CN1887864A - Method of purifying and detecting metal ion in dimethyl sulfoxide - Google Patents

Method of purifying and detecting metal ion in dimethyl sulfoxide Download PDF

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CN1887864A
CN1887864A CN 200610029253 CN200610029253A CN1887864A CN 1887864 A CN1887864 A CN 1887864A CN 200610029253 CN200610029253 CN 200610029253 CN 200610029253 A CN200610029253 A CN 200610029253A CN 1887864 A CN1887864 A CN 1887864A
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milliliters
solution
milliliter
dimethyl sulfoxide
dmso
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黄晓宇
谭久青
陈娟
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Shanghai Institute of Organic Chemistry of CAS
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Shanghai Institute of Organic Chemistry of CAS
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Abstract

The present invention relates to method of purifying and detecting metal ion in dimetyl sulfoxide as the solution for polymerizing polyactylonitrile carbon fiber. The metal impurities are eliminated from dimetyl sulfoxide based on static adsorption and exchange principle, and the elimination includes eliminating iron ion from dimetyl sulfoxide with macroporous weak alkali type anion exchange resin and eliminating calcium, magnesium, sodium and potassium ions from dimetyl sulfoxide with macroporous strong base type cation exchange resin. The detection includes ultraviolet spectrophotometry to detect the concentrations of various metal ions in the organic solvent, o-phenanthroline colorimetry to detect iron ion content, chloroposphonazo I colorimetry to detect calcium and magnesium ion content, and 18-crown-6 synergistic extraction process to detect potassium ion content.

Description

The purifying of metal ion and detection method in the dimethyl sulfoxide (DMSO)
Technical field
The present invention relates generally to the purifying and the detection method of metal ion in the dimethyl sulfoxide (DMSO), specifically potassium, sodium, calcium, magnesium and ferrous metal ionic purifying and detection method in polyacrylonitrile carbon fiber polymer solvent-dimethyl sulfoxide (DMSO) (DMSO).The principle of proposition utilization Static Adsorption exchange removes the metallic impurity in the methyl-sulphoxide; Remove iron ion in the organic phase with macropore weak base type acrylic acid type anion exchange resin, remove calcium, magnesium, sodium, potassium ion in the organic solution with macropore strong acid styrene type Zeo-karb.Use the concentration of each metal ion in the ultraviolet spectrophotometry rapid detection organic solvent simultaneously, propose with phenanthroline colorimetric method for determining Fe 3+Content, chlorophosphonazo I colorimetric method for determining Ca 2+, Mg 2+Content, 18-hat-6 synergistic extraction methods are measured K +The method of content.
Background technology
The production of whole world carbon fiber mainly concentrates in the developed country, there are toray company in main development and the unit that produces, east nation Beslon, mitsubishi rayon and the hexlex of the U.S., the BP-Amoco company of Britain also have the Taiwan plastic cement group of China, the safe light group and the India of Korea S.From the properties of carbon aspect, high performance polyacrylonitrile carbon fiber is with horizontal T-300 (the intensity 3.5GPa from the initial stage, modulus 230GPa) progressively upgrades to T-400H (intensity 4.4GPa, modulus 250GPa), T-700S (intensity 4.92GPa, modulus 230GPa), T-800H (intensity 5.5GPa, modulus 296GPa) and T-1000 (intensity 6.40GPa, modulus 296GPa).At present even report is arranged, developed the high-performance carbon fibre of intensity in the laboratory scope up to 9.3GPa.In addition, the modulus of high model polypropylene fibre has also reached 690GPa (M70J), and the development of performance is very rapid.On output, the high-performance polypropylene carbon fiber was with the speed increase in every year 15% in recent years.At present, international high-performance polyacrylonitrile carbon fiber market has basically formed that quality height, output increase, price descends, the general layout of the excessive such benign development of Application Areas, emphasizes that the high ratio of performance to price is the development general trend of carbon fiber.
China's carbon fiber no matter still in quantity from quality, it is very big to compare gap in foreign country, quantity only accounts for 0.4% of Gross World Product, the basic dependence on import of required carbon fiber.Still can not stably manufactured even even be doomed T-300 grade carbon fiber on the verge of being replaced at present.Major cause is that there is following problem in domestic carbon fibre: performance is low, and fluctuation is big, and fiber surface is handled problems does not have fine solution, and kind is single, linear density is inhomogeneous, has lousiness, hair ball, and continuous length is not enough, inconsistent, possible knitting property is poor, colludes with powerful lowly, and price is expensive.
Tracing it to its cause, mainly is that the polyacrylonitrile fibre precursor does not pass a test, and the quality problems of precursor have become " bottleneck " of restriction China development carbon fiber industry.And the inorganic and organic impurity in the raw material has fatal influence to the quality of precursor, experimental results demonstrate that the polyacrylonitrile fibril that impurity is high can not make high performance carbon fiber.Thereby requiring basic metal in the polyacrylonitrile resin, the total content of alkaline-earth metal is controlled at below the 50mg/Kg, preferably is controlled at below the 30mg/Kg; Polymer raw, solvent to synthetic precursor have very high requirement, and metallic impurity should be reduced to 10 -6The level level.
The cost of purified feed stock is high simultaneously, is directly restricting the price of carbon fiber.The purifying of employed solvent dimethyl sulfoxide (DMSO) in the acrylonitrile polymerization mainly is the method that adopts repeatedly rectifying at present; Because the boiling point of dimethyl sulfoxide (DMSO) is very high, suction need make the cost of carbon fiber improve greatly through repeatedly rectifying easily.But never to how to reduce cost, high efficiency purifying polymer solvent carries out intensive research for many years.
Therefore, a kind of purification process of necessary searching, this method requires the yield height, and is easy and simple to handle, with low cost, is fit to the mass production of carbon fiber.
Summary of the invention
The present invention relates generally to the middle potassium of polyacrylonitrile carbon fiber polymer solvent-dimethyl sulfoxide (DMSO) (DMSO), sodium, calcium, magnesium or/and ferrous metal ionic purifying and detection method.The principle of proposition utilization Static Adsorption exchange removes the metallic impurity in the methyl-sulphoxide; Remove iron ion in the organic phase with macropore weak base type acrylic acid type anion exchange resin, remove calcium, magnesium, sodium and potassium ion in the organic solution with macropore strong acid styrene type Zeo-karb.Use the concentration of each metal ion in the ultraviolet spectrophotometry rapid detection organic solvent simultaneously, proposition is with phenanthroline colorimetric method for determining Fe ionic content, chlorophosphonazo I colorimetric method for determining Ca, Mg ionic content, 18-hat-6 synergistic extraction methods are measured the method for K ion content.
The working method of the metallic impurity in the utilization absorption exchange principle purifying dimethyl sulfoxide (DMSO):
The pre-treatment of resin and the activation of resin:
Selected resin is macropore strong acid styrene type Zeo-karb and macropore weak base type acrylic acid type anion exchange resin; The granularity of used resin is 0.3-1.2mm.The pretreatment process of above-mentioned yin, yang ion exchange resin is that 25 ℃ of dry activation are standby after 8 hours in vacuum drying oven.
The general operation method:
Get a certain amount of organic solvent to be purified and put into reaction flask, press V: M=1.5-50 (V: the volume of dimethyl sulfoxide (DMSO); M: the ratio quality of used resin) adds the good macropore weak base type acrylic acid type anion exchange resin of activation, stirs 1-5 hour down at 30 ℃, again with V: M=1.5-50 (V: the volume of dimethyl sulfoxide (DMSO); M: the macropore strong acid styrene type Zeo-karb that it is good that the ratio quality of used resin) adds activation continues to stir 1-5 hour at 30 ℃, filter with sand core funnel, the ionic concn of filtrate is measured by atomic absorption spectrometry and ultraviolet visible spectrophotometry.
Described macropore weak base type acrylic acid type anion exchange resin is D315 macropore weak base type acrylic acid type anion exchange resin, D301 macropore weak base type acrylic acid type anion exchange resin, D311 macropore weak base type acrylic acid type anion exchange resin and D335 macropore weak base type acrylic acid type anion exchange resin, and described macropore strong acid styrene type Zeo-karb is D001 macropore strong acid styrene type Zeo-karb, D-62 macropore strong acid styrene type Zeo-karb and D002 macropore strong acid styrene type Zeo-karb.
The measuring method of each metal ion content:
The content of phenanthroline spectrophotometry iron ion
Reagent:
1. oxammonium hydrochloride methanol solution (4%): 4 gram oxammonium hydrochlorides are dissolved in 100 ml methanol
2. phenanthroline methanol solution (0.4%): 0.4 gram phenanthroline is dissolved in 100 ml methanol
3. acetum (5%): 5 milliliters of analytically pure Glacial acetic acid are dissolved in 95 ml methanol
Iron standardized solution: accurately take by weighing impurity and the organism of removing the surface with ether or ethanol, and drying analytical pure iron wire 0.1 gram, be placed in the beaker and and cover it, earlier with 1: 1 nitric acid dissolve with watch-glass, heating is near then does, and removes wherein NO with 1: 1 HCl 3 -, 2 times repeatedly, also quantitatively transfer in 250 milliliters of volumetric flasks with 15 milliliter 10% HCl dissolving at last, be diluted with water to scale again, promptly get the storing solution of the iron of 1 milliliter=400 microgram Fe; Its solution is got 10 milliliters to be placed in 100 milliliters the volumetric flask, again with distilled water diluting to scale, both got the standardized solution (mark liquid 1) (1 milliliter=40 microgram Fe) of iron, its solution is got 1 milliliter to be placed in 10 milliliters the volumetric flask, again with distilled water diluting to scale, both the standardized solution (mark liquid 2) (1 milliliter=4 microgram Fe) of iron.
The drafting of typical curve: the iron mark liquid 2 that pipettes 0,0.5,1.0,2.0,2.5 milliliter, 0.5,1.0 milliliters iron mark liquid 1 places 10 milliliters of volumetric flasks respectively, adding 2 milliliters again contains 4% oxammonium hydrochloride methanol solution and 1 milliliter and contains 0.4% phenanthroline methanol solution, with the extremely nearly scale of distilled water diluting, regulate its pH value about 5 with 5% Glacial acetic acid, be diluted to scale at last, in the wavelength place of 510nm, read its absorbance, the drawing standard curve.(Y-axis: absorbance, X-axis: Fe% (ppm)).
The test sample product: draw 1 milliliter of polyacrylonitrile carbon fiber polymerization organic solvent dimethyl sulfoxide (DMSO) sample solution,, below operation is the same
Chlorophosphonazo I spectrophotometry micrometer simultaneously amount Ca, Mg ionic content
Reagent:
1. chlorophosphonazo I: 0.25% the aqueous solution
2. the pH=10.5 buffered soln of sodium tetraborate (borax)-sodium hydroxide: take by weighing 1.05 gram boraxs, 0.2 gram sodium hydroxide is dissolved in water, and is diluted to 50 milliliters.
3. trolamine: 25% the aqueous solution
4. phenanthroline: 0.2% solution.Take by weighing 0.2 gram phenanthroline, be dissolved in 20% the ethanol.
5. ethylene glycol diethyl ether ethylenediamine tetraacetic acid (EDTA) (EGTA) lead solution: take by weighing 1.9 gram ethylene glycol diethyl ether ethylenediamine tetraacetic acid (EDTA)s, add 40 ml waters, heating, drip the sodium hydroxide solution of 40 grams per liters, transfer to neutrality, add 1.82 gram lead nitrates, transfer to neutrality after the stirring and dissolving again, be diluted to 50 milliliters, it is standby to be stored in drop bottle.
6. magnesium standardized solution: get the pure metal magnesium rod, handle through dilute hydrochloric acid, washing, wipe away do after, place moisture eliminator dry, take by weighing 0.0050 gram magnesium rod, place 50 ml beakers,, move into 50 milliliters of volumetric flasks with a small amount of 50% dissolving with hydrochloric acid, thin up gets per 1 milliliter and contains 100 microgram magnesium standardized solution to scale.
7. calcium standard solution: get 0.0125 gram lime carbonate and place 50 ml beakers, wetting with less water, cover watch-glass, drip a small amount of 50% dissolving with hydrochloric acid, moves into 50 milliliters of volumetric flasks, thin up is to scale, must per 1 milliliter contains 100 microgram calcium standard solutions.
8. calcium-magnesium mixed standard solution: draw 1 milliliter of calcium standard solution and 2.5 milliliters of magnesium standardized solution are dissolved in same 50 milliliters of volumetric flasks, thin up is to scale, per 1 milliliter contains 2 microgram calcium and 5 microgram magnesium standardized solution.
Typical curve is drawn:
Draw 0.0,1.0,2.0,3.0,4.0,5.0,6.0 the calcium-magnesium mixed standard solution of milliliter places 50 milliliters of volumetric flasks respectively, add 1 milliliter of trolamine, 1 milliliter of ethanolic soln that contains 0.2% phenanthroline, 5 milliliters of borax buffer solution, 1 milliliter of 0.25% chlorophosphonazo I solution, after adding, every kind of solution all shakes up, thin up is to scale, pipette 10 milliliters of these solution respectively in two 10 milliliters colorimetric cylinder (numbering 1,2) in, in 1, add 3 EGTA-Pb solution, in 2, add 0.2 milliliter the methyl ethyl diketone aqueous solution (V: V=1: 40), shake up the back respectively at the 575nm place, reagent blank compares the mensuration absorbance A 1, A 2Respectively with A 1Draw magnesium ion quantity typical curve (Y-axis: absorbance, X-axis: Mg% (ppm)), with A 2Draw calcium ion amount typical curve (Y-axis: absorbance, X-axis: Ca% (ppm)).
Sample determination: draw 1 milliliter of polyacrylonitrile carbon fiber polymerization organic solvent dimethyl sulfoxide (DMSO) sample solution, in 50 milliliters of volumetric flasks, below operation is the same.
18-hat-6 extraction spectrophotometric methods are measured the content of potassium ion
Reagent:
1. potassium is marked liquid (10 mcg/ml K): take by weighing 0.0191 gram KCl with 100 milliliters of volumetric flask constant volumes, get potassium mark liquid (100 mcg/ml K), draw this solution and be mixed with the potassium mark liquid that contains potassium 10 mcg/ml.
2.EDTA-lithium solution: take by weighing 2.9 gram EDTA, add 50 ml waters, about about 1.3 grams of repeated hydrogenation Lithium Oxide 98min, to solution clarification, pH=7.Then get the EDTA-Li of 0.2M 2Solution.
3.Li 2C 2O 4-EDTA-lithium mixed solution: with 0.08M Li 2C 2O 4Solution mixes with 0.2M EDTA-lithium solution equal-volume.
4. acetic acid-Lithium Acetate damping fluid: 42 milliliters of 85 milliliters of hydro-oxidation lithiums of acetic acid (0.5M) (0.5M) solution, pH=4.1.
5. bromine potassium phenol green solution: it is green to take by weighing 0.08 gram bromine potassium phenol, is dissolved in 100 milliliters 20% ethanolic soln.
6.18-the dichloromethane solution of hat-6: take by weighing 0.30 gram 18-hat-6, be dissolved in 100 milliliters of methylene dichloride.
Experimental technique:
Divide the standardized solution get a certain amount of potassium in 25 milliliters of separating funnels, add 2.5 milliliters of acetic acid-Lithium Acetate damping fluid successively, 2.0 milliliters of bromine potassium phenol green solutions, Li 2C 2O 4-EDTA-Li 21.0 milliliters of sequestering agents, adding water, to make cumulative volume be 10.0 milliliters.Add 3.5 milliliters of trichloromethanes, 1.5 milliliters of the dichloromethane solutions of 18-hat-6, jolting 1.5 minutes.Separation of C HCl after the phase-splitting 3-CH 2Cl 2Layer is airtight in dried test tube, uses the 1cm colorimetric pool with reagent blank reference measurement absorbancy in the 465nm place after half an hour.
Sample determination: draw 1 milliliter of polyacrylonitrile carbon fiber polymerization organic solvent dimethyl sulfoxide (DMSO) sample solution, in 25 milliliters of separating funnels, below operation is the same.
Characteristics of the present invention are: the method for metal ion in a kind of polymer solvent-dimethyl sulfoxide (DMSO) of using Static Adsorption exchange process purifying polyacrylonitrile carbon fiber is provided, and this method cost is low, and is easy and simple to handle, can be extensive use of.Especially select macroporous resin polymeric adsorbent in return for use, need not carry out swelling in advance, can directly come into operation.In addition, used resin can be regenerated, and reuses.In addition, the utilization ultraviolet spectrophotometry that the present invention proposes detects the method for the concentration of metal ion in the organic solvent, and is easy and simple to handle, fast, with low cost.
Description of drawings
Fig. 1 is the typical curve of phenanthroline spectrophotometry iron ion;
Fig. 2 is chlorophosphonazo I spectrophotometry micrometer simultaneously amount Ca, Mg ionic typical curve;
Fig. 3 is the typical curve that 18-hat-6 extraction spectrophotometric methods are measured potassium ion.
Wherein, Fig. 2-the 1st, chlorophosphonazo I spectrophotometry survey micro Mg ionic standard song simultaneously; Fig. 2-the 2nd, chlorophosphonazo I spectrophotometry micrometer simultaneously amount Ca ionic typical curve.
Nomenclature
Among Fig. 1, Y-axis: absorbance, X-axis: Fe% (ppm); Among Fig. 2, Y-axis: absorbance, X-axis: Mg% (ppm) or Ca% (ppm); A 1Be the magnesium ion quantity typical curve, A 2It is calcium ion amount typical curve; Among Fig. 3, Y-axis: absorbance, X-axis: K% (ppm).
Embodiment
To help to understand the present invention by following embodiment, but not limit content of the present invention.
Among the embodiment, the content of phenanthroline spectrophotometry iron ion
Reagent:
1. oxammonium hydrochloride methanol solution (4%): 4 gram oxammonium hydrochlorides are dissolved in 100 ml methanol
2. phenanthroline methanol solution (0.4%): 0.4 gram phenanthroline is dissolved in 100 ml methanol
3. acetum (5%): 5 milliliters of analytically pure Glacial acetic acid are dissolved in 95 ml methanol
Iron standardized solution: accurately take by weighing impurity and the organism of removing the surface with ether or ethanol, and drying analytical pure iron wire 0.1 gram, be placed in the beaker and and cover it, earlier with 1: 1 nitric acid dissolve with watch-glass, heating is near then does, and removes wherein NO with 1: 1 HCl 3 -, 2 times repeatedly, also quantitatively transfer in 250 milliliters of volumetric flasks with 15 milliliter 10% HCl dissolving at last, be diluted with water to scale again, promptly get the storing solution of the iron of 1 milliliter=400 microgram Fe; Its solution is got 10 milliliters to be placed in 100 milliliters the volumetric flask, again with distilled water diluting to scale, both got the standardized solution (mark liquid 1) (1 milliliter=40 microgram Fe) of iron, its solution is got 1 milliliter to be placed in 10 milliliters the volumetric flask, again with distilled water diluting to scale, both the standardized solution (mark liquid 2) (1 milliliter=4 microgram Fe) of iron.
The drafting of typical curve: the iron mark liquid 2 that pipettes 0,0.5,1.0,2.0,2.5 milliliter, 0.5,1.0 milliliters iron mark liquid 1 places 10 milliliters of volumetric flasks respectively, adding 2 milliliters again contains 4% oxammonium hydrochloride methanol solution and 1 milliliter and contains 0.4% phenanthroline methanol solution, with the extremely nearly scale of distilled water diluting, regulate its pH value about 5 with 5% Glacial acetic acid, be diluted to scale at last, in the wavelength place of 510nm, read its absorbance, the drawing standard curve.(Y-axis: absorbance, X-axis: Fe% (ppm)).Test sample product: draw 1 milliliter of polyacrylonitrile carbon fiber polymerization organic solvent dimethyl sulfoxide (DMSO) sample solution, below operation is the same, place 10 milliliters of volumetric flasks respectively, add 2 milliliters again and contain 4% oxammonium hydrochloride methanol solution and 1 milliliter and contain 0.4% phenanthroline methanol solution, to nearly scale, regulate its pH value about 5 with 5% Glacial acetic acid with distilled water diluting, be diluted to scale at last, wavelength place in 510nm reads its absorbance, tries to achieve Fe according to typical curve 3+Content.
Chlorophosphonazo I spectrophotometry micrometer simultaneously amount Ca, Mg ionic content
Reagent:
1. chlorophosphonazo I: 0.25% the aqueous solution
2. the pH=10.5 buffered soln of sodium tetraborate (borax)-sodium hydroxide: take by weighing 1.05 gram boraxs, 0.2 gram sodium hydroxide is dissolved in water, and is diluted to 50 milliliters.
3. trolamine: 25% the aqueous solution
4. phenanthroline: 0.2% solution.Take by weighing 0.2 gram phenanthroline, be dissolved in 20% the ethanol.
5. ethylene glycol diethyl ether ethylenediamine tetraacetic acid (EDTA) (EGTA) lead solution: take by weighing 1.9 gram ethylene glycol diethyl ether ethylenediamine tetraacetic acid (EDTA)s, add 40 ml waters, heating, drip the sodium hydroxide solution of 40 grams per liters, transfer to neutrality, add 1.82 gram lead nitrates, transfer to neutrality after the stirring and dissolving again, be diluted to 50 milliliters, it is standby to be stored in drop bottle.
6. magnesium standardized solution: get the pure metal magnesium rod, handle through dilute hydrochloric acid, washing, wipe away do after, place moisture eliminator dry, take by weighing 0.0050 gram magnesium rod, place 50 ml beakers,, move into 50 milliliters of volumetric flasks with a small amount of 50% dissolving with hydrochloric acid, thin up gets per 1 milliliter and contains 100 microgram magnesium standardized solution to scale.
7. calcium standard solution: get 0.0125 gram lime carbonate and place 50 ml beakers, wetting with less water, cover watch-glass, drip a small amount of 50% dissolving with hydrochloric acid, moves into 50 milliliters of volumetric flasks, thin up is to scale, must per 1 milliliter contains 100 microgram calcium standard solutions.
8. calcium-magnesium mixed standard solution: draw 1 milliliter of calcium standard solution and 2.5 milliliters of magnesium standardized solution are dissolved in same 50 milliliters of volumetric flasks, thin up is to scale, per 1 milliliter contains 2 microgram calcium and 5 microgram magnesium standardized solution.
Typical curve is drawn:
Draw 0.0,1.0,2.0,3.0,4.0,5.0,6.0 the calcium-magnesium mixed standard solution of milliliter places 50 milliliters of volumetric flasks respectively, add 1 milliliter of trolamine, 1 milliliter of ethanolic soln that contains 0.2% phenanthroline, 5 milliliters of borax buffer solution, 1 milliliter of 0.25% chlorophosphonazo I solution, after adding, every kind of solution all shakes up, thin up is to scale, pipette 10 milliliters of these solution respectively in two 10 milliliters colorimetric cylinder (numbering 1,2) in, in 1, add 3 EGTA-Pb solution, in 2, add 0.2 milliliter the methyl ethyl diketone aqueous solution (V: V=1: 40), shake up the back respectively at the 575nm place, reagent blank compares the mensuration absorbance A 1, A 2Respectively with A 1Draw magnesium ion quantity typical curve (Y-axis: absorbance, X-axis: Mg% (ppm)), with A 2Draw calcium ion amount typical curve (Y-axis: absorbance, X-axis: Ca% (ppm)).
Sample determination: draw 1 milliliter of polyacrylonitrile carbon fiber polymerization organic solvent dimethyl sulfoxide (DMSO) sample solution, in 50 milliliters of volumetric flasks, below operation is the same, respectively at the 575nm place, reads Ca 2+, Mg 2+Absorbance is tried to achieve Ca according to typical curve 2+, Mg 2+Content.
18-hat-6 extraction spectrophotometric methods are measured the content of potassium ion
Reagent:
1. potassium is marked liquid (10 mcg/ml K): take by weighing 0.0191 gram KCl with 100 milliliters of volumetric flask constant volumes, get potassium mark liquid (100 mcg/ml K), draw this solution and be mixed with the potassium mark liquid that contains potassium 10 mcg/ml.
2.EDTA-lithium solution: take by weighing 2.9 gram EDTA, add 50 ml waters, about about 1.3 grams of repeated hydrogenation Lithium Oxide 98min, to solution clarification, pH=7.Then get the EDTA-Li of 0.2M 2Solution.
3.Li 2C 2O 4-EDTA-lithium mixed solution: with 0.08M Li 2C 2O 4Solution mixes with 0.2M EDTA-lithium solution equal-volume.
4. acetic acid-Lithium Acetate damping fluid: 42 milliliters of 85 milliliters of hydro-oxidation lithiums of acetic acid (0.5M) (0.5M) solution, pH=4.1.
5. bromine potassium phenol green solution: it is green to take by weighing 0.08 gram bromine potassium phenol, is dissolved in 100 milliliters 20% ethanolic soln.
6.18-the dichloromethane solution of hat-6: take by weighing 0.30 gram 18-hat-6, be dissolved in 100 milliliters of methylene dichloride.
Experimental technique:
Divide the standardized solution get a certain amount of potassium in 25 milliliters of separating funnels, add 2.5 milliliters of acetic acid-Lithium Acetate damping fluid successively, 2.0 milliliters of bromine potassium phenol green solutions, Li 2C 2O 4-EDTA-Li 21.0 milliliters of sequestering agents, adding water, to make cumulative volume be 10.0 milliliters.Add 3.5 milliliters of trichloromethanes, 1.5 milliliters of the dichloromethane solutions of 18-hat-6, jolting 1.5 minutes.Separation of C HCl after the phase-splitting 3-CH 2Cl 2Layer is airtight in dried test tube, uses the 1cm colorimetric pool with reagent blank reference measurement absorbancy in the 465nm place after half an hour.
Sample determination: draw 1 milliliter of polyacrylonitrile carbon fiber polymerization organic solvent dimethyl sulfoxide (DMSO) sample solution, in 25 milliliters of separating funnels, repeat aforesaid operations,, read K in the 465nm place +Absorbance is tried to achieve K according to typical curve +Content.(Y-axis: absorbance, X-axis: K +% (ppm))
Embodiment 1
Get the dimethyl sulfoxide (DMSO) polymer solvent of a certain amount of polyacrylonitrile carbon fiber to be purified and put into reaction flask, press V: M=25: 1 (V: the volume of dimethyl sulfoxide (DMSO); M: the ratio quality of used resin) adds the good macropore weak base type acrylic acid type anion exchange resin of activation; D315 macropore weak base type acrylic acid type anion exchange resin as Shanghai Huazhen Science and Technology Co., Ltd.; at 30 ℃ of following stir abouts after 1～5 hour; add the good macropore strong acid styrene type Zeo-karb of activation in identical ratio again; D001 macropore strong acid styrene type Zeo-karb as Shanghai Huazhen Science and Technology Co., Ltd.; continuation was 30 ℃ of following stir abouts 1～5 hour; stop to stir; filter with sand core funnel, filtrate is made the mensuration of each concentration of metal ions with atomic absorption spectrometry and ultraviolet visible spectrophotometry.The result is as shown in the table:
Metal ion Initial ionic concn (ppm) Each ionic concentration (ppm) behind the purifying
Atomic absorption spectrometry Ultraviolet visible spectrophotometry
1 Fe 3+ Ca 2+ Mg 2+ Na + K + 42 38 38 27 19 ＜1 ＜1 ＜1 13 ＜1 ＜1 1.5 1.7 - ＜1
2 Fe 3+ Ca 2+ Mg 2+ Na + K + 54 33 23 64 43 3 ＜1 ＜1 40 ＜1 2 ＜1 3 - ＜1
3 Fe 3+ Ca 2+ Mg 2+ Na + K + 98 60 47 64 81 ＜1 ＜1 ＜1 8 2 ＜1 ＜1 ＜1 - 6

Claims (6)

1. the purifying and the detection method of metal ion in the dimethyl sulfoxide (DMSO), it is characterized in that described dimethyl sulfoxide (DMSO) is a polyacrylonitrile carbon fiber polymerization organic solvent dimethyl sulfoxide (DMSO), described metal ion is that potassium, sodium, calcium, magnesium are or/and the ferrous metal ion, iron ion in the organic phase is removed with macropore weak base type acrylic acid type anion exchange resin by system, removes calcium, magnesium, sodium, potassium ion in the organic solution with macropore strong acid styrene type Zeo-karb; Adopt the concentration of each metal ion in the ultraviolet spectrophotometry rapid detection organic solvent then, with phenanthroline colorimetric method for determining Fe 3+Content, chlorophosphonazo I colorimetric method for determining Ca 2+And Mg 2+Content, 18-hat-6 synergistic extraction methods are measured K +The method of content.
2. the purifying and the detection method of metal ion in the dimethyl sulfoxide (DMSO) as claimed in claim 1, it is characterized in that described macropore weak base type acrylic acid type anion exchange resin is a D315 macropore weak base type acrylic acid type anion exchange resin, D301 macropore weak base type acrylic acid type anion exchange resin, D311 macropore weak base type acrylic acid type anion exchange resin or D335 macropore weak base type acrylic acid type anion exchange resin, described macropore strong acid styrene type Zeo-karb is a D001 macropore strong acid styrene type Zeo-karb, D-62 macropore strong acid styrene type Zeo-karb or D002 macropore strong acid styrene type Zeo-karb.
3. the purifying and the detection method of metal ion in the dimethyl sulfoxide (DMSO) as claimed in claim 1 is characterized in that in the described ultraviolet spectrophotometry rapid detection organic solvent with phenanthroline colorimetric method for determining Fe 3+The method of content, elder generation's drawing standard curve: the iron mark liquid 2 that pipettes 0,0.5,1.0,2.0,2.5 milliliter, 0.5,1.0 milliliters iron mark liquid 1 places 10 milliliters of volumetric flasks respectively, add 2 milliliters again and contain 4% oxammonium hydrochloride methanol solution and 1 milliliter and contain 0.4% phenanthroline methanol solution, to nearly scale, regulate its pH value about 5 with 5% Glacial acetic acid with distilled water diluting, be diluted to scale at last, wavelength place in 510nm reads its absorbance, the drawing standard curve;
Draw 1 milliliter of polyacrylonitrile carbon fiber polymerization organic solvent dimethyl sulfoxide (DMSO) sample solution, place 10 milliliters of volumetric flasks respectively, adding 2 milliliters again contains 4% oxammonium hydrochloride methanol solution and 1 milliliter and contains 0.4% phenanthroline methanol solution, with the extremely nearly scale of distilled water diluting, regulate its pH value about 5 with 5% Glacial acetic acid, be diluted to scale at last, in the wavelength place of 510nm, read its absorbance, try to achieve Fe according to typical curve 3+Content.，
4. the purifying and the detection method of metal ion in the dimethyl sulfoxide (DMSO) as claimed in claim 1 is characterized in that in the described ultraviolet spectrophotometry rapid detection organic solvent with chlorophosphonazo I colorimetric method for determining Ca 2+And Mg 2+The method of content be first drawing standard curve: draw 0.0,1.0,2.0,3.0,4.0,5.0,6.0 the calcium-magnesium mixed standard solution of milliliter places 50 milliliters of volumetric flasks respectively, add 1 milliliter of trolamine, 1 milliliter of ethanolic soln that contains 0.2% phenanthroline, 5 milliliters of borax buffer solution, 1 milliliter of 0.25% chlorophosphonazo I solution, after adding, every kind of solution all shakes up, thin up is to scale, pipette 10 milliliters of these solution respectively in two 10 milliliters colorimetric cylinder (numbering 1,2) in, in 1, add 3 EGTA-Pb solution, the methyl ethyl diketone aqueous solution (the V: V=1: 40) that in 2, adds 0.2 milliliter, shake up the back respectively at the 575nm place, reagent blank compares the mensuration absorbance A 1, A 2Respectively with A 1Draw the magnesium ion quantity typical curve, with A 2Draw calcium ion amount typical curve; Sample determination: draw polyacrylonitrile carbon fiber polymerization organic solvent dimethyl sulfoxide (DMSO) sample solution 1 ml soln in 50 milliliters of volumetric flasks, repeat aforesaid operations,, read Ca respectively at respectively at the 575nm place 2+, Mg 2+Absorbance is tried to achieve Ca according to typical curve 2+, Mg 2+Content.
5. the purifying and the detection method of metal ion in the dimethyl sulfoxide (DMSO) as claimed in claim 1 is characterized in that measuring K with 18-hat-6 synergistic extraction methods in the described ultraviolet spectrophotometry rapid detection organic solvent +The method of content is first drawing standard curve: divide the standardized solution get a certain amount of potassium in 25 milliliters of separating funnels, add 2.5 milliliters of acetic acid-Lithium Acetate damping fluid successively, 2.0 milliliters of bromine potassium phenol green solutions, Li 2C 2O 4-EDTA-Li 21.0 milliliters of sequestering agents, adding water, to make cumulative volume be 10.0 milliliters, adds 3.5 milliliters of trichloromethanes, 1.5 milliliters of the dichloromethane solutions of 18-hat-6, jolting 1.5 minutes; Separation of C HCl after the phase-splitting 3-CH 2Cl 2Layer is airtight in dried test tube, uses colorimetric pool with reagent blank reference measurement absorbancy in the 465nm place after half an hour; Sample determination: draw polyacrylonitrile carbon fiber polymerization organic solvent dimethyl sulfoxide (DMSO) sample solution 1 ml soln in 25 milliliters of separating funnels, repeat aforesaid operations,, read K in the 465nm place +Absorbance is tried to achieve K according to typical curve +Content.
6. the purifying and the detection method of metal ion in the dimethyl sulfoxide (DMSO) as claimed in claim 1 is characterized in that described macropore weak base type acrylic acid type anion exchange resin and macropore strong acid styrene type Zeo-karb carry out following pre-treatment: 25 ℃ of dryings activate 8 hours in vacuum drying oven.
CN 200610029253 2006-07-21 2006-07-21 Method of purifying and detecting metal ion in dimethyl sulfoxide Pending CN1887864A (en)

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CN102336902A (en) * 2010-07-27 2012-02-01 中国石油化工集团公司 Refining method of polyether polyol
RU2516656C1 (en) * 2012-10-31 2014-05-20 Федеральное государственное бюджетное учреждение науки Институт элементоорганических соединений им. А.Н. Несмеянова Российской академии наук (ИНЭОС РАН) Zinc dimeric complexes of crown-containing styryl phenanthrolines as optical sensors on cations of alkali-earth and heavy metals and method of their obtaining
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CN107991257A (en) * 2018-01-30 2018-05-04 石家庄市和合化工化肥有限公司 The quantitative detecting method of Sulphur Monochloride and sulphur dichloride impurity content in thionyl chloride
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CN102336902A (en) * 2010-07-27 2012-02-01 中国石油化工集团公司 Refining method of polyether polyol
RU2516656C1 (en) * 2012-10-31 2014-05-20 Федеральное государственное бюджетное учреждение науки Институт элементоорганических соединений им. А.Н. Несмеянова Российской академии наук (ИНЭОС РАН) Zinc dimeric complexes of crown-containing styryl phenanthrolines as optical sensors on cations of alkali-earth and heavy metals and method of their obtaining
CN105606558A (en) * 2016-03-11 2016-05-25 河南科技大学 Method for determining content of sodium fulvate
CN107991257A (en) * 2018-01-30 2018-05-04 石家庄市和合化工化肥有限公司 The quantitative detecting method of Sulphur Monochloride and sulphur dichloride impurity content in thionyl chloride
CN107991257B (en) * 2018-01-30 2020-06-09 石家庄市和合化工化肥有限公司 Quantitative detection method for content of sulfur monochloride and sulfur dichloride impurities in thionyl chloride
US11786841B2 (en) 2020-01-16 2023-10-17 Fujifilm Electronic Materials U.S.A., Inc. Systems and methods for purifying solvents
CN115279486A (en) * 2020-01-16 2022-11-01 富士胶片电子材料美国有限公司 System and method for purifying solvent
CN111392778B (en) * 2020-03-23 2022-08-02 安徽工业大学 Method for deeply purifying and removing potassium from ammonium perrhenate solution
CN111392778A (en) * 2020-03-23 2020-07-10 安徽工业大学 Method for deeply purifying and removing potassium from ammonium perrhenate solution
CN112345478A (en) * 2020-10-12 2021-02-09 威海市计量所 Method for testing content of residual dimethyl sulfoxide in polyacrylonitrile protofilament
CN114436916A (en) * 2020-10-20 2022-05-06 中国石油化工股份有限公司 System and method for recovering and refining dimethyl sulfoxide in carbon fiber production and application of system and method
CN114436916B (en) * 2020-10-20 2024-06-28 中国石油化工股份有限公司 Dimethyl sulfoxide recycling and refining system and method in carbon fiber production and application thereof
CN113267489A (en) * 2021-05-10 2021-08-17 焦作金叶醋酸纤维有限公司 Method for detecting iron ions in slurry

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