CN114426467A - 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 43
- 238000000034 method Methods 0.000 title claims abstract description 29
- 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 78
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims abstract description 39
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000003054 catalyst Substances 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- 238000002360 preparation method Methods 0.000 claims abstract description 7
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 17
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 14
- 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 12
- 229960001545 hydrotalcite Drugs 0.000 claims description 12
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000007254 oxidation reaction Methods 0.000 claims description 11
- 238000002156 mixing Methods 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
- 230000003197 catalytic effect Effects 0.000 claims description 7
- 239000002994 raw material Substances 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
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 claims description 6
- 229910001868 water Inorganic materials 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 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
- 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
- 238000001914 filtration Methods 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 238000005406 washing Methods 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
- 238000005342 ion exchange Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 239000007800 oxidant agent Substances 0.000 abstract description 5
- 229910052721 tungsten Inorganic materials 0.000 abstract description 5
- 239000010937 tungsten Substances 0.000 abstract description 5
- 230000001590 oxidative effect Effects 0.000 abstract description 4
- 239000000758 substrate Substances 0.000 abstract description 4
- 239000002638 heterogeneous catalyst Substances 0.000 abstract description 3
- 238000004064 recycling Methods 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 13
- 239000000126 substance Substances 0.000 description 9
- 238000005303 weighing Methods 0.000 description 9
- 238000004817 gas chromatography Methods 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 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
- 238000003786 synthesis reaction Methods 0.000 description 2
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 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
- 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
- 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
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 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
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- -1 uses a pyran method Chemical compound 0.000 description 1
- 239000002699 waste material Substances 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
- B01J23/70—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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- Chemical & Material Sciences (AREA)
- 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. The preparation method takes a tungsten-based heterogeneous catalyst and uses aqueous hydrogen peroxide as an oxidant to catalyze and oxidize cyclopentene to prepare glutaraldehyde, the cyclopentene can be completely converted under mild conditions, and the yield of the glutaraldehyde exceeds 70%. The method has the advantages of high substrate conversion rate, high yield of the target product glutaraldehyde, environment-friendly reaction system, convenient separation of the catalyst and recycling.
Description
Technical Field
The invention belongs to the technical field of preparation of glutaraldehyde, 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 sterilization disinfectant, and has wide application field. The industrial production method of glutaraldehyde mainly uses a pyran method, which has complex process and difficult raw material source, so that the wide application of the method is limited (Chinese patent, with the patent number being CN 1298690C).
The selective oxidation of cyclopentene as raw material to prepare glutaraldehyde is favored, and the method has the advantages of abundant raw materials and easy realization of reaction conditions (document 1: Yan, high Jianrong, research progress on synthesis of glutaraldehyde by catalytic oxidation of cyclopentene, 2007, 21,2: 57-59). In the method, tungstic acid is used as a homogeneous catalyst, hydrogen peroxide is used as an oxidizing agent, and cyclopentene is oxidized into glutaraldehyde (Japanese patent, patent number: JP 01190647; document 2: Xunxinghua, Chenhaiying, Dengjing and the like, and cyclopentene is catalytically oxidized by aqueous hydrogen peroxide to prepare glutaraldehyde, the chemical science reports, 1993,4:399-403), the method can realize the yield of the glutaraldehyde exceeding 60%, but the catalyst is difficult to separate, and waste liquid is generated.
The catalyst which uses microporous molecular sieve to load tungsten species and uses hydrogen peroxide as an oxidant can also oxidize the cyclopentene into the glutaraldehyde (Chinese patent, patent publication number: CN 110372483A), the catalyst is easy to separate and recycle, the target product yield is high, but the preparation process of the catalyst is complicated and needs to be optimized. The mesoporous molecular sieve loaded active tungsten species is used as a catalyst, and the yield of a target product can reach 70 percent when cyclopentene is oxidized by hydrogen peroxide (Chinese patent, patent publication No. CN 168032A), but the catalyst has high preparation cost and complicated process, and the application of the catalyst is influenced. Tungstic acid loaded on a metal organic framework material MOF-101 is used as a catalyst to catalyze cyclopentene to perform oxidation reaction to prepare glutaraldehyde, the aldehyde selectivity exceeds 70% (document 3: preparation, characterization and catalytic performance of a Yangxianli, Lihaobo, Miao-Yongxia and novel HPWs @ MIL-101 catalyst, chemical research and application 2015, 5: 642-648), but the catalyst stability needs to be improved.
Hydrotalcite (LDHs) is an inorganic layered material with a special structure and has excellent properties such as interlayer ion exchangeability, memory effect and thermal stability. The invention provides a heterogeneous catalysis technology for preparing glutaraldehyde by selective oxidation of cyclopentene, which is characterized in that simple anions WO 42-are exchanged into M (II)/M (III) type hydrotalcite and are used for catalyzing the reaction of preparing glutaraldehyde by 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. The invention takes a tungsten-based heterogeneous catalyst and uses aqueous hydrogen peroxide as an oxidant to catalyze and oxidize cyclopentene to prepare glutaraldehyde, the cyclopentene can be completely converted under mild conditions, and the yield of the glutaraldehyde exceeds 70%. The method has the advantages of high substrate conversion rate, high yield of the target product glutaraldehyde, environment-friendly reaction system, convenient separation of the catalyst and recycling.
The following is a specific technical solution of the present invention.
The invention provides a method for preparing glutaraldehyde based on a heterogeneous catalysis technology, which comprises the following steps:
(1) preparation of M by hydrothermal reaction2+/N3+Hydrotalcite type, said M2+/N3+M in hydrotalcite-like compounds2+Is Mg2+Or Cu2+，/N3+Is Fe3+、Cr3+Or Al3+,M2+And N3+In a molar ratio of 1: 3;
(2) adding the hydrotalcite prepared in the step (1) into a tungstate aqueous solution by adopting an ion exchange method, stirring for 24 hours at the temperature of 75-85 ℃, carrying out full exchange reaction, and then carrying outFiltering and drying to obtain M2+/N3+-WO4 2—LDH hydrotalcite solid catalyst;
(3) mixing a solvent with aqueous hydrogen peroxide, adding the solid catalyst prepared in the step (2) in an amount which is 1-10% of the mass of cyclopentene by taking the catalyst as a substrate, stirring and mixing for 0.5-3 h, adding cyclopentene, and continuously stirring for carrying out heterogeneous catalytic oxidation reaction to obtain the target product glutaraldehyde.
Further, the step (1) adopts a hydrothermal reaction method to prepare M (II)/M (III) type hydrotalcite, which specifically comprises the following steps:
a. mixing raw material M2+(An-)2/n.m H2O and N3+(An-)3/n.m H2O according to M2+And N3+Mixing and dissolving the mixture in deionized water in a molar ratio of 1:3 to obtain a solution A (M)2+Concentration 0.3M); dissolving sodium carbonate in deionized water to obtain solution B (with the concentration of 0.1M); mixing the solution A, B at 30 ℃ while stirring to obtain a reaction solution; wherein A isn-Is CO3 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, reacting in a hydrothermal kettle at 110-130 ℃ for 24h in an oven, performing suction filtration, washing to be neutral, and drying at 90-110 ℃ overnight;
c. after drying, calcining for 3-5h at 600 ℃ to obtain M (II)/M (III) type hydrotalcite.
Further, the concentration of the tungstate aqueous solution in the step (2) is 0.005-0.02 mol/l, and preferably 0.01 mol/l; the tungstate is selected from any one of ammonium tungstate, ammonium metatungstate and sodium tungstate dihydrate.
Further, the solvent in the step (3) is selected from one of tert-butyl alcohol, 1, 4-dioxane, tetrahydrofuran or acetonitrile; the concentration of the aqueous hydrogen peroxide solution is from 30% to 60% by weight, preferably 50% by weight; the ratio of the solvent to the aqueous hydrogen peroxide solution is 1: 2-5.
Further, the mass ratio of the cyclopentene to the solvent in the step (3) is 1: 6-12, preferably 1: 10; the mass ratio of the cyclopentene to the hydrogen peroxide is 1: 2-4, preferably 1: 3.
Further, in the step (3), the heterogeneous catalytic oxidation reaction is carried out at the reaction temperature of 28-40 ℃, preferably 35 ℃; the reaction time is 16-48 h, preferably 36h.
Compared with the prior art, the invention has the beneficial effects that:
the invention takes a tungsten-based heterogeneous catalyst and uses aqueous hydrogen peroxide as an oxidant to catalyze and oxidize cyclopentene to prepare glutaraldehyde, the cyclopentene can be completely converted under mild conditions, and the yield of the glutaraldehyde exceeds 70%. The method has the advantages of high substrate conversion rate, high yield of the target product glutaraldehyde, environment-friendly reaction system, convenient separation of the 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 invention, but are not intended to limit the invention in any way. It should be noted that it would be apparent to those skilled in the art that several modifications and improvements can be made without departing from the inventive concept. All falling within the scope of the present invention.
Example 1
Synthesis of Mg/Fe-WO4 of Mg/Fe-32-Catalyst for LDH:
(1) solution A: weighing raw materials according to the molar ratio of Mg/Fe to 3, and dissolving the raw materials in 70ml of deionized water; solution B: dissolving a certain mass of sodium carbonate in 70ml of deionized water;
(2) the A, B solution is added dropwise at 30 ℃ while stirring;
(3) adjusting the pH value to about 11 by using a 2M NaOH solution, aging for 10min, carrying out oven reaction for 24h at 120 ℃ in a hydrothermal kettle, then carrying out suction filtration and washing to neutrality, and drying overnight at 100 ℃;
(4) the prepared sample is calcined for 4 hours at the temperature of 600 ℃ to obtain Mg/Fe-LDH.
(5) Weighing 0.1980g of sodium tungstate dihydrate, dissolving in 50ml of water, adding 1g of roasting carrier, adjusting the pH value to 4.5-5 by using 0.2M dilute nitric acid, and stirring for 24 hours at 80 ℃;
(6) the resulting product was de-ionizedWashing the seed with water, filtering, and drying at 80 deg.C for more than 24 hr to obtain Mg/Fe-WO42--an LDH catalyst.
Example 2
Weighing the catalyst Mg/Fe-WO4 prepared in example 12-0.2g of-LDH, in a 100ml round-bottomed flask, 3.4ml of 30% wt hydrogen peroxide solution was mixed with 15ml of t-butanol, then the weighed catalyst was added, after the above three substances were completely mixed, 1.4ml of cyclopentene was further added, the reaction was stirred at 35 ℃ for 24 hours, and the product was analyzed by GC-2060 gas chromatography, and the conversion of cyclopentene was 79% and the yield of glutaraldehyde was 56%.
Example 3
Weighing the catalyst Mg/Fe-WO4 prepared in example 12-0.3g of-LDH, in a 100ml round-bottomed flask, 3.4ml of 45% wt hydrogen peroxide solution were mixed with 15ml of 1, 4-dioxane, then the weighed catalyst was added, after the above three substances were thoroughly mixed, 1.4ml of cyclopentene was further added, the reaction was stirred at 36 ℃ for 24 hours, and the product was analyzed by GC-2060 gas chromatography for cyclopentene conversion of 85% and glutaraldehyde yield of 62%.
Example 4
Weighing the catalyst Mg/Fe-WO4 prepared in example 12-0.5g of-LDH, in a 100ml round-bottom flask, 3.4ml of 35% by weight hydrogen peroxide solution is mixed with 15ml of tetrahydrofuran, then the weighed catalyst is added, after the three substances are completely mixed, 1.4ml of cyclopentene is added, the reaction temperature is set at 37 ℃, the reaction time is 24h, and the product is analyzed by GC-2060 gas chromatography, the cyclopentene conversion rate is 89%, and the glutaraldehyde yield is 66%.
Example 5
Weighing the catalyst Mg/Fe-WO4 prepared in example 12-0.3g of LDH, in a 100ml round-bottomed flask, 3.4ml of 35% wt hydrogen peroxide solution was mixed with 15m of tert-butanol, then the weighed catalyst was added, after the above three substances were completely mixed, 1.4ml of cyclopentene was further added, and the reaction was stirred at 37 ℃ for 36 hours, and the product was analyzed by GC-2060 gas chromatography, and the conversion of cyclopentene was 95% and the yield of glutaraldehyde was 71%.
Example 6
Weighing examples1 catalyst Mg/Fe-WO42-0.3g of LDH, in a 100ml round-bottomed flask, 3.4ml of 50% wt hydrogen peroxide solution was mixed with 15ml of t-butanol, then the weighed catalyst was added, after the above three substances were completely mixed, 1.6ml of cyclopentene was further added, and the reaction was stirred at 40 ℃ for 36 hours, and the product was analyzed by GC-2060 gas chromatography, the conversion of cyclopentene was 96%, and the yield of glutaraldehyde was 69%.
Example 7
Weighing the catalyst Mg/Cr-WO4 prepared in example 12-0.3g of-LDH, in a 100mL round-bottomed flask, 3.4mL of a 40% wt hydrogen peroxide solution was mixed with 15mL of acetonitrile, then the weighed catalyst was added, after the above three substances were completely mixed, 1.2mL of cyclopentene was further added, the reaction was stirred at 35 ℃ for 36 hours, and the product was analyzed by GC-2060 gas chromatography, and the conversion of cyclopentene was 90% and the yield of glutaraldehyde was 67%.
Example 8
Weighing the catalyst Mg/Fe-WO4 prepared in example 12-0.3g of-LDH, 3.4ml of 30% wt hydrogen peroxide solution was mixed with 15ml of t-butanol in a 100ml round-bottomed flask, then the weighed catalyst was added, and after the above three substances were completely mixed, 1.4ml of cyclopentene was further added, and the reaction was stirred at 37 ℃ for 36 hours.
After the reaction is finished, the catalyst is separated out by filtration, and the separated catalyst is washed and dried to be used for the next catalytic reaction, and the reaction conditions are unchanged (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 reuse performance table
While the preferred embodiments of the present invention have been described in detail, it will be understood by those skilled in the art that the invention is not limited thereto, and that various changes and modifications may be made without departing from the spirit of the invention, and the scope of the appended claims is to be accorded the full scope of the invention.
Claims (8)
1. A method for preparing glutaraldehyde based on a heterogeneous catalysis technology comprises the following steps:
(1) preparation of M by hydrothermal reaction2+/N3+Hydrotalcite type, said M2+/N3+M in hydrotalcite-like compounds2+Is Mg2+Or Cu2+，/N3+Is Fe3+、Cr3+Or Al3+,M2+And N3+In a molar ratio of 1: 3;
(2) adding the hydrotalcite prepared in the step (1) into a tungstate aqueous solution by adopting an ion exchange method, stirring for 24 hours at the temperature of 75-85 ℃, fully exchanging and reacting, filtering and drying to obtain M2+/N3+-WO4 2—LDH hydrotalcite solid catalyst;
(3) and (3) mixing a solvent and aqueous hydrogen peroxide, adding the solid catalyst prepared in the step (2), wherein the amount of the catalyst is 1-10% of the mass of cyclopentene, stirring and mixing for 0.5-3 h, then adding the cyclopentene, and continuously stirring to perform heterogeneous catalytic oxidation reaction to obtain the target product glutaraldehyde.
2. The method for preparing glutaraldehyde based on heterogeneous catalysis technology, according to claim 1, characterized in that: the step (1) adopts a hydrothermal reaction method to prepare M (II)/M (III) type hydrotalcite, and specifically comprises the following steps:
a. mixing raw material M2+(An-)2/n.m H2O and N3+(An-)3/n.m H2O according to M2+And N3+Mixing and dissolving the mixture in deionized water according to the molar ratio of 1:3 to obtain M2+Solution A at a concentration of 0.3M; dissolving sodium carbonate in deionized water to obtain solution B with the concentration of 0.1M; mixing the solution A, B at 30 ℃ while stirring to obtain a reaction solution; wherein A isn-Is CO3 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, reacting in a hydrothermal kettle at 110-130 ℃ for 24h in an oven, performing suction filtration, washing to be neutral, and drying at 90-110 ℃ overnight;
c. after drying, calcining for 3-5h at 600 ℃ to obtain M (II)/M (III) type hydrotalcite.
3. The method for preparing glutaraldehyde based on heterogeneous catalysis technology, 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 metatungstate and sodium tungstate dihydrate.
4. The method for preparing glutaraldehyde based on heterogeneous catalysis technology, according to claim 1, characterized in that: the solvent in the step (3) is selected from one of tert-butyl alcohol, 1, 4-dioxane, tetrahydrofuran or acetonitrile; the concentration of the aqueous hydrogen peroxide 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 technology, 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 1: 2-4.
6. The method for preparing glutaraldehyde based on heterogeneous catalysis technology, according to claim 5, wherein: the mass ratio of the cyclopentene to the 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 technology, according to claim 1, characterized in that: the heterogeneous catalytic oxidation reaction in the step (3) is carried out at the reaction temperature of 28-40 ℃; the reaction time is 16-48 h.
8. The method for preparing glutaraldehyde based on heterogeneous catalysis technology, according to claim 7, wherein: the heterogeneous catalytic oxidation reaction in the step (3) is carried out at the reaction temperature of 35 ℃; the reaction time was 36h.
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