CN110776400B - Purification method of LC-MS (liquid chromatography-mass spectrometry) grade methanol - Google Patents
Purification method of LC-MS (liquid chromatography-mass spectrometry) grade methanol Download PDFInfo
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 312
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 title claims abstract description 62
- 238000000034 method Methods 0.000 title claims abstract description 29
- 238000000746 purification Methods 0.000 title claims abstract description 21
- 238000001179 sorption measurement Methods 0.000 claims abstract description 56
- 239000012535 impurity Substances 0.000 claims abstract description 50
- 239000012528 membrane Substances 0.000 claims abstract description 30
- 239000002808 molecular sieve Substances 0.000 claims abstract description 23
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000001914 filtration Methods 0.000 claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 15
- 239000003729 cation exchange resin Substances 0.000 claims abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 11
- 239000010439 graphite Substances 0.000 claims abstract description 11
- 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 abstract description 10
- 230000002378 acidificating effect Effects 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 239000011347 resin Substances 0.000 claims abstract description 9
- 229920005989 resin Polymers 0.000 claims abstract description 9
- 238000005516 engineering process Methods 0.000 claims abstract description 8
- 150000002148 esters Chemical class 0.000 claims abstract description 8
- 238000010531 catalytic reduction reaction Methods 0.000 claims abstract description 5
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 5
- 230000001590 oxidative effect Effects 0.000 claims abstract description 5
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 4
- -1 polydimethylsiloxane Polymers 0.000 claims abstract description 4
- 239000002131 composite material Substances 0.000 claims abstract description 3
- 239000004205 dimethyl polysiloxane Substances 0.000 claims abstract description 3
- 150000002500 ions Chemical class 0.000 claims abstract description 3
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims abstract description 3
- 239000007788 liquid Substances 0.000 claims description 30
- 239000000523 sample Substances 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 27
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 26
- 238000005086 pumping Methods 0.000 claims description 26
- 238000010438 heat treatment Methods 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 239000012488 sample solution Substances 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000011049 filling Methods 0.000 claims description 10
- 239000003638 chemical reducing agent Substances 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 7
- 230000007062 hydrolysis Effects 0.000 claims description 6
- 238000006460 hydrolysis reaction Methods 0.000 claims description 6
- 238000005342 ion exchange Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000009834 vaporization Methods 0.000 claims description 6
- 230000008016 vaporization Effects 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 229940023913 cation exchange resins Drugs 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 4
- 238000005374 membrane filtration Methods 0.000 claims description 4
- 238000002715 modification method Methods 0.000 claims description 4
- 238000005373 pervaporation Methods 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 230000004048 modification Effects 0.000 claims description 3
- 238000012986 modification Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 238000000643 oven drying Methods 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 229910021654 trace metal Inorganic materials 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 2
- 150000001299 aldehydes Chemical class 0.000 abstract description 4
- 238000012797 qualification Methods 0.000 abstract description 2
- 238000006266 etherification reaction Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 13
- 230000009467 reduction Effects 0.000 description 6
- 238000006722 reduction reaction Methods 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 238000001819 mass spectrum Methods 0.000 description 4
- 208000005156 Dehydration Diseases 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 238000002309 gasification Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000011481 absorbance measurement Methods 0.000 description 2
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- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
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- 230000000694 effects Effects 0.000 description 2
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- 230000008020 evaporation Effects 0.000 description 2
- 238000007689 inspection Methods 0.000 description 2
- 238000004811 liquid chromatography Methods 0.000 description 2
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- 238000004949 mass spectrometry Methods 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 239000012286 potassium permanganate Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000000895 extractive distillation Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
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- 238000012544 monitoring process Methods 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
- B01D15/10—Selective adsorption, e.g. chromatography characterised by constructional or operational features
- B01D15/18—Selective adsorption, e.g. chromatography characterised by constructional or operational features relating to flow patterns
- B01D15/1864—Selective adsorption, e.g. chromatography characterised by constructional or operational features relating to flow patterns using two or more columns
- B01D15/1871—Selective adsorption, e.g. chromatography characterised by constructional or operational features relating to flow patterns using two or more columns placed in series
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D29/00—Filters with filtering elements stationary during filtration, e.g. pressure or suction filters, not covered by groups B01D24/00 - B01D27/00; Filtering elements therefor
- B01D29/01—Filters with filtering elements stationary during filtration, e.g. pressure or suction filters, not covered by groups B01D24/00 - B01D27/00; Filtering elements therefor with flat filtering elements
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
- B01D46/54—Particle separators, e.g. dust precipitators, using ultra-fine filter sheets or diaphragms
- B01D46/543—Particle separators, e.g. dust precipitators, using ultra-fine filter sheets or diaphragms using membranes
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- 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
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
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- 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
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
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Abstract
The invention relates to a purification method of LC-MS grade methanol, which comprises the following steps: adsorbing and filtering a methanol raw material through a modified multi-wall CNTS graphite adsorption column; carrying out de-etherification treatment on a methanol raw material by taking an IM-5 type molecular sieve as a catalyst; hydrolyzing with 732 type acidic cation exchange resin as catalyst to remove ester impurities; removing acidic and alkaline impurities by adsorption of a modified 13X molecular sieve and LS-40 macroporous resin; reducing and removing aldehydes and partial oxidizing impurities by an ultraviolet light catalytic reduction technology; removing metal ion impurities in the methanol by cation exchange resin; removing macromolecular impurities by using a PF5A ion composite membrane material; and (3) dehydrating the methanol by using a polydimethylsiloxane membrane material to obtain a methanol sample meeting the LC-MS grade methanol index requirement. The purity of the LC-MS grade high-purity methanol for liquid chromatography-mass spectrometry produced by the invention is more than 99.99%, the purity can reach the index of the LC-MS grade high-purity methanol for liquid chromatography-mass spectrometry after being purified by the method, and the qualification rate of the product is more than 90%.
Description
Technical Field
The invention belongs to the field of chemical reagents, relates to a purification technology, and particularly relates to a purification method of liquid chromatography-mass spectrometry (LC-MS) grade methanol.
Background
The online combination of the chromatogram and the mass spectrum combines the separating capability of the chromatogram and the qualitative function of the mass spectrum, and realizes more accurate quantitative and qualitative analysis of the complex mixture. The Liquid Chromatography (LC) can effectively separate organic matter components in a sample to be detected of organic matters, and the Mass Spectrum (MS) can analyze the separated organic matters one by one to obtain information such as molecular weight, structure, concentration and the like of the organic matters. LC-MS is an indispensable analytical tool for departments of organic matter analysis laboratories, drug and food inspection rooms, production process control, quality inspection and the like.
The mobile phase commonly used for LC-MS is methanol and water. The solvent with high purity can avoid the phenomenon of insufficient ionization of the measured object caused by the existence of impurities as much as possible, particularly metal ions are complexed with the measured object in mass spectrometry to produce interference peaks in the mass spectrometry, so that misjudgment on the measurement of parameters such as molecular weight and the like is caused, and the accuracy of the measurement result of the liquid chromatography-mass spectrometer is greatly reduced.
At present, imported products almost cover the whole domestic LC-MS grade high-purity methanol market, the analysis monitoring amount is increased along with the high-speed development of economy in China, the market demand of LC-MS grade methanol reagents is increased, and the purification method of liquid chromatography-mass spectrometry grade methanol, which has the advantages of good purification effect, controllable process and low cost, has important application significance.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a preparation method of LC-MS (liquid chromatography-mass spectrometry) grade methanol, and the methanol prepared by the method can remove aldehyde ketone, alcohol, ester, ether and unsaturated hydrocarbon impurities which are difficult to remove, so that the indexes and the application requirements of the LC-MS grade methanol for liquid chromatography-mass spectrometry are met.
The technical problem to be solved by the invention is realized by adopting the following technical scheme:
a purification method of LC-MS grade methanol is characterized in that: the method comprises the following steps:
(1) Adsorbing and filtering a methanol raw material through a modified multiwalled CNTS graphite adsorption column;
(2) Removing ether from a methanol raw material by taking an IM-5 type molecular sieve as a catalyst;
(3) Hydrolyzing with 732 type acidic cation exchange resin as catalyst to remove ester impurities;
(4) Removing acidic and alkaline impurities by adsorption through a modified 13X molecular sieve and LS-40 macroporous resin;
(5) Reducing and removing aldehydes and partial oxidizing impurities by an ultraviolet light catalytic reduction technology;
(6) Removing metal ion impurities in the methanol through cation exchange resin;
(7) Removing macromolecular impurities by using a PF5A ion composite membrane material;
(8) And (3) dehydrating the methanol by using a polydimethylsiloxane membrane material to obtain a methanol sample meeting the LC-MS grade methanol index requirement.
In addition, in the step (1), the purity of the raw material methanol is 99.5%, the adsorption flow rate is 100-500 mL/min, and the modification method of the CNTS graphite adsorption column comprises the following steps: adding CNTS graphite to 5% Al (OH) 3 Soaking in the solution for 3-5h, standing for 8-15h, oven drying in oven at 105 deg.C, roasting in muffle furnace at 350 deg.C for 3-5h, and cooling to room temperature.
Moreover, the ether removing treatment process in the step (2) comprises the following steps: and (2) pumping the methanol sample liquid subjected to adsorption and filtration in the step (1) into a reaction rectifying kettle, adding an IM-5 type molecular sieve catalyst according to the mass fraction of 0.05-0.3% of methanol, controlling the heating temperature of the rectifying kettle to be 30-45 ℃, reacting for 0.1-0.5 h under the condition of continuous stirring, then filling nitrogen into the reaction kettle, and replacing low-boiling-point ethers and ammonia gases in the reaction kettle.
And (3) after the ether removal treatment in the step (2) is finished, adding 732 type acidic cation exchange resin catalyst into a reaction rectifying still, controlling the heating temperature of the rectifying still to be 30-45 ℃, carrying out heating reaction for 0.5-1 h, hydrolyzing ester impurities in the methanol sample liquid into acid and alcohol impurities, simultaneously refluxing and steaming out light components, continuously heating, controlling the bottom temperature of the rectifying still to be 70-77 ℃, the top temperature of the rectifying still to be 65-67 ℃, and adjusting the reflux ratio to be 2.
And (4) pumping the methanol sample liquid after hydrolysis and evaporation into a 13X molecular sieve and LS-40 macroporous resin adsorption system connected in series for adsorption and impurity removal, and controlling the adsorption flow rate to be 300-500 mL/min.
And (5) pumping the sample solution after adsorption and filtration into an ultraviolet irradiation reaction kettle, adding a reducing agent accounting for 0.05-0.3% of the sample solution by mass, performing irradiation reaction for 0.5-1 h, and reducing to remove aldehyde impurities and reducing impurities to obtain a reduced sample solution.
And in the step (6), the dried methanol sample solution is injected into two cation exchange resins connected in series for ion exchange to remove trace metal impurities, and the drying process comprises the following steps: and pumping the reduced methanol sample solution into a drying column, controlling the adsorption flow rate to be 300-500 mL/min, and reducing the water content to be below 0.05%.
And then, pumping the dried methanol sample liquid into a filtering membrane component for adsorption and filtration, pumping the methanol sample liquid subjected to membrane filtration and impurity removal into a vaporization distillation kettle, heating by utilizing heat conduction oil, controlling the temperature of the heat conduction oil to be 80-100 ℃, controlling the liquid temperature to be 65-75 ℃, and introducing the gas-phase methanol in the tower kettle into a pervaporation membrane component for further treatment.
Moreover, the modified 13X molecular sieve is a CTMAB-13X molecular sieve, and the modification method comprises the following steps: adding 200g of 13x molecular sieve into 3000mL of 0.4mol/L hexadecyl trimethyl ammonium bromide with molar concentration for surface modification, stirring for 60min, standing for 30min, washing bottom precipitate with water, filtering, standing in an oven for drying at 105 ℃, and grinding for later use.
And the LS-40 macroporous resin adsorption column is soaked for 3-5h by 15-30% sulfuric acid, taken out and dried in an oven at 150 ℃ for use.
The invention has the advantages and positive effects that:
1. the invention adopts the modified CNTS graphite as the adsorption material, the material is formed by curling multilayer graphite, and the hollow and nano-layered structure of the carbon nano tube ensures the natural endowment of the carbon nano tube in the field of adsorption and impurity removal. In addition, the modified material has the advantages of small size, large specific surface area, high mechanical property, special electrical property, high chemical stability and the like. Meanwhile, the 13X molecular sieve is modified by utilizing hexadecyl trimethyl ammonium bromide, and a large amount of amino is introduced under the condition of not damaging the structure of the molecular sieve, so that the adsorption performance of the molecular sieve is greatly improved.
2. At present, aldehyde and olefin impurities are usually removed by using a strong oxidant such as potassium permanganate, and the like, and although the impurity removal effect is good, in the impurity removal process, the strong oxidant such as potassium permanganate and the like can react with methanol to generate new impurities, so that the recovery rate of the methanol is reduced. The invention adopts an ultraviolet light catalytic reduction technology, the ultraviolet light catalytic reduction is to radiate a reducing agent by using ultraviolet light with special wavelength to generate sulfite radicals, the reducibility of the reducing agent is enhanced, and impurities in the methanol sample liquid are reduced by using the strong reducibility of the sulfite radicals. The technology enhances the reducibility of the reducing agent and improves the efficiency.
3. The invention adopts the membrane separation technology to carry out dehydration and impurity removal treatment on the methanol product, and has the outstanding advantages of high efficiency, energy saving, environmental protection, simple and convenient operation and the like. The invention adopts two different membrane materials, wherein, the dehydration gasification membrane has the advantages of high flux, high stability and the like. The invention contacts the raw material with the membrane in the form of steam, eliminates the influence of solid impurities and greatly prolongs the service life of the membrane. In addition, the membrane material is selected for impurity removal to replace an extraction rectification technology, so that the energy loss is greatly reduced, and the method is a bright point. The method has the characteristics of high separation degree, simple and convenient operation, no pollution and low energy consumption.
4. The invention takes methanol with the content of 99.5 percent as a raw material, and the methanol is produced by a preparation method of multi-stage adsorption, multi-stage reaction, drying and dewatering and extractive distillation, thereby meeting the indexes and application requirements of LC-MS grade methanol for liquid chromatography-mass spectrometry. Compared with the prior art, the method has the advantages of high product quality, good batch stability, stable operation, high recovery rate of more than 93 percent and suitability for large-scale production.
5. The purity of the LC-MS high-purity methanol for liquid chromatography-mass spectrometry produced by the invention is more than 99.99 percent, the purity of the LC-MS high-purity methanol can reach the index of the LC-MS high-purity methanol for liquid chromatography-mass spectrometry after the purification by the method, and the qualification rate of the product is more than 90 percent. The method can meet the application requirements of the LC-MS grade high-purity methanol client for liquid chromatography-mass spectrometry in scientific research tests, fills the blank of domestic LC-MS grade high-purity methanol production, reduces the dependence on foreign reagents, and provides high-quality reagents for the separation and the qualitative determination of complex medicines.
Detailed Description
The present invention will be further described by the following specific examples, which are illustrative only and not intended to be limiting, and the scope of the present invention is not limited thereby.
Example 1
A purification method of LC-MS grade methanol for liquid chromatography-mass spectrometry comprises the following steps:
(1) A first adsorption step: the methanol raw material is pre-adsorbed by a modified multi-wall CNTS graphite adsorption column to remove partial unsaturated olefin impurities by adsorption, and the adsorption flow rate is controlled to be 100-800 mL/min.
(2) And (3) ether removal treatment: pumping the adsorbed and filtered methanol sample liquid into a reaction rectifying kettle, adding 3-5 g of IM-5 type molecular sieve, controlling the heating temperature of the rectifying kettle to be 30-45 ℃, reacting for 0.1-0.5 h under the condition of continuous stirring, charging nitrogen into the reaction kettle, and replacing low-boiling-point ether and ammonia gas in the reaction kettle.
(3) Hydrolysis: after the ether removal treatment is finished, 5-10g 732 type acidic cation exchange resin is added into a reaction rectifying kettle, the heating temperature of the rectifying kettle is controlled to be 30-45 ℃, the heating reaction is carried out for 0.5-1 h, ester impurities in the methanol sample liquid are hydrolyzed into acid and alcohol impurities, meanwhile, after light components are distilled out in a backflow mode, the temperature is continuously increased, the bottom temperature of the rectifying kettle is controlled to be 70-77 ℃, the top temperature of the rectifying kettle is 65-67 ℃, and the reflux ratio is adjusted to be 2.
(4) And (2) an adsorption step II: and (3) pumping the methanol sample liquid after hydrolysis and evaporation into an adsorption system formed by connecting a CTMAB-13X molecular sieve, an LS-40 macroporous resin adsorption column and a kieselguhr adsorption column in series for adsorption and impurity removal. Controlling the adsorption flow rate to be 300 mL-800 mL/min.
(5) Reduction: and (3) pumping the sample solution after adsorption and filtration into an ultraviolet irradiation reaction kettle, adding a reducing agent (the mass percent of the reducing agent added is 0.05-0.3 percent of the sample solution), and performing irradiation reaction for 0.5-1 h to obtain a reduction sample solution.
(6) And (3) drying: and (3) pumping the methanol sample solution into a drying column, and controlling the adsorption flow rate to be 300-500 mL/min.
(7) Ion exchange: and (3) pumping the dried methanol sample liquid into two cation exchange resins connected in series for ion exchange.
(8) And (3) filtering: and pumping the primarily dried methanol sample liquid into a filtering membrane component for adsorption and filtration.
(9) Vaporization: and (3) pumping the methanol sample liquid subjected to membrane filtration and impurity removal into a vaporization distillation kettle, heating by utilizing heat conduction oil, controlling the temperature of the heat conduction oil to be 80-100 ℃, controlling the liquid temperature to be 65-75 ℃, and introducing the gas-phase methanol in the tower kettle into a pervaporation membrane assembly for next treatment.
(10) And (3) dehydration treatment: and the vacuum pump is used for carrying out pressure reduction treatment in the membrane component, so that pressure difference is generated on two sides of the membrane, water molecules are small and can pass through the permeation gasification membrane material, while methanol molecules are large and cannot pass through the membrane material, and the LC-MS grade methanol finished product is obtained after condensation by a condenser arranged in the membrane component.
(11) Filling nitrogen and filling: and (3) automatically filling nitrogen into the product, and obtaining a 4L LC-MS grade methanol product for liquid chromatography-mass spectrometry. The purity of the obtained product is 99.99 percent, the water content is 0.011 percent, and all detection results meet the index requirements. Can meet the customer requirements of LC-MS grade methanol for liquid chromatography-mass spectrometry. The results of the tests of the product are shown in table 1. (the absorbance measurement is the result of a 1cm quartz cuvette using water as a reference)
Table 1: LC-MS grade methanol index detection result for liquid chromatography-mass spectrometry
Example 2
A purification method of LC-MS grade methanol for liquid chromatography-mass spectrometry comprises the following steps:
(1) A first adsorption step: the methanol raw material is pre-adsorbed by a modified multi-wall CNTS graphite adsorption column, partial unsaturated olefin impurities are removed by adsorption, and the adsorption flow rate is controlled to be 100-700 mL/min.
(2) And (3) ether removal treatment: pumping the adsorbed and filtered methanol sample liquid into a reaction rectifying kettle, adding 3-5 g of IM-5 type molecular sieve, controlling the heating temperature of the rectifying kettle to be 30-45 ℃, reacting for 0.2-0.5 h under the condition of continuous stirring, filling nitrogen into the reaction kettle, and replacing low-boiling-point ether and ammonia gases in the reaction kettle.
(3) Hydrolysis: after the ether removal treatment is finished, 5-10g 732 type acidic cation exchange resin is added into a reactive rectifying kettle, the heating temperature of the rectifying kettle is controlled to be 30-45 ℃, the heating reaction is carried out for 0.5-1 h, ester impurities in the methanol sample liquid are hydrolyzed into acid and alcohol impurities, meanwhile, after light components are evaporated out in a refluxing mode, the temperature is continuously increased, the bottom temperature of the rectifying kettle is controlled to be 70-77 ℃, the top temperature of the rectifying kettle is 65-67 ℃, and the reflux ratio is adjusted to be 2.
(4) And an adsorption step two: and (3) pumping the methanol sample liquid distilled out through hydrolysis into an adsorption system formed by connecting a CTMAB-13X molecular sieve, an LS-40 macroporous resin adsorption column and a diatomite adsorption column in series for adsorption and impurity removal. Controlling the adsorption flow rate to be 300 mL-500 mL/min.
(5) Reduction: and (3) pumping the sample solution after adsorption and filtration into an ultraviolet irradiation reaction kettle, adding a reducing agent (the mass percent of the reducing agent added is 0.05-0.3 percent of the sample solution), and performing irradiation reaction for 0.5-1 h to obtain a reduction sample solution.
(6) And (3) drying: and (3) pumping the methanol sample solution into a drying column, and controlling the adsorption flow rate to be 300-500 mL/min.
(7) Ion exchange: and (3) pumping the dried methanol sample liquid into two cation exchange resins connected in series for ion exchange.
(8) And (3) filtering: and pumping the primarily dried methanol sample solution into a filtering membrane component for adsorption and filtration.
(9) And (3) vaporization: and (3) pumping the methanol sample liquid subjected to membrane filtration and impurity removal into a vaporization distillation kettle, heating by utilizing heat conduction oil, controlling the temperature of the heat conduction oil to be 80-100 ℃, controlling the liquid temperature to be 65-75 ℃, and introducing the gas-phase methanol in the tower kettle into a pervaporation membrane assembly for next treatment.
(10) And (3) dewatering treatment: and a vacuum pump is utilized to carry out pressure reduction treatment in the membrane component, so that pressure difference is generated on two sides of the membrane, water molecules are small and can pass through the permeation gasification membrane material, methanol molecules are large and cannot pass through the membrane material, and an LC-MS grade methanol finished product is obtained after condensation through a condenser arranged in the membrane component.
(11) Filling nitrogen and filling: and (3) automatically filling nitrogen and filling to obtain 500mL LC-MS grade methanol product for liquid chromatography-mass spectrometry. The purity of the obtained product is 99.99%, the water content is 0.010%, and all detection results meet the index requirements. Can meet the customer requirements of LC-MS grade methanol for liquid chromatography-mass spectrometry. The results of the tests of this product are shown in Table 2. (the absorbance measurement is a result of measurement using a 1cm quartz cuvette and water as a reference.)
Table 2: LC-MS grade methanol index detection result for liquid chromatography-mass spectrometry
Although the embodiments of the present invention have been disclosed for illustrative purposes, those skilled in the art will appreciate that: various substitutions, changes and modifications are possible without departing from the spirit and scope of the invention and the appended claims, and therefore the scope of the invention is not limited to the embodiments disclosed.
Claims (10)
1. A purification method of LC-MS grade methanol is characterized in that: the method comprises the following steps:
(1) Adsorbing and filtering a methanol raw material through a modified multi-wall CNTS graphite adsorption column;
(2) Removing ether from a methanol raw material by taking an IM-5 type molecular sieve as a catalyst;
(3) Hydrolyzing 732 type acidic cation exchange resin as catalyst to remove ester impurities;
(4) Removing acidic and alkaline impurities by adsorption through a modified 13X molecular sieve and LS-40 macroporous resin;
(5) Reducing and removing aldehydes and partial oxidizing impurities by an ultraviolet light catalytic reduction technology;
(6) Removing metal ion impurities in the methanol through cation exchange resin;
(7) Removing macromolecular impurities by using a PF5A ion composite membrane material;
(8) And (3) dehydrating the methanol by using a polydimethylsiloxane membrane material to obtain a methanol sample meeting the LC-MS grade methanol index requirement.
2. The purification method of LC-MS grade methanol according to claim 1,the method is characterized in that: in the step (1), the purity of the methanol raw material is 99.5%, the adsorption flow rate is 100-500 mL/min, and the modification method of the CNTS graphite adsorption column comprises the following steps: adding CNTS graphite to 5% Al (OH) 3 Soaking in the solution for 3-5h, standing for 8-15h, oven drying in oven at 105 deg.C, roasting in muffle furnace at 350 deg.C for 3-5h, and cooling to room temperature.
3. The purification process of LC-MS grade methanol according to claim 1, characterized in that:
the ether removal treatment process in the step (2) comprises the following steps: and (2) pumping the methanol sample liquid subjected to adsorption and filtration in the step (1) into a reaction rectifying kettle, adding an IM-5 type molecular sieve catalyst according to the mass fraction of 0.05-0.3% of methanol, controlling the heating temperature of the rectifying kettle to be 30-45 ℃, reacting for 0.1-0.5 h under the condition of continuous stirring, then filling nitrogen into the reaction kettle, and replacing low-boiling-point ethers and ammonia gases in the reaction kettle.
4. The purification method of LC-MS grade methanol according to claim 1, characterized in that:
after the ether removal treatment in the step (2) is finished, adding 732 type acidic cation exchange resin catalyst into a reaction rectifying still, controlling the heating temperature of the rectifying still to be 30-45 ℃, carrying out heating reaction for 0.5-1 h, hydrolyzing ester impurities in the methanol sample liquid into acid and alcohol impurities, continuously heating after distilling out light components in a refluxing manner, controlling the bottom temperature of the rectifying still to be 70-77 ℃, the top temperature of the rectifying still to be 65-67 ℃, and adjusting the reflux ratio to be 2.
5. The purification method of LC-MS grade methanol according to claim 1, characterized in that:
and (4) pumping the methanol sample liquid distilled out through hydrolysis into a 13X molecular sieve and LS-40 macroporous resin adsorption system connected in series for adsorption and impurity removal, and controlling the adsorption flow rate to be 300-500 mL/min.
6. The purification method of LC-MS grade methanol according to claim 1, characterized in that:
and (5) pumping the sample liquid after adsorption and filtration into an ultraviolet irradiation reaction kettle, adding a reducing agent accounting for 0.05-0.3% of the sample liquid by mass percent, performing irradiation reaction for 0.5-1 h, and reducing to remove aldehyde impurities and reducing impurities to obtain a reduced sample liquid.
7. The purification process of LC-MS grade methanol according to claim 1, characterized in that:
in the step (6), the dried methanol sample solution is injected into two cation exchange resins connected in series for ion exchange to remove trace metal impurities, and the drying process comprises the following steps: and pumping the reduced methanol sample solution into a drying column, controlling the adsorption flow rate to be 300-500 mL/min, and reducing the water content to be below 0.05%.
8. The purification process of LC-MS grade methanol according to claim 7, characterized in that:
pumping the dried methanol sample liquid into a filtering membrane component for adsorption and filtration, pumping the methanol sample liquid subjected to membrane filtration and impurity removal into a vaporization distillation kettle, heating by utilizing heat conduction oil, controlling the temperature of the heat conduction oil to be 80-100 ℃, controlling the liquid temperature to be 65-75 ℃, and introducing the gas-phase methanol in the tower kettle into a pervaporation membrane component for next treatment.
9. The purification method of LC-MS grade methanol according to claim 1, characterized in that:
the modified 13X molecular sieve is a CTMAB-13X molecular sieve, and the modification method comprises the following steps: adding 200g of 13x molecular sieve into 3000mL of 0.4mol/L hexadecyl trimethyl ammonium bromide with molar concentration for surface modification, stirring for 60min, standing for 30min, washing bottom precipitate with water, filtering, standing in an oven for drying at 105 ℃, and grinding for later use.
10. The purification method of LC-MS grade methanol according to claim 1, characterized in that: the LS-40 macroporous resin adsorption column is soaked for 3-5 hours by 15% -30% sulfuric acid, and is dried in an oven at 150 ℃ after being taken out for use.
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| CN103183582A (en) * | 2011-12-27 | 2013-07-03 | 湖北杜克化学科技有限公司 | Method for preparing chromatographically pure methanol from industrial methanol |
| CN107556161A (en) * | 2017-09-06 | 2018-01-09 | 湖北富森盐湖化工科技有限公司 | Chromatographic Pure Methanol and preparation method thereof, production system |
| CN109438413A (en) * | 2018-12-13 | 2019-03-08 | 天津康科德医药化工有限公司 | A kind of purification process of chromatographically pure 1,4- dioxane |
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| CN103183582A (en) * | 2011-12-27 | 2013-07-03 | 湖北杜克化学科技有限公司 | Method for preparing chromatographically pure methanol from industrial methanol |
| CN107556161A (en) * | 2017-09-06 | 2018-01-09 | 湖北富森盐湖化工科技有限公司 | Chromatographic Pure Methanol and preparation method thereof, production system |
| CN109438413A (en) * | 2018-12-13 | 2019-03-08 | 天津康科德医药化工有限公司 | A kind of purification process of chromatographically pure 1,4- dioxane |
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