CN102775327A - Composite oxidizer and method for preparing high efficiency liquid chromatography eluate acetonitrile by using same - Google Patents
Composite oxidizer and method for preparing high efficiency liquid chromatography eluate acetonitrile by using same Download PDFInfo
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- CN102775327A CN102775327A CN201210299189XA CN201210299189A CN102775327A CN 102775327 A CN102775327 A CN 102775327A CN 201210299189X A CN201210299189X A CN 201210299189XA CN 201210299189 A CN201210299189 A CN 201210299189A CN 102775327 A CN102775327 A CN 102775327A
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Abstract
The invention belongs to the technical field of purification of chemical products, and particularly relates to a composite oxidizer and a method for preparing high efficiency liquid chromatography eluate acetonitrile by using the same. The composite oxidizer is composed of potassium superoxide, potassium hydroxide and sodium hydroxide. The method for preparing high efficiency liquid chromatography eluate acetonitrile by using the composite oxidizer comprises the following steps: adsorbing the raw material acetonitrile with the content of more than 99.5% with an active aluminum oxide-activated carbon-3A molecular sieve three-layer adsorption bed, oxidizing by the composite oxidizer, rectifying, and filtering to obtain the high efficiency liquid chromatography eluate acetonitrile. The composite oxidizer provided by the invention overcomes the defect of long oxidization time in the use of the single oxidizer, saves the reaction time, and has better oxidization effect; the preparation method has the advantage of simple and stable operation, and is suitable for large-scale production; and when the method is used for preparing the chromatography acetonitrile, the product yield can reach more than 95%, and the product quality achieves the quality level of like products abroad.
Description
Technical field
The present invention relates to the purification technique field of Chemicals, be specifically related to a kind of composite oxidant and utilize the method for its preparative high-performance liquid chromatographic leacheate acetonitrile.
Background technology
Performance liquid chromatography leacheate acetonitrile is one of liquid chromatography moving phase of using always; The purity requirement of chromatographic grade acetonitrile reaches more than 99.9%; Water cut will be lower than 1ppm; And the main source of grade acetonitrile is a by product of producing vinyl cyanide, so can produce or bring into impurity inevitably aborning at acetonitrile.The impurity that possibly contain in the commercial product acetonitrile mainly comprise prussic acid, vinyl cyanide, acetaldehyde, acetone, propionitrile, methyl alcohol, propenal, methacrylonitrile, cis and trans-2-butene nitrile, uh azoles, vinyl carbinol, water etc., need take the chemistry or physical method further remove these impurity.
So far; Reported the process for refining of multiple acetonitrile both at home and abroad; Wherein main purification process comprises: multistage rectification, oxidation distillation combination, absorption, oxidation-absorption combination etc., choose different purification process to different impurities in the primary industry acetonitrile.In these methods; The overwhelming majority has all adopted oxidation as means of purification; And at present many be the oxidation that oxygenant carries out commercial product acetonitrile with sodium hydroxide, potassium permanganate, Vanadium Pentoxide in FLAKES etc. or ozone; And combine the means of distillation or absorption can obtain the chromatographic grade acetonitrile, but its shortcoming is that the oxygenant consumption is big, oxidization time long, reaction is violent, has residue manganese salt, contaminate environment and product yield on the low side.
And along with the isolating needs of liquid chromatography; The demand of low uv-absorbing, low suspended particle, low potential of hydrogen and low evaporation of residual reagent increases; Wherein the leacheate of liquid chromatography gradient elution need be than the chromatographically pure ultrapure acetonitrile product of performance liquid chromatography leacheate more, to satisfy the needs of scientific research.
Summary of the invention
First purpose of the present invention is the problem that exists in used reagent of oxide treatment among the present performance liquid chromatography leacheate acetonitrile preparation technology and the oxidising process a kind of composite oxidant to be provided.Used oxygenant is compared in this composite oxidant and the present existing acetonitrile purification process; Oxidization time is shorter; Oxidation effectiveness is better; Through simple rectification process, can reach the standard of offshore company's chromatogram acetonitrile through the acetonitrile after the composite oxidant oxidation of the present invention, finished product chromatographic grade acetonitrile yield reaches more than 95%.
Second purpose of the present invention has been to provide a kind of method of utilizing above-mentioned composite oxidant preparative high-performance liquid chromatographic leacheate acetonitrile.
In order to realize above-mentioned first purpose, the present invention has taked following technical measures:
A kind of composite oxidant is made up of potassium superoxide, Pottasium Hydroxide and sodium hydroxide, and the quality percentage composition of each component is following:
Potassium superoxide 5-10%,
Pottasium Hydroxide 30-45%,
Sodium hydroxide 50-65%.
In order to realize above-mentioned second purpose, the present invention has taked following technical measures:
A kind of method of utilizing above-mentioned composite oxidant preparative high-performance liquid chromatographic leacheate acetonitrile, its step is following:
(1), the raw material acetonitrile is passed through three layers of adsorption bed;
Said three layers of adsorption bed are in series by active oxidation aluminium lamination, active carbon layer, 3A molecular sieve layer from top to bottom;
Be equipped with the perforate that is connected with water pump on the exit passageway of each layer adsorption bed, to produce negative pressure, in order to control acetonitrile take-off rate;
(2), the effluent in the step (1) is squeezed into stainless steel cauldron through preheater after being preheated to 30 ~ 50 ℃; Add the composite oxidant that accounts for raw material acetonitrile weight 0.5～2% then; Under nitrogen protection, be heated with stirring to 85-90 ℃ of oxidation 0.5h～2h, steam oxidation liquid;
(3), oxidation liquid that step (2) is obtained sends into rectifying still, the heated oil temperature is 100～140 ℃ in the control rectifying still, rectifying still liquid temperature is 85～90 ℃; 80 ℃～83 ℃ of rectifying still top temperature; Total reflux 1.5～3 hours, control reflux ratio 10: 1～5, fluid; Cut before and after removing promptly gets performance liquid chromatography leacheate acetonitrile through the filtration of 0.2 μ m teflon membrane filter;
The purity of said raw material acetonitrile is not less than 99.5%.
The particle diameter of said activated alumina and gac is 0.2mm.
Compared with prior art, advantage of the present invention and beneficial effect are following:
1, the present invention obtains performance liquid chromatography leacheate acetonitrile with the raw material acetonitrile through multi-compartment bed absorption, combined oxidation, rectifying and filtration, and it is easy, stable and be suitable for the advantage of large-scale production to have method;
2, the product yield for preparing by the inventive method can reach more than 95%, and quality product reaches external like product quality level;
3, the present invention has avoided using the long shortcoming of single-oxidizer oxidization time, has saved the reaction times, and oxidation effectiveness is better.
Embodiment
It should be appreciated by those skilled in the art that following examples only are used for further setting forth technical scheme of the present invention and technique effect, but not the application's claims are asked for protection the restriction of scope.
Embodiment 1:
A kind of preparation method of performance liquid chromatography leacheate acetonitrile, step is following:
(1) raw material acetonitrile (purity is 99.9%) is injected three layers of adsorption bed, three layers of adsorption bed are in series by active oxidation aluminium lamination, active carbon layer, 3A molecular sieve layer from top to bottom, and trilaminar specification is: long 1 meter, high 1 meter, wide 1.2 meters;
Be equipped with the perforate that is connected with water pump on the exit passageway of each layer adsorption bed, to produce negative pressure, in order to control acetonitrile take-off rate;
Wherein, active oxidation aluminium lamination, active carbon layer, 3A molecular sieve layer are filled with the activated alumina that particle diameter is 0.2mm, gac, the 3A molecular sieve that particle diameter is 0.2mm respectively, and the loadings of three kinds of sorbent materials is 1/2 of each layer adsorption bed height;
After acetonitrile injected the active oxidation aluminium lamination, to control three layers of adsorption bed internal pressure size, the control acetonitrile was 110mL/min through the whole flow velocity of three layers of adsorption bed, collects effluent through the adjustment pump power;
(2) effluent that step (1) is obtained is squeezed into stainless steel cauldron after preheater is preheated to 40 ℃, add the composite oxidant that accounts for raw material acetonitrile weight 2%, under nitrogen protection, is heated with stirring to 85 ℃ of oxidation 0.5h, steams oxidation liquid;
The component of described composite oxidant and weight percent are: potassium superoxide 5%, Pottasium Hydroxide 40%, sodium hydroxide 55%;
(3) the oxidation liquid that step (2) is obtained is sent into rectifying still, and the heated oil temperature is 140 ℃ in the control rectifying still, and rectifying still liquid temperature is 90 ℃; 83 ℃ of rectifying still top temperature, total reflux 3 hours, control reflux ratio 10: 3～5; Fluid, cut before and after removing filters bottling with 0.2 μ m teflon membrane filter; Inflated with nitrogen is preserved, and promptly gets performance liquid chromatography leacheate acetonitrile, total recovery 96.1%.
Embodiment 2:
A kind of preparation method of performance liquid chromatography leacheate acetonitrile, step is following:
(1) raw material acetonitrile (purity is 99.5%) is injected three layers of adsorption bed, three layers of adsorption bed are in series by active oxidation aluminium lamination, active carbon layer, 3A molecular sieve layer from top to bottom, and trilaminar specification is: long 0.5 meter, high 0.5 meter, wide 0.6 meter;
Be equipped with the perforate that is connected with water pump on the exit passageway of each layer adsorption bed, to produce negative pressure, in order to control acetonitrile take-off rate;
Wherein, active oxidation aluminium lamination, active carbon layer, 3A molecular sieve layer are filled with the activated alumina that particle diameter is 0.2mm, gac, the 3A molecular sieve that particle diameter is 0.2mm respectively, and the loadings of three kinds of sorbent materials is 1/2 of each adsorption bed height;
After acetonitrile injected the active oxidation aluminium lamination, to control three layers of adsorption bed internal pressure size, the control acetonitrile was 50mL/min through the whole flow velocity of three layers of adsorption bed, collects effluent through the adjustment pump power;
(2) effluent that step (1) is obtained is squeezed into stainless steel cauldron after preheater is preheated to 35 ℃, add the composite oxidant that accounts for raw material acetonitrile weight 0.5%, under nitrogen protection, is heated with stirring to 90 ℃ of oxidation 1.0h, steams oxidation liquid;
The component of described composite oxidant and weight percent are: potassium superoxide 7%, Pottasium Hydroxide 35%, sodium hydroxide 58%;
(3) the oxidation liquid that step (2) is obtained is sent into rectifying still, and the heated oil temperature is 130 ℃ in the control rectifying still, and rectifying still liquid temperature is 85 ℃; 80 ℃ of rectifying still top temperature, total reflux 1.5 hours, control reflux ratio 10: 1～3; Fluid, cut before and after removing filters bottling with 0.2 μ m teflon membrane filter; Inflated with nitrogen is preserved, and promptly gets performance liquid chromatography leacheate acetonitrile, total recovery 95.9%.
The performance liquid chromatography leacheate acetonitrile that embodiment 1 and 2 obtains, through detecting, its quality index all can reach following index:
Claims (5)
1. a composite oxidant is characterized in that: be made up of potassium superoxide, Pottasium Hydroxide and sodium hydroxide.
2. composite oxidant according to claim 1 is characterized in that, the quality percentage composition of each component is following:
Potassium superoxide 5-10%,
Pottasium Hydroxide 30-45%,
Sodium hydroxide 50-65%.
3. method of utilizing claim 1 or 2 described composite oxidant preparative high-performance liquid chromatographic leacheate acetonitriles, its step is following:
(1), the raw material acetonitrile is passed through three layers of adsorption bed;
Said three layers of adsorption bed are in series by active oxidation aluminium lamination, active carbon layer, 3A molecular sieve layer from top to bottom;
Be equipped with the perforate that is connected with water pump on the exit passageway of each layer adsorption bed, to produce negative pressure, in order to control acetonitrile take-off rate;
(2), the effluent in the step (1) is squeezed into stainless steel cauldron through preheater after being preheated to 30 ~ 50 ℃; Add the composite oxidant that accounts for raw material acetonitrile weight 0.5～2% then; Under nitrogen protection, be heated with stirring to 85-90 ℃ of oxidation 0.5 h～2h, steam oxidation liquid;
(3), oxidation liquid that step (2) is obtained sends into rectifying still, the heated oil temperature is 100～140 ℃ in the control rectifying still, rectifying still liquid temperature is 85～90 ℃; 80 ℃～83 ℃ of rectifying still top temperature; Total reflux 1.5～3 hours, control reflux ratio 10: 1～5, fluid; Cut before and after removing promptly gets performance liquid chromatography leacheate acetonitrile through the filtration of 0.2 μ m teflon membrane filter.
4. method according to claim 3 is characterized in that: the purity of said raw material acetonitrile is not less than 99.5%.
5. method according to claim 3 is characterized in that: the particle diameter of said activated alumina and gac is 0.2mm.
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| CN104058994A (en) * | 2014-07-02 | 2014-09-24 | 中国计量科学研究院 | High-purity acetonitrile and method and device for preparing high-purity acetonitrile |
| CN107382776A (en) * | 2017-09-06 | 2017-11-24 | 湖北富森盐湖化工科技有限公司 | A kind of trifluoroacetic acid aqueous solution and preparation method thereof, production system |
| CN111393326A (en) * | 2020-04-14 | 2020-07-10 | 湖北弗顿科学技术有限公司 | Acetonitrile purification process for ultra-high performance liquid chromatography-mass spectrometer |
| CN111413441A (en) * | 2020-05-06 | 2020-07-14 | 湖北弗顿生化科技有限公司 | Acetonitrile purification process for improved ultra-high liquid chromatography-mass spectrometer |
| CN116987008A (en) * | 2023-08-14 | 2023-11-03 | 西陇科学股份有限公司 | Process for preparing gradient acetonitrile by using metal oxide supported catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104058994A (en) * | 2014-07-02 | 2014-09-24 | 中国计量科学研究院 | High-purity acetonitrile and method and device for preparing high-purity acetonitrile |
| CN104058994B (en) * | 2014-07-02 | 2016-07-06 | 中国计量科学研究院 | High-purity acetonitrile and preparation method thereof and device |
| CN107382776A (en) * | 2017-09-06 | 2017-11-24 | 湖北富森盐湖化工科技有限公司 | A kind of trifluoroacetic acid aqueous solution and preparation method thereof, production system |
| CN111393326A (en) * | 2020-04-14 | 2020-07-10 | 湖北弗顿科学技术有限公司 | Acetonitrile purification process for ultra-high performance liquid chromatography-mass spectrometer |
| WO2021208023A1 (en) * | 2020-04-14 | 2021-10-21 | 湖北弗顿科学技术有限公司 | Acetonitrile purification process for ultra-high performance liquid chromatography-mass spectrometer |
| CN111413441A (en) * | 2020-05-06 | 2020-07-14 | 湖北弗顿生化科技有限公司 | Acetonitrile purification process for improved ultra-high liquid chromatography-mass spectrometer |
| WO2021223145A1 (en) * | 2020-05-06 | 2021-11-11 | 湖北弗顿生化科技有限公司 | Improved acetonitrile purification process for ultra-performance liquid chromatography-mass spectrometry instrument |
| US11945766B2 (en) | 2020-05-06 | 2024-04-02 | Ftsci (Hubei) Biotech Co., Ltd. | Acetonitrile purification process for ultrahigh performance liquid chromatography-mass spectrometer |
| CN116987008A (en) * | 2023-08-14 | 2023-11-03 | 西陇科学股份有限公司 | Process for preparing gradient acetonitrile by using metal oxide supported catalyst |
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