CN114426467B - Method for preparing glutaraldehyde based on heterogeneous catalysis technology - Google Patents
Method for preparing glutaraldehyde based on heterogeneous catalysis technology Download PDFInfo
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- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 26
- 238000007210 heterogeneous catalysis Methods 0.000 title claims abstract description 15
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 claims abstract description 74
- 239000003054 catalyst Substances 0.000 claims abstract description 38
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims abstract description 37
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 239000007864 aqueous solution Substances 0.000 claims abstract description 9
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 18
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 15
- 229960001545 hydrotalcite Drugs 0.000 claims description 15
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 15
- 238000007254 oxidation reaction Methods 0.000 claims description 15
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 12
- 230000003197 catalytic effect Effects 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000011949 solid catalyst Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- QWMFKVNJIYNWII-UHFFFAOYSA-N 5-bromo-2-(2,5-dimethylpyrrol-1-yl)pyridine Chemical compound CC1=CC=C(C)N1C1=CC=C(Br)C=N1 QWMFKVNJIYNWII-UHFFFAOYSA-N 0.000 claims description 3
- 230000032683 aging Effects 0.000 claims description 3
- 238000005342 ion exchange Methods 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical compound O.OO QOSATHPSBFQAML-UHFFFAOYSA-N 0.000 claims 1
- 239000007800 oxidant agent Substances 0.000 abstract description 5
- 230000001590 oxidative effect Effects 0.000 abstract description 5
- 238000002360 preparation method Methods 0.000 abstract description 5
- 229910052721 tungsten Inorganic materials 0.000 abstract description 5
- 239000010937 tungsten Substances 0.000 abstract description 5
- 238000000926 separation method Methods 0.000 abstract description 4
- 239000000758 substrate Substances 0.000 abstract description 4
- 238000004064 recycling Methods 0.000 abstract description 3
- 230000003647 oxidation Effects 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 238000004817 gas chromatography Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- MGADZUXDNSDTHW-UHFFFAOYSA-N 2H-pyran Chemical compound C1OC=CC=C1 MGADZUXDNSDTHW-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000011365 complex material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
- -1 uses pyran method Chemical compound 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
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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
- B01J23/70—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
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/232—Carbonates
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/30—Ion-exchange
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- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a method for preparing glutaraldehyde based on a heterogeneous catalysis technology. According to the preparation method, a tungsten-based multi-phase catalyst is used, a hydrogen peroxide aqueous solution is used as an oxidant, cyclopentene is catalyzed and oxidized to prepare glutaraldehyde, and the cyclopentene can be completely converted under a mild condition, and the glutaraldehyde yield is over 70%. The invention has high substrate conversion rate, high glutaraldehyde yield of target product, environment-friendly reaction system, convenient separation of catalyst and recycling.
Description
Technical Field
The invention belongs to the technical field of glutaraldehyde preparation, and particularly relates to a method for preparing glutaraldehyde by selective oxidation of cyclopentene based on a heterogeneous catalysis technology.
Background
Glutaraldehyde is an important fine chemical product and intermediate, is also a high-efficiency low-toxicity sterilizing disinfectant, and has wide application fields. The industrial production method of glutaraldehyde mainly uses pyran method, and its process is complex and raw material source is difficult, so that its extensive application is limited (Chinese patent, patent number is CN 1298690C).
The selective oxidation of cyclopentene to glutaraldehyde is favored, and the method has the advantages of abundant raw materials, easy realization of reaction conditions and the like (document 1: qidong, gao Jianrong, research progress on synthesizing glutaraldehyde by catalytic oxidation of cyclopentene, 2007, 21,2: 57-59). The oxidation of cyclopentene to glutaraldehyde with tungstic acid as homogeneous catalyst and hydrogen peroxide as oxidant (Japanese patent No. JP01190647; patent No. 2: xu Xinhua, chen Haiying, deng Jingfa, etc., catalytic oxidation of cyclopentene with aqueous hydrogen peroxide to glutaraldehyde, chemical journal, 1993, 4:399-403) can achieve glutaraldehyde yields exceeding 60%, but catalyst separation is difficult and waste solutions are produced.
The catalyst of tungsten species is supported by a microporous molecular sieve, cyclopentene can be oxidized into glutaraldehyde by taking hydrogen peroxide as an oxidant (Chinese patent, patent publication number: CN 110372483A), the catalyst is easy to separate and recycle, the yield of a target object is high, but the preparation process of the catalyst is complicated and needs to be optimized. The mesoporous molecular sieve is used for loading active tungsten species as a catalyst, the hydrogen peroxide oxidizes cyclopentene to prepare glutaraldehyde, the yield of a target substance can reach 70% (Chinese patent, patent publication number: CN 168032A), but the catalyst has high preparation cost, complicated process and influence on the application of the catalyst. The metal organic framework material MOF-101 is used as a catalyst to catalyze cyclopentene to perform oxidation reaction to prepare glutaraldehyde, the aldehyde selectivity is more than 70% (3: yang Xinli, li Haobo, miao Yongxia, preparation, characterization and catalytic performance of the novel HPWs@MIL-101 catalyst, 2015, 5:642-648), but the stability of the catalyst is required to be improved.
Hydrotalcite (LDHs) is an inorganic layered material with a special structure, and has excellent properties such as interlayer ion exchange property, memory effect, thermal stability and the like. The invention provides a heterogeneous catalysis technology for preparing glutaraldehyde by selective oxidation of cyclopentene, which is formed by exchanging simple anions WO 42-into M (II)/M (III) hydrotalcite and using the hydrotalcite in the reaction for preparing glutaraldehyde by catalyzing the oxidation of cyclopentene.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for preparing glutaraldehyde based on a heterogeneous catalysis technology. According to the invention, a tungsten-based multi-phase catalyst is used, a hydrogen peroxide aqueous solution is used as an oxidant, and the catalytic oxidation of cyclopentene is used for preparing glutaraldehyde, so that the cyclopentene can be completely converted under a mild condition, and the glutaraldehyde yield is over 70%. The invention has high substrate conversion rate, high glutaraldehyde yield of target product, environment-friendly reaction system, convenient separation of catalyst and recycling.
The following is a specific technical scheme of the invention.
The invention provides a method for preparing glutaraldehyde based on heterogeneous catalysis technology, which comprises the following steps:
(1) Preparing M 2+/N3+ hydrotalcite by a hydrothermal reaction method, wherein M 2+ in the M 2+/N3+ hydrotalcite is Mg 2+ or Cu 2+,/N3+ is Fe 3+、Cr3+ or the molar ratio of Al 3+,M2+ to N 3+ is 1:3;
(2) Adding hydrotalcite prepared in the step (1) into an aqueous solution of tungstate by adopting an ion exchange method, stirring for 24 hours at 75-85 ℃, fully carrying out an exchange reaction, and filtering and drying to obtain the M 2+/N3+-WO4 2- LDH hydrotalcite solid catalyst;
(3) Mixing a solvent with a hydrogen peroxide aqueous solution, adding the solid catalyst prepared in the step (2) by taking the catalyst as a substrate and adding the catalyst in an amount which is 1-10% of the mass of cyclopentene, stirring and mixing for 0.5-3 h, then adding cyclopentene, and continuously stirring for carrying out heterogeneous catalytic oxidation reaction to obtain the target product glutaraldehyde.
Furthermore, the step (1) adopts a hydrothermal reaction method to prepare M (II)/N (III) hydrotalcite, and specifically comprises the following steps:
a. Mixing and dissolving raw materials M 2+(An-)2/n.m H2 O and N 3+(An-)3/n.m H2 O in deionized water according to a molar ratio of M 2+ to N 3+ of 1:3 to obtain a solution A (M 2+ concentration of 0.3M); sodium carbonate is dissolved in deionized water to obtain solution B (concentration 0.1M); mixing the solution A, B at 30 ℃ under stirring to obtain a reaction solution; wherein, A n- is CO 3 2-、NO3 -、Cl– or OH -;
b. adjusting the pH value of the reaction solution to 10.5-11.5 by using 2M NaOH solution, aging for 10min, performing oven reaction at 110-130 ℃ for 24h in a hydrothermal kettle, performing suction filtration, washing to neutrality, and drying at 90-110 ℃ overnight;
c. And (3) calcining at 600 ℃ for 3-5h after drying to obtain the M (II)/N (III) hydrotalcite.
Further, the concentration of the aqueous solution of the tungstate in the step (2) is 0.005 to 0.02mol/l, preferably 0.01mol/l; the tungstate is selected from any one of ammonium tungstate, ammonium meta-tungstate and sodium tungstate dihydrate.
Further, the solvent in the step (3) is selected from one of tert-butanol, 1, 4-dioxane, tetrahydrofuran or acetonitrile; the concentration of the aqueous hydrogen peroxide solution is 30-60 wt%, preferably 50wt%; the ratio of the solvent to the aqueous hydrogen peroxide solution is 1:2-5.
Further, the mass ratio of cyclopentene to solvent in the step (3) is 1:6-12, preferably 1:10; the mass ratio of cyclopentene to hydrogen peroxide is 1:2-4, preferably 1:3.
Further, the heterogeneous catalytic oxidation reaction in the step (3) is carried out at a reaction temperature of 28-40 ℃, preferably 35 ℃; the reaction time is 16 to 48 hours, preferably 36 hours.
Compared with the prior art, the invention has the beneficial effects that:
According to the invention, a tungsten-based multi-phase catalyst is used, a hydrogen peroxide aqueous solution is used as an oxidant, and the catalytic oxidation of cyclopentene is used for preparing glutaraldehyde, so that the cyclopentene can be completely converted under a mild condition, and the glutaraldehyde yield is over 70%. The invention has high substrate conversion rate, high glutaraldehyde yield of target product, environment-friendly reaction system, convenient separation of catalyst and recycling.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the present invention, but are not intended to limit the invention in any way. It should be noted that several modifications and improvements can be made by those skilled in the art without departing from the inventive concept. These are all within the scope of the present invention.
Example 1
Catalyst for synthesis of Mg/fe=3 Mg/Fe-WO4 2- -LDH:
(1) Solution A: raw materials were weighed according to a molar ratio of Mg/fe=3 and dissolved in 70ml deionized water; solution B: dissolving sodium carbonate with a certain mass into 70ml of deionized water;
(2) The A, B solution is added dropwise at 30 ℃ while stirring;
(3) Adjusting pH to about 11 with 2M NaOH solution, aging for 10min, reacting in a 120 ℃ oven in a hydrothermal kettle for 24h, filtering, washing to neutrality, and drying at 100 ℃ overnight;
(4) The prepared sample was calcined at 600℃for 4 hours to give Mg/Fe-LDH.
(5) Weighing 0.1980g of sodium tungstate dihydrate, dissolving in 50ml of water, adding 1g of calcined carrier, adjusting the pH to 4.5-5 by using 0.2M dilute nitric acid, and stirring at 80 ℃ for 24 hours;
(6) Washing the obtained product with deionized water, filtering, and drying at 80 ℃ for more than 24 hours to obtain the Mg/Fe-WO4 2- -LDH catalyst.
Example 2
0.2G of the catalyst Mg/Fe-WO4 2- -LDH prepared in example 1 was weighed, 3.4ml of 30% wt hydrogen peroxide solution was mixed with 15ml of t-butanol in a 100ml round bottom flask, then the weighed catalyst was added, after the above three materials were completely mixed, 1.4ml of cyclopentene was added, and the mixture was stirred at 35℃for 24 hours, and the product was analyzed by GC-2060 gas chromatography, the cyclopentene conversion was 79%, and the glutaraldehyde yield was 56%.
Example 3
0.3G of the catalyst Mg/Fe-WO4 2- -LDH prepared in example 1 was weighed, 3.4ml of 45% wt hydrogen peroxide solution was mixed with 15ml of 1, 4-dioxane in a 100ml round bottom flask, then the weighed catalyst was added, after the three substances were completely mixed, 1.4ml of cyclopentene was added, and the mixture was stirred at 36℃for 24 hours, and the product was analyzed by GC-2060 gas chromatography, the cyclopentene conversion was 85%, and the glutaraldehyde yield was 62%.
Example 4
0.5G of the catalyst Mg/Fe-WO4 2- -LDH prepared in example 1 was weighed, 3.4ml of 35% wt hydrogen peroxide solution was mixed with 15ml of tetrahydrofuran in a 100ml round bottom flask, then the weighed catalyst was added, after the above three substances were completely mixed, 1.4ml of cyclopentene was added, the reaction temperature was set to 37℃and the reaction time was 24 hours.
Example 5
0.3G of the catalyst Mg/Fe-WO4 2- -LDH prepared in example 1 was weighed, 3.4ml of 35% wt hydrogen peroxide solution was mixed with 15m t-butanol in a 100ml round bottom flask, then the weighed catalyst was added, after the above three materials were completely mixed, 1.4ml of cyclopentene was added, and the reaction was stirred at 37℃for 36 hours.
Example 6
0.3G of the catalyst Mg/Fe-WO4 2- -LDH prepared in example 1 was weighed, 3.4ml of a 50% wt hydrogen peroxide solution was mixed with 15ml of t-butanol in a 100ml round bottom flask, then the weighed catalyst was added, after the above three materials were completely mixed, 1.6ml of cyclopentene was added, and the reaction was stirred at 40℃for 36 hours.
Example 7
0.3G of the catalyst Mg/Fe-WO4 2- -LDH prepared in example 1 was weighed, 3.4mL of 40% wt hydrogen peroxide solution was mixed with 15mL of acetonitrile in a 100mL round bottom flask, then the weighed catalyst was added, after the above three materials were completely mixed, 1.2mL of cyclopentene was added, and the mixture was stirred at 35 ℃ for reaction for 36 hours, the product was analyzed by GC-2060 gas chromatography, the cyclopentene conversion was 90%, and the glutaraldehyde yield was 67%.
Example 8
0.3G of the catalyst Mg/Fe-WO4 2- -LDH prepared in example 1 was weighed, 3.4ml of a 30% wt hydrogen peroxide solution was mixed with 15ml of t-butanol in a 100ml round bottom flask, then the weighed catalyst was added, after the above three materials were completely mixed, 1.4ml of cyclopentene was added, and the mixture was stirred at 37℃for 36 hours.
After the reaction is finished, the catalyst is separated by filtration, and the separated catalyst is used for the next catalytic reaction after being washed and dried, and the reaction condition is unchanged (the same as the previous experiment). Each reaction product was analyzed by GC-2060 gas chromatography, and the results are shown in the following table.
Catalyst reusability table
While the preferred embodiments of the present application have been described in detail, the present application is not limited to the embodiments, and various equivalent modifications and substitutions can be made by those skilled in the art without departing from the spirit of the present application, and these equivalent modifications and substitutions are intended to be included in the scope of the present application as defined in the appended claims.
Claims (8)
1. A method for preparing glutaraldehyde based on heterogeneous catalysis techniques, comprising:
(1) Preparing M 2+/N3+ hydrotalcite by a hydrothermal reaction method, wherein M 2+ in the M 2+/N3+ hydrotalcite is Mg 2+,/N3+, and the molar ratio of Fe 3+ M2+ to N 3+ is 1:3;
(2) Adding hydrotalcite prepared in the step (1) into an aqueous solution of tungstate by adopting an ion exchange method, stirring for 24 h at 75-85 ℃, fully carrying out an exchange reaction, and filtering and drying to obtain an M 2+/N3+- WO4 2— LDH hydrotalcite solid catalyst;
(3) Mixing a solvent with a hydrogen peroxide aqueous solution, adding the solid catalyst prepared in the step (2), wherein the catalyst accounts for 1-10% of the mass of cyclopentene, stirring and mixing for 0.5-3 hours, adding cyclopentene, and continuously stirring for carrying out heterogeneous catalytic oxidation reaction to obtain the target product glutaraldehyde.
2. The method for preparing glutaraldehyde based on heterogeneous catalysis according to claim 1, characterized in that: the step (1) adopts a hydrothermal reaction method to prepare M 2+/N3+ hydrotalcite, and specifically comprises the following steps:
a. Mixing and dissolving raw materials M 2+ (An-)2/n .m H2 O and N 3+ (An-)3/n .m H2 O in deionized water according to a molar ratio of M 2+ to N 3+ of 1:3 to obtain a solution A with the concentration of M 2+ of 0.3M; dissolving sodium carbonate in deionized water to obtain a solution B with the concentration of 0.1M; mixing the solution A, B at 30 ℃ under stirring to obtain a reaction solution; wherein, A n- is CO 3 2-、 NO3 -、 Cl– or OH -;
b. Adjusting the pH value of the reaction solution to 10.5-11.5 by using 2M NaOH solution, aging for 10min, carrying out oven reaction at 110-130 ℃ in a hydrothermal kettle for 24h, carrying out suction filtration, washing to neutrality, and drying at 90-110 ℃ overnight;
c. And (3) calcining at 600 ℃ for 3-5h after drying to obtain the M 2+/N3+ hydrotalcite.
3. The method for preparing glutaraldehyde based on heterogeneous catalysis according to claim 1, characterized in that: the concentration of the tungstate aqueous solution in the step (2) is 0.005-0.02 mol/l; the tungstate is selected from any one of ammonium tungstate, ammonium meta-tungstate and sodium tungstate dihydrate.
4. The method for preparing glutaraldehyde based on heterogeneous catalysis according to claim 1, characterized in that: the solvent in the step (3) is selected from one of tert-butanol, 1, 4-dioxane, tetrahydrofuran or acetonitrile; the concentration of the hydrogen peroxide water solution is 30-60 wt%; the ratio of the solvent to the aqueous hydrogen peroxide solution is 1:2-5.
5. The method for preparing glutaraldehyde based on heterogeneous catalysis according to claim 1, characterized in that: the mass ratio of the cyclopentene to the solvent in the step (3) is 1:6-12; the mass ratio of the cyclopentene to the hydrogen peroxide is that the cyclopentene is hydrogen peroxide=1 and 2-4.
6. The method for preparing glutaraldehyde based on heterogeneous catalysis according to claim 5, characterized in that: the mass ratio of cyclopentene to solvent in the step (3) is 1:10; the mass ratio of cyclopentene to hydrogen peroxide was 1:3.
7. The method for preparing glutaraldehyde based on heterogeneous catalysis according to claim 1, characterized in that: the heterogeneous catalytic oxidation reaction in the step (3) is carried out at a reaction temperature of 28-40 ℃; the reaction time is 16-48 h.
8. The method for preparing glutaraldehyde based on heterogeneous catalysis according to claim 7, characterized in that: the heterogeneous catalytic oxidation reaction in the step (3) is carried out at a reaction temperature of 35 ℃; the reaction time was 36h.
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