CN114426468B - Method for preparing glutaraldehyde by taking cyclopentene as raw material - Google Patents
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- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 title claims abstract description 92
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 title claims abstract description 49
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 27
- 239000002994 raw material Substances 0.000 title claims abstract description 22
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000003054 catalyst Substances 0.000 claims abstract description 50
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- 238000007254 oxidation reaction Methods 0.000 claims description 29
- 230000003647 oxidation Effects 0.000 claims description 23
- 239000000463 material Substances 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 9
- 239000002808 molecular sieve Substances 0.000 claims description 9
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 6
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 4
- -1 cyclopentane epoxide Chemical class 0.000 claims description 4
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 claims description 3
- 239000000047 product Substances 0.000 abstract description 8
- 229910052721 tungsten Inorganic materials 0.000 abstract description 7
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 abstract description 6
- 239000010937 tungsten Substances 0.000 abstract description 6
- 239000002253 acid Substances 0.000 abstract description 4
- 239000006227 byproduct Substances 0.000 abstract description 3
- 238000002474 experimental method Methods 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 239000000758 substrate Substances 0.000 abstract description 2
- 230000008569 process Effects 0.000 description 7
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 238000004519 manufacturing process Methods 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
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 2
- GJEZBVHHZQAEDB-UHFFFAOYSA-N 6-oxabicyclo[3.1.0]hexane Chemical compound C1CCC2OC21 GJEZBVHHZQAEDB-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000010985 leather Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- VCVOSERVUCJNPR-UHFFFAOYSA-N cyclopentane-1,2-diol Chemical compound OC1CCCC1O VCVOSERVUCJNPR-UHFFFAOYSA-N 0.000 description 1
- KQBURNAXWQWQLS-UHFFFAOYSA-N cyclopentene hydrogen peroxide Chemical compound OO.C1=CCCC1 KQBURNAXWQWQLS-UHFFFAOYSA-N 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920000428 triblock copolymer Polymers 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- C07C45/56—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds
- C07C45/57—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom
- C07C45/58—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom in three-membered rings
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
- B01J29/0341—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a method for preparing glutaraldehyde by taking cyclopentene as a raw material. According to the invention, a sectional experiment is adopted, tungsten-based multi-phase catalysts with different acid strengths are used, and the reaction progress is controlled and the reaction selectivity is improved by adjusting the addition amount of hydrogen peroxide and the concentration of hydrogen peroxide on the surface of the catalyst. Under mild conditions, the conversion rate of cyclopentene is more than 98%, and the glutaraldehyde yield is more than 80%. The invention has high substrate conversion rate, environment-friendly reaction system, less byproducts and convenient separation to obtain qualified products.
Description
Technical Field
The invention belongs to the technical field of solid-liquid catalysis and glutaraldehyde preparation, and in particular relates to a heterogeneous catalysis process technology for preparing glutaraldehyde by selectively oxidizing cyclopentene serving as a raw material.
Background
Glutaraldehyde (GA for short) is an important fine chemical product and intermediate, and has the functions of crosslinking and solidifying protein. Can be used as a high-efficiency low-toxicity sterilizing disinfectant, an excellent leather tanning agent, a color kinescope film hardening agent, an organic synthetic agent and the like, and can be widely applied to the fields of biomedical engineering, cell immunology, biochemistry, leather chemistry, histochemistry, microorganism industry, environmental protection and the like. Currently, the main synthesis methods of glutaraldehyde include pyridine method, acrolein method, polyol oxidation method, glutaric acid reduction method, cyclopentene oxidation method, and the like. The earliest used in industrial production is the pyridine method, but the pyridine method is eliminated due to high raw material consumption, high cost, high pollution and poor product quality. The pentanediol oxidation method has short reaction route, but the oxidation depth is not easy to control, the yield is low, the raw materials are in shortage, the production cost is high, and the possibility of realizing industrialization is not great. Therefore, cyclopentene is used as a raw material, glutaraldehyde is favored to be prepared through selective oxidation, and the method has the advantages of abundant raw materials, easy realization of reaction conditions and the like.
The catalytic process for preparing glutaraldehyde by oxidizing cyclopentene mainly comprises homogeneous phase and heterogeneous phase catalysis, wherein the catalytic reaction is carried out in a homogeneous system, and the catalyst is not easy to recover after the reaction is finished, so that heterogeneous catalytic oxidation is adopted for synthesizing glutaraldehyde by oxidizing cyclopentene at present, and the catalyst is usually a tungsten-containing solid-phase catalyst. As introduced in CN1425498, a TiO2 microsphere is prepared by closed crystallization and is used as a carrier to prepare the tungsten-containing catalyst, and the maximum glutaraldehyde yield is 69.4 percent, the minimum glutaraldehyde yield is 60.3 percent, and the average glutaraldehyde yield is 65.4 percent. CN1380138 is a catalyst for preparing oxidation reaction by introducing tungsten component in situ in the process of synthesizing MCM-41 type all-silicon mesoporous molecular sieve, and the glutaraldehyde yield is up to 72%, 50% and 66.5% on average. CN1446631 is a catalyst for preparing oxidation reaction by introducing tungsten oxide component in situ in the process of synthesizing SBA-15 type full-silicon mesoporous molecular sieve, and the yield of glutaraldehyde is at least 47.0%, at most 78.9% and average 63.1%. The technology disclosed in CN107652170A adopts [ C6H5CH2N (CH 3) 2 (CH 2) 3SO3H ] Ti0.5PW4O16 as a catalyst, acetone as a solvent, the volume of the solvent is 56 times that of cyclopentene, the reaction is carried out for 3 hours at the temperature of 35 ℃, and the glutaraldehyde yield is 70%.
In summary, the existing special technology is basically focused on the preparation and modification of catalysts, and the catalysts are used for obtaining a relatively ideal conversion rate of cyclopentene, but have the defects that the selectivity of target products is relatively low, the average yield of glutaraldehyde is generally below 70%, the boiling points of main byproducts such as 1, 2-cyclopentanediol, cyclopentene epoxy compounds, glutaric acid and the like are higher than that of glutaraldehyde, and the glutaraldehyde has active chemical properties and is easy to polymerize, so that the reaction easily occurs in the separation process, and the glutaraldehyde product suitable for medical use is difficult to prepare.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for preparing glutaraldehyde by taking cyclopentene as a raw material. The preparation method of the invention is adjusted on the basis of the prior art, takes the supported heteropolyacid as the catalyst, adopts a stepwise oxidation method, strengthens the control of the reaction, improves the selectivity of the reaction on the premise of ensuring good conversion rate, and overcomes the defects in the prior art.
The following is a specific technical scheme of the invention:
The invention provides a method for preparing glutaraldehyde by taking cyclopentene as a raw material, which comprises the following steps:
1) Mixing raw material cyclopentene, solvent, catalyst and hydrogen peroxide, and then entering a first oxidation reactor for pre-oxidation reaction, wherein cyclopentene is oxidized into cyclopentane epoxide, the reaction temperature is 30-45 ℃, and the reaction time is 4-10 hours; wherein the dosage of the catalyst is 2.0-8.0wt% of cyclopentene, the mass ratio of cyclopentene to hydrogen peroxide is 1: (0.5-1.5), and the mass ratio of cyclopentene to solvent is 1: (2-10);
2) Mixing the material obtained after the reaction in the step 1) with hydrogen peroxide and a catalyst, and sending the mixture into a second oxidation reactor for reaction at the temperature of 45-60 ℃ for 8-16 hours; wherein the dosage of the catalyst is 2.0-8.0 wt% of cyclopentene, and the mass ratio of the material to hydrogen peroxide is (5-10) to 1;
3) Mixing the material obtained after the reaction in the step 2) with hydrogen peroxide and a catalyst, and sending the mixture into a third oxidation reactor for reaction at the temperature of 45-60 ℃ for 4-10 hours to prepare glutaraldehyde; wherein the dosage of the catalyst is 2.0-8.0 wt% of cyclopentene, and the mass ratio of the material to hydrogen peroxide is (5-10) to 1.
Further, the catalyst in the step 1) is a W-SBA-15 mesoporous molecular sieve catalyst, and the mass fraction of WO3 is 20-25%.
Further, the catalyst dosage in the step 1) is 3.0-6.0 wt% of cyclopentene, the feeding mass ratio of cyclopentene to hydrogen peroxide is 1: (0.7-1.3), the mass ratio of cyclopentene to solvent tert-butanol is 1: (4-8), the reaction temperature is 35-41 ℃, and the reaction time is 5-8 hours.
Further, the catalyst in the step 1) is a W-SBA-15 mesoporous molecular sieve catalyst, and the mass fraction of WO3 is 15-20%.
Further, the catalyst dosage in the step 2) is 3.0-6.0 wt% of cyclopentene, the feeding mass ratio of the material to hydrogen peroxide is (6-8) to 1, the reaction temperature is 50-56 ℃, and the reaction time is 10-14 hours.
Further, the catalyst in the step 1) is a W-SBA-15 mesoporous molecular sieve catalyst, and the mass fraction of WO3 is 10-15%.
Further, the catalyst dosage in the step 3) is 3.0-6.0 wt% of cyclopentene, the feeding mass ratio of the material to hydrogen peroxide is (6-8) to 1, the reaction temperature is 50-56 ℃, and the reaction time is 5-8 hours.
Further, the solvent in the steps 1), 2) and 3) is tertiary butanol, tertiary amyl alcohol or isopropanol and the like.
Further, the concentration of the hydrogen peroxide in the steps 1), 2) and 3) is 30-50 wt%.
The process of synthesizing glutaraldehyde by oxidizing cyclopentene hydroperoxide is that cyclopentene first reacts to form cyclopentene epoxide, then cyclopentene oxide is converted into beta-hydroxycyclopentyl hydroperoxide intermediate product, and beta-hydroxycyclopentyl hydroperoxide rearrangement is converted into glutaraldehyde. The inventor finds that the oxidation reaction is influenced by interaction of peroxytungstic acid and cyclopentene and the intermediate process of series reaction, especially the concentration of hydrogen peroxide on the surface of the catalyst has very obvious influence on the reaction progress and glutaraldehyde yield. By adopting a sectional experiment and using catalysts with different acid strengths, the process of the reaction is controlled by adjusting the adding amount of hydrogen peroxide and the concentration of the hydrogen peroxide on the surface of the catalyst, so that the aim of improving the selectivity can be fulfilled.
According to the invention, a sectional experiment is adopted, tungsten-based multi-phase catalysts with different acid strengths are used, and the reaction progress is controlled and the reaction selectivity is improved by adjusting the addition amount of hydrogen peroxide and the concentration of hydrogen peroxide on the surface of the catalyst. Under mild conditions, the conversion rate of cyclopentene is more than 98%, and the glutaraldehyde yield is more than 80%. The method has the advantages of high substrate conversion rate, environment-friendly reaction system, less byproducts and convenient separation to obtain qualified products.
Drawings
FIG. 1 is a flow chart of the process for preparing glutaraldehyde by using cyclopentene as a raw material.
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 a person skilled in the art without departing from the inventive concept. These are all within the scope of the present invention.
Examples 1 to 10
The W-SBA-15 mesoporous molecular sieve catalyst is prepared by taking sodium tungstate as a tungsten source, taking a polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (P123) as a template agent and tetraethyl orthosilicate (TEOS) as a silicon source through an in-situ synthesis method under an acidic condition, and comprises the following specific steps of:
Starting materials P123, TEOS, HCl, H, 2 and O, W were reacted in the following order in a molar ratio of 1.0:60:350:900: 6-0.75, transferring the solution into a reaction kettle, crystallizing for 3 days at 95 ℃, respectively washing with absolute ethyl alcohol and deionized water for three times, drying overnight at 80 ℃, and finally roasting at 550 ℃ for 6 hours to obtain the W-SBA-15 molecular sieve (WO 3 mass fraction 10-30%).
The preparation method of glutaraldehyde by using cyclopentene as a raw material comprises the following specific steps:
1) Mixing raw material cyclopentene, solvent, catalyst and hydrogen peroxide, and then entering a first oxidation reactor for pre-oxidation reaction to oxidize cyclopentene into cyclopentane epoxide;
2) Mixing the material obtained after the reaction in the step 1) with hydrogen peroxide and a catalyst, and sending the mixture into a second oxidation reactor for reaction;
3) Mixing the material obtained after the reaction in the step 2) with hydrogen peroxide and a catalyst, and sending the mixture into a third oxidation reactor for reaction to prepare glutaraldehyde.
In each example, the types and specifications of the reaction materials selected are shown in Table 1. The process flows of examples 1 to 10 are shown in fig. 1, and the glutaraldehyde product W2 is obtained by sequentially reacting the raw material W1 and the solvent in three oxidation reactors, wherein each reactor adopts a different catalyst and adds hydrogen peroxide in a certain proportion. Raw material W1 is high-purity cyclopentene, in each example, the technological operation conditions of the first oxidation reactor, the second oxidation reactor and the third oxidation reactor are shown in tables 2,3 and 4, and after the reaction is finished, the composition analysis of the product is carried out by using a gas chromatography, and glutaraldehyde selectivity and yield are shown in Table 5. The glutaraldehyde yield and selectivity are defined as:
TABLE 1 reaction raw materials selected for each example
TABLE 2 reaction conditions in the first oxidation reactor of the examples
TABLE 3 reaction conditions in the second oxidation reactor of each example
TABLE 4 reaction conditions in the third oxidation reactor of each example
TABLE 5 glutaraldehyde yield and selectivity from various examples
| Glutaraldehyde yield (%) | Glutaraldehyde Selectivity (%) | |
| Example 1 | 78.8 | 79.8 |
| Example 2 | 80.5 | 81.1 |
| Example 3 | 81.9 | 82.9 |
| Example 4 | 81.6 | 82.6 |
| Example 5 | 82.7 | 83.1 |
| Example 6 | 82.9 | 84.3 |
| Example 7 | 85.1 | 85.1 |
| Example 8 | 84.0 | 84.2 |
| Example 9 | 80.6 | 81.2 |
| Example 10 | 79.3 | 80.5 |
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 (4)
1. A method for preparing glutaraldehyde by taking cyclopentene as a raw material, comprising the following steps:
1) Mixing raw material cyclopentene, solvent, catalyst and hydrogen peroxide, and then entering a first oxidation reactor for pre-oxidation reaction, wherein cyclopentene is oxidized into cyclopentane epoxide, the reaction temperature is 35-41 ℃, and the reaction time is 5-8 hours; wherein the dosage of the catalyst is 3.0-6.0wt% of cyclopentene, the mass ratio of cyclopentene to hydrogen peroxide is 1: (0.7-1.3), and the mass ratio of cyclopentene to solvent is 1: (4-8); the catalyst is a W-SBA-15 mesoporous molecular sieve catalyst, and the mass fraction of WO3 is 20-25%;
2) Mixing the material obtained after the reaction in the step 1) with hydrogen peroxide and a catalyst, and sending the mixture into a second oxidation reactor for reaction at a temperature of 50-56 ℃ for 10-14 hours; wherein the dosage of the catalyst is 3.0-6.0 wt% of cyclopentene, and the mass ratio of the material to hydrogen peroxide is (6-8) to 1; the catalyst is a W-SBA-15 mesoporous molecular sieve catalyst, and the mass fraction of WO3 is 15-20%;
3) Mixing the material obtained after the reaction in the step 2) with hydrogen peroxide and a catalyst, and sending the mixture into a third oxidation reactor for reaction at the temperature of 45-60 ℃ for 4-10 hours to prepare glutaraldehyde; wherein the dosage of the catalyst is 2.0-8.0 wt% of cyclopentene, and the mass ratio of the material to hydrogen peroxide is (5-10) to 1; the catalyst is a W-SBA-15 mesoporous molecular sieve catalyst, and the mass fraction of WO3 is 10-15%.
2. The method for preparing glutaraldehyde by taking cyclopentene as a raw material according to claim 1, wherein: the catalyst dosage in the step 3) is 3.0-6.0 wt% of cyclopentene, the feeding mass ratio of the material to hydrogen peroxide is (6-8) to 1, the reaction temperature is 50-56 ℃, and the reaction time is 5-8 hours.
3. The method for preparing glutaraldehyde by taking cyclopentene as a raw material according to claim 1, wherein: the solvent in the steps 1), 2) and 3) is tertiary butanol, tertiary amyl alcohol or isopropanol.
4. The method for preparing glutaraldehyde by taking cyclopentene as a raw material according to claim 1, wherein: the concentration of the hydrogen peroxide in the steps 1), 2) and 3) is 30-50 wt%.
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