL neutrality water sample is added in nut cap, is added in centrifugation bottom of the tube
0.1mL 0.1mol/LNaOH solution, covers nut cap, is carefully inverted centrifuge tube, and nut cap end is placed in temperature automatically controlled electric boiling plate
On；
(3) electric plate temperature is adjusted to 65 DEG C, automatic temperature control heating first heats 3h, and the moisture in nut cap slowly evaporates
To the headspace of centrifuge tube, other components remain in nut cap；10h is reheated, boron sublimes up into headspace in the form of boric acid,
And absorbed by the NaOH solution of centrifugation bottom of the tube, dobell's solution is formed, inverted centrifuge tube is removed, it is normal to place.
(4) dobell's solution of centrifugation bottom of the tube is sucked out, then uses 0.5mL high purity water washing centrifuge tube 5 times, collects and merges
All liquid measures the content of total boron after constant volume using ICP-OES method.
The measurement of boron istope composition in effective boron:
After dobell's solution is first passed through effects of boron resin, with high-purity water washing resin 3 times, 10mL 0.1mol/ is then used
L HCl solution washs resin, collects eluent, the mannitol solution that 2 drop mass fractions are 1% is added into eluent, then
0.1mL or so is evaporated at 60 DEG C；0.5mL high purity water is added, by it by zwitterion hybrid resin, with 1mL high purity water
Residual solution and resin column 5 times are washed, all solution is collected, obtains leacheate；2 drop mass fractions are added into leacheate is
Then 1% mannitol solution is evaporated to solution about 0.1mL at 60 DEG C, obtains prepare liquid.Using Cs2BO2 +The thermoelectricity of ion
Composition from mass spectrometric determination boron istope.
The content δ of boron istope in the effective boron of Examples 1 to 3 water sample11B indicates, wherein δ11B value uses formula δ11B
(‰)=(Rsam/Rstd- 1) it × 1000 calculates, RsamFor boron istope ratio in sample；RstdFor boron istope international standard NIST
The isotopic ratio of SRM 951；2SD (‰) indicates standard deviation.Measurement result is listed in Table 1 below.In addition, the present invention also carries out
Recovery of standard addition experiment, the experimental result of recovery of standard addition are listed in Table 1 below.
Boron istope forms in the 1 effective boron of Examples 1 to 3 water sample of table
According to 1 test result of table it is found that the method for the invention can test to obtain boron istope in the effective boron of water sample
Content.And the test accuracy of the method for the invention is higher, and 2SD (‰) value is lower than 0.1 ‰.In addition, mark-on of the present invention returns
Yield is 98.7%~103.3%, it is possible thereby to illustrate that method provided by the invention can extract the boron in water sample completely, is not had
Cause the loss of boron.Method provided by the invention effectively can extract purifying to effective boron in water sample, so that this
Prepare liquid after invention the method extraction purification can be used in testing boron istope composition.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (9)
1. the method for extraction and purification of effective boron in a kind of water sample, comprising the following steps:
(1) adjusting water sample pH value is 6~7, obtains neutral water sample；
(2) the neutral water sample that the step (1) obtains is placed in the nut cap of centrifuge tube；By sodium hydroxide solution be placed in it is described from
The bottom of heart pipe；The volume ratio of the sodium hydroxide solution and centrifuge tube is 1:10~20；Neutral water sample and sodium hydroxide solution
Volume ratio be 1:0.8~1.2；
(3) the neutral water sample in the step (2) nut cap is heated, the boric acid molecule volatilization in neutral water sample, with
The sodium hydroxide solution of centrifugation bottom of the tube reacts to obtain dobell's solution；
(4) adsorption treatment is carried out to the dobell's solution that the step (3) obtains using effects of boron resin, obtains being adsorbed with boric acid
The resin column of radical ion；Then the resin column is eluted with hydrochloric acid, collects eluent；
(5) after mixing the eluent that the step (4) obtains with mannitol, it is evaporated processing, obtains concentrate；
(6) concentrate that the step (5) obtains is mixed with water, obtains dilution；Using zwitterion hybrid resin to institute
It states dilution and carries out ion-exchange treatment, obtain leacheate；
(7) after mixing the leacheate that the step (6) obtains with mannitol, it is evaporated processing.
2. method for extraction and purification according to claim 1, which is characterized in that water sample is river water, well in the step (1)
One of water, tap water, underground water and industrial wastewater are a variety of.
3. method for extraction and purification according to claim 1, which is characterized in that the temperature heated in the step (3)
It is 65~75 DEG C, the time of heat treatment is 13~15h.
4. method for extraction and purification according to claim 1, which is characterized in that hydrochloric acid and resin column in the step (4)
Volume ratio is 1:1~1.2, and the concentration of the hydrochloric acid is 0.05~0.15mol/L.
5. method for extraction and purification according to claim 1, which is characterized in that in the step (5) in eluent boron with it is sweet
The molar ratio for revealing alcohol is 1:1~1.2；The molar ratio of boron and mannitol is 1:1~1.2 in leacheate in the step (7)；It is described
The mass concentration of mannitol independently is 0.5~1.5% in step (5) and step (7).
6. method for extraction and purification according to claim 1 or 5, which is characterized in that steamed in the step (5) and step (7)
The temperature of hair processing independently is 55~65 DEG C；The degree of evaporation process is independently by steaming in the step (5) and step (7)
The fixing fabric structure for sending out surplus solution, when the volume of the evaporation surplus solution is to evaporate the 0.5~1.5% of preceding liquor capacity,
Stop evaporation process.
7. method for extraction and purification according to claim 1, which is characterized in that zwitterion compound tree in the step (6)
Rouge is strongly acidic cation-exchange and weak base type anion exchange resin；The strongly acidic cation-exchange and weak base
The mass ratio of type anion exchange resin is 1:0.8~1.2.
8. method for extraction and purification according to claim 1 or claim 7, which is characterized in that step (6) the intermediate ion exchange processing
Eluent include ultrapure water.
9. the test method of the boron istope composition of effective boron in a kind of water sample, comprising: using any one of claim 1~8 institute
The method for extraction and purification stated extracts effective boron in water sample, obtains prepare liquid；Institute is tested using PTIMS method method
Boron istope in prepare liquid is stated to form.
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| 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 |
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