CN114192141A - Preparation method of glutaraldehyde - Google Patents
Preparation method of glutaraldehyde Download PDFInfo
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- CN114192141A CN114192141A CN202111420610.3A CN202111420610A CN114192141A CN 114192141 A CN114192141 A CN 114192141A CN 202111420610 A CN202111420610 A CN 202111420610A CN 114192141 A CN114192141 A CN 114192141A
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- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 claims abstract description 86
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000003054 catalyst Substances 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N activated carbon Substances [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 230000003647 oxidation Effects 0.000 claims abstract description 18
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 18
- 230000003197 catalytic effect Effects 0.000 claims abstract description 16
- 239000007800 oxidant agent Substances 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 230000001590 oxidative effect Effects 0.000 claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- 239000012847 fine chemical Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 4
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims description 15
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 4
- 125000003158 alcohol group Chemical group 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 3
- 239000010955 niobium Substances 0.000 description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000002638 heterogeneous catalyst Substances 0.000 description 5
- 229910052758 niobium Inorganic materials 0.000 description 5
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000000645 desinfectant Substances 0.000 description 4
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000002815 homogeneous catalyst Substances 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 239000010985 leather Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 150000003462 sulfoxides Chemical class 0.000 description 3
- VZJFPIXCMVSTID-UHFFFAOYSA-N 2-ethoxy-3,4-dihydro-2h-pyran Chemical compound CCOC1CCC=CO1 VZJFPIXCMVSTID-UHFFFAOYSA-N 0.000 description 2
- MGADZUXDNSDTHW-UHFFFAOYSA-N 2H-pyran Chemical compound C1OC=CC=C1 MGADZUXDNSDTHW-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- JEHCHYAKAXDFKV-UHFFFAOYSA-J lead tetraacetate Chemical compound CC(=O)O[Pb](OC(C)=O)(OC(C)=O)OC(C)=O JEHCHYAKAXDFKV-UHFFFAOYSA-J 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- KHIWWQKSHDUIBK-UHFFFAOYSA-N periodic acid Chemical compound OI(=O)(=O)=O KHIWWQKSHDUIBK-UHFFFAOYSA-N 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- YNGDWRXWKFWCJY-UHFFFAOYSA-N 1,4-Dihydropyridine Chemical compound C1C=CNC=C1 YNGDWRXWKFWCJY-UHFFFAOYSA-N 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- 239000013207 UiO-66 Substances 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- -1 alkoxy dihydropyran Chemical compound 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 210000004666 bacterial spore Anatomy 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229960001948 caffeine Drugs 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- VCVOSERVUCJNPR-UHFFFAOYSA-N cyclopentane-1,2-diol Chemical compound OC1CCCC1O VCVOSERVUCJNPR-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000834 fixative Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 208000006454 hepatitis Diseases 0.000 description 1
- 231100000283 hepatitis Toxicity 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 244000000010 microbial pathogen Species 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000002821 niobium Chemical class 0.000 description 1
- XNHGKSMNCCTMFO-UHFFFAOYSA-D niobium(5+);oxalate Chemical compound [Nb+5].[Nb+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O XNHGKSMNCCTMFO-UHFFFAOYSA-D 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- RYYVLZVUVIJVGH-UHFFFAOYSA-N trimethylxanthine Natural products CN1C(=O)N(C)C(=O)C2=C1N=CN2C RYYVLZVUVIJVGH-UHFFFAOYSA-N 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/28—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of CHx-moieties
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/648—Vanadium, niobium or tantalum or polonium
- B01J23/6484—Niobium
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of glutaraldehyde. The preparation method of glutaraldehyde comprises the following steps: mixing cyclopentene, an oxidant and a catalyst in a solvent, and reacting to obtain glutaraldehyde; amorphous Nb with catalyst being activated carbon2O5. The invention discloses amorphous Nb loaded by active carbon for the first time2O5The application in preparing glutaraldehyde by catalytic oxidation of cyclopentene and the preparation method for preparing glutaraldehyde by catalytic oxidation of cyclopentene are provided; the preparation method has the advantages of simple process, high product yield, greenness, high efficiency, wide application prospect, simple preparation process of the catalyst used for reaction, low production cost and wide material source; the preparation method of glutaraldehyde provided by the invention can be widely applied to the field of fine chemicals.
Description
Technical Field
The invention belongs to the field of chemistry, and particularly relates to a preparation method of glutaraldehyde.
Background
Glutaraldehyde is a fine chemical with important applications, widely used as a disinfectant, a leather tanning agent, a tissue fixing agent, a protein cross-linking agent and the like, and can be used in the fields of biomedical engineering, cellular immunology, biochemistry, leather chemistry, histochemistry, food, microbial industry, environmental protection and the like. Glutaraldehyde disinfectant is a neutral intensified disinfectant with high efficiency and low toxicity, and can kill pathogenic microorganisms such as bacterial propagules, bacterial spores, hepatitis viruses and the like, glutaraldehyde mainly kills microorganisms through two active aldehyde groups, and the glutaraldehyde disinfectant is widely applied to the sterilization of environments and articles in industries such as medical instruments, cosmetics, electronic industry, hotel industry, sanitary products and the like.
The existing glutaraldehyde preparation methods include a pyridine method, a pyran method and an alcohol oxidation method. The pyridine method is to reduce pyridine into dihydropyridine, then to treat with hydroxylamine to obtain glutaroxime, and finally to react with sodium nitrite and hydrochloric acid to obtain glutaraldehyde. The conversion rate of the method reaches 90 percent, but the yield is less than 50 percent, and the method has been produced in the early period, but the method is basically eliminated at present because of more reaction steps, less raw material sources, high production cost, serious pollution and poor product quality. The pyran method is characterized in that acrolein and vinyl ethyl ether are used as raw materials, the acrolein and the vinyl ethyl ether are cyclized to synthesize 2-ethoxy-3, 4 dihydropyran under the action of a catalyst, and then the 2-ethoxy-3, 4 dihydropyran is hydrolyzed to be subjected to ring opening to form glutaraldehyde. The invention application CN102066302A discloses a method for preparing glutaraldehyde by alkoxy dihydropyran and water under the condition of an acid catalyst, but the preparation method has the technical problems of high raw material cost, long process route and low product yield. The oxidation method is to oxidize 1, 2-cyclopentanediol to prepare glutaraldehyde by adopting an oxidant, wherein the oxidant in the method is generally lead tetraacetate or periodic acid, but the lead tetraacetate and the periodic acid are expensive and are not beneficial to industrial production, and lead is heavy metal and is not beneficial to industrial application, so that the oxidation method does not realize industrial production.
With the rapid development of petrochemical industry, the cracked by-product C5The fraction cyclopentene provides a sufficient raw material source for the production of glutaraldehyde, and thus a synthetic route for preparing glutaraldehyde by catalytic oxidation of cyclopentene is receiving much attention. A common oxidant for producing glutaraldehyde by the catalytic oxidation of cyclopentene is hydrogen peroxide, but common catalysts include both homogeneous catalysts and heterogeneous catalysts. Common homogeneous catalysts include tungstic acid, niobium complexes and heteropolyacids, and heterogeneous catalysts include WO3/SiO2、WO3/TiO2、WO3SBA-15, W-MCM-41, W-HMS, phosphotungstic acid/UiO-66 and the like. Compared with homogeneous catalysts, the heterogeneous catalyst is easy to separate from a reaction system and is convenient for recyclingThe advantages are favored by the industry; from the industrial point of view, the heterogeneous catalyst has the advantages of industrial production and low cost. The Nb-based catalyst has the advantage of high catalytic efficiency, but the reports of the Nb-based catalyst on the preparation of glutaraldehyde by catalytic oxidation of cyclopentene are less at present, so that a new Nb-based heterogeneous catalyst for realizing the efficient catalytic oxidation of cyclopentene to prepare glutaraldehyde is needed to be developed.
Disclosure of Invention
In order to overcome the problems of the prior art, the invention provides an active carbon supported amorphous Nb2O5The use of (a); the second object of the present invention is to provide a process for the preparation of glutaraldehyde; the invention also aims to provide the application of the preparation method of the glutaraldehyde.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the invention provides an active carbon loaded amorphous Nb in a first aspect2O5The application of (1) is the application in the preparation of glutaraldehyde by catalytic oxidation of cyclopentene.
The second aspect of the invention provides a preparation method of glutaraldehyde, which comprises the following steps:
mixing cyclopentene, an oxidant and a catalyst in a solvent, and reacting to obtain glutaraldehyde;
the catalyst is amorphous Nb loaded by active carbon2O5。
Preferably, the mass ratio of the catalyst to the cyclopentene is 1: (4-15); further preferably, the mass ratio of the catalyst to the cyclopentene is 1: (5-13); still further preferably, the mass ratio of the catalyst to the cyclopentene is 1: (5-10); still more preferably, the mass ratio of the catalyst to the cyclopentene is 1: 5. 1:6.7 or 1: 10.
Preferably, in the catalyst, amorphous Nb2O5The mass percentage of (A) is 8% -20%; further preferably, in the catalyst, amorphous Nb is used2O5The mass percentage of the component (A) is 9-18%; still further preferably, theIn the catalyst, amorphous Nb2O5The mass percentage of the component (A) is 10-15%; still more preferably, in the catalyst, amorphous Nb2O5Is 10%, 15% or 12% by mass.
Preferably, the solvent is an alcohol solvent; further preferably, the solvent comprises at least one of methanol, propanol, tert-butanol, ethanol and isopropanol; still further preferably, the solvent includes at least one of t-butanol, ethanol, and isopropanol.
Preferably, the molar ratio of the solvent to the cyclopentene is (6-15): 1; further preferably, the molar ratio of the solvent to the cyclopentene is (7-14): 1; still further preferably, the molar ratio of the solvent to cyclopentene is (8-13): 1; still more preferably, the molar ratio of the solvent to cyclopentene is (8-12): 1.
preferably, the oxidizing agent is hydrogen peroxide; further preferably, the oxidizing agent is an aqueous hydrogen peroxide solution; still more preferably, the oxidant is 10-70% by mass of aqueous hydrogen peroxide solution; more preferably, the oxidizing agent is 30 to 70 mass percent aqueous hydrogen peroxide solution.
Preferably, the molar ratio of the oxidant to the cyclopentene is (2-3): 1; further preferably, the molar ratio of the oxidant to cyclopentene is (2-2.7): 1; still further preferably, the molar ratio of the oxidizing agent to cyclopentene is (2-2.5): 1.
preferably, the reaction temperature is 20-40 ℃; further preferably, the reaction temperature is 25-40 ℃; still more preferably, the temperature of the reaction is 30 to 40 ℃.
Preferably, the reaction time is 10h-40 h; further preferably, the reaction time is 15h-35 h; still more preferably, the reaction time is 20h to 30 h.
The third aspect of the present invention provides the use of the process for the preparation of glutaraldehyde according to the second aspect of the present invention in the field of fine chemicals.
Preferably, the fine chemical comprises a sanitizer, a leather tanning agent, a tissue fixative, or a protein cross-linking agent.
The invention has the beneficial effects that:
the invention discloses amorphous Nb loaded by active carbon for the first time2O5The application of the catalyst in preparing glutaraldehyde by catalytic oxidation of cyclopentene also provides a method for preparing glutaraldehyde by catalytic oxidation of cyclopentene, which comprises adding oxidant and amorphous Nb loaded with activated carbon2O5The catalyst participates in the reaction; the method has the advantages of simple process, high product yield, greenness, high efficiency, wide application prospect, simple preparation process of the catalyst used for reaction, low production cost and wide material source; the preparation method of glutaraldehyde provided by the invention can be widely applied to the field of fine chemicals.
Specifically, the invention has the following advantages:
1. the invention firstly loads the disclosed active carbon with amorphous Nb2O5The catalyst is applied to the preparation of glutaraldehyde by catalytic oxidation of cyclopentene, and the preparation method of glutaraldehyde provided by the invention has the advantages of simple process, high product yield, greenness, high efficiency and wide application prospect.
2. The active carbon loaded amorphous Nb adopted by the invention2O5The catalyst has the advantages of simple preparation process, low production cost, wide material source and industrial mass production.
3. The preparation method of glutaraldehyde provided by the invention has high product yield, the conversion rate of the pentene in the reaction is 86% -99%, and the selectivity is 60% -75%.
Drawings
FIG. 1 shows catalyst 10% Nb2O5XRD pattern of activated carbon.
Detailed Description
The present invention will be described in further detail with reference to specific examples. The starting materials, reagents or equipment used in the examples are, unless otherwise specified, either conventionally commercially available or may be obtained by methods known in the art. Unless otherwise indicated, the testing or testing methods are conventional in the art.
Amorphous Nb Supported on activated carbon used in the following examples2O5The catalyst is selected catalytic oxidation of sulfoxides to sulfoxides or sulfoxides over Amorphous Nb2O5The catalyst is prepared by the preparation method of the catalyst described in/AC catalysts in aqueous phase at room temperature, Catalysis Communications,2019,127, 10-14. According to the characterization results in the literature, Nb prepared by the method is shown2O5Nb in activated carbon catalyst2O5Is amorphous.
Nb2O5The specific preparation method of the activated carbon catalyst comprises the following steps:
preparing a niobium oxalate aqueous solution with a certain concentration, and adding a calculated amount of activated carbon to ensure that Nb is contained in the catalyst2O5The content is 10%. Mixing uniformly, standing for 12h, drying the sample at 110 ℃ for 12h, and roasting at 300 ℃ for 4h in nitrogen atmosphere to obtain 10% Nb2O5Active carbon catalyst. 10% -15% Nb can be prepared by changing the concentration of Nb salt2O5A supported catalyst in a supported amount.
10% Nb obtained by the preparation2O5XRD characterization of the activated carbon catalyst is carried out, and figure 1 shows that the catalyst is 10% Nb2O5XRD pattern of activated carbon. As can be seen from FIG. 1, although Nb2O5Up to 10% loading, but no Nb is observed2O5Characteristic diffraction peak of (1). The above results show that 10% Nb is produced by the present invention2O5Nb in active carbon2O5Is amorphous Nb2O5。
Example 1
The specific steps for preparing glutaraldehyde by catalytic oxidation of cyclopentene in the example are as follows:
10mmol of cyclopentene was added to a 50mL round bottom flask, then 100mmol of tert-butanol was added, then 30 wt% H was added2O2Aqueous solution (H)2O2The addition amount is ring2.2 times of the molar amount of pentene) and 12% of Nb was added2O5Activated carbon (the addition amount is 15 percent of the mass of cyclopentene), evenly stirred and mixed, placed in an oil bath, and reacted for 24 hours at 35 ℃. After the reaction was completed, a sample of the reaction mixture was taken for gas phase analysis.
The cyclopentene conversion was 86% and the glutaraldehyde selectivity was 75% as tested in this example.
Example 2
The specific steps for preparing glutaraldehyde by catalytic oxidation of cyclopentene in the example are as follows:
10mmol of cyclopentene was added to a 50mL round-bottom flask, followed by 80mmol of ethanol, followed by 50 wt% H2O2Aqueous solution (H)2O2The addition amount is 2 times of the mol amount of cyclopentene), and 10 percent of Nb is added2O5Active carbon (the addition amount is 20 percent of the mass of cyclopentene), evenly stirred and mixed, placed in an oil bath, and reacted for 30 hours at the temperature of 30 ℃. After the reaction was completed, a sample of the reaction mixture was taken for gas phase analysis.
The cyclopentene conversion of this example was tested to be 98% and the glutaraldehyde selectivity to be 62%.
Example 3
The specific steps for preparing glutaraldehyde by catalytic oxidation of cyclopentene in the example are as follows:
10mmol of cyclopentene were added to a 50mL round-bottom flask, followed by 120mmol of isopropanol, followed by 70 wt% H2O2Aqueous solution (H)2O2The addition amount is 2.5 times of the mol amount of cyclopentene), and 15 percent of Nb is added2O5Activated carbon (the addition amount is 10 percent of the mass of cyclopentene), evenly stirred and mixed, placed in an oil bath, and reacted for 20 hours at 40 ℃. After the reaction was completed, a sample of the reaction mixture was taken for gas phase analysis.
The cyclopentene conversion of this example was tested to be 99% and the glutaraldehyde selectivity to be 60%.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. Activated carbon loaded amorphous Nb2O5The application of the catalyst in preparing glutaraldehyde by catalytic oxidation of cyclopentene.
2. A preparation method of glutaraldehyde is characterized by comprising the following steps: the method comprises the following steps:
mixing cyclopentene, an oxidant and a catalyst in a solvent, and reacting to obtain glutaraldehyde;
the catalyst is amorphous Nb loaded by active carbon2O5。
3. The method of claim 2, wherein: the mass ratio of the catalyst to the cyclopentene is 1: (4-15).
4. The production method according to claim 2 or 3, characterized in that: in the catalyst, amorphous Nb2O5The mass percentage of (B) is 8-20%.
5. The method of claim 2, wherein: the solvent is an alcohol solvent.
6. The method of claim 5, wherein: the molar ratio of the solvent to the cyclopentene is (6-15): 1.
7. the method of claim 2, wherein: the oxidant is hydrogen peroxide.
8. The method of claim 7, wherein: the molar ratio of the oxidant to the cyclopentene is (2-3): 1.
9. the method of claim 1, wherein: the reaction temperature is 20-40 ℃; the reaction time is 10-40 h.
10. Use of a process for the preparation of glutaraldehyde according to any one of claims 2 to 9 in the field of fine chemicals.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57145826A (en) * | 1981-03-05 | 1982-09-09 | Nippon Oil Co Ltd | Preparation of glutaraldehyde |
| CN1557551A (en) * | 2004-01-16 | 2004-12-29 | 复旦大学 | Mesoporous molecular sieve multiphase catalyst containing niobium for oxidative synthesis of glutaraldehyde by cyclopentene and preparation method thereof |
| CN102898291A (en) * | 2012-10-12 | 2013-01-30 | 常州大学 | Method for synthesizing pentanedial from cyclopentene in presence of niobium peroxide and formic acid peroxide |
| CN110372483A (en) * | 2019-07-17 | 2019-10-25 | 上海应用技术大学 | A kind of catalytic oxidation of cyclopentene prepares the process of glutaraldehyde |
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2021
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57145826A (en) * | 1981-03-05 | 1982-09-09 | Nippon Oil Co Ltd | Preparation of glutaraldehyde |
| CN1557551A (en) * | 2004-01-16 | 2004-12-29 | 复旦大学 | Mesoporous molecular sieve multiphase catalyst containing niobium for oxidative synthesis of glutaraldehyde by cyclopentene and preparation method thereof |
| CN102898291A (en) * | 2012-10-12 | 2013-01-30 | 常州大学 | Method for synthesizing pentanedial from cyclopentene in presence of niobium peroxide and formic acid peroxide |
| CN110372483A (en) * | 2019-07-17 | 2019-10-25 | 上海应用技术大学 | A kind of catalytic oxidation of cyclopentene prepares the process of glutaraldehyde |
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| JUNJIE ZHANG，ET AL.: "Selective catalytic oxidation of sulfides to sulfoxides or sulfones over amorphous Nb2O5/AC catalysts in aqueous phase at room temperature", 《CATALYSIS COMMUNICATIONS》, vol. 127, pages 10 - 14 * |
| 徐建华等: "新型MCM-41固载化铌酸催化氧化环戊烯制备戊二醛", 《化学学报》, vol. 62, no. 16, pages 1467 - 1471 * |
| 陈浩等: "过氧铌酸催化下双氧水选择氧化环戊烯制备戊二醛", 《复旦学报（自然科学版）》, vol. 41, no. 3, pages 317 - 324 * |
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