CN116987009A - Gradient acetonitrile and preparation method thereof - Google Patents
Gradient acetonitrile and preparation method thereof Download PDFInfo
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- CN116987009A CN116987009A CN202311016406.4A CN202311016406A CN116987009A CN 116987009 A CN116987009 A CN 116987009A CN 202311016406 A CN202311016406 A CN 202311016406A CN 116987009 A CN116987009 A CN 116987009A
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- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 title claims abstract description 210
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 56
- 239000003463 adsorbent Substances 0.000 claims abstract description 29
- 238000001179 sorption measurement Methods 0.000 claims abstract description 29
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 27
- 230000003197 catalytic effect Effects 0.000 claims abstract description 26
- 230000003647 oxidation Effects 0.000 claims abstract description 25
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 239000007800 oxidant agent Substances 0.000 claims abstract description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910017566 Cu-Mn Inorganic materials 0.000 claims abstract description 9
- 229910017871 Cu—Mn Inorganic materials 0.000 claims abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 9
- 239000001301 oxygen Substances 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims abstract description 8
- 239000002131 composite material Substances 0.000 claims abstract description 7
- 238000011049 filling Methods 0.000 claims abstract description 7
- 239000007791 liquid phase Substances 0.000 claims abstract description 7
- 230000001590 oxidative effect Effects 0.000 claims abstract description 7
- 238000004806 packaging method and process Methods 0.000 claims abstract description 7
- 230000001172 regenerating effect Effects 0.000 claims abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 43
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- 239000012535 impurity Substances 0.000 claims description 17
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 16
- 239000002808 molecular sieve Substances 0.000 claims description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 238000010926 purge Methods 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000004064 recycling Methods 0.000 claims description 8
- 229910002651 NO3 Inorganic materials 0.000 claims description 7
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 7
- 238000002835 absorbance Methods 0.000 claims description 7
- 238000010828 elution Methods 0.000 claims description 7
- 229910044991 metal oxide Inorganic materials 0.000 claims description 7
- 150000004706 metal oxides Chemical class 0.000 claims description 7
- 239000010412 oxide-supported catalyst Substances 0.000 claims description 7
- AKYHKWQPZHDOBW-UHFFFAOYSA-N (5-ethenyl-1-azabicyclo[2.2.2]octan-7-yl)-(6-methoxyquinolin-4-yl)methanol Chemical compound OS(O)(=O)=O.C1C(C(C2)C=C)CCN2C1C(O)C1=CC=NC2=CC=C(OC)C=C21 AKYHKWQPZHDOBW-UHFFFAOYSA-N 0.000 claims description 6
- 239000001576 FEMA 2977 Substances 0.000 claims description 6
- 125000003713 acetylimino group Chemical group [H]C([H])([H])C(=O)N=[*] 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 6
- LOUPRKONTZGTKE-UHFFFAOYSA-N cinchonine Natural products C1C(C(C2)C=C)CCN2C1C(O)C1=CC=NC2=CC=C(OC)C=C21 LOUPRKONTZGTKE-UHFFFAOYSA-N 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 6
- 230000008020 evaporation Effects 0.000 claims description 6
- 238000000643 oven drying Methods 0.000 claims description 6
- 229960003110 quinine sulfate Drugs 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 230000008929 regeneration Effects 0.000 abstract description 15
- 238000011069 regeneration method Methods 0.000 abstract description 15
- 239000003054 catalyst Substances 0.000 abstract description 10
- 238000000746 purification Methods 0.000 abstract description 4
- 239000000047 product Substances 0.000 description 11
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910021389 graphene Inorganic materials 0.000 description 3
- 238000006385 ozonation reaction Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 239000011949 solid catalyst Substances 0.000 description 2
- 230000006820 DNA synthesis Effects 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000006819 RNA synthesis Effects 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000463 material Substances 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
- 150000002825 nitriles Chemical class 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
- C07C255/02—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms of an acyclic and saturated carbon skeleton
- C07C255/03—Mononitriles
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Abstract
The invention discloses gradient acetonitrile and a preparation method thereof, comprising the following steps: filling a catalytic oxidant in an ozone reaction contact tower; introducing oxygen containing ozone with a certain concentration from the bottom of the tower at room temperature and normal pressure, and introducing industrial acetonitrile from the top of the tower at a certain flow rate; after ozone and raw acetonitrile are fully contacted and oxidized in countercurrent in a reaction contact tower, a liquid phase pump switch is turned on, and an oxidation product is subjected to a composite adsorption column at a fixed flow rate; after the liquid in the adsorption process is completed, rectifying, and recovering and regenerating the adsorbent; and (5) detecting that the finished product is qualified, and carrying out clean packaging. According to the invention, an acetonitrile purification process combining continuous oxidation, adsorption and rectification is developed by combining a catalytic oxidation process, an adsorption process, a rectification process and an adsorbent regeneration process; the novel Cu-Mn/gamma-Al 2O3 oxidation catalyst is applied to the catalytic oxidation process of acetonitrile, so that the catalytic efficiency is higher and the reaction rate is faster.
Description
Technical Field
The invention relates to the technical field of acetonitrile, in particular to gradient grade acetonitrile and a preparation method thereof.
Background
At present, all foreign acetonitrile is derived from acrylonitrile byproduct produced by ammoxidation of propylene, and the acetonitrile synthesized by the method can hardly survive due to low cost of extracting acetonitrile from acrylonitrile wastewater. The current world acrylonitrile production device adopts the BP patent technology of the United states company, so the acetonitrile continuous recovery refining process must be matched with the main technical process. The method is characterized in that the concentration of hydrocyanic acid in the used crude acetonitrile is higher, the concentration of acetonitrile is properly reduced to avoid polymerization, and the crude acetonitrile is required to be concentrated in advance and then refined to obtain refined acetonitrile. The starting time for developing high-quality acetonitrile in China is late, and the gradient acetonitrile refining technology is monopoly abroad.
In the prior patent, CN110683967A discloses a preparation method of anhydrous acetonitrile for DNA/RNA synthesis, which comprises the steps of adsorbing and removing impurities by using an activated carbon fiber adsorption column, oxidatively decomposing impurities in an acetonitrile sample by using H2O2 under ultraviolet light catalysis, adsorbing and removing hydrocyanic acid and acid impurities generated after oxidation by using a sodium hydroxide alkaline adsorption column, adsorbing and removing metal ion impurities by using a modified SBA15 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. According to the method, H2O2 is promoted to be rapidly decomposed by ultraviolet light catalysis to release atomic oxygen, so that the oxidation speed is improved, but a large amount of byproduct water is generated in the H2O2 decomposition process, and the subsequent separation treatment steps are more;
CN105439903a discloses a method for preparing chromatographic grade acetonitrile by adsorbing and removing impurities by using graphene oxide and then rectifying. The graphene oxide serving as the adsorbent is a selective adsorbent, the adsorption effect on part of organic impurities is poor, the adsorption process is carried out in a reflux state, the adsorption process is a high-temperature process, and impurities adsorbed by the graphene oxide are easy to dissociate, so that the impurity removal effect is affected;
CN101570497B discloses that unsaturated nitrile is removed by using solid strong alkali at low temperature, then zeolite and adsorption resin are used for adsorption and impurity removal, and finally chromatographic grade acetonitrile is obtained by rectifying after molecular sieve water removal. The process is complex, and has a further optimized space;
CN1328994B discloses a method for industrially producing high-purity acetonitrile, the process mainly uses a dehydrocyanate tower for rectification, the process parameters of the method are difficult to control, and the industrial production is still to be optimized.
Disclosure of Invention
The invention aims to provide gradient acetonitrile and a preparation method thereof, and a continuous oxidation and adsorption and rectification combined acetonitrile purification process is developed by combining a catalytic oxidation process, an adsorption process, a rectification process and an adsorbent regeneration process.
In order to achieve the above purpose, the invention is realized by the following technical scheme: gradient acetonitrile, C2H3N content w/% -99.9, chromaticity less than or equal to 10, evaporation residue, w/% -0.0001, moisture, w/% -0.02, acidity, mmol/g less than or equal to 0.0005, alkalinity, mmol/g less than or equal to 0.0003.
In one or more embodiments of the invention, the gradient elution, mAU, described above: 210nm less than or equal to 5, 254nm less than or equal to 1, maximum fluorescence impurity (calculated by quinine sulfate), ρ/(ng/mL) less than or equal to 1.0, absorbance λ1 (190 nm) less than or equal to 1.00, λ2 (200 nm) less than or equal to 0.05, λ3 (210 nm) less than or equal to 0.04, λ4 (220 nm) less than or equal to 0.02, λ5 (230 nm) less than or equal to 0.01, λ6 (254 nm) less than or equal to 0.005, and λ7 (400 nm) less than or equal to 0.005.
The invention also provides a preparation method of the gradient grade acetonitrile, which is used for preparing the gradient grade acetonitrile and comprises the following steps:
s1, filling a catalytic oxidant in an ozone reaction contact tower;
s2, introducing oxygen containing ozone with a certain concentration at a certain flow rate from the bottom of the tower at room temperature and normal pressure, and introducing industrial acetonitrile at a certain flow rate from the top of the tower;
s3, after ozone and raw acetonitrile are fully contacted and oxidized in countercurrent in a reaction contact tower, a liquid phase pump switch is turned on, and an oxidation product is subjected to a composite adsorption column at a fixed flow rate;
s4, rectifying the liquid after the adsorption process is completed, and recycling and regenerating the adsorbent;
s5, detecting that the finished product is qualified, and carrying out clean packaging.
In one or more embodiments of the present invention, the above-described sequentially passes through three adsorbents including a combined Activated Carbon (AC), a molecular sieve (3A), and Activated Alumina (AA).
In one or more embodiments of the present invention, the catalytic oxidizer is prepared as follows:
step one: taking a certain amount of gamma-Al 2O3, and soaking the gamma-Al 2O3 in a dilute sulfuric acid solution with pH=4.0 for 24-30h;
step two: washing with deionized water to neutrality, boiling in deionized water for 3-5 times, washing with deionized water to neutrality, and oven drying at 100-150deg.C for 2 hr;
step three: respectively placing a certain amount of gamma-Al 2O3 into a nitrate impregnating solution mixed with Cu-Mn with the concentration of 0.5mol/L, and then placing into a shaking table;
step four: roasting for 3 hours at 550 ℃ in a muffle furnace to prepare a series of metal oxide supported catalysts MOx/gamma-Al 2O3.
In one or more embodiments of the present invention, the above-mentioned materials are immersed for 12 hours at 30-45r/min after being added to the shaking table, and then dried in an oven at 100-150 ℃ for 2 hours.
In one or more embodiments of the present invention, the adsorbent recovery regeneration is performed by nitrogen purge heating as described above, with the flow rate nitrogen purge heating the molecular sieve and activated alumina to above 350 ℃ for regeneration, and the activated carbon to 120 ℃ for complete regeneration.
Advantageous effects
The invention provides gradient acetonitrile and a preparation method thereof. Compared with the prior art, the method has the following beneficial effects:
according to the invention, an acetonitrile purification process combining continuous oxidation, adsorption and rectification is developed by combining a catalytic oxidation process, an adsorption process, a rectification process and an adsorbent regeneration process; the novel Cu-Mn/gamma-Al 2O3 oxidation catalyst is applied to the catalytic oxidation process of acetonitrile, so that the catalytic efficiency is higher, and the reaction rate is faster; the heterogeneous catalytic ozonation method is adopted to accelerate the oxidation reaction of acetonitrile in the raw material industry under normal pressure by using a solid catalyst, the catalyst is filled in a solid state, and the ozone is directly decomposed into oxygen, so that the process pollution is avoided, and the process flow is greatly simplified; the combination of the activated carbon, the molecular sieve and the activated alumina as the adsorbent can remove impurities more effectively, and the adsorbent can be regenerated for recycling, so that the process cost is better saved, and the resource utilization rate is improved.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
Various embodiments of the invention are disclosed in the accompanying drawings, and for purposes of explanation, numerous practical details are set forth in the following description. However, it should be understood that these practical details are not to be taken as limiting the invention. That is, in some embodiments of the invention, these practical details are unnecessary. Furthermore, for the purpose of simplifying the drawings, some of the presently available structures and elements are shown in a simplified schematic form, and the same reference numerals will be used throughout the drawings to designate the same or similar elements. And features of different embodiments may be interactively applied, if implementation is possible.
Unless otherwise defined, all terms (including technical and scientific terms) used herein have their ordinary meaning as understood by one of ordinary skill in the art. Furthermore, the definitions of the words and phrases used herein should be understood and interpreted to have a meaning consistent with the understanding of the relevant art and technology. These terms are not to be construed as idealized or overly formal meanings unless expressly so defined.
Embodiment one:
referring to FIG. 1, the invention provides gradient acetonitrile, wherein the content w/% > of C2H3N is more than or equal to 99.9, the chromaticity is less than or equal to 10, the evaporation residue is less than or equal to 0.0001, the moisture is less than or equal to 0.02, the acidity, the mmol/g is less than or equal to 0.0005, the alkalinity and the mmol/g is less than or equal to 0.0003.
Gradient elution in this example, mAU:210nm less than or equal to 5, 254nm less than or equal to 1, maximum fluorescence impurity (calculated by quinine sulfate), ρ/(ng/mL) less than or equal to 1.0, absorbance λ1 (190 nm) less than or equal to 1.00, λ2 (200 nm) less than or equal to 0.05, λ3 (210 nm) less than or equal to 0.04, λ4 (220 nm) less than or equal to 0.02, λ5 (230 nm) less than or equal to 0.01, λ6 (254 nm) less than or equal to 0.005, and λ7 (400 nm) less than or equal to 0.005.
The embodiment also provides a preparation method of the gradient grade acetonitrile, which is used for preparing the gradient grade acetonitrile and comprises the following steps:
s1, filling a catalytic oxidant in an ozone reaction contact tower;
s2, introducing oxygen containing ozone with a certain concentration at a certain flow rate from the bottom of the tower at room temperature and normal pressure, and introducing industrial acetonitrile at a certain flow rate from the top of the tower;
s3, after ozone and raw acetonitrile are fully contacted and oxidized in countercurrent in a reaction contact tower, a liquid phase pump switch is turned on, and an oxidation product is subjected to a composite adsorption column at a fixed flow rate;
s4, rectifying the liquid after the adsorption process is completed, and recycling and regenerating the adsorbent;
s5, detecting that the finished product is qualified, and carrying out clean packaging.
In this example, three adsorbents, i.e., a combined Activated Carbon (AC), a molecular sieve (3A), and Activated Alumina (AA), were passed through in this order.
The catalytic oxidizer in this example was prepared as follows:
step one: taking a certain amount of gamma-Al 2O3, and soaking the gamma-Al 2O3 in a dilute sulfuric acid solution with pH=4.0 for 24 hours;
step two: washing with deionized water to neutrality, boiling in deionized water for 3 times, washing with deionized water to neutrality, and oven drying at 100deg.C for 2 hr;
step three: respectively placing a certain amount of gamma-Al 2O3 into a nitrate impregnating solution mixed with Cu-Mn with the concentration of 0.5mol/L, and then placing into a shaking table;
step four: roasting for 3 hours at 550 ℃ in a muffle furnace to prepare a series of metal oxide supported catalysts MOx/gamma-Al 2O3.
In this example, after addition of the shaker, the mixture was immersed for 12 hours at 30r/min, and then dried in an oven at 100℃for 2 hours.
In this example, the adsorbent was recovered and regenerated by nitrogen purge heating at a flow rate of nitrogen purge to heat the molecular sieve and activated alumina to above 350 ℃ for regeneration and to 120 ℃ for complete regeneration of the activated carbon.
Embodiment two:
referring to FIG. 1, the invention provides gradient acetonitrile, wherein the content w/% > of C2H3N is more than or equal to 99.9, the chromaticity is less than or equal to 10, the evaporation residue is less than or equal to 0.0001, the moisture is less than or equal to 0.02, the acidity, the mmol/g is less than or equal to 0.0005, the alkalinity and the mmol/g is less than or equal to 0.0003.
Gradient elution in this example, mAU:210nm less than or equal to 5, 254nm less than or equal to 1, maximum fluorescence impurity (calculated by quinine sulfate), ρ/(ng/mL) less than or equal to 1.0, absorbance λ1 (190 nm) less than or equal to 1.00, λ2 (200 nm) less than or equal to 0.05, λ3 (210 nm) less than or equal to 0.04, λ4 (220 nm) less than or equal to 0.02, λ5 (230 nm) less than or equal to 0.01, λ6 (254 nm) less than or equal to 0.005, and λ7 (400 nm) less than or equal to 0.005.
The embodiment also provides a preparation method of the gradient grade acetonitrile, which is used for preparing the gradient grade acetonitrile and comprises the following steps:
s1, filling a catalytic oxidant in an ozone reaction contact tower;
s2, introducing oxygen containing ozone with a certain concentration at a certain flow rate from the bottom of the tower at room temperature and normal pressure, and introducing industrial acetonitrile at a certain flow rate from the top of the tower;
s3, after ozone and raw acetonitrile are fully contacted and oxidized in countercurrent in a reaction contact tower, a liquid phase pump switch is turned on, and an oxidation product is subjected to a composite adsorption column at a fixed flow rate;
s4, rectifying the liquid after the adsorption process is completed, and recycling and regenerating the adsorbent;
s5, detecting that the finished product is qualified, and carrying out clean packaging.
In this example, three adsorbents, i.e., a combined Activated Carbon (AC), a molecular sieve (3A), and Activated Alumina (AA), were passed through in this order.
The catalytic oxidizer in this example was prepared as follows:
step one: taking a certain amount of gamma-Al 2O3, and soaking the gamma-Al 2O3 in a dilute sulfuric acid solution with pH=4.0 for 30 hours;
step two: washing with deionized water to neutrality, boiling in deionized water for 5 times, washing with deionized water to neutrality, and oven drying at 150deg.C for 2 hr;
step three: respectively placing a certain amount of gamma-Al 2O3 into a nitrate impregnating solution mixed with Cu-Mn with the concentration of 0.5mol/L, and then placing into a shaking table;
step four: roasting for 3 hours at 550 ℃ in a muffle furnace to prepare a series of metal oxide supported catalysts MOx/gamma-Al 2O3.
In this example, after addition of the shaker, 45r/min was immersed for 12h, followed by drying in an oven at 150℃for 2h.
In this example, the adsorbent was recovered and regenerated by nitrogen purge heating at a flow rate of nitrogen purge to heat the molecular sieve and activated alumina to above 350 ℃ for regeneration and to 120 ℃ for complete regeneration of the activated carbon.
Embodiment III:
referring to FIG. 1, the invention provides gradient acetonitrile, wherein the content w/% > of C2H3N is more than or equal to 99.9, the chromaticity is less than or equal to 10, the evaporation residue is less than or equal to 0.0001, the moisture is less than or equal to 0.02, the acidity, the mmol/g is less than or equal to 0.0005, the alkalinity and the mmol/g is less than or equal to 0.0003.
Gradient elution in this example, mAU:210nm less than or equal to 5, 254nm less than or equal to 1, maximum fluorescence impurity (calculated by quinine sulfate), ρ/(ng/mL) less than or equal to 1.0, absorbance λ1 (190 nm) less than or equal to 1.00, λ2 (200 nm) less than or equal to 0.05, λ3 (210 nm) less than or equal to 0.04, λ4 (220 nm) less than or equal to 0.02, λ5 (230 nm) less than or equal to 0.01, λ6 (254 nm) less than or equal to 0.005, and λ7 (400 nm) less than or equal to 0.005.
The embodiment also provides a preparation method of the gradient grade acetonitrile, which is used for preparing the gradient grade acetonitrile and comprises the following steps:
s1, filling a catalytic oxidant in an ozone reaction contact tower;
s2, introducing oxygen containing ozone with a certain concentration at a certain flow rate from the bottom of the tower at room temperature and normal pressure, and introducing industrial acetonitrile at a certain flow rate from the top of the tower;
s3, after ozone and raw acetonitrile are fully contacted and oxidized in countercurrent in a reaction contact tower, a liquid phase pump switch is turned on, and an oxidation product is subjected to a composite adsorption column at a fixed flow rate;
s4, rectifying the liquid after the adsorption process is completed, and recycling and regenerating the adsorbent;
s5, detecting that the finished product is qualified, and carrying out clean packaging.
In this example, three adsorbents, i.e., a combined Activated Carbon (AC), a molecular sieve (3A), and Activated Alumina (AA), were passed through in this order.
The catalytic oxidizer in this example was prepared as follows:
step one: taking a certain amount of gamma-Al 2O3, and soaking the gamma-Al 2O3 in a dilute sulfuric acid solution with pH=4.0 for 26 hours;
step two: washing with deionized water to neutrality, boiling in deionized water for 4 times, washing with deionized water to neutrality, and oven drying at 130deg.C for 2 hr;
step three: respectively placing a certain amount of gamma-Al 2O3 into a nitrate impregnating solution mixed with Cu-Mn with the concentration of 0.5mol/L, and then placing into a shaking table;
step four: roasting for 3 hours at 550 ℃ in a muffle furnace to prepare a series of metal oxide supported catalysts MOx/gamma-Al 2O3.
In this example, after addition of the shaker, the mixture was immersed for 12 hours at 40r/min and then dried in an oven at 130℃for 2 hours.
In this example, the adsorbent was recovered and regenerated by nitrogen purge heating at a flow rate of nitrogen purge to heat the molecular sieve and activated alumina to above 350 ℃ for regeneration and to 120 ℃ for complete regeneration of the activated carbon.
Embodiment four:
referring to FIG. 1, the invention provides gradient acetonitrile, wherein the content w/% > of C2H3N is more than or equal to 99.9, the chromaticity is less than or equal to 10, the evaporation residue is less than or equal to 0.0001, the moisture is less than or equal to 0.02, the acidity, the mmol/g is less than or equal to 0.0005, the alkalinity and the mmol/g is less than or equal to 0.0003.
Gradient elution in this example, mAU:210nm less than or equal to 5, 254nm less than or equal to 1, maximum fluorescence impurity (calculated by quinine sulfate), ρ/(ng/mL) less than or equal to 1.0, absorbance λ1 (190 nm) less than or equal to 1.00, λ2 (200 nm) less than or equal to 0.05, λ3 (210 nm) less than or equal to 0.04, λ4 (220 nm) less than or equal to 0.02, λ5 (230 nm) less than or equal to 0.01, λ6 (254 nm) less than or equal to 0.005, and λ7 (400 nm) less than or equal to 0.005.
The embodiment also provides a preparation method of the gradient grade acetonitrile, which is used for preparing the gradient grade acetonitrile and comprises the following steps:
s1, filling a catalytic oxidant in an ozone reaction contact tower;
s2, introducing oxygen containing ozone with a certain concentration at a certain flow rate from the bottom of the tower at room temperature and normal pressure, and introducing industrial acetonitrile at a certain flow rate from the top of the tower;
s3, after ozone and raw acetonitrile are fully contacted and oxidized in countercurrent in a reaction contact tower, a liquid phase pump switch is turned on, and an oxidation product is subjected to a composite adsorption column at a fixed flow rate;
s4, rectifying the liquid after the adsorption process is completed, and recycling and regenerating the adsorbent;
s5, detecting that the finished product is qualified, and carrying out clean packaging.
In this example, three adsorbents, i.e., a combined Activated Carbon (AC), a molecular sieve (3A), and Activated Alumina (AA), were passed through in this order.
The catalytic oxidizer in this example was prepared as follows:
step one: taking a certain amount of gamma-Al 2O3, and soaking the gamma-Al 2O3 in a dilute sulfuric acid solution with pH=4.0 for 24 hours;
step two: washing with deionized water to neutrality, boiling in deionized water for 5 times, washing with deionized water to neutrality, and oven drying at 100deg.C for 2 hr;
step three: respectively placing a certain amount of gamma-Al 2O3 into a nitrate impregnating solution mixed with Cu-Mn with the concentration of 0.5mol/L, and then placing into a shaking table;
step four: roasting for 3 hours at 550 ℃ in a muffle furnace to prepare a series of metal oxide supported catalysts MOx/gamma-Al 2O3.
In this example, 45r/min after addition of the shaker, was immersed for 12h, after which it was dried in an oven at 100℃for 2h.
In this example, the adsorbent was recovered and regenerated by nitrogen purge heating at a flow rate of nitrogen purge to heat the molecular sieve and activated alumina to above 350 ℃ for regeneration and to 120 ℃ for complete regeneration of the activated carbon.
Wherein, the oxidation catalyst uses gamma-Al 2O3 as a catalyst carrier, uses nitrate of transition metal as impregnating solution, adopts an impregnating method to prepare a series of metal oxide supported catalysts with different impregnating solution types, different impregnating solution concentrations and different roasting temperatures, forms a heterogeneous catalysis ozonization system together with ozone, and uses the change of gradient elution value of rectification treatment after acetonitrile oxidation as a reference indexBy different impregnating liquids Ni (NO 3 ) 2 、Cu(NO 3 ) 2 、Mn(NO 3 ) 2 And the like and the influence of preparation conditions such as different concentrations of the impregnating solution on the catalytic performance of the catalyst, and the preparation condition of the corresponding catalyst when the absorbance minimum value is determined is the optimal preparation condition of the catalyst.
In summary, the technical solution disclosed in the above embodiment of the present invention has at least the following advantages:
according to the invention, an acetonitrile purification process combining continuous oxidation, adsorption and rectification is developed by combining a catalytic oxidation process, an adsorption process, a rectification process and an adsorbent regeneration process; the novel Cu-Mn/gamma-Al 2O3 oxidation catalyst is applied to the catalytic oxidation process of acetonitrile, so that the catalytic efficiency is higher, and the reaction rate is faster; the heterogeneous catalytic ozonation method is adopted to accelerate the oxidation reaction of acetonitrile in the raw material industry under normal pressure by using a solid catalyst, the catalyst is filled in a solid state, and the ozone is directly decomposed into oxygen, so that the process pollution is avoided, and the process flow is greatly simplified; the combination of the activated carbon, the molecular sieve and the activated alumina as the adsorbent can remove impurities more effectively, and the adsorbent can be regenerated for recycling, so that the process cost is better saved, and the resource utilization rate is improved.
Although the present invention has been described in connection with the above embodiments, it should be understood that the invention is not limited thereto, but may be variously modified and modified by those skilled in the art without departing from the spirit and scope of the invention, and the scope of the invention is accordingly defined by the appended claims.
Claims (7)
1. A gradient acetonitrile is characterized in that the content w/% > of C2H3N is more than or equal to 99.9, the chromaticity is less than or equal to 10, the evaporation residue is less than or equal to 0.0001, the moisture content w/% -is less than or equal to 0.02, the acidity, mmol/g is less than or equal to 0.0005, the alkalinity and mmol/g is less than or equal to 0.0003.
2. The gradient acetonitrile according to claim 1, wherein the gradient is elution, mAU:210nm less than or equal to 5, 254nm less than or equal to 1, maximum fluorescence impurity (calculated by quinine sulfate), ρ/(ng/mL) less than or equal to 1.0, absorbance λ1 (190 nm) less than or equal to 1.00, λ2 (200 nm) less than or equal to 0.05, λ3 (210 nm) less than or equal to 0.04, λ4 (220 nm) less than or equal to 0.02, λ5 (230 nm) less than or equal to 0.01, λ6 (254 nm) less than or equal to 0.005, and λ7 (400 nm) less than or equal to 0.005.
3. A process for the preparation of graded acetonitrile, for use in the graded acetonitrile according to any of claims 1-2, comprising the steps of:
s1, filling a catalytic oxidant in an ozone reaction contact tower;
s2, introducing oxygen containing ozone with a certain concentration at a certain flow rate from the bottom of the tower at room temperature and normal pressure, and introducing industrial acetonitrile at a certain flow rate from the top of the tower;
s3, after ozone and raw acetonitrile are fully contacted and oxidized in countercurrent in a reaction contact tower, a liquid phase pump switch is turned on, and an oxidation product is subjected to a composite adsorption column at a fixed flow rate;
s4, rectifying the liquid after the adsorption process is completed, and recycling and regenerating the adsorbent;
s5, detecting that the finished product is qualified, and carrying out clean packaging.
4. A process for the preparation of graded acetonitrile according to claim 3, wherein the three adsorbents, combined Activated Carbon (AC), molecular sieve (3A) and Activated Alumina (AA), are passed sequentially.
5. A method for preparing graded acetonitrile according to claim 3, wherein the catalytic oxidizer is prepared as follows:
step one: taking a certain amount of gamma-Al 2O3, and soaking the gamma-Al 2O3 in a dilute sulfuric acid solution with pH=4.0 for 24-30h;
step two: washing with deionized water to neutrality, boiling in deionized water for 3-5 times, washing with deionized water to neutrality, and oven drying at 100-150deg.C for 2 hr;
step three: respectively placing a certain amount of gamma-Al 2O3 into a nitrate impregnating solution mixed with Cu-Mn with the concentration of 0.5mol/L, and then placing into a shaking table;
step four: roasting for 3 hours at 550 ℃ in a muffle furnace to prepare a series of metal oxide supported catalysts MOx/gamma-Al 2O3.
6. The method for preparing graded acetonitrile according to claim 5, wherein after adding the shaking table, the mixture is immersed for 12 hours at 30-45r/min, and then dried in an oven at 100-150 ℃ for 2 hours.
7. A graded acetonitrile and process for preparing the same according to claim 3, wherein the adsorbent is recovered and regenerated by nitrogen purge heating, the molecular sieve and activated alumina are regenerated by nitrogen purge heating at a flow rate above 350 ℃ and the activated carbon is fully regenerated by heating to 120 ℃.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0532605A (en) * | 1991-08-01 | 1993-02-09 | Asahi Chem Ind Co Ltd | Method for purifying acetonitrile |
| US5292919A (en) * | 1992-05-21 | 1994-03-08 | Cryodyne Technologies, Inc. | Method for purification of acetonitrile |
| JP2000128846A (en) * | 1998-10-20 | 2000-05-09 | Asahi Chem Ind Co Ltd | Method for treating acetonitrile |
| CN101575302A (en) * | 2009-04-27 | 2009-11-11 | 大连理工大学 | Method for preparing high-purity acetonitrile by combination of continuous oxidation and composite absorption |
| CN109364913A (en) * | 2018-11-09 | 2019-02-22 | 南京工业大学 | A kind of ultraviolet light self-excitation ozone cooperative catalysis oxidation VOCs catalyst and its preparation method and application |
| CN113416151A (en) * | 2021-07-28 | 2021-09-21 | 西陇科学股份有限公司 | Preparation method of pure acetonitrile for chromatographic analysis and production equipment thereof |
| US20220111362A1 (en) * | 2020-03-30 | 2022-04-14 | Chinese Research Academy Of Environment Sciences | Supported two-component metal oxide catalyst for advanced treatment of petrochemical wastewater and method for preparing same |
| US20230073691A1 (en) * | 2020-05-06 | 2023-03-09 | Ftsci (Hubei) Biotech Co., Ltd. | Acetonitrile purification process for ultrahigh performance liquid chromatography-mass spectrometer |
-
2023
- 2023-08-14 CN CN202311016406.4A patent/CN116987009A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0532605A (en) * | 1991-08-01 | 1993-02-09 | Asahi Chem Ind Co Ltd | Method for purifying acetonitrile |
| US5292919A (en) * | 1992-05-21 | 1994-03-08 | Cryodyne Technologies, Inc. | Method for purification of acetonitrile |
| JP2000128846A (en) * | 1998-10-20 | 2000-05-09 | Asahi Chem Ind Co Ltd | Method for treating acetonitrile |
| CN101575302A (en) * | 2009-04-27 | 2009-11-11 | 大连理工大学 | Method for preparing high-purity acetonitrile by combination of continuous oxidation and composite absorption |
| CN109364913A (en) * | 2018-11-09 | 2019-02-22 | 南京工业大学 | A kind of ultraviolet light self-excitation ozone cooperative catalysis oxidation VOCs catalyst and its preparation method and application |
| US20220111362A1 (en) * | 2020-03-30 | 2022-04-14 | Chinese Research Academy Of Environment Sciences | Supported two-component metal oxide catalyst for advanced treatment of petrochemical wastewater and method for preparing same |
| US20230073691A1 (en) * | 2020-05-06 | 2023-03-09 | Ftsci (Hubei) Biotech Co., Ltd. | Acetonitrile purification process for ultrahigh performance liquid chromatography-mass spectrometer |
| CN113416151A (en) * | 2021-07-28 | 2021-09-21 | 西陇科学股份有限公司 | Preparation method of pure acetonitrile for chromatographic analysis and production equipment thereof |
Non-Patent Citations (2)
| Title |
|---|
| 杜然: "质谱级乙腈制备及其化工行业标准制订", 《中国优秀硕士学位论文全文数据库 工程科技I辑》, vol. 6, pages 016 - 29 * |
| 魏东: "利用工业乙腈制备色谱级乙腈的研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》, vol. 9, pages 016 - 22 * |
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