CN116102459A - HPLC acetonitrile purification process and application thereof - Google Patents
HPLC acetonitrile purification process and application thereof Download PDFInfo
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- CN116102459A CN116102459A CN202211722951.0A CN202211722951A CN116102459A CN 116102459 A CN116102459 A CN 116102459A CN 202211722951 A CN202211722951 A CN 202211722951A CN 116102459 A CN116102459 A CN 116102459A
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- acetonitrile
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- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 title claims abstract description 223
- 238000000746 purification Methods 0.000 title claims abstract description 16
- 238000004128 high performance liquid chromatography Methods 0.000 title claims abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 53
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 51
- 239000003463 adsorbent Substances 0.000 claims abstract description 40
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 26
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052751 metal Inorganic materials 0.000 claims abstract description 17
- 239000002184 metal Substances 0.000 claims abstract description 17
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 13
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052742 iron Inorganic materials 0.000 claims abstract description 11
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 11
- 239000011777 magnesium Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims description 32
- 239000002699 waste material Substances 0.000 claims description 27
- 230000008569 process Effects 0.000 claims description 20
- 238000001179 sorption measurement Methods 0.000 claims description 20
- 238000001354 calcination Methods 0.000 claims description 16
- 230000003647 oxidation Effects 0.000 claims description 13
- 238000007254 oxidation reaction Methods 0.000 claims description 13
- 238000002360 preparation method Methods 0.000 claims description 8
- 239000002028 Biomass Substances 0.000 claims description 5
- 229910044991 metal oxide Inorganic materials 0.000 claims description 4
- 150000004706 metal oxides Chemical class 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 238000004134 energy conservation Methods 0.000 abstract description 2
- 230000009467 reduction Effects 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 11
- 238000010992 reflux Methods 0.000 description 11
- 239000010902 straw Substances 0.000 description 9
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 8
- 239000012535 impurity Substances 0.000 description 8
- 239000012286 potassium permanganate Substances 0.000 description 7
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 5
- 239000011790 ferrous sulphate Substances 0.000 description 4
- 235000003891 ferrous sulphate Nutrition 0.000 description 4
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 4
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 4
- 229910001629 magnesium chloride Inorganic materials 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 150000003841 chloride salts Chemical class 0.000 description 2
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 235000017060 Arachis glabrata Nutrition 0.000 description 1
- 244000105624 Arachis hypogaea Species 0.000 description 1
- 235000010777 Arachis hypogaea Nutrition 0.000 description 1
- 235000018262 Arachis monticola Nutrition 0.000 description 1
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 230000006820 DNA synthesis Effects 0.000 description 1
- LELOWRISYMNNSU-UHFFFAOYSA-N Hydrocyanic acid Natural products N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 240000007049 Juglans regia Species 0.000 description 1
- 235000009496 Juglans regia Nutrition 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 244000082204 Phyllostachys viridis Species 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 230000006819 RNA synthesis Effects 0.000 description 1
- 244000126002 Ziziphus vulgaris Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000010533 azeotropic distillation Methods 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 235000009120 camo Nutrition 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000012938 design process Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- 239000010903 husk Substances 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000004807 localization Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 235000020232 peanut Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- -1 saturated aliphatic nitrile Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 235000020234 walnut Nutrition 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/32—Separation; Purification; Stabilisation; Use of additives
- C07C253/34—Separation; Purification
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
- B01J20/041—Oxides or hydroxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention provides an HPLC acetonitrile purification process, which is characterized in that industrial acetonitrile is adsorbed by using a modified porous carbon adsorbent column attached with metal, wherein the attached amount of the metal in the modified porous carbon adsorbent column is 25-35wt% of the total mass of the adsorbent column, and the metal is one or more selected from iron, magnesium and nickel. The modified porous carbon adopted by the invention can be recycled, so that the production cost is reduced, and the energy conservation and emission reduction are realized; the purification process has the advantages of simple operation, stable operation, high safety, low yield and loss rate, standard and stable quality, and is suitable for industrial mass production.
Description
Technical Field
The invention relates to the field of C07C255/03, in particular to an HPLC acetonitrile purification process and application thereof.
Background
Acetonitrile, also known as methylnitrile, is the most single saturated aliphatic nitrile, and because it has unique functional groups, it has excellent solvent properties, can dissolve various organic, inorganic and gaseous substances, has better partition ratio and desorption capacity, can be used as mobile phase and common organic solvent for high performance liquid chromatography, but has extremely high purity requirements and huge demand. At present, domestic high-purity acetonitrile mainly depends on import. Therefore, the research of the separation technology of the high-purity acetonitrile is significant for realizing localization.
In the prior art, little research has been disclosed on the purification process of acetonitrile. Since the common contaminants in commercial acetonitrile are water, acetamide, acetic acid and ammonia. The conventional purification method is to separate impurities in acetonitrile by adopting an extraction or adsorption mode, then dry the acetonitrile for 24 hours by adopting anhydrous potassium carbonate, dry the acetonitrile for 24 hours by adopting a 3A molecular sieve, and finally obtain purified acetonitrile by adopting normal pressure distillation.
CN110683967a discloses a method for preparing anhydrous acetonitrile for DNA/RNA synthesis, which comprises the steps of adsorbing impurities with activated carbon fiber, decomposing the impurities with ultraviolet light catalytic oxidation technology, removing acid impurities with NaOH intermittent adsorption column, removing metal ion impurities and moisture with molecular sieve, and finally obtaining finished acetonitrile through distillation, vacuum rectification and pressure rectification.
CN112174852a provides a purification method of chromatographic grade acetonitrile, which sequentially performs oxidation neutralization reaction, adsorption column impurity removal treatment and rectification treatment on industrial acetonitrile to finally obtain the chromatographic grade acetonitrile, but the process has low treatment capacity and is not suitable for industrial mass production.
CN1328994a discloses a method for refining high-purity acetonitrile, which adopts a systematic and combined process flow, including dehydrogenation cyanate, chemical treatment, decompression, pressurization and azeotropic distillation, and adopts liquid phase extraction at the upper side line of the rectifying section of the dehydrogenation cyanate. However, the design process in the process is long, the control parameters are complex, and the process is not suitable for industrialized mass production.
Disclosure of Invention
In view of the above problems, the invention discloses a purification process of HPLC acetonitrile, which is characterized in that industrial acetonitrile is adsorbed by using an adsorbent column of modified porous carbon attached with metal.
As a preferred embodiment, the amount of metal attached to the modified porous carbon adsorbent column is 25 to 35wt%, preferably 30wt% of the total mass of the adsorbent column.
As a preferred technical scheme, the metal is selected from one or more of iron, magnesium and nickel.
Preferably, the metal is selected from the group consisting of iron, magnesium, nickel, and combinations of any two thereof.
Further preferably, the mass ratio of any two metals attached to the modified porous carbon adsorbent column is 1:1.
as a preferable technical scheme, the modified porous carbon adsorbent column is obtained by immersing a porous carbon carrier in a metal oxide solution at 850-950 ℃ and calcining for 1-3 h.
Preferably, the modified porous carbon adsorbent column is obtained by immersing a porous carbon carrier in a metal oxide solution at 900 ℃ and calcining for 2 hours.
As a preferred technical scheme, the preparation method of the porous carbon carrier comprises the following steps: calcining the waste biomass for 1-3 hours at 550-700 ℃.
Preferably, the waste biomass is calcined at 600 ℃ for 2 hours.
As a preferable technical scheme, the waste biomass is selected from any one of waste straw, waste rice husk, waste hemp stalk, waste wood dust, waste bark, waste bamboo dust, waste branch, waste coconut shell, waste walnut shell, waste palm shell, waste peanut shell, waste jujube core and waste pine cone; preferably waste straw.
As a preferable embodiment, when the adhesion metal is iron, the metal oxide solution is selected from any one of a sulfate solution, a chloride solution, and a nitrate solution, and preferably ferrous sulfate.
As a preferable embodiment, when the adhesion metal is magnesium, the oxide solution of the metal is selected from any one of a sulfate solution, a chloride salt solution, and a nitrate solution, and preferably magnesium chloride.
As a preferable embodiment, when the adhesion metal is nickel, the oxide solution of the metal is selected from any one of a sulfate solution, a chloride salt solution, and a nitrate solution, and preferably nickel chloride.
As a preferable technical scheme, the temperature of the adsorption process is 30-50 ℃ and the time is 30-60min.
As a preferable technical scheme, the purity of the industrial acetonitrile is more than or equal to 99 weight percent, and preferably, the purity of the industrial acetonitrile is more than or equal to 99.9 weight percent.
As a preferred embodiment, the industrial acetonitrile is subjected to an oxidation treatment before being adsorbed by the metal-attached modified porous carbon adsorbent column.
Preferably, the oxidation process is carried out at a temperature of 75-82 ℃ for 10-60min; more preferably, the temperature is 80℃and the time is 30 minutes.
As a preferred technical scheme, the oxidant in the oxidation process is not limited, preferably potassium permanganate, and the mass ratio of industrial acetonitrile to potassium permanganate is 1: (0.00001-0.01).
As a preferred embodiment, industrial acetonitrile is adsorbed by using a metal-attached modified porous carbon adsorbent column, and then rectified.
As a preferable technical scheme, the heating temperature of the rectifying still is 110-130 ℃, the temperature of acetonitrile liquid in the rectifying still is 85-90 ℃, the temperature of distilled liquid is 80-85 ℃, and the reflux ratio is controlled to be 10: (1-8).
In the prior art, the industrial acetonitrile purification process is complex and complicated, takes long time, has high cost, low yield and other problems, and the applicant optimizes the adsorbent column through a large number of experiments, prepares the modified porous carbon adsorbent column by using waste straws, thereby realizing the process index requirement that the acetonitrile yield is more than or equal to 90wt% and the purity is more than or equal to 99.999wt%. The applicant creatively discovers that the porous carbon carrier obtained by calcining the waste straws for 1-3 hours at 550-700 ℃ has higher porosity and specific surface area compared with the porous carbon adsorbent column obtained by frequently using activated carbon or carbon fiber in the prior art, has higher activity and adsorption performance after metal modification at 850-950 ℃, can remove impurities such as unsaturated organic compounds containing carbon-carbon double bonds in acetonitrile, and finally obtains the high-purity organic solvent acetonitrile with the purity of more than or equal to 99.999wt%.
The invention also discloses application of the preparation process to mobile phases of high performance liquid chromatography.
Advantageous effects
1. The modified porous carbon adopted by the invention utilizes waste biomass and waste, and accords with the production mode of green chemical industry.
2. The purification method of the high-purity organic solvent acetonitrile disclosed by the invention can effectively remove impurities in industrial acetonitrile through a series of procedures of oxidation of oxide and adsorption of modified porous carbon, and is safe, simple, convenient, green and environment-friendly in the purification process.
3. The modified porous carbon adopted by the invention can be recycled, so that the production cost is reduced, and the energy conservation and emission reduction are realized.
4. The purification process has the advantages of simple operation, stable operation, high safety, low yield and loss rate of the purification method, standard and stable quality, and is suitable for industrial mass production.
Detailed Description
Example 1
This example 1 discloses a process for purifying HPLC acetonitrile, comprising the steps of:
(1) 0.12g potassium permanganate is added into 2kg industrial acetonitrile (purity is more than or equal to 99.9 wt%) for oxidation treatment, and the acetonitrile is distilled out after heating and refluxing for 30min at 80 ℃.
(2) And introducing the obtained acetonitrile into an adsorbent column of modified porous carbon attached with iron and magnesium for adsorption, (15 wt% of iron and 15wt% of magnesium are calculated by mass of the adsorbent), and rectifying the acetonitrile obtained by adsorption treatment at 40 ℃ for 30min.
And (3) immersing the porous carbon carrier in a mixed solution of ferrous sulfate and magnesium chloride at 900 ℃ by the modified porous carbon adsorbent column, and calcining for 2 hours to obtain the modified porous carbon adsorbent column.
The preparation method of the porous carbon carrier comprises the following steps: and calcining the waste straws for 2 hours at 600 ℃.
(3) The heating temperature of the rectifying still is 130 ℃, the temperature of acetonitrile liquid in the rectifying still is 85 ℃, the temperature of distilled liquid is 80 ℃, and the reflux ratio is controlled to be 10:8, and finally, a rectification method with a flow rate of 20 mL/min.
1808g of purified acetonitrile was collected, and the yield was 90.4wt% and the purity was 99.999wt%.
Example 2
This example 2 discloses a process for purifying HPLC acetonitrile, comprising the following steps:
(1) 0.12g potassium permanganate is added into 2kg industrial acetonitrile (purity is more than or equal to 99.9 wt%) for oxidation treatment, and the acetonitrile is distilled out after heating and refluxing for 30min at 80 ℃.
(2) And introducing the obtained acetonitrile into an adsorbent column of modified porous carbon attached with iron and nickel for adsorption, (15 wt% of iron and 15wt% of nickel are calculated by mass of the adsorbent), and rectifying the acetonitrile obtained by adsorption treatment at 35 ℃ for 30min.
And (3) immersing the porous carbon carrier in a mixed solution of ferrous sulfate and nickel chloride at 900 ℃ by the modified porous carbon adsorbent column, and calcining for 2 hours to obtain the modified porous carbon adsorbent column.
The preparation method of the porous carbon carrier comprises the following steps: and calcining the waste straws for 2 hours at 600 ℃.
(3) The heating temperature of the rectifying still is 130 ℃, the temperature of acetonitrile liquid in the rectifying still is 85 ℃, the temperature of distilled liquid is 80 ℃, and the reflux ratio is controlled to be 10:8, and finally, a rectification method with a flow rate of 20 mL/min.
1812g of purified acetonitrile was collected in a yield of 90.6wt% and a purity of 99.999wt%.
Example 3
This example 3 discloses a process for purifying HPLC acetonitrile, comprising the following steps:
(1) 0.12g potassium permanganate is added into 2kg industrial acetonitrile (purity is more than or equal to 99.9 wt%) for oxidation treatment, and the acetonitrile is distilled out after heating and refluxing for 30min at 80 ℃.
(2) Introducing the obtained acetonitrile into an adsorbent column attached with modified porous carbon of magnesium and nickel for adsorption, (15 wt% of magnesium and 15wt% of nickel are calculated by mass of the adsorbent), and rectifying the acetonitrile obtained by adsorption treatment at 40 ℃ for 40 min.
And (3) immersing the porous carbon carrier in a mixed solution of magnesium chloride and nickel chloride at 900 ℃ by the modified porous carbon adsorbent column, and calcining for 2 hours to obtain the modified porous carbon adsorbent column.
The preparation method of the porous carbon carrier comprises the following steps: and calcining the waste straws for 2 hours at 600 ℃.
(3) The heating temperature of the rectifying still is 130 ℃, the temperature of acetonitrile liquid in the rectifying still is 85 ℃, the temperature of distilled liquid is 80 ℃, and the reflux ratio is controlled to be 10:8, and finally, a rectification method with a flow rate of 20 mL/min.
1822ml of purified acetonitrile was collected in a yield of 91.1wt% and a purity of 99.999wt%.
Example 4
The process for purifying HPLC acetonitrile in this example 4 comprises the following steps:
(1) 0.12g potassium permanganate is added into 2kg industrial acetonitrile (purity is more than or equal to 99.9 wt%) for oxidation treatment, and the acetonitrile is distilled out after heating and refluxing for 30min at 80 ℃.
(2) The obtained acetonitrile is introduced into an adsorbent column of modified porous carbon attached with magnesium and nickel for adsorption, (10 wt% of magnesium and 20wt% of nickel are calculated by mass of the adsorbent), the adsorption temperature is 40 ℃ and the time is 30min, and the acetonitrile obtained by adsorption treatment is rectified.
And (3) immersing the porous carbon carrier in a mixed solution of magnesium chloride and nickel chloride at 900 ℃ by the modified porous carbon adsorbent column, and calcining for 2 hours to obtain the modified porous carbon adsorbent column.
The preparation method of the porous carbon carrier comprises the following steps: and calcining the waste straws for 2 hours at 600 ℃.
(3) The heating temperature of the rectifying still is 130 ℃, the temperature of acetonitrile liquid in the rectifying still is 85 ℃, the temperature of distilled liquid is 80 ℃, and the reflux ratio is controlled to be 10:8, and finally, a rectification method with a flow rate of 20 mL/min.
Purified acetonitrile 1795ml was collected in a yield of 88.4wt% and purity of 99.999wt%.
Example 5
The HPLC acetonitrile purification process of this example 5 comprises the following steps:
(1) 0.12g potassium permanganate is added into 2kg industrial acetonitrile (purity is more than or equal to 99.9 wt%) for oxidation treatment, and the acetonitrile is distilled out after heating and refluxing for 30min at 80 ℃.
(2) And introducing the obtained acetonitrile into an adsorbent column of modified porous carbon attached with iron and nickel for adsorption, (the iron accounts for 20wt percent, the nickel accounts for 10wt percent, and the mass of the adsorbent) at the adsorption temperature of 35 ℃ for 30min, and rectifying the acetonitrile obtained by the adsorption treatment.
And (3) immersing the porous carbon carrier in a mixed solution of ferrous sulfate and nickel chloride at 900 ℃ by the modified porous carbon adsorbent column, and calcining for 2 hours to obtain the modified porous carbon adsorbent column.
The preparation method of the porous carbon carrier comprises the following steps: and calcining the waste straws for 2 hours at 600 ℃.
(3) The heating temperature of the rectifying still is 130 ℃, the temperature of acetonitrile liquid in the rectifying still is 85 ℃, the temperature of distilled liquid is 80 ℃, and the reflux ratio is controlled to be 10:8, and finally, a rectification method with a flow rate of 20 mL/min.
1856g of purified acetonitrile was collected in a yield of 85.6wt% and a purity of 99.999wt%.
Claims (10)
1. An HPLC acetonitrile purification process is characterized in that industrial acetonitrile is adsorbed by an adsorbent column of modified porous carbon attached with metal.
2. The process of claim 1, wherein the amount of metal attached to the modified porous carbon adsorbent column is 25-35wt% of the total mass of the adsorbent column.
3. The process according to claim 2, wherein the metal is selected from one or more of iron, magnesium, nickel.
4. The process according to claim 1, wherein the modified porous carbon adsorbent column is obtained by impregnating a porous carbon support with a metal oxide solution at 850-950 ℃ and calcining for 1-3 hours.
5. The process of claim 4, wherein the porous carbon support is prepared by: calcining the waste biomass for 1-3 hours at 550-700 ℃.
6. The process according to any one of claims 1 to 5, wherein the industrial acetonitrile has a purity of not less than 99% by weight.
7. The process of claim 6, wherein the industrial acetonitrile is subjected to an oxidation treatment prior to adsorption using a metal-attached modified porous carbon adsorbent column.
8. The process of claim 7, wherein the oxidation is carried out at a temperature of 75-82 ℃ for a period of 10-60 minutes.
9. The process of claim 8, wherein industrial acetonitrile is rectified after adsorption using a metal-attached modified porous carbon adsorbent column.
10. Use of a preparation process according to any one of claims 1-9, characterized by being applied to a mobile phase of high performance liquid chromatography.
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