CN114192141B - Preparation method of glutaraldehyde - Google Patents
Preparation method of glutaraldehyde Download PDFInfo
- Publication number
- CN114192141B CN114192141B CN202111420610.3A CN202111420610A CN114192141B CN 114192141 B CN114192141 B CN 114192141B CN 202111420610 A CN202111420610 A CN 202111420610A CN 114192141 B CN114192141 B CN 114192141B
- Authority
- CN
- China
- Prior art keywords
- glutaraldehyde
- cyclopentene
- catalyst
- preparation
- amorphous
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 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 38
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000000034 method Methods 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 16
- 239000002904 solvent Substances 0.000 claims abstract description 13
- 230000001590 oxidative effect Effects 0.000 claims abstract description 11
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 8
- 239000012847 fine chemical Substances 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 abstract description 17
- 238000007254 oxidation reaction Methods 0.000 abstract description 17
- 230000003197 catalytic effect Effects 0.000 abstract description 15
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 3
- 239000010955 niobium Substances 0.000 description 22
- 229910052758 niobium Inorganic materials 0.000 description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000002638 heterogeneous catalyst Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Natural products CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- -1 vinyl diethyl ether Chemical compound 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
- 239000000645 desinfectant Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000002815 homogeneous catalyst Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 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
- 238000003756 stirring Methods 0.000 description 3
- YNGDWRXWKFWCJY-UHFFFAOYSA-N 1,4-Dihydropyridine Chemical compound C1C=CNC=C1 YNGDWRXWKFWCJY-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
- 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
- 238000009776 industrial production Methods 0.000 description 2
- ACKFDYCQCBEDNU-UHFFFAOYSA-J lead(2+);tetraacetate Chemical compound [Pb+2].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O ACKFDYCQCBEDNU-UHFFFAOYSA-J 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
- 230000001954 sterilising effect Effects 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- VZJFPIXCMVSTID-UHFFFAOYSA-N 2-ethoxy-3,4-dihydro-2h-pyran Chemical compound CCOC1CCC=CO1 VZJFPIXCMVSTID-UHFFFAOYSA-N 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 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
- 125000003158 alcohol group Chemical group 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 238000003556 assay Methods 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
- 238000006555 catalytic reaction Methods 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000005336 cracking Methods 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
- 239000011964 heteropoly acid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 244000000010 microbial pathogen Species 0.000 description 1
- 230000002906 microbiologic effect Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 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
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 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
- 238000004064 recycling Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000003206 sterilizing agent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 150000003568 thioethers Chemical class 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
Classifications
-
- 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
Landscapes
- 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; the catalyst is amorphous Nb loaded by active carbon 2 O 5 . The invention discloses an amorphous Nb loaded by active carbon for the first time 2 O 5 The application of the catalyst 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, environment friendliness, high efficiency, wide application prospect, simple preparation process of the catalyst used for reaction, low production cost and wide material sources; 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 application, is widely used as a sterilizing and disinfecting agent, a leather tanning agent, a tissue fixing agent, a protein crosslinking agent and the like, and can be used in the fields of biomedical engineering, cell immunology, biochemistry, leather chemistry, histochemistry, food, microbiological industry, environmental protection and the like. Glutaraldehyde disinfectant is a high-efficiency and low-toxicity neutral intensified disinfectant, can kill pathogenic microorganisms such as bacterial propagules, bacterial spores and hepatitis viruses, and mainly kills the microorganisms through two active aldehyde groups, and is widely applied to sterilization of medical instruments, cosmetics industry, electronic industry, hotel industry, sanitary articles and other industries.
The existing glutaraldehyde preparation methods include pyridine method, pyran method and alcohol oxidation method. The pyridine method is to reduce pyridine into dihydropyridine, treat the dihydropyridine with hydroxylamine to obtain glutaraldehyde, and react the glutaraldehyde with sodium nitrite and hydrochloric acid to obtain glutaraldehyde. The conversion rate of the method reaches 90%, but the yield is less than 50%, production is carried out in the early stage, but the method has the advantages of more reaction steps, less raw material sources, high production cost, serious pollution and poor product quality, and is basically eliminated. The pyran method is to take acrolein and vinyl diethyl ether as raw materials, and the acrolein and the vinyl diethyl ether are cyclized to synthesize 2-ethoxy-3, 4-dihydropyran under the action of a catalyst, and then are hydrolyzed to open loops to form glutaraldehyde. The invention application CN102066302A discloses a method for preparing glutaraldehyde by using 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 using an oxidant, and the oxidant of the method is generally lead tetraacetate or periodic acid, but the lead tetraacetate and periodic acid are expensive, which is not beneficial to industrial production, and lead is heavy metal, which is not beneficial to industrial application, so the oxidation method does not realize industrial production.
With the rapid development of petrochemical industry, the by-product C of cracking 5 The fraction cyclopentene provides a sufficient source of raw materials for glutaraldehyde production, so that a synthetic route for preparing glutaraldehyde by catalytic oxidation of cyclopentene is widely focused. The oxidant commonly used for preparing glutaraldehyde by catalytic oxidation of cyclopentene is hydrogen peroxide, but common catalysts include two kinds of homogeneous catalysts and heterogeneous catalysts. Common homogeneous catalysts are tungstic acid, niobium complex, heteropolyacid, etc., heterogeneous catalysts are WO 3 /SiO 2 、WO 3 /TiO 2 、WO 3 SBA-15, W-MCM-41, W-HMS and phosphotungstic acid/UiO-66, etc. Compared with a homogeneous catalyst, the heterogeneous catalyst has the advantages of easy separation from a reaction system and convenient recycling of the catalyst, and is favored by industry; from the industrial point of view, the heterogeneous catalyst has the advantages of industrialized production and low cost. Nb-based catalysts have the advantage of high catalytic efficiency, but few reports are currently made on Nb-based catalysts for preparing glutaraldehyde by catalytic oxidation of cyclopentene, so that it is necessary to develop a new method for preparing glutaraldehyde by efficient catalytic oxidation of cyclopentene by using Nb-based heterogeneous catalysts.
Disclosure of Invention
In order to overcome the problems of the prior art, one of the purposes of the present invention is to provide an activated carbon supported amorphous Nb 2 O 5 Is used in the application of (a); the second purpose of the invention is to provide a preparation method of glutaraldehyde; it is a further object of the present invention to provide the use of such a glutaraldehyde preparation method.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the first aspect of the invention provides an activated carbon-supported amorphous Nb 2 O 5 The application is in preparing glutaraldehyde by catalytic oxidation of cyclopentene.
The second aspect of the invention provides a method for preparing glutaraldehyde, comprising the steps of:
mixing cyclopentene, an oxidant and a catalyst in a solvent, and reacting to obtain glutaraldehyde;
the catalyst is amorphous Nb loaded by active carbon 2 O 5 。
Preferably, the mass ratio of the catalyst to the cyclopentene is 1: (4-15); further preferably, the mass ratio of the catalyst to cyclopentene is 1: (5-13); still further preferably, the mass ratio of the catalyst to cyclopentene is 1: (5-10); still more preferably, the mass ratio of catalyst to cyclopentene is 1: 5. 1:6.7 or 1:10.
Preferably, in the catalyst, the amorphous Nb 2 O 5 The mass percentage of (2) is 8-20%; further preferably, in the catalyst, the amorphous Nb 2 O 5 9-18% by mass; still further preferably, in the catalyst, the amorphous Nb 2 O 5 The mass percentage of (2) is 10-15%; still more preferably, in the catalyst, the amorphous Nb 2 O 5 Is 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, isopropanol; still further preferably, the solvent comprises at least one of t-butanol, ethanol, isopropanol.
Preferably, the molar ratio of solvent to cyclopentene is (6-15): 1, a step of; further preferably, the molar ratio of solvent to cyclopentene is (7-14): 1, a step of; still further preferably, the molar ratio of solvent to cyclopentene is (8-13): 1, a step of; still more preferably, the molar ratio of 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 hydrogen peroxide aqueous solution with the mass percent of 10-70%; still more preferably, the oxidant is 30-70% hydrogen peroxide aqueous solution by mass percent.
Preferably, the molar ratio of the oxidizing agent to cyclopentene is (2-3): 1, a step of; further preferably, the molar ratio of the oxidizing agent to cyclopentene is (2-2.7): 1, a step of; still further preferably, the molar ratio of the oxidizing agent to cyclopentene is (2-2.5): 1.
preferably, the temperature of the reaction is 20-40 ℃; further preferably, the temperature of the reaction is 25-40 ℃; still more preferably, the temperature of the reaction is from 30℃to 40 ℃.
Preferably, the reaction time is 10h-40h; further preferably, the reaction time is 15h-35h; still more preferably, the reaction time is 20h to 30h.
In a third aspect, the invention provides the use of the process for the preparation of glutaraldehyde according to the second aspect of the invention in the field of fine chemicals.
Preferably, the fine chemicals include sanitizers, leather tanning agents, tissue fixatives, or protein cross-linking agents.
The beneficial effects of the invention are as follows:
the invention discloses an amorphous Nb loaded by active carbon for the first time 2 O 5 Application of catalytic oxidation of cyclopentene to prepare glutaraldehyde is provided, and a preparation method of catalytic oxidation of cyclopentene to prepare glutaraldehyde is provided, which further comprises adding an oxidant and amorphous Nb loaded with active carbon 2 O 5 The catalyst participates in the reaction; the method has the advantages of simple process, high product yield, environment friendliness, high efficiency, wide application prospect, simple preparation process of the catalyst used for reaction, low production cost and wide material sources; the preparation method of glutaraldehyde provided by the invention can be widely applied to the field of fine chemicals.
In particular, the invention has the following advantages:
1. the invention loads the disclosed active carbon with amorphous Nb for the first time 2 O 5 The catalyst is applied to the preparation of glutaraldehyde by catalytic oxidation of cyclopentene, and the glutaraldehyde preparation method provided by the invention has the advantages of simple process, high product yield, greenness, high efficiency and wide application prospect.
2. Amorphous Nb loaded by active carbon adopted by the invention 2 O 5 The catalyst has the advantages of simple preparation process, low production cost, wide material source and industrialized mass production.
3. The glutaraldehyde preparation method provided by the invention has high product yield, the conversion rate of the reacted pentene is 86% -99%, and the selectivity is 60% -75%, and can be widely applied to the field of fine chemicals.
Drawings
FIG. 1 shows a catalyst of 10% Nb 2 O 5 XRD 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 apparatus used in the examples are all commercially available from conventional sources or may be obtained by methods known in the art unless otherwise specified. Unless otherwise indicated, assays or testing methods are routine in the art.
Activated carbon-supported amorphous Nb used in the following examples 2 O 5 The catalyst is according to document Selective catalytic oxidation of sulfides to sulfoxides or sulfones over amorphous Nb 2 O 5 Process for preparing catalysts described in/AC catalysts in aqueous phase at room temperature, catalysis Communications,2019,127,10-14Is prepared. From the characterization results in the literature, nb prepared by this method 2 O 5 Nb in activated carbon catalyst 2 O 5 Is an amorphous species.
Nb 2 O 5 The preparation method of the activated carbon catalyst comprises the following steps:
preparing a niobium oxalate aqueous solution with a certain concentration, adding a calculated amount of activated carbon to ensure that Nb in the catalyst 2 O 5 The content is 10%. Mixing uniformly, standing for 12h, drying the sample at 110deg.C for 12h, and roasting at 300deg.C under nitrogen atmosphere for 4h to obtain 10% Nb 2 O 5 Activated carbon catalyst. 10% -15% Nb can be prepared by varying the concentration of Nb salt 2 O 5 Supported catalyst.
10% Nb to be prepared 2 O 5 XRD characterization of activated carbon catalyst, FIG. 1 shows 10% Nb of catalyst 2 O 5 XRD pattern of activated carbon. As can be seen from FIG. 1, although Nb 2 O 5 Up to 10% loading, but no Nb was observed 2 O 5 Is a characteristic diffraction peak of (2). The above results indicate that 10% Nb is prepared according to the present invention 2 O 5 Nb in activated carbon 2 O 5 Is amorphous Nb 2 O 5 。
Example 1
The specific steps for preparing glutaraldehyde by catalytic oxidation of cyclopentene in this example are as follows:
10mmol of cyclopentene were introduced into a 50mL round-bottomed flask, followed by 100mmol of t-butanol and then 30wt% H 2 O 2 Aqueous solution (H) 2 O 2 The addition amount is 2.2 times of the mole amount of cyclopentene, and 12 percent of Nb is added 2 O 5 Activated carbon (the addition amount is 15% of the mass of cyclopentene), stirring and mixing uniformly, placing in an oil bath, and reacting for 24 hours at 35 ℃. After the reaction was completed, a sample of the reaction mixture was taken for gas phase analysis.
The conversion of cyclopentene was 86% and glutaraldehyde selectivity was 75% as tested.
Example 2
The specific steps for preparing glutaraldehyde by catalytic oxidation of cyclopentene in this example are as follows:
10mmol of cyclopentene were added to a 50mL round bottom flask, followed by 80mmol of ethanol and then 50wt% H 2 O 2 Aqueous solution (H) 2 O 2 The addition amount is 2 times of the mole amount of cyclopentene), and 10 percent of Nb is added 2 O 5 Activated carbon (the addition amount is 20% of the mass of cyclopentene), stirring and mixing uniformly, placing in an oil bath, and reacting for 30 hours at 30 ℃. After the reaction was completed, a sample of the reaction mixture was taken for gas phase analysis.
The conversion of cyclopentene was 98% and glutaraldehyde selectivity was 62% as tested.
Example 3
The specific steps for preparing glutaraldehyde by catalytic oxidation of cyclopentene in this example are as follows:
10mmol of cyclopentene were introduced into a 50mL round-bottomed flask, followed by 120mmol of isopropanol and then 70wt% H 2 O 2 Aqueous solution (H) 2 O 2 The addition amount is 2.5 times of the mole amount of cyclopentene, and 15 percent of Nb is added 2 O 5 Activated carbon (the addition amount is 10% of the mass of cyclopentene), stirring and mixing uniformly, placing in an oil bath, and reacting for 20h at 40 ℃. After the reaction was completed, a sample of the reaction mixture was taken for gas phase analysis.
The conversion of cyclopentene was 99% and glutaraldehyde selectivity was 60% as tested.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (2)
1. A preparation method of glutaraldehyde is characterized in that: 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 carbon 2 O 5 The method comprises the steps of carrying out a first treatment on the surface of the In the catalyst, amorphous Nb 2 O 5 Is 10%, 15% or 12% by mass;
the oxidant is hydrogen peroxide;
the solvent is selected from one of tertiary butanol, ethanol and isopropanol;
the molar ratio of the solvent to the cyclopentene is (8-12): 1, a step of;
the mass ratio of the catalyst to the cyclopentene is 1: (4-15);
the molar ratio of the oxidant to the cyclopentene is (2-3): 1, a step of;
the temperature of the reaction is 20-40 ℃; the reaction time is 10-40 h.
2. Use of the process for the preparation of glutaraldehyde according to claim 1 in the field of fine chemicals.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111420610.3A CN114192141B (en) | 2021-11-26 | 2021-11-26 | Preparation method of glutaraldehyde |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111420610.3A CN114192141B (en) | 2021-11-26 | 2021-11-26 | Preparation method of glutaraldehyde |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114192141A CN114192141A (en) | 2022-03-18 |
| CN114192141B true CN114192141B (en) | 2024-03-19 |
Family
ID=80649216
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111420610.3A Active CN114192141B (en) | 2021-11-26 | 2021-11-26 | Preparation method of glutaraldehyde |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114192141B (en) |
Citations (4)
| 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 |
-
2021
- 2021-11-26 CN CN202111420610.3A patent/CN114192141B/en active Active
Patent Citations (4)
| 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 |
Non-Patent Citations (3)
| Title |
|---|
| Selective catalytic oxidation of sulfides to sulfoxides or sulfones over amorphous Nb2O5/AC catalysts in aqueous phase at room temperature;Junjie Zhang，et al.;《Catalysis Communications》;第127卷;10-14 * |
| 新型MCM-41固载化铌酸催化氧化环戊烯制备戊二醛;徐建华等;《化学学报》;第62卷(第16期);1467-1471 * |
| 过氧铌酸催化下双氧水选择氧化环戊烯制备戊二醛;陈浩等;《复旦学报（自然科学版）》;第41卷(第3期);317-324 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114192141A (en) | 2022-03-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US6716976B1 (en) | Process for selective oxidation of cellulose | |
| CN110372483B (en) | Process method for preparing glutaraldehyde by catalytic oxidation of cyclopentene | |
| Dapurkar et al. | Mesoporous VMCM-41: highly efficient and remarkable catalyst for selective oxidation of cyclohexane to cyclohexanol | |
| Cheng et al. | Preparation of nano-CuO-loaded halloysite nanotubes with high catalytic activity for selective oxidation of cyclohexene | |
| CN107715861B (en) | Culm biology carbon quantum dot modifies Bi4Ti3O12The preparation and its application of composite photo-catalyst | |
| CN106925349A (en) | A kind of solid supported type metal porphyrin catalyst and its application in terms of maleic acid is prepared | |
| CN113926448B (en) | Niobium oxide-loaded catalyst and method for catalyzing and degrading dimethyl sulfoxide by using same | |
| CN107216245A (en) | A kind of method that Cu Pd alloy catalysts catalysis high concentration glycerine prepares lactic acid | |
| Li et al. | Synthesis, characterizations and catalytic allylic oxidation of limonene to carvone of cobalt doped mesoporous silica templated by reed leaves | |
| CN115178282B (en) | Catalyst for preparing methyl glyoxylate by selective oxidative dehydrogenation of methyl glycolate and preparation and application methods thereof | |
| CN112645908A (en) | Method for preparing maleic anhydride | |
| Dumitriu et al. | Heterogeneous sulfoxidation of thioethers by hydrogen peroxide over layered double hydroxides as catalysts | |
| KR960007001A (en) | Novel photocatalyst and its production method and hydrogen production method using the same | |
| Jafarpour et al. | A synergistic effect of a cobalt Schiff base complex and TiO 2 nanoparticles on aerobic olefin epoxidation | |
| CN114192141B (en) | Preparation method of glutaraldehyde | |
| CN107812518A (en) | A kind of method that high selectivity photocatalysis cyclohexane oxidation prepares cyclohexene | |
| CN108191635B (en) | Method for preparing gluconic acid by catalytic oxidation | |
| CN105085216B (en) | It is a kind of while producing the method for acetone and benzenediol | |
| WO2018157817A1 (en) | Selective hydrogenation catalyst, preparation method therefor, and evaluation method for catalytic preparation of 2-methylallyl alcohol | |
| Selvaraj et al. | Highly selective synthesis of trans-stilbene oxide over mesoporous Mn-MCM-41 and Zr–Mn-MCM-41 molecular sieves | |
| CN101591233A (en) | The preparation method of gluconic acid | |
| TW200307664A (en) | High yield cyclohexyl hydroperoxide decomposition process | |
| CN114426468B (en) | Method for preparing glutaraldehyde by taking cyclopentene as raw material | |
| CN109529833A (en) | A kind of graphene oxide-loaded copper catalyst and its preparation method and application | |
| CN113713826A (en) | Fe3+/CoWO4Composite acoustic catalyst and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |