CN113416151A - Preparation method of pure acetonitrile for chromatographic analysis and production equipment thereof - Google Patents
Preparation method of pure acetonitrile for chromatographic analysis and production equipment thereof Download PDFInfo
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- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 title claims abstract description 263
- 238000004587 chromatography analysis Methods 0.000 title claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 238000001179 sorption measurement Methods 0.000 claims abstract description 104
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 55
- 230000003647 oxidation Effects 0.000 claims abstract description 51
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 41
- 230000003197 catalytic effect Effects 0.000 claims abstract description 33
- 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
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 22
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- 238000000746 purification Methods 0.000 claims abstract description 10
- UPWOEMHINGJHOB-UHFFFAOYSA-N cobalt(III) oxide Inorganic materials O=[Co]O[Co]=O UPWOEMHINGJHOB-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims description 34
- 239000002994 raw material Substances 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 239000012535 impurity Substances 0.000 claims description 14
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 9
- 229910052753 mercury Inorganic materials 0.000 claims description 8
- 238000009835 boiling Methods 0.000 claims description 7
- 239000003245 coal Substances 0.000 claims description 7
- 238000010521 absorption reaction Methods 0.000 claims description 5
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 3
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical group [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- VZDYWEUILIUIDF-UHFFFAOYSA-J cerium(4+);disulfate Chemical compound [Ce+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VZDYWEUILIUIDF-UHFFFAOYSA-J 0.000 claims description 2
- 229910000355 cerium(IV) sulfate Inorganic materials 0.000 claims description 2
- 238000004064 recycling Methods 0.000 claims description 2
- 239000007858 starting material Substances 0.000 claims 2
- 239000000047 product Substances 0.000 description 21
- 238000010992 reflux Methods 0.000 description 10
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- 239000000243 solution Substances 0.000 description 7
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- 230000008929 regeneration Effects 0.000 description 6
- 238000011069 regeneration method Methods 0.000 description 6
- 239000003463 adsorbent Substances 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000007800 oxidant agent Substances 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000005281 excited state Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
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- 238000004806 packaging method and process Methods 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 230000006820 DNA synthesis Effects 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 230000006819 RNA synthesis Effects 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- PGJHGXFYDZHMAV-UHFFFAOYSA-K azanium;cerium(3+);disulfate Chemical compound [NH4+].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O PGJHGXFYDZHMAV-UHFFFAOYSA-K 0.000 description 1
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- 229940079593 drug Drugs 0.000 description 1
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- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
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- 230000001678 irradiating effect Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- -1 organic synthesis Substances 0.000 description 1
- 238000004816 paper chromatography Methods 0.000 description 1
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- 239000012286 potassium permanganate Substances 0.000 description 1
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- 238000012958 reprocessing Methods 0.000 description 1
- 238000004007 reversed phase HPLC Methods 0.000 description 1
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- 229910002027 silica gel Inorganic materials 0.000 description 1
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- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention provides a preparation method and production equipment of green, environment-friendly and efficient pure acetonitrile for chromatographic analysis2O5Or nano Co2O3Mixing the catalyst with air, performing ultraviolet irradiation catalytic oxidation to obtain an oxidation solution, sequentially performing adsorption purification on the oxidation solution through an activated carbon adsorption layer, a 13X molecular sieve adsorption layer, an activated alumina adsorption layer and a 3A molecular sieve adsorption layer, and rectifying to obtain the pure acetonitrile for chromatographic analysis.
Description
Technical Field
The invention relates to a purification technology of organic chemical products, in particular to a preparation method of pure acetonitrile for chromatographic analysis and production equipment thereof.
Background
Acetonitrile is an organic chemical product widely used as an organic solvent, as well as a raw material for fine chemicals such as organic synthesis, medicines, agricultural chemicals, surfactants, dyes, etc., and also as a raw material for biosynthesis, organic EL material synthesis, electronic component cleaning agents, etc., and these applications are highly required for the purity of acetonitrile.
With the use of acetonitrile as an organic modifier and solvent for high performance liquid chromatography, thin layer chromatography, paper chromatography, spectroscopy and polarographic analysis, particularly chromatographic grade (HPLC) acetonitrile as a solvent for reversed phase high performance liquid chromatography, acetonitrile is required to have low absorbance in the ultraviolet low wavelength region (200-400 nm) and strict requirements for impurities in the solvent, and the acetonitrile needs to be refined by a special method.
So far, various acetonitrile refining processes have been reported at home and abroad, wherein the main purification method comprises the following steps: multi-stage rectification, pressure swing rectification, combination of oxidation and distillation, adsorption, combination of oxidation and adsorption and the like, and different purification methods are selected according to different impurities in the raw material industrial acetonitrile. A plurality of patents related to acetonitrile purification methods and devices exist in China, various designed purification devices are more in types, the patents mainly focus on the primary acetonitrile purification step, and the grade of the purified acetonitrile is lower. Most of the methods adopt oxidation as a purification means, but at present, potassium dichromate, potassium permanganate, phosphorus pentoxide and the like or ozone is mostly used as an oxidant to carry out the oxidation of industrial acetonitrile, and a distillation or adsorption means is combined, but the methods have the defects of large oxidant consumption, long oxidation time, violent reaction, residual manganese salt, environmental pollution and low product yield. Therefore, a new green and clean process method is explored for preparing and producing chromatographic grade pure acetonitrile by industrial acetonitrile, and the method has good market development potential and practical application value.
CN110683967A discloses a method for preparing anhydrous acetonitrile for DNA/RNA synthesis, which utilizes activated carbon fiber adsorption column to remove impurities by adsorption, and adopts H2O2Oxidizing and decomposing impurities in the acetonitrile sample under the catalysis of ultraviolet light, and then utilizing sodium hydroxide alkaliAdsorbing and removing hydrocyanic acid and acid impurities generated after oxidation by using a sexual adsorption column, adsorbing and removing metal ion impurities by using a modified SBA-15 molecular sieve, and drying and dehydrating by using a 3A molecular sieve; the acetonitrile product is obtained through the steps of distillation, decompression, extraction, rectification and pressurization. The method promotes H by ultraviolet light catalysis2O2Rapidly decompose to release atomic oxygen, increase oxidation rate, but H2O2The decomposition process produces water as a by-product, which is difficult to remove in subsequent separations.
Disclosure of Invention
The invention aims to provide a preparation method of pure acetonitrile for chromatographic analysis, which is environment-friendly and efficient, aims at the environmental problem caused by the adoption of inorganic oxidants mostly at present, and has the characteristics of almost no waste residue emission and high product yield.
The invention also aims to provide production equipment for realizing the method, which well combines the ultraviolet catalytic oxidation, adsorption and rectification processes together, realizes continuous operation and can be used for large-scale production of pure acetonitrile.
Adding a catalyst into an acetonitrile raw material, mixing the acetonitrile raw material with air, irradiating the mixture by ultraviolet light, performing catalytic oxidation to obtain an oxidation solution, sequentially performing adsorption and purification on the oxidation solution by an activated carbon adsorption layer, a 13X molecular sieve adsorption layer, an activated alumina adsorption layer and a 3A molecular sieve adsorption layer, and rectifying the adsorption solution to obtain pure acetonitrile for chromatographic analysis; the catalyst is cerium sulfate, ammonium ceric sulfate, ammonium vanadate, and nanometer V2O5Or nano Co2O3Wherein the volume ratio of acetonitrile to air is 1: 50-500.
Preferably, the ultraviolet light is from medium-pressure mercury lamp with power of 2-12 kW/M3。
The UV irradiation time is preferably between 5 and 30 minutes.
The activated carbon in the activated carbon adsorption layer is coal columnar activated carbon with the diameter of 1-3 mm and the CTC value larger than 80, the 13X molecular sieve in the 13X molecular sieve adsorption layer, the activated alumina in the activated alumina adsorption layer and the 3A molecular sieve in the 3A molecular sieve adsorption layer are spheres with the diameter of 1-3 mm.
The acetonitrile content of the acetonitrile raw material is preferably not less than 99%, and the ultraviolet absorption at 190nm is not more than 3.
The addition amount of the catalyst is 0.5-3 ten thousandth of the weight of the acetonitrile raw material.
The invention relates to a production device of pure acetonitrile for chromatographic analysis, which comprises:
the gas-liquid mixing pump is used for mixing the acetonitrile raw material, the catalyst and air;
the ultraviolet light catalytic oxidation tower is characterized in that a medium-pressure mercury lamp is arranged in the center of the tower, a spiral reaction tube is arranged around the tower, and a mercury lamp and a shading layer are arranged outside the tower; the gas-liquid mixing pump is connected with the spiral reaction tube through a pipeline; the top of the spiral reaction tube is connected with a low-temperature heat exchanger for condensing and recycling raw materials in the emptied air flow;
the comprehensive adsorption tower is connected with the heat exchanger and sequentially provided with an active carbon adsorption layer, a 13X molecular sieve adsorption layer, an active alumina adsorption layer and a 3A molecular sieve adsorption layer, wherein the active carbon in the active carbon adsorption layer is coal columnar active carbon with the diameter of 1-3 mm and the CTC value of more than 80, the 13X molecular sieve in the 13X molecular sieve adsorption layer, the active alumina in the active alumina adsorption layer and the 3A molecular sieve in the 3A molecular sieve adsorption layer are spheres with the diameter of 1-3 mm; and the number of the first and second groups,
the rectifying still and the rectifying tower which are connected with the comprehensive adsorption tower are used for rectifying the oxidation liquid to remove impurities with high boiling point and low boiling point.
The inner surface of the shading layer is a reflecting mirror surface.
The embodiment of the invention has the beneficial effects that:
the preparation method takes the industrial acetonitrile as a raw material, utilizes a clean pollution-free ultraviolet catalytic oxidation technology to carry out oxidation reaction, and then carries out comprehensive adsorption and rectification treatment by using various adsorption materials to remove various organic impurities such as olefin and the like contained in the industrial acetonitrile.
The production equipment can realize large-scale industrial production of chromatographic pure acetonitrile. The device consists of a catalytic oxidation system, a comprehensive adsorption column, a rectifying still, a rectifying column and an adsorption column regeneration system, and has the characteristics of simple structure, easiness in operation, high production efficiency and the like.
Drawings
FIG. 1 shows an embodiment of the apparatus for producing pure acetonitrile for chromatography according to the present invention.
The device name corresponding to the icon is: 11-elevated tank; 12-a rectifying still; 13-front cut storage tank; 14-finished product storage tank; 21-ultraviolet light catalytic oxidation tower; 22-a comprehensive adsorption tower; 23-a rectification column; 24-a helical reaction tube; 31-a gas-liquid mixing pump; 32-industrial air heater; 33-a light-shielding layer; 34-a cryogenic heat exchanger; 35-1#A heat exchanger; 36-2#A heat exchanger; 37-gas-liquid separator.
Detailed Description
The attached drawing is an embodiment of the production apparatus of the present invention, which comprises:
the head tank 11 is used for storing the raw material and supplying a mixture of the raw material acetonitrile and the catalyst to the gas-liquid mixing pump 31.
And the gas-liquid mixing pump 31 is connected with the elevated tank 11 and an air source and mixes the mixture of the raw material acetonitrile and the catalyst with air.
The ultraviolet catalytic oxidation tower 21 is characterized in that an ultraviolet light source is arranged in the center of the ultraviolet catalytic oxidation tower 21, a spiral reaction tube 24 is arranged around the ultraviolet catalytic oxidation tower 21, the ultraviolet light source is arranged outside the spiral reaction tube 24, a light shielding layer 33 is arranged on the outermost layer, and the inner surface of the light shielding layer is a reflecting mirror surface; the lower part of the spiral reaction tube 24 is communicated with a gas-liquid mixing pump 31 through a pipeline; the ultraviolet light source adopts a medium-pressure mercury lamp with mercury vapor pressure of about 102kPa, the volume of the ultraviolet light catalytic oxidation tower 21 is taken as a reference, and the total power of the medium-pressure mercury lamp is 32—12kW/MThe cooling mode is air cooling, air is provided by a fan at the lower part of the catalytic oxidation tower 21, and exhaust air at the upper part of the catalytic oxidation tower 21 forms convection air for air cooling.
And the low-temperature heat exchanger 34 is positioned at the top of the ultraviolet catalytic oxidation tower 21, is communicated with the spiral reaction tube 24 through a pipeline, and is used for condensing and recovering the raw material acetonitrile in the air flow discharged from the spiral reaction tube 24.
The comprehensive adsorption tower 22 is provided with a plurality of adsorbent layers, is connected with the top of the ultraviolet catalytic oxidation tower 21, and is sequentially filled with an activated carbon adsorption layer, a 13X molecular sieve adsorption layer, an activated alumina adsorption layer and a 3A molecular sieve adsorption layer for adsorbing various impurities in the oxidation liquid.
Rectifying still 12 and rectifying column 23, the raw materials entry of rectifying still 12 communicates the upper portion of synthesizing adsorption tower 22 through the pipeline for heat the evaporation to the oxidizing liquid, rectifying still 12 top is connected rectifying column 23 through the pipeline, to rectifying column 23 delivery steam, rectifying still 12 lower part intercommunication rectifying column 23 lower part receives the reflux liquid. The rectifying tower 23 is used for separating and removing high-boiling point and low-boiling point impurities; the top of the rectifying tower 23 is connected with a connecting pipe 1#The heat exchanger 35 cools the steam 1#The heat exchanger 35 is connected with a gas-liquid separator 37 to separate low boiling point substances, and the rear end of the gas-liquid separator 37 is communicated with a return pipe of the rectifying tower 23 and the gas-liquid separator 2# Heat exchanger 36, by controlling the ratio of fraction collection and reflux heating by means of valves, 2#The heat exchanger 36 further cools the distillate, and the rear end of the heat exchanger is connected with the front distillate storage tank 13 and the finished product storage tank 14 to collect finished products.
And the industrial hot air blower 32 is connected with the lower part of the comprehensive adsorption tower 22 and is used for regenerating the adsorbent filler in the comprehensive adsorption tower 22.
The oxidation catalyst can be cerium sulfate, ammonium cerous sulfate, ammonium vanadate, nanometer V2O5Or nano Co2O3One kind of (1). Under the excitation action of ultraviolet light, oxygen molecules in the air are transited from a ground state to an excited state after being irradiated by the ultraviolet light, the process needs to be completed under the action of a catalyst, the oxygen in the excited state reacts with water and organic matters to generate peroxide and free radicals, and the peroxide and the free radicals further participate in the reaction, so that the effect which cannot be achieved by using an oxidant alone is generated, the oxidation capacity and the reaction rate of the photocatalytic oxidation are greatly improved, the required amount of the catalyst is little, no secondary pollution is generated, the equipment is simple,the process is simplified. In order to sufficiently oxidize impurities in the raw material, the ultraviolet light irradiation time generally requires 5 minutes or more, preferably 5 to 30 minutes, and more than 30 minutes is allowed, but the production efficiency is thereby lowered.
Adsorbents can be broadly classified into two broad categories, polar and non-polar, according to the nature of the surface. The former mainly comprises silica gel, molecular sieve and activated alumina, and the latter mainly comprises carbonaceous materials such as activated carbon, activated carbon fiber and carbon molecular sieve. The zeolite molecular sieve has two effects of hydrophilicity and hydrophobicity due to different silicon-aluminum ratios. The low-silica-alumina ratio zeolite has strong electrostatic field, easy adsorption of polar molecules and strong water adsorption capacity. The high silica to alumina ratio zeolites have a greater adsorption capacity for hydrocarbon molecules than water. These adsorbents can be used in the present invention.
The 13X molecular sieve used in the invention has large surface area, is a high-efficiency adsorbent, still has higher adsorption capacity when the concentration of adsorbate is very low, the 3A molecular sieve is mainly used for adsorbing molecules with the diameter less than 0.3nm, the two molecular sieves, the activated carbon and the activated alumina are matched to generate a synergistic effect, and organic impurities and water with different sizes and different polarities can be effectively removed. More preferably, coal columnar activated carbon with the diameter of 1-3 mm and the CTC value of more than 80 is used, and spheres with the diameter of 1-3 mm can be selected from activated alumina, 13X molecular sieve and 3A molecular sieve, so that the fluid resistance is reduced, and the regeneration treatment is facilitated.
The invention preferably uses industrial grade acetonitrile with the content of not less than 99 percent and the ultraviolet absorption of 190nm of not more than 3 as the raw material.
When the production system works, the raw material industrial grade acetonitrile meeting the requirements is sent into the elevated tank 11, and a proper amount of catalyst is added and uniformly mixed. And starting the ultraviolet light source, and adjusting and stabilizing the power. Starting the gas-liquid mixing pump 31, adjusting the flow rate of the raw material acetonitrile and the air to ensure that the stroke of the raw material acetonitrile in the ultraviolet catalytic oxidation tower 21 is 5-30 minutes, and fully mixing the acetonitrile and the air in the gas-liquid mixing pump 31 according to the volume ratio of 1: 50-500. And (3) opening the low-temperature heat exchanger at the top of the ultraviolet catalytic oxidation tower 21, and closing a connecting valve between the bottom of the comprehensive adsorption tower 22 and the industrial hot air blower 32. The mixed liquid is conveyed into an ultraviolet catalytic oxidation tower 21 through a pipeline, catalytic oxidation reaction is carried out in a spiral reaction tube 24 under the catalysis of ultraviolet light, and partial impurities in the raw materials are oxidized to form oxidation products which are convenient to remove in the subsequent working procedures. Then the oxidized liquid enters a comprehensive adsorption tower 22, passes through an activated carbon adsorption layer, a 13X molecular sieve adsorption layer, an activated alumina adsorption layer and a 3A molecular sieve adsorption layer in sequence, and the obtained adsorption liquid is stored in a rectifying still 12. The gas flow is discharged to the air from the top of the low-temperature heat exchanger 34, and the acetonitrile carried in the gas flow is cooled and recovered by the low-temperature heat exchanger 34 at the top of the tower and enters the adsorption tower again.
When the volume of the adsorption liquid in the rectifying still 12 reaches 1/5, starting steam in the rectifying still 12 to heat, after refluxing at the top of the rectifying tower for 0.5-3 h, starting fraction collection, controlling the collection reflux ratio to be 1-5: 1, storing the front fraction in a front fraction storage tank 13, and taking the front fraction as a preparation-grade acetonitrile product or merging the front fraction into raw material acetonitrile for reprocessing, and then taking the collected fraction as a pure acetonitrile product for chromatographic analysis to enter a finished product storage tank.
After the production is finished, the raw materials in the comprehensive adsorption tower 22 are pumped out, the vacuum is continuously pumped for 1 to 3 hours, then steam is introduced for 0.1 to 1 hour, a hot air system is opened, the comprehensive adsorption tower 22 is dried by hot air at the temperature of 100 to 150 ℃, then the temperature is gradually increased to 300 to 350 ℃, the regeneration is continuously carried out for 1 to 6 hours, and the regeneration of the comprehensive adsorption tower 22 can be finished.
Example 1:
the content of the industrial acetonitrile serving as the raw material is 99.16% by detection, and the ultraviolet absorption at 190nm is 2.609%.
The head tank 11 is purged with nitrogen gas to remove moist air. Adding raw material industrial grade acetonitrile into Ce (SO) with the mass of 0.01 percent of acetonitrile4)2•4H2And feeding the O into the head tank.
Starting an ultraviolet light source with the power of 3kW/M3。
And starting a gas-liquid mixing pump, adjusting the flow rate of acetonitrile and air, wherein the volume ratio of acetonitrile to air is 1:50, the stroke of acetonitrile in the catalytic oxidation tower 21 is 20 minutes, and the acetonitrile and the air are mixed in the gas-liquid mixing pump.
Opening a low-temperature heat exchanger 34 on the top of the catalytic oxidation tower 21, closing a bottom valve and a side valve of the comprehensive adsorption tower 2, conveying a mixed solution into the catalytic oxidation tower 21 through a pipeline, performing catalytic oxidation reaction in a spiral reaction tube 24 under ultraviolet catalysis, then entering the comprehensive adsorption tower 22, allowing an oxidation solution to pass through a coal columnar activated carbon adsorption layer with the diameter of 2mm and the CTC value of 85, a spherical 13X molecular sieve adsorption layer with the diameter of 2mm, a spherical activated alumina adsorption layer with the diameter of 2mm and a spherical 3A molecular sieve adsorption layer with the diameter of 2mm in sequence, and allowing acetonitrile to contact in each adsorption layer for about 20 minutes to obtain an adsorption solution.
The gas flow passes through a low-temperature heat exchanger 34 at the top of the catalytic oxidation tower 22, acetonitrile carried in the gas flow is cooled and recovered by the low-temperature heat exchanger 34, and air is discharged from the top of the low-temperature heat exchanger 34.
And (3) feeding the adsorption liquid into a rectifying still, starting steam of the rectifying still to heat when the volume of the adsorption liquid in the rectifying still reaches 1/5, and completely refluxing for 0.5h after the top of the rectifying tower begins to reflux, and then beginning to extract.
Controlling the reflux ratio at 3: 1, collecting front cut fraction 50L, feeding into front cut fraction storage tank 13, continuously producing to obtain acetonitrile product meeting chromatographic purity specification totaling 3700Kg, feeding into finished product storage tank 14, and feeding into packaging system via pipeline. Stopping adding the raw materials, and discharging residual liquid in the catalytic oxidation tower, the comprehensive adsorption tower and the rectifying kettle to be merged into the raw materials for later use. And after the production is finished, the product enters a comprehensive adsorption tower for regeneration.
Example 2
Adopts NH with the mass of 0.01 percent of acetonitrile4VO3In place of Ce (SO) in example 14)2•4H2O is used as a catalyst, the process method and the parameters are the same as those of the example 1, and 3500Kg of acetonitrile product which meets the chromatographic purity specification is obtained.
Example 3
The content of the industrial acetonitrile serving as the raw material is 99.16% by detection, and the ultraviolet absorption at 190nm is 2.609%.
The head tank is purged with nitrogen to remove moist air. Adding raw material industrial grade acetonitrile into nano Co with the mass of 0.005 percent of acetonitrile2O3Feeding into a head tank to remove nanometer Co2O3Fully stirring and dispersing.
The ultraviolet light source is turned on and,the power is 5kW/M3。
And starting a gas-liquid mixing pump, adjusting the flow rate of acetonitrile and air, wherein the volume ratio of acetonitrile to air is 1: 100, the stroke of acetonitrile in the catalytic oxidation tower 21 is 10 minutes, and the acetonitrile and the air are mixed in the gas-liquid mixing pump.
Opening a low-temperature heat exchanger 34 on the top of the catalytic oxidation tower 21, closing a bottom valve and a side valve of the comprehensive adsorption tower 2, conveying a mixed solution into the catalytic oxidation tower 21 through a pipeline, performing catalytic oxidation reaction in a spiral reaction tube 24 under ultraviolet catalysis, then entering the comprehensive adsorption tower 22, allowing an oxidation solution to pass through a coal columnar activated carbon adsorption layer with the diameter of 2mm and the CTC value of 85, a spherical 13X molecular sieve adsorption layer with the diameter of 2mm, a spherical activated alumina adsorption layer with the diameter of 2mm and a spherical 3A molecular sieve adsorption layer with the diameter of 2mm in sequence, and allowing acetonitrile to contact in each adsorption layer for about 20 minutes to obtain an adsorption solution.
The gas flow passes through a low-temperature heat exchanger 34 at the top of the catalytic oxidation tower 22, acetonitrile carried in the gas flow is cooled and recovered by the low-temperature heat exchanger 34, and air is discharged from the top of the low-temperature heat exchanger 34.
And (3) feeding the adsorption liquid into a rectifying still, starting steam in the rectifying still for heating when the volume of the adsorption liquid in the rectifying still reaches 1/5, and completely refluxing for 1.0 hour after the top of the rectifying tower begins to reflux, and then beginning to extract.
Controlling the reflux ratio at 3: 1, collecting front fraction at 60L, introducing into front fraction storage tank 13, continuously producing to obtain 3320Kg acetonitrile product meeting the chromatographic purity specification, introducing into finished product storage tank 14, and delivering into packaging system via pipeline. Stopping adding the raw materials, discharging residual liquid in the catalytic oxidation tower 21, the comprehensive adsorption tower 22 and the rectifying still 23, and merging the residual liquid into the raw materials for later use. And after the production is finished, the product enters a comprehensive adsorption tower for regeneration.
Example 4
Adopts nano V with the mass of 0.01 percent of acetonitrile2O5Instead of nano Co in example 32O3As a catalyst, the process method and the parameters are the same as those of the example 3, and 3400Kg of acetonitrile product which meets the chromatographic purity specification is obtained.
The quality indexes of the acetonitrile products obtained in the embodiments 1 to 4 can reach the following indexes through detection:
Claims (8)
1. a method for preparing pure acetonitrile for chromatographic analysis is characterized in that a catalyst is added into an acetonitrile raw material and mixed with air, an oxidation solution is obtained through ultraviolet light irradiation catalytic oxidation, then the pure acetonitrile for chromatographic analysis is obtained through adsorption and purification of an activated carbon adsorption layer, a 13X molecular sieve adsorption layer, an activated alumina adsorption layer and a 3A molecular sieve adsorption layer in sequence and rectification; the catalyst is cerium sulfate, ammonium ceric sulfate, ammonium vanadate, and nanometer V2O5Or nano Co2O3Wherein the volume ratio of acetonitrile to air is 1: 50-500.
2. The process for preparing pure acetonitrile for chromatographic analysis according to claim 1, wherein the ultraviolet light is from a medium pressure mercury lamp and has a power of 2-12 kW/M3。
3. The process for preparing pure acetonitrile for chromatography according to claim 2, wherein the irradiation time of ultraviolet light is 5 to 30 minutes.
4. The process for preparing pure acetonitrile for chromatographic analysis according to claim 1, 2 or 3, wherein the activated carbon in the activated carbon adsorption layer is coal columnar activated carbon with a diameter of 1-3 mm and a CTC value of more than 80, the 13X molecular sieve in the 13X molecular sieve adsorption layer, the activated alumina in the activated alumina adsorption layer, and the 3A molecular sieve in the 3A molecular sieve adsorption layer are spheres with a diameter of 1-3 mm.
5. A process for the preparation of pure acetonitrile for chromatography according to claim 1, 2 or 3 wherein the acetonitrile content of the acetonitrile starting material is not less than 99% and the uv absorption at 190nm is not more than 3.
6. A process for the preparation of pure acetonitrile for chromatography according to claim 1, 2 or 3 wherein the catalyst is added in an amount of 0.1 to 3 parts per million by weight based on the weight of the acetonitrile starting material.
7. A production apparatus of pure acetonitrile for chromatography, comprising:
the gas-liquid mixing pump is used for mixing the acetonitrile raw material, the catalyst and air;
the ultraviolet light catalytic oxidation tower is characterized in that a medium-pressure mercury lamp is arranged in the center of the tower, a spiral reaction tube is arranged around the tower, and a mercury lamp and a shading layer are arranged outside the tower; the gas-liquid mixing pump is connected with the spiral reaction tube through a pipeline; the top of the spiral reaction tube is connected with a low-temperature heat exchanger for condensing and recycling raw materials in the emptied air flow;
the comprehensive adsorption tower is connected with the heat exchanger and sequentially provided with an active carbon adsorption layer, a 13X molecular sieve adsorption layer, an active alumina adsorption layer and a 3A molecular sieve adsorption layer, wherein the active carbon in the active carbon adsorption layer is coal columnar active carbon with the diameter of 1-3 mm and the CTC value of more than 80, the 13X molecular sieve in the 13X molecular sieve adsorption layer, the active alumina in the active alumina adsorption layer and the 3A molecular sieve in the 3A molecular sieve adsorption layer are spheres with the diameter of 1-3 mm;
the rectifying still and the rectifying tower which are connected with the comprehensive adsorption tower are used for rectifying the oxidation liquid to remove impurities with high boiling point and low boiling point.
8. The environmentally friendly high efficiency production apparatus of pure acetonitrile for chromatography as claimed in claim 6, wherein the inner surface of the light shielding layer is a mirror surface.
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| CN116102459A (en) * | 2022-12-30 | 2023-05-12 | 南通立洋化学有限公司 | HPLC acetonitrile purification process and application thereof |
| 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 |
| CN116987009A (en) * | 2023-08-14 | 2023-11-03 | 西陇科学股份有限公司 | Gradient acetonitrile and preparation method thereof |
| CN117417269A (en) * | 2023-12-19 | 2024-01-19 | 潍坊中汇化工有限公司 | Preparation method of anhydrous acetonitrile |
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| CN116102459A (en) * | 2022-12-30 | 2023-05-12 | 南通立洋化学有限公司 | HPLC acetonitrile purification process and application thereof |
| 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 |
| CN116987009A (en) * | 2023-08-14 | 2023-11-03 | 西陇科学股份有限公司 | Gradient acetonitrile and preparation method thereof |
| CN117417269A (en) * | 2023-12-19 | 2024-01-19 | 潍坊中汇化工有限公司 | Preparation method of anhydrous acetonitrile |
| CN117417269B (en) * | 2023-12-19 | 2024-03-12 | 潍坊中汇化工有限公司 | Preparation method of anhydrous acetonitrile |
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