CN104744300A - Method for purifying acetonitrile for liquid chromatogram-mass spectrometer - Google Patents
Method for purifying acetonitrile for liquid chromatogram-mass spectrometer Download PDFInfo
- Publication number
- CN104744300A CN104744300A CN201310754188.4A CN201310754188A CN104744300A CN 104744300 A CN104744300 A CN 104744300A CN 201310754188 A CN201310754188 A CN 201310754188A CN 104744300 A CN104744300 A CN 104744300A
- Authority
- CN
- China
- Prior art keywords
- acetonitrile
- mass spectrometer
- purification
- liquid chromatograph
- housed
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 title claims abstract description 336
- 239000007788 liquid Substances 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000002994 raw material Substances 0.000 claims abstract description 15
- 238000001179 sorption measurement Methods 0.000 claims abstract description 11
- 239000002594 sorbent Substances 0.000 claims description 30
- 239000012286 potassium permanganate Substances 0.000 claims description 26
- 238000000746 purification Methods 0.000 claims description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- -1 alcohol compound Chemical class 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 21
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 14
- 239000000706 filtrate Substances 0.000 claims description 12
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 10
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 10
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 claims description 10
- 239000003456 ion exchange resin Substances 0.000 claims description 10
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 230000002829 reductive effect Effects 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 7
- 239000000292 calcium oxide Substances 0.000 claims description 7
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000010410 layer Substances 0.000 claims description 7
- 239000012044 organic layer Substances 0.000 claims description 7
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 7
- 239000000741 silica gel Substances 0.000 claims description 7
- 229910002027 silica gel Inorganic materials 0.000 claims description 7
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 5
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 238000005342 ion exchange Methods 0.000 claims description 3
- IJCMDGBKHKZSJL-UHFFFAOYSA-N acetonitrile sulfuric acid Chemical compound S(=O)(=O)(O)O.S(O)(O)(=O)=O.C(C)#N IJCMDGBKHKZSJL-UHFFFAOYSA-N 0.000 claims 1
- 238000013517 stratification Methods 0.000 claims 1
- 239000012535 impurity Substances 0.000 abstract description 29
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- 229910021645 metal ion Inorganic materials 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 238000004949 mass spectrometry Methods 0.000 description 7
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 6
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 6
- 230000002378 acidificating effect Effects 0.000 description 6
- 150000001299 aldehydes Chemical class 0.000 description 6
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 6
- 230000000536 complexating effect Effects 0.000 description 6
- 238000006386 neutralization reaction Methods 0.000 description 6
- 150000002894 organic compounds Chemical class 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 6
- 241001120493 Arene Species 0.000 description 5
- 239000012530 fluid Substances 0.000 description 5
- 238000004811 liquid chromatography Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000002904 solvent Substances 0.000 description 4
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 238000001819 mass spectrum Methods 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
Landscapes
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
The invention discloses a method for purifying acetonitrile for a liquid chromatogram-mass spectrometer. The method is characterized in that impurities in a raw material acetonitrile are removed through procedures such as modified activated carbon adsorption, and thus acetonitrile for the liquid chromatogram-mass spectrometer can be obtained. By adopting the method for purifying acetonitrile for the liquid chromatogram-mass spectrometer, acetonitrile of which the purity is greater than or equal to 99.99% (wt) can be obtained, the requirements of the liquid chromatogram-mass spectrometer on high purity can be met, the purified acetonitrile can be applied to the field of liquid chromatogram-mass spectrometers, and the application range is widened.
Description
Technical field
The present invention relates to solvent purification field, particularly a kind of method of purification of liquid chromatograph-mass spectrometer acetonitrile.
Background technology
The separating power of chromatogram combines with mass spectrographic qualitative function by the on-line coupling of chromatography-mass spectroscopy, realizes complex mixture quantitative and qualitative analysis more accurately.And also simplify the pretreatment process of sample, make sample analysis easier.Chromatograph-mass spectrometer coupling comprises gas chromatography-mass spectrography and liquid chromatography mass coupling, and LC-MS and gas chromatography mass spectrometry complement one another, and analyzes compound of different nature.
Liquid chromatography mass combined instrument (liquid Chromatograph Mass Spectrometer), being called for short LC-MS, is the high end instrument in Analysis of Organic Substances market.Organic components in organism testing sample can effectively be separated by liquid chromatography (LC), and mass spectrum (MS) to the organism separated analysis one by one, can obtain organic matter molecular mass, the information such as structure and concentration.LC-MS is Analysis of Organic Substances laboratory, medicine, food test room, the requisite analysis tools of department such as production process control, quality inspection.Need to use moving phase in LC organic components to be separated, conventional moving phase is the mixture of methyl alcohol, acetonitrile, water and their different ratioss.As the solvent of moving phase, purity is higher, in sample, separating organic matters effect is better, and the phenomenon that the measured object ionization that the existence because of impurity can be avoided as much as possible to cause of the high solvent of purity is insufficient, particularly metal ion, with measured object complexing in mass spectroscopy, production Interference Peaks in mass spectrum, thus cause causing erroneous judgement to the isoparametric mensuration of molecular weight, greatly reduce the precision of liquid chromatograph-mass spectrometer measuring result.
Acetonitrile, as a kind of solvent of excellent property, can dissolve multiple organic and inorganic and gaseous matter, but its purification is very difficult.Because commercial product acetonitrile is made from petroleum chemicals, so in product containing the many organic impuritys produced in the course of processing as the heterocyclic arene of carbon-carbon double bonds, their boiling range and acetonitrile only have the difference in several years, simultaneously because the chemical property of acetonitrile, as height dissolving power and azeotropic system can be formed with a lot of organism mass-energy, although impurity is very micro-, because there is a lot of azeotropic system, even if use very outstanding rectifying device, be also difficult to remove above-mentioned impurity.On the other hand, traditional acetonitrile purifying technique does not have the operation of ad hoc removal metal ion, makes impurity metal ion content in acetonitrile higher.So be difficult to the acetonitrile accomplishing to meet the requirement of liquid chromatograph-mass spectrometer high purity by existing purification techniques.
Summary of the invention
The object of the invention is to overcome deficiency of the prior art, a kind of method of purification improving the liquid chromatograph-mass spectrometer acetonitrile of acetonitrile purity is provided.
For realizing above object, the present invention is achieved through the following technical solutions:
The method of purification of liquid chromatograph-mass spectrometer acetonitrile, is characterized in that, comprises the steps:
A. get raw material acetonitrile, add potassium permanganate or superoxide wherein and stir, distilling out acetonitrile, remove unsaturated hydrocarbons impurity in raw material acetonitrile as the impurity such as vinyl cyanide, ethanamide.Wherein, superoxide includes but not limited to hydrogen peroxide.
B. the acetonitrile after oxide treatment is passed into the sorbent material post that modified activated carbon is housed and carry out adsorption treatment, for removing the unsaturated organic compound of carbon-carbon double bonds as heterocyclic arene etc.
C. the acetonitrile of step b gained is passed into the sorbent material post that ion exchange resin is housed and carries out ion exchange treatment, remove the impurity such as aldehydes, metal ion, namely obtain purity >=99.99%(wt) liquid chromatograph-mass spectrometer acetonitrile.
Preferably, in described step a, while adding potassium permanganate or superoxide, add sodium hydroxide and calcium oxide, slow down the oxidisability of potassium permanganate, the acidic substance that neutralization oxidation simultaneously produces, adjust ph is in 7 ~ 7.5 scopes.
Preferably, in described step a, before adding potassium permanganate or superoxide, in raw material acetonitrile, add sulfuric acid vibration, generate sulfuric acid ester throw out, and leave standstill under the environment of-30 ~ 20 DEG C, water layer is discarded after layering, and organic layer is filtered, remove sulfuric acid ester precipitation, retain the filtrate being dissolved with acetonitrile.
Preferably, in described step a, before adding potassium permanganate or superoxide, in raw material acetonitrile, add activated carbon, stir 1 ~ 2 hour, make raw material acetonitrile be attached to activated carbon surface, increase the contact area of potassium permanganate or superoxide and raw material acetonitrile, improve oxidation efficiency.
Preferably, also comprise step a ˊ, by adding reductive agent in the acetonitrile to step a gained and stirring, distill out acetonitrile; Described reductive agent is iron protoxide or sodium bicarbonate.
Preferably, in described step b, modified activated carbon is the activated carbon of surface attachment ethylenediamine tetraacetic acid (EDTA).
Preferably, in described step b, before acetonitrile being passed into the sorbent material post that modified activated carbon is housed, first acetonitrile is passed into respectively the sorbent material post that aluminum oxide is housed and the sorbent material post that silica gel is housed, remove peroxide, arene and polar compound class impurity.
Preferably, in described step c, the surface attachment of ion exchange resin has alcohol compound; Described alcohols includes but not limited to methyl alcohol.
Preferably, also comprise steps d, the acetonitrile of adsorption treatment gained is carried out rectifying; Rectifying still Heating temperature is 100 ~ 140 DEG C, acetonitrile liquid temperature 85 ~ 90 DEG C in still, distill out liquid temp and be 80 ~ 83 DEG C, control reflux ratio 10: 1 ~ 8.
The method of purification of liquid chromatograph-mass spectrometer acetonitrile provided by the invention, after potassium permanganate oxidation, carry out ion-exchange through modified active carbon adsorption and ion exchange resin and obtain purity >=99.99%(wt) acetonitrile, meet the high purity requirement of liquid chromatograph-mass spectrometer, the acetonitrile that purification is obtained is applied to liquid chromatograph-mass spectrometer field, expands range of application.Method of purification provided by the invention, the production having filled up domestic acetonitrile of high purity is blank, reduces cost needed for import, alleviates the degree pind down by foreign technology simultaneously.Method of purification provided by the invention also has that energy consumption is low, production process is easy, stable, be applicable to the advantages such as suitability for industrialized production.
Embodiment
Below in conjunction with embodiment, the present invention is described in detail:
Embodiment 1
The method of purification of LC-MS analysis acetonitrile, is characterized in that, comprises the steps:
A. get raw material acetonitrile, add sulfuric acid vibration wherein, generate sulfuric acid ester throw out, and leave standstill under the environment of-30 DEG C, discard water layer after layering, and organic layer is filtered, remove sulfuric acid ester precipitation, retain filtrate.And then in filtrate, add activated carbon, stir 1 hour.Add potassium permanganate after stirring completes and carry out oxide treatment, remove unsaturated hydrocarbons impurity as the impurity such as vinyl cyanide, ethanamide.While adding potassium permanganate, add sodium hydroxide and calcium oxide, slow down the oxidisability of potassium permanganate, the acidic substance that neutralization oxidation simultaneously produces, adjust ph is 7.After oxide treatment, distill out acetonitrile rapidly.
A ˊ. by adding reductive agent iron protoxide in the acetonitrile to step a gained and stirring, distill out acetonitrile.
B. the acetonitrile that step a ˊ distills out being passed into respectively the sorbent material post that aluminum oxide is housed, the sorbent material post that silica gel is housed and surface attachment is housed has the sorbent material post of the modified activated carbon of ethylenediamine tetraacetic acid (EDTA) to carry out adsorption treatment, for removing the unsaturated organic compound of oxide-based, arene, polar compound class and carbon-carbon double bonds as impurity such as heterocyclic arenes.
C. the acetonitrile of step b gained is passed into and the sorbent material post that surface attachment has the ion exchange resin of methyl alcohol is housed, remove the impurity such as aldehydes, metal ion.Avoid metal ion in mass spectroscopy with measured object complexing and production Interference Peaks, improve the precision of liquid chromatograph-mass spectrometer measuring result.
D. the acetonitrile of step c gained carried out rectifying, rectifying still Heating temperature is 100 DEG C, acetonitrile liquid temperature 85 DEG C in still, distill out liquid temp and be 80 DEG C, control reflux ratio 10: 1.Rectifying fluid detect qualified rear bottling, inflated with nitrogen preserve, namely obtain purity >=99.99%(wt) liquid chromatograph-mass spectrometer acetonitrile.
Embodiment 2
The method of purification of LC-MS analysis acetonitrile, is characterized in that, comprises the steps:
A. get raw material acetonitrile, add sulfuric acid vibration wherein, generate sulfuric acid ester throw out, and leave standstill under the environment of 20 DEG C, discard water layer after layering, and organic layer is filtered, remove sulfuric acid ester precipitation, retain filtrate.And then in filtrate, add activated carbon, stir 2 hours.Add potassium permanganate after stirring completes and carry out oxide treatment, remove unsaturated hydrocarbons impurity as the impurity such as vinyl cyanide, ethanamide.While adding potassium permanganate, add sodium hydroxide and calcium oxide, slow down the oxidisability of potassium permanganate, the acidic substance that neutralization oxidation simultaneously produces, adjust ph is 7.5.After oxide treatment, distill out acetonitrile rapidly.
A ˊ. by adding reductive agent iron protoxide in the acetonitrile to step a gained and stirring, distill out acetonitrile.
B. the acetonitrile that step a ˊ distills out being passed into respectively the sorbent material post that aluminum oxide is housed, the sorbent material post that silica gel is housed and surface attachment is housed has the sorbent material post of the modified activated carbon of ethylenediamine tetraacetic acid (EDTA) to carry out adsorption treatment, for removing the unsaturated organic compound of oxide-based, arene, polar compound class and carbon-carbon double bonds as impurity such as heterocyclic arenes.
C. the acetonitrile of step b gained is passed into and the sorbent material post that surface attachment has the ion exchange resin of methyl alcohol is housed, remove the impurity such as aldehydes, metal ion.Avoid metal ion in mass spectroscopy with measured object complexing and production Interference Peaks, improve the precision of liquid chromatograph-mass spectrometer measuring result.
D. the acetonitrile of step c gained carried out rectifying, rectifying still Heating temperature is 140 DEG C, acetonitrile liquid temperature 90 DEG C in still, distill out liquid temp and be 83 DEG C, control reflux ratio 10: 8.Rectifying fluid detect qualified rear bottling, inflated with nitrogen preserve, namely obtain purity >=99.99%(wt) liquid chromatograph-mass spectrometer acetonitrile.
Embodiment 3
The method of purification of LC-MS analysis acetonitrile, is characterized in that, comprises the steps:
A. get raw material acetonitrile, add sulfuric acid vibration wherein, generate sulfuric acid ester throw out, and leave standstill under the environment of-10 DEG C, discard water layer after layering, and organic layer is filtered, remove sulfuric acid ester precipitation, retain filtrate.And then in filtrate, add activated carbon, stir 1.5 hours.Add potassium permanganate after stirring completes and carry out oxide treatment, remove unsaturated hydrocarbons impurity as the impurity such as vinyl cyanide, ethanamide.While adding potassium permanganate, add sodium hydroxide and calcium oxide, slow down the oxidisability of potassium permanganate, the acidic substance that neutralization oxidation simultaneously produces, adjust ph is 7.After oxide treatment, distill out acetonitrile rapidly.
A ˊ. by adding reductive agent sodium bicarbonate in the acetonitrile to step a gained and stirring, distill out acetonitrile.
B. the acetonitrile that step a ˊ distills out being passed into respectively the sorbent material post that aluminum oxide is housed, the sorbent material post that silica gel is housed and surface attachment is housed has the sorbent material post of the modified activated carbon of ethylenediamine tetraacetic acid (EDTA) to carry out adsorption treatment, for removing the unsaturated organic compound of oxide-based, arene, polar compound class and carbon-carbon double bonds as impurity such as heterocyclic arenes.
C. the acetonitrile of step b gained is passed into and the sorbent material post that surface attachment has the ion exchange resin of methyl alcohol is housed, remove the impurity such as aldehydes, metal ion.Avoid metal ion in mass spectroscopy with measured object complexing and production Interference Peaks, improve the precision of liquid chromatograph-mass spectrometer measuring result.
D. the acetonitrile of step c gained carried out rectifying, rectifying still Heating temperature is 120 DEG C, acetonitrile liquid temperature 86 DEG C in still, distill out liquid temp and be 82 DEG C, control reflux ratio 10: 5.Rectifying fluid detect qualified rear bottling, inflated with nitrogen preserve, namely obtain purity >=99.99%(wt) liquid chromatograph-mass spectrometer acetonitrile.
Embodiment 4
The method of purification of LC-MS analysis acetonitrile, is characterized in that, comprises the steps:
A. get raw material acetonitrile, add sulfuric acid vibration wherein, generate sulfuric acid ester throw out, and leave standstill under the environment of 10 DEG C, discard water layer after layering, and organic layer is filtered, remove sulfuric acid ester precipitation, retain filtrate.And then in filtrate, add activated carbon, stir 2 hours.Add potassium permanganate after stirring completes and carry out oxide treatment, remove unsaturated hydrocarbons impurity as the impurity such as vinyl cyanide, ethanamide.While adding potassium permanganate, add sodium hydroxide and calcium oxide, slow down the oxidisability of potassium permanganate, the acidic substance that neutralization oxidation simultaneously produces, adjust ph is 7.After oxide treatment, distill out acetonitrile rapidly.
A ˊ. by adding reductive agent sodium bicarbonate in the acetonitrile to step a gained and stirring, distill out acetonitrile.
B. the acetonitrile that step a ˊ distills out being passed into respectively the sorbent material post that aluminum oxide is housed, the sorbent material post that silica gel is housed and surface attachment is housed has the sorbent material post of the modified activated carbon of ethylenediamine tetraacetic acid (EDTA) to carry out adsorption treatment, for removing the unsaturated organic compound of oxide-based, arene, polar compound class and carbon-carbon double bonds as impurity such as heterocyclic arenes.
C. the acetonitrile of step b gained is passed into and the sorbent material post that surface attachment has the ion exchange resin of methyl alcohol is housed, remove the impurity such as aldehydes, metal ion.Avoid metal ion in mass spectroscopy with measured object complexing and production Interference Peaks, improve the precision of liquid chromatograph-mass spectrometer measuring result.
D. the acetonitrile of step c gained carried out rectifying, rectifying still Heating temperature is 130 DEG C, acetonitrile liquid temperature 89 DEG C in still, distill out liquid temp and be 81 DEG C, control reflux ratio 10: 6.Rectifying fluid detect qualified rear bottling, inflated with nitrogen preserve, namely obtain purity >=99.99%(wt) liquid chromatograph-mass spectrometer acetonitrile.
Embodiment 5
The method of purification of LC-MS analysis acetonitrile, is characterized in that, comprises the steps:
A. get raw material acetonitrile, add sulfuric acid vibration wherein, generate sulfuric acid ester throw out, and leave standstill under the environment of 7 DEG C, discard water layer after layering, and organic layer is filtered, remove sulfuric acid ester precipitation, retain filtrate.And then in filtrate, add activated carbon, stir 1.2 hours.Add potassium permanganate after stirring completes and carry out oxide treatment, remove unsaturated hydrocarbons impurity as the impurity such as vinyl cyanide, ethanamide.While adding potassium permanganate, add sodium hydroxide and calcium oxide, slow down the oxidisability of potassium permanganate, the acidic substance that neutralization oxidation simultaneously produces, adjust ph is 7.4.After oxide treatment, distill out acetonitrile rapidly.
A ˊ. by adding reductive agent sodium bicarbonate in the acetonitrile to step a gained and stirring, distill out acetonitrile.
B. the acetonitrile that step a ˊ distills out being passed into respectively the sorbent material post that aluminum oxide is housed, the sorbent material post that silica gel is housed and surface attachment is housed has the sorbent material post of the modified activated carbon of ethylenediamine tetraacetic acid (EDTA) to carry out adsorption treatment, for removing the unsaturated organic compound of oxide-based, arene, polar compound class and carbon-carbon double bonds as impurity such as heterocyclic arenes.
C. the acetonitrile of step b gained is passed into and the sorbent material post that surface attachment has the ion exchange resin of methyl alcohol is housed, remove the impurity such as aldehydes, metal ion.Avoid metal ion in mass spectroscopy with measured object complexing and production Interference Peaks, improve the precision of liquid chromatograph-mass spectrometer measuring result.
D. the acetonitrile of step c gained carried out rectifying, rectifying still Heating temperature is 140 DEG C, acetonitrile liquid temperature 90 DEG C in still, distill out liquid temp and be 82 DEG C, control reflux ratio 10: 4.Rectifying fluid detect qualified rear bottling, inflated with nitrogen preserve, namely obtain purity >=99.99%(wt) liquid chromatograph-mass spectrometer acetonitrile.
Embodiment in the present invention, only for the present invention will be described, does not form the restriction to right, other equivalent in fact substituting, all in scope that those skilled in that art can expect.
Claims (9)
1. the method for purification of liquid chromatograph-mass spectrometer acetonitrile, is characterized in that, comprises the steps:
A. get raw material acetonitrile, add potassium permanganate or superoxide wherein and after stirring, distill out acetonitrile;
B. the acetonitrile distilled out in step a is passed into the sorbent material post that modified activated carbon is housed and carry out adsorption treatment;
C. the acetonitrile of step b gained is passed into the sorbent material post that ion exchange resin is housed and carries out ion exchange treatment, obtain purity >=99.99%(wt) liquid chromatograph-mass spectrometer acetonitrile.
2. the method for purification of liquid chromatograph-mass spectrometer acetonitrile according to claim 1, is characterized in that, in described step a, while adding potassium permanganate or superoxide, adds sodium hydroxide and calcium oxide.
3. the method for purification of liquid chromatograph-mass spectrometer acetonitrile according to claim 1, it is characterized in that, in described step a, before adding potassium permanganate or superoxide, add in raw material acetonitrile sulfuric acid vibration, and under the environment of-30 ~ 20 DEG C stratification, discard water layer, and organic layer is filtered, retain filtrate.
4. the method for purification of liquid chromatograph-mass spectrometer acetonitrile according to claim 1, is characterized in that, in described step a, before adding potassium permanganate or superoxide, in raw material acetonitrile, adds activated carbon, stirs 1 ~ 2 hour.
5. the method for purification of liquid chromatograph-mass spectrometer acetonitrile according to claim 1, is characterized in that, also comprises step a ˊ, will add reductive agent and after stirring, distill out acetonitrile in the acetonitrile to step a gained; Described reductive agent is iron protoxide or sodium bicarbonate.
6. the method for purification of liquid chromatograph-mass spectrometer acetonitrile according to claim 1, is characterized in that, in described step b, modified activated carbon is the activated carbon of surface attachment ethylenediamine tetraacetic acid (EDTA).
7. the method for purification of liquid chromatograph-mass spectrometer acetonitrile according to claim 1, it is characterized in that, in described step b, before acetonitrile being passed into the sorbent material post that modified activated carbon is housed, first acetonitrile is passed into respectively the sorbent material post that aluminum oxide is housed and the sorbent material post that silica gel is housed.
8. the method for purification of liquid chromatograph-mass spectrometer acetonitrile according to claim 1, is characterized in that, in described step c, the surface attachment of ion exchange resin has alcohol compound.
9. the method for purification of the liquid chromatograph-mass spectrometer acetonitrile according to above-mentioned any one claim, is characterized in that, also comprise steps d, and the acetonitrile of adsorption treatment gained is carried out rectifying; Rectifying still Heating temperature is 100 ~ 140 DEG C, acetonitrile liquid temperature 85 ~ 90 DEG C in still, distill out liquid temp and be 80 ~ 83 DEG C, control reflux ratio 10: 1 ~ 8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310754188.4A CN104744300A (en) | 2013-12-31 | 2013-12-31 | Method for purifying acetonitrile for liquid chromatogram-mass spectrometer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310754188.4A CN104744300A (en) | 2013-12-31 | 2013-12-31 | Method for purifying acetonitrile for liquid chromatogram-mass spectrometer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104744300A true CN104744300A (en) | 2015-07-01 |
Family
ID=53584656
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310754188.4A Pending CN104744300A (en) | 2013-12-31 | 2013-12-31 | Method for purifying acetonitrile for liquid chromatogram-mass spectrometer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104744300A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105085317A (en) * | 2014-05-16 | 2015-11-25 | 上海星可高纯溶剂有限公司 | Purification method of acetonitrile for liquid chromatography-mass spectrometer |
| CN105439903A (en) * | 2015-12-05 | 2016-03-30 | 山东汇海医药化工有限公司 | Method for preparing chromatographic acetonitrile by utilizing industrial acetonitrile |
| CN111413441A (en) * | 2020-05-06 | 2020-07-14 | 湖北弗顿生化科技有限公司 | An improved acetonitrile purification process for ultra-high liquid chromatography-mass spectrometry |
| CN116120210A (en) * | 2022-12-29 | 2023-05-16 | 南通立洋化学有限公司 | A kind of purification method and its application of acetonitrile produced by ammoniation of acetic acid |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5292919A (en) * | 1992-05-21 | 1994-03-08 | Cryodyne Technologies, Inc. | Method for purification of acetonitrile |
| EP0890572A1 (en) * | 1997-07-08 | 1999-01-13 | The Standard Oil Company | Purification of acetonitrile by a distillative recovery/ion exchange resin treatment process |
| WO2005044783A2 (en) * | 2003-11-04 | 2005-05-19 | Lonza Ag | Acetonitrile recycling process |
| CN101171233A (en) * | 2005-05-10 | 2008-04-30 | 旭化成化学株式会社 | High-purity acetonitrile and its manufacturing method |
| CN101570498A (en) * | 2009-05-27 | 2009-11-04 | 安庆市时菱化工有限公司 | Method for producing HPLC acetonitrile by multistage reaction-fractionating method |
| CN102746187A (en) * | 2012-07-18 | 2012-10-24 | 天津康科德医药化工有限公司 | Preparation method for liquid chromatography mass spectrometry (LC-MS)-grade high-purity acetonitrile reagents |
-
2013
- 2013-12-31 CN CN201310754188.4A patent/CN104744300A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5292919A (en) * | 1992-05-21 | 1994-03-08 | Cryodyne Technologies, Inc. | Method for purification of acetonitrile |
| EP0890572A1 (en) * | 1997-07-08 | 1999-01-13 | The Standard Oil Company | Purification of acetonitrile by a distillative recovery/ion exchange resin treatment process |
| WO2005044783A2 (en) * | 2003-11-04 | 2005-05-19 | Lonza Ag | Acetonitrile recycling process |
| CN101171233A (en) * | 2005-05-10 | 2008-04-30 | 旭化成化学株式会社 | High-purity acetonitrile and its manufacturing method |
| CN101570498A (en) * | 2009-05-27 | 2009-11-04 | 安庆市时菱化工有限公司 | Method for producing HPLC acetonitrile by multistage reaction-fractionating method |
| CN102746187A (en) * | 2012-07-18 | 2012-10-24 | 天津康科德医药化工有限公司 | Preparation method for liquid chromatography mass spectrometry (LC-MS)-grade high-purity acetonitrile reagents |
Non-Patent Citations (4)
| Title |
|---|
| LARS CARLSEN 等: "Purification of Acetonitrile", 《ANALYTICAL CHEMISTRY》 * |
| 白聪丽 等: "用于乙腈精制的高效氧化剂的筛选", 《石油化工》 * |
| 白聪丽 等: "高纯乙腈的应用及其提纯与精制工艺", 《山东化工》 * |
| 郑学根: "色谱级乙腈的研究与应用", 《化工科技市场》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105085317A (en) * | 2014-05-16 | 2015-11-25 | 上海星可高纯溶剂有限公司 | Purification method of acetonitrile for liquid chromatography-mass spectrometer |
| CN105439903A (en) * | 2015-12-05 | 2016-03-30 | 山东汇海医药化工有限公司 | Method for preparing chromatographic acetonitrile by utilizing industrial acetonitrile |
| CN111413441A (en) * | 2020-05-06 | 2020-07-14 | 湖北弗顿生化科技有限公司 | An improved acetonitrile purification process for ultra-high liquid chromatography-mass spectrometry |
| CN111413441B (en) * | 2020-05-06 | 2022-04-19 | 湖北弗顿生化科技有限公司 | An improved method for purification of acetonitrile by ultra-high liquid chromatography-mass spectrometry |
| CN116120210A (en) * | 2022-12-29 | 2023-05-16 | 南通立洋化学有限公司 | A kind of purification method and its application of acetonitrile produced by ammoniation of acetic acid |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Walter et al. | Purification of acetonitrile | |
| Iranifam et al. | A novel selenium nanoparticles-enhanced chemiluminescence system for determination of dinitrobutylphenol | |
| CN107300598B (en) | A pretreatment method for the detection of multiple pesticide residues in tea | |
| CN104744300A (en) | Method for purifying acetonitrile for liquid chromatogram-mass spectrometer | |
| CN103389349B (en) | Method for detecting content of malachite green and metabolin thereof in aquiculture environment water body | |
| CN104535669A (en) | Method capable of simultaneous determination of various trace anions in water vapor of thermal power generating unit | |
| CN103399096A (en) | Method for detecting content of malachite green and metabolin thereof in sediment of aquaculture environment | |
| CN105085140A (en) | Purification method of n-hexane for liquid chromatography-mass spectrometer | |
| CN106596751B (en) | A kind of high performance liquid chromatography-electrospray mass spectrometry detection method of chlorinated disinfection by-products dichloroacetamide and trichloroacetamide | |
| CN102967680B (en) | Analysis system with combined capillary tube ion chromatography and mass spectrum | |
| CN104374857B (en) | Flumetralim, butralin and the measuring method except the logical residual quantity of bud in a kind of tobacco | |
| CN107935887A (en) | A kind of preparation method of gradient level acetonitrile | |
| CN105085184A (en) | Purification method of isopropyl alcohol for liquid chromatography-mass spectrometer | |
| CN105085317A (en) | Purification method of acetonitrile for liquid chromatography-mass spectrometer | |
| CN101949910B (en) | Ion chromatography for analyzing various trace metal ions in dye at the same time | |
| CN106588844B (en) | A kind of water-soluble coumarin class fluorescence probe and its preparation method and application | |
| CN110668909B (en) | Purification method of environment-friendly n-hexane | |
| CN106645539B (en) | A kind of method of ultra performance liquid chromatography tandem mass spectrum detection phosethyl-Al | |
| CN103983736A (en) | Method for analyzing and detecting fluorine ions in complex matrix through membrane distillation technology as sample pretreatment method combined with ion chromatography | |
| CN105085179A (en) | Purification method of methanol for liquid chromatography-mass spectrometer | |
| CN105085260A (en) | Purification method of ethyl acetate for liquid chromatography-mass spectrometer | |
| CN1397802A (en) | Method for separating and analyzing Nb, Ta, Zr and Hf | |
| JP6348193B1 (en) | Amino acid origin discrimination method | |
| CN104280491B (en) | An analytical method for detecting 11 kinds of ionic liquid cations in soil | |
| JP5085436B2 (en) | Analysis method of organic fluorine compounds |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20150701 |