CN110372483B - Process method for preparing glutaraldehyde by catalytic oxidation of cyclopentene - Google Patents
Process method for preparing glutaraldehyde by catalytic oxidation of cyclopentene Download PDFInfo
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/06—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/36—Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
- C01B39/38—Type ZSM-5
- C01B39/40—Type ZSM-5 using at least one organic template directing agent
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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
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention relates to a process method for preparing glutaraldehyde by catalytic oxidation of cyclopentene, which comprises mixing hydrogen peroxide solution and reaction solvent, adding tungsten-based molecular sieve catalyst according to the addition amount of the catalyst being 1-4% of the cyclopentene, mixing uniformly, adding cyclopentene, stirring, and carrying out catalytic oxidation reaction in a reaction system to obtain glutaraldehyde product. Compared with the prior art, the method has the advantages of high conversion rate of cyclopentene, high selectivity of pentadiene, high yield, environment-friendly reaction process, simple post-treatment and the like.
Description
Technical Field
The invention relates to solid-liquid heterogeneous catalytic reaction, in particular to a process method for preparing glutaraldehyde by catalytic oxidation of cyclopentene.
Background
Glutaraldehyde (GA for short), colorless or pale yellow oily liquid with pungent odor, easy to dissolve in water and ethanol, soluble in benzene, nonflammable, nonvolatile, and unstable in air. Can be oxidized by air at normal temperature, and is easy to have condensation, polymerization and other reactions. It is an important saturated straight-chain aliphatic dialdehyde, an important fine chemical product and an intermediate, and has the functions of crosslinking and solidifying protein. It is a high-effective low-toxic sterilizing disinfectant, excellent leather tanning agent, colour kinescope firming agent and organic synthetic agent, and can be extensively used in the fields of biomedical engineering, cell immunology, biochemistry, leather chemistry, histochemistry and microbial industry and environmental protection, etc..
The main synthesis methods at present include a pyridine method, an acrolein method, a polyol oxidation method, a glutaric acid reduction method, a cyclopentene oxidation method, and the like. The pyridine method is used for industrial production at first, but is eliminated due to large consumption of raw materials, high cost, large pollution and poor product quality. The pentanediol oxidation method has a short reaction route, and is not very likely to be industrially used because the oxidation depth of the oxidation reaction is not easily controlled, the yield is low, the raw materials are in short supply, and the production cost is high. The cyclopentene oxidation method is a method which is currently studied, and a tungsten-containing molecular sieve is favored by researchers.
The prior heterogeneous catalysts used for the reaction mainly comprise heteropoly acid immobilized, composite metal oxide, tungsten-mesoporous molecular sieve and the like, and the catalysts are applied to the reaction of preparing glutaral by oxidizing cyclopentene, such as W-SBA-15, W-MCM-41, W-MCM-48 and the like, but tungsten-based molecular sieves are not proposed for the catalytic oxidation reaction.
Chinese patent CN1680032a discloses a novel heterogeneous tungsten-containing catalyst for preparing glutaraldehyde by selectively oxidizing cyclopentene with aqueous hydrogen peroxide as an oxidant and a preparation method thereof. The novel tungsten-containing catalyst is prepared by introducing a tungsten oxide component with catalytic oxidation activity into a framework of an HMS mesoporous molecular sieve in situ by a synthesis method of adding a tungstic acid precursor in the process of synthesizing the HMS type all-silicon mesoporous molecular sieve, but when the catalyst is used for catalyzing the oxidation reaction of cyclopentene, the yield of a target product glutaraldehyde is 56.9-75.1%, the selectivity of the glutaraldehyde is 73.5-82.0%, the catalytic effect is not good, and the activity and the selectivity of the catalyst are both to be improved.
Today, the environmental problems in China have been serious, the environmental problems have received great attention, and green chemistry has been the inevitable direction for research and development in the chemical industry field. The development of an excellent catalyst and the optimal process conditions are important parts for realizing green chemical engineering, and the synthesis of the catalyst with good catalytic activity for the reaction of preparing glutaraldehyde by catalytic oxidation of cyclopentene has important research significance aiming at realizing green chemistry.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a process method for preparing glutaraldehyde by catalytic oxidation of cyclopentene.
The purpose of the invention can be realized by the following technical scheme:
a process method for preparing glutaraldehyde by catalytic oxidation of cyclopentene comprises the following steps:
mixing a hydrogen peroxide solution with a reaction solvent, adding a tungsten-based molecular sieve catalyst according to the addition amount of the catalyst which is 1-4% of the mass of cyclopentene, uniformly mixing, adding cyclopentene, stirring, and carrying out catalytic oxidation reaction on a reaction system to obtain a glutaraldehyde product.
Wherein the reaction solvent is selected from one or more of methanol, ethanol, isopropanol or tert-butanol.
The reaction temperature of the catalytic oxidation reaction is 20-50 ℃, preferably 25-35 ℃.
The reaction time of the catalytic oxidation reaction is 12 to 48 hours, preferably 24 to 36 hours.
The mol ratio of the cyclopentene to the hydrogen peroxide is 1-2.
The mass loading capacity of tungsten oxide in the tungsten-based molecular sieve catalyst is 2-15%.
The invention adopts the reaction of preparing glutaraldehyde by catalyzing cyclopentene and oxidizing with tungsten-based molecular sieve, and optimizes the reaction conditions:
in the reaction process, the addition amount of the catalyst is very important, when the addition amount of the catalyst is too large, the conversion rate of cyclopentene is high, but the selectivity of glutaraldehyde is low, too many side reactions are generated, and the utilization of reaction raw materials is not facilitated, and when the addition amount of the catalyst is too low, the conversion rate of cyclopentene and the selectivity of glutaraldehyde are both low, and the generation of glutaraldehyde is not facilitated. Compared with the addition amount of 8-17% of the catalyst in the Chinese patent CN1680032A by the mass of cyclopentene, the yield of the obtained glutaraldehyde is up to 87.1% by adopting the addition amount of 1-4%, the selectivity of the glutaraldehyde is up to 87.1%, and the data of the yield of 76% and the selectivity of 77% are superior to those of the Chinese patent CN 1680032A. By optimizing the addition amount of the catalyst, the yield of the glutaraldehyde is greatly improved, the atom utilization rate is favorably improved, and the method is more economic and environment-friendly.
The reaction temperature is too high or too low, the conversion rate of cyclopentene and the selectivity of glutaraldehyde are both low, and the catalytic activity is low; the reaction time needs to be controlled to be about 24 hours, the reaction time is short, cyclopentene does not completely react, the conversion rate is too low, the reaction time is long, the product glutaraldehyde is excessively converted, the selectivity of glutaraldehyde is reduced, the yield of the final glutaraldehyde is reduced, and the atom economy is not facilitated.
The tungsten-based molecular sieve catalyst is prepared by introducing a tungsten oxide active component in situ in the process of synthesizing a molecular sieve.
Specifically, the preparation method of the tungsten-based molecular sieve catalyst comprises the following steps:
preparing materials: respectively weighing raw materials including a silicon source, an aluminum source, an inorganic alkali source, a template agent TPABr, water and a tungsten source;
adding the inorganic alkali source into water, adding a template machine TPABr, adding an aluminum source after dissolving, stirring for dissolving, adding a tungsten source, stirring at room temperature, adding a silicon source, stirring and aging the mixture;
transferring the aged mixture to a polytetrafluoroethylene reaction kettle for crystallization;
and filtering, washing, drying and roasting the crystallized mixture to remove the template agent to obtain the tungsten-based molecular sieve catalyst.
According to 100SiO in the material preparation process 2 :1.0Al 2 O 3 :8.75Na 2 O:12TPABr:2600H 2 O:10～1.25WO 3 Weighing the raw material components according to the molar ratio; the silicon source in the raw material is SiO 2 The aluminum source is aluminum sulfate octadecahydrate, the inorganic alkali source is sodium hydroxide, and the tungsten source is sodium tungstate.
In the aging process, the aging temperature of the mixture is 20-40 ℃, preferably 30 ℃, and the aging time is 8-12 hours;
in the crystallization process, the crystallization temperature is 150-220 ℃, preferably 180 ℃, and the crystallization time is 30-40 hours, preferably 36 hours;
the roasting temperature of the roasting removal template machine is 450-600 ℃, preferably 550 ℃, and the roasting time is 4-8 hours, preferably 6 hours.
Compared with the prior art, the invention has the following advantages:
(1) In the preparation process, the conversion rate of cyclopentene reaches 100%, the selectivity of a target product glutaraldehyde reaches 87.1%, the yield of glutaraldehyde reaches 87.1%, and the reaction effect is good;
(2) The catalyst in the reaction process has high activity and good stability, and the yield of glutaraldehyde in the activity data of the catalyst is not greatly reduced after 3 test cycles, which shows that the catalyst has a stable structure and can be repeatedly used; and the preparation process of the catalyst is simple, and the expanded production is easy.
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 variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the invention.
Example 1
A preparation method of a tungsten-based molecular sieve catalyst comprises the following steps:
(1) 0.527g NaOH was added to 36.715gH 2 Adding 2.5066gTPABr into O, dissolving, adding 0.5228gAl 2 (SO 4 ) 3 ·18H 2 O, stirring at room temperature until the mixture is completely dissolved;
(2) 0.4438g Na was added 2 WO 4 Stirring at room temperature for 30min, and adding 4.707gSiO 2 The mixture was stirred at 30 ℃ overnight for aging;
(3) Transferring the materials to a polytetrafluoroethylene reaction kettle, reacting for 36 hours at 180 ℃, filtering, washing and drying;
(4) And calcining the sample in a muffle furnace at 550 ℃ for 6h to obtain the product.
The raw materials in the preparation process are shown in table 1.
TABLE 1 Source of raw reagents in the preparation Process
Example 2
An application method of a tungsten-based molecular sieve catalyst is used for catalyzing reaction of cyclopentene with catalytic oxidation value glutaraldehyde, and comprises the following specific steps:
(1) In a 100mL round bottom flask, 3.89mL of 30 wt% hydrogen peroxide solution was mixed with 14mL of t-butanol, 0.1g of the catalyst prepared in example 1 was weighed, and when the above three substances were completely mixed, 5.74mL of cyclopentene was added, and the reaction was stirred at 35 ℃ in an oil bath for 24 hours.
(2) After the reaction, the liquid mixture after the reaction was analyzed by GC-9790 gas chromatograph (FID, AE PEG-20M 30m.times.0.32 mm.times.0.5 um).
The conversion of cyclopentene and the selectivity and yield of glutaraldehyde were calculated from the analysis results, and the catalyst formation test results are shown in table 2.
Table 2 example 2 summary of catalyst performance test results
From table 2, it can be seen that, with the catalyst in example 1, the conversion rate of cyclopentene is as high as 100%, the selectivity of glutaraldehyde is 87.1%, and the yield is 87.1%, since the activity data of the catalyst in chinese patent CN1680032a, it indicates that the catalyst of the present invention has better catalytic effect.
Example 3
This example is to investigate the influence of the reaction solvent on the reaction effect during the reaction process of preparing glutaraldehyde by catalytic oxidation of cyclopentene.
The method comprises the following specific steps:
(1) Weighing 0.1g of the catalyst prepared in example 1, mixing 3.89mL of a 30% wt hydrogen peroxide solution with 14mL of an alcohol solvent in a 100mL round-bottom flask, adding the weighed catalyst, adding 5.74mL of cyclopentene after the above three substances are completely mixed, and stirring and reacting at 35 ℃ for 24h to test the catalytic effect of the catalyst in catalytic oxidation of cyclopentene;
(2) After the reaction was completed under different temperature conditions, the mixed liquids after the reaction were analyzed by GC-9790 gas chromatograph (FID, AE PEG-20M 30m × 0.32mm × 0.5 um), respectively.
The data analysis was performed on the reaction effect obtained with different alcohol solvents as shown in table 3.
TABLE 3 summary of catalyst Performance test results under different alcohol solvent conditions
As can be seen from Table 3, the reaction was more facilitated by the use of t-butanol as a solvent.
Example 4
This example is to investigate the influence of the amount of catalyst on the reaction effect during the reaction of preparing glutaraldehyde by catalytic oxidation of cyclopentene.
The method comprises the following specific steps:
(1) 0.05 g, 0.08 g, 0.10 g and 0.15g of the catalyst prepared in example 1 are weighed respectively, 3.89mL of 30 wt% hydrogen peroxide solution is mixed with 14mL of tertiary butanol in a 100mL round-bottom flask, then the weighed catalyst is added, after the three substances are completely mixed, 5.74mL of cyclopentene is added, and the mixture is stirred and reacted at 35 ℃ for 24 hours to test the catalytic effect of the catalyst in the catalytic oxidation of the cyclopentene;
(2) After the reaction was completed under different temperature conditions, the mixed liquids after the reaction were analyzed by GC-9790 gas chromatograph (FID, AE PEG-20M 30m × 0.32mm × 0.5 um), respectively.
The data for the reaction results obtained with different catalyst dosages are presented in table 4.
TABLE 4 influence of the amount of catalyst on the reaction results
As can be seen from Table 4, the use of too high or too low amount of the catalyst is not favorable for the yield of glutaraldehyde, i.e., for the improvement of the catalytic performance.
Example 5
This example is to investigate the influence of the reaction temperature on the reaction effect during the reaction process of preparing glutaraldehyde by catalytic oxidation of cyclopentene.
The method comprises the following specific steps:
(1) Weighing 0.1g of the catalyst prepared in example 1, mixing 3.89mL30 wt% hydrogen peroxide solution with 14mL of tert-butyl alcohol in a 100mL round-bottom flask, adding the weighed catalyst, adding 5.74mL of cyclopentene when the three substances are fully mixed, and stirring and reacting at 25 ℃, 35 ℃, 45 ℃ and 55 ℃ for 24h respectively to test the catalytic effect of the catalyst in catalytic oxidation of the cyclopentene;
(2) After the reaction was completed under different temperature conditions, the mixed liquids after the reaction were analyzed by GC-9790 gas chromatograph (FID, AE PEG-20M 30m × 0.32mm × 0.5 um), respectively.
The data analysis was performed on the reaction effects obtained under the conditions of different reaction temperatures, as shown in table 5.
TABLE 5 summary of catalyst Performance test results under different reaction temperature conditions
As can be seen from Table 5, during the reaction, too high or too low reaction temperature is not good for the reaction to proceed smoothly, and when the reaction temperature is 35 ℃, the catalyst activity is the best.
Example 6
This example is to investigate the influence of the reaction time on the reaction effect during the reaction process of preparing glutaraldehyde by catalytic oxidation of cyclopentene.
The method comprises the following specific steps:
(1) Weighing 0.1g of the catalyst prepared in example 1, mixing 3.89mL30 wt% hydrogen peroxide solution with 14mL of tertiary butanol in a 100mL round bottom flask, adding the weighed catalyst, adding 5.74mL of cyclopentene when the three substances are fully mixed, setting the reaction temperature at 35 ℃, controlling the reaction time at 12h, 24h, 36h and 48h respectively, and comparing the catalytic effect of the catalyst in the catalytic oxidation of the cyclopentene;
(2) After the reaction, the mixed solutions after the reaction were each analyzed by GC-9790 gas chromatograph (FID, AE PEG-20M 30m.times.0.32 mm.times.0.5 um).
The data analysis was performed on the reaction effects obtained with different reaction times, as shown in table 6.
TABLE 6 summary of catalyst Performance test results under different reaction time conditions
As can be seen from Table 6, the yield of glutaraldehyde reached the highest at a reaction time of 24 hours, at which the best yield was obtained by terminating the reaction.
Example 7
In this example, the stability of the catalyst was investigated for the influence of the cycle number of the catalyst on the catalytic performance of the catalyst in the reaction process of preparing glutaraldehyde by catalytic oxidation of cyclopentene.
The method comprises the following specific steps:
(1) 0.1g of the catalyst prepared in example 1 was weighed out and used.
(2) In a 100mL round bottom flask, 3.89mL of 30 wt% hydrogen peroxide solution was mixed with 14mL of t-butanol, 0.1g of the catalyst prepared above was weighed, and when the above three substances were completely mixed, 5.74mL of cyclopentene was added, and the reaction was stirred at 35 ℃ in an oil bath for 24 hours.
(3) After the reaction, the liquid mixture after the reaction was analyzed by GC-9790 gas chromatograph (FID, AE PEG-20M 30m.times.0.32 mm.times.0.5 um).
(4) After each reaction, the catalyst is separated, and then the steps (2), (3) and (4) are repeated.
The data of the reaction effect obtained by the catalyst with different cycle times are analyzed, and are shown in table 7.
TABLE 7 summary of catalyst Performance test results for different repeat numbers
As can be seen from Table 6, after the catalyst is circulated for 3 times, the catalyst still can maintain good catalytic activity, and the yield of glutaraldehyde corresponding to the catalyst is 73.4%, which shows that the catalyst of the invention has good stability.
Example 8
A tungsten-based molecular sieve catalyst, wherein the W/Si molar ratio in the catalyst is 0.0125, and the preparation method comprises the following steps:
(1) 0.527g NaOH was added to 36.715gH 2 Adding 2.5066gTPABr into O, dissolving, adding 0.5228gAl 2 (SO 4 ) 3 ·18H 2 O, stirring at room temperature until the mixture is completely dissolved;
(2) 0.2878g Na was added 2 WO 4 Stirring at room temperature for 30min, and adding 4.707gSiO 2 Stirring the mixture at 20 ℃ overnight for aging, wherein the aging time is 8 hours;
(3) Transferring the materials to a polytetrafluoroethylene reaction kettle, reacting for 40h at 150 ℃, filtering, washing and drying;
(4) And calcining the sample in a muffle furnace at 450 ℃ for 8h to obtain the product.
The raw materials in the preparation process are shown in table 1.
The conversion of cyclopentene and the selectivity and yield of glutaraldehyde were calculated from the analysis results, and the catalyst formation test results are shown in table 8.
Table 8 summary of the results of the catalyst performance tests of example 2
Example 9
A tungsten-based molecular sieve catalyst, wherein the W/Si molar ratio in the catalyst is 0.1, and the preparation method comprises the following steps:
(1) 0.527g NaOH was added to 36.715gH 2 Adding 2.5066gTPABr into O, dissolving, adding 0.5228gAl 2 (SO 4 ) 3 ·18H 2 O, stirring at room temperature until the mixture is completely dissolved;
(2) 0.2.302g of Na was added 2 WO 4 Stirring at room temperature for 30min, and adding 4.707gSiO 2 Stirring the mixture at 40 ℃ overnight for aging, wherein the aging time is 12 hours;
(3) Transferring the materials into a polytetrafluoroethylene reaction kettle, reacting for 30 hours at 220 ℃, filtering, washing and drying;
(4) And calcining the sample in a muffle furnace at 600 ℃ for 8h to obtain a product.
The raw materials in the preparation process are shown in table 1.
The conversion of cyclopentene and the selectivity and yield of glutaraldehyde were calculated from the analysis results, and the catalyst formation test results are shown in table 9.
Table 9 summary of the results of the catalyst performance tests of example 2
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention.
Claims (5)
1. A process method for preparing glutaraldehyde by catalytic oxidation of cyclopentene is characterized by comprising the following steps:
mixing a hydrogen peroxide solution and a reaction solvent, adding a tungsten-based molecular sieve catalyst according to the addition amount of 1~4% of the mass of the catalyst, uniformly mixing, adding cyclopentene, stirring, and carrying out catalytic oxidation reaction on a reaction system to obtain a glutaraldehyde product;
the reaction solvent is tert-butyl alcohol; the reaction temperature of the catalytic oxidation reaction is 25 to 35 ℃; the reaction time of the catalytic oxidation reaction is 24 to 36 hours;
the mass loading capacity of tungsten oxide in the tungsten-based molecular sieve catalyst is 2-15%, and the preparation method of the tungsten-based molecular sieve catalyst comprises the following steps:
preparing materials: respectively weighing raw materials including a silicon source, an aluminum source, an inorganic alkali source, a template agent TPABr, water and a tungsten source;
adding the inorganic alkali source into water, adding a template machine TPABr, adding an aluminum source after dissolving, stirring for dissolving, adding a tungsten source, stirring at room temperature, adding a silicon source, stirring and aging the mixture;
transferring the aged mixture to a polytetrafluoroethylene reaction kettle for crystallization;
filtering, washing, drying and roasting the crystallized mixture to remove the template agent to obtain the tungsten-based molecular sieve catalyst;
the baking temperature for baking and removing the template agent is 450 to 600 ℃, and the baking time is 4~8 hours.
2. The process method for preparing glutaraldehyde through catalytic oxidation of cyclopentene according to claim 1, wherein the molar ratio of cyclopentene to hydrogen peroxide is 1~2.
3. The process method for preparing glutaraldehyde by catalytic oxidation of cyclopentene according to claim 1, wherein 100SiO is used in the preparation process 2 : 1.0Al 2 O 3 : 8.75Na 2 O: 12TPABr: 2600H 2 O: 10~1.25WO 3 Weighing each raw material component according to the molar ratio; the silicon source in the raw material is SiO 2 The aluminum source is aluminum sulfate octadecahydrate, the inorganic alkali source is sodium hydroxide, and the tungsten source is sodium tungstate.
4. The process for preparing glutaraldehyde by catalytic oxidation of cyclopentene according to claim 1, wherein in the aging process, the aging temperature of the mixture is 20 to 40 ℃, and the aging time is 8 to 12 hours;
in the crystallization process, the crystallization temperature is 150 to 220 ℃, and the crystallization time is 30 to 40 hours.
5. The process for preparing glutaraldehyde by catalytic oxidation of cyclopentene according to claim 4, wherein the aging temperature of the mixture is 30 ℃ in the aging process;
in the crystallization process, the crystallization temperature is 180 ℃, and the crystallization time is 36 hours;
the roasting temperature for roasting to remove the template agent is 550 ℃, and the roasting time is 6 hours.
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| CN111138256B (en) * | 2019-12-16 | 2021-07-13 | 中国科学院大连化学物理研究所 | Preparation method of hexanediol |
| CN114426468A (en) * | 2020-10-16 | 2022-05-03 | 中国石油化工股份有限公司 | Method for preparing glutaraldehyde by taking cyclopentene as raw material |
| CN113828253B (en) * | 2021-09-10 | 2022-10-18 | 天津渤化永利化工股份有限公司 | Reaction device and process method for continuously synthesizing glutaraldehyde |
| CN113603574B (en) * | 2021-09-23 | 2023-11-10 | 广东新华粤石化集团股份公司 | Method for catalyzing catalytic oxidation reaction of cyclopentene by using short-site silicotungstic heteropolyacid salt catalyst |
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