CN110372483A - A kind of catalytic oxidation of cyclopentene prepares the process of glutaraldehyde - Google Patents
A kind of catalytic oxidation of cyclopentene prepares the process of glutaraldehyde Download PDFInfo
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- CN110372483A CN110372483A CN201910646190.7A CN201910646190A CN110372483A CN 110372483 A CN110372483 A CN 110372483A CN 201910646190 A CN201910646190 A CN 201910646190A CN 110372483 A CN110372483 A CN 110372483A
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- cyclopentene
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- 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
- B01J29/04—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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- 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
- B01J37/0009—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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- C—CHEMISTRY; METALLURGY
- 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 present invention relates to the processes that a kind of catalytic oxidation of cyclopentene prepares glutaraldehyde, hydrogenperoxide steam generator and reaction dissolvent are mixed, tungsten based molecular sieve catalyst is added according to 1~4% additive amount that catalyst is cyclopentene quality, it is uniformly mixed, cyclopentene is added, stirring, reaction system carry out catalytic oxidation, obtain glutaraldehyde product.Compared with prior art, the present invention has many advantages, such as that the high conversion rate of cyclopentene, the selectivity of pentadiene height, high income, reaction process is environmental-friendly, post-processing is simple.
Description
Technical field
The present invention relates to solid-liquid heterogeneous catalytic reaction, the technique side for preparing glutaraldehyde more particularly, to catalytic oxidation of cyclopentene
Method.
Background technique
Glutaraldehyde (abbreviation GA), the oily liquids of colourless or light yellow irritant smell, soluble easily in water, ethyl alcohol are dissolved in
Benzene, it is nonflammable, non-volatile, it is unstable in air.At normal temperature can oxidation by air, it is anti-to be also easy to happen condensation, polymerization etc.
It answers.It is a kind of important saturated straight chain binary aliphatic aldehyde, is important fine chemical product and intermediate, have crosslinking and
Solidify the effect of protein.It is the antibacterial disinfectant, excellent leather tanning agent, color picture tube hardener of a kind of high-efficiency low-toxicity
And organic synthesis agent, it is widely used in biomedical engineering, cellular immunology, biochemistry, leather chemistry, histochemistry and micro-
The fields such as biological industry, environmental protection.
Current main synthetic method has pyridine method, acryladehyde method, polyalcohol oxidizing process, glutaric acid reduction method and cyclopentene
Oxidizing process etc..Used in industrial production earliest is pyridine method, but because its consumption of raw materials is big, at high cost, pollution is big, product quality
Difference and be eliminated.Although pentanediol oxidizing process reaction route is short, can be difficult to control due to the oxidation depth of its oxidation reaction, yield
It is low, there is lack of raw materials and high production cost, therefore realize industrialized possibility also and less.Cyclopentene oxidizing is to study now
A kind of more method, tungstenic molecular sieve are favored by scholar.
Heterogeneous catalysis currently used for this reaction mainly has mesoporous point of immobilized heteropoly acid, metal composite oxide, tungsten-
Son sieve etc., above-mentioned catalyst have W-SBA-15, W-MCM-41, W-MCM-48 applied to the reaction of oxidation of cyclopentene preparing glutaric dialdehyde
Deng, but tungsten based molecular sieve for this catalytic oxidation also not it has been proposed that.
Chinese patent CN1680032A discloses a kind of for using aqueous hydrogen peroxide solution as oxidant selective oxidation ring penta
Alkene prepares the novel multi-phase tungsten-containing catalyst and its manufacturing method of glutaraldehyde.The novel tungsten-containing catalyst is by synthesis HMS
The synthetic method of wolframic acid presoma is added during type total silicon mesopore molecular sieve by the tungsten oxide group with catalytic oxidation activity
Prepared by dividing in the skeleton in situ for being introduced into HMS mesopore molecular sieve, but the oxidation that the catalyst is used to be catalyzed cyclopentene is anti-
When answering middle, the yield of target product glutaraldehyde is 56.9~75.1%, and the selectivity of glutaraldehyde is 73.5~82.0%, catalysis
Effect is not very well that catalyst activity and selectivity is to be improved.
China Today environmental problem has seemed that seriously, environmental problem is greatly paid close attention to, and Green Chemistry has been
The inevitable direction of chemical industrial field research and development.It develops excellent catalyst and optimal process conditions is to realize green chemical industry
Pith synthesize a kind of catalyst that catalytic activity is good for catalytic oxidation of cyclopentene to realize Green Chemistry as objective
Preparing glutaraldehyde reaction has important research significance.
Summary of the invention
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of cyclopentene to be catalyzed oxygen
Change prepares the process of glutaraldehyde.
The purpose of the present invention can be achieved through the following technical solutions:
A kind of catalytic oxidation of cyclopentene prepares the process of glutaraldehyde, comprising the following steps:
Hydrogenperoxide steam generator and reaction dissolvent are mixed, added according to 1~4% additive amount that catalyst is cyclopentene quality
Enter tungsten based molecular sieve catalyst, be uniformly mixed, cyclopentene, stirring is added, reaction system carries out catalytic oxidation, obtains penta 2
Aldehyde product.
Wherein, the reaction dissolvent is selected from the one or more of methanol, ethyl alcohol, isopropanol or the tert-butyl alcohol.
The reaction temperature of the catalytic oxidation is 20~50 DEG C, preferably 25~35 DEG C.
The reaction time of the catalytic oxidation is 12~48 hours, preferably 24~36 hours.
The molar ratio of the cyclopentene and hydrogen peroxide is 1~2.
The mass loading amount of tungsten oxide is 2~15% in the tungsten based molecular sieve catalyst.
The present invention prepares the reaction of glutaraldehyde using tungsten based molecular sieve catalysis catalytic oxidation of cyclopentene, and optimizes reaction
Condition:
During the reaction, the additive amount of catalyst is particularly significant, when the additive amount of catalyst is excessive, the conversion of cyclopentene
Rate is higher, but the selectivity of glutaraldehyde is lower, generates excessive side reaction, is unfavorable for the utilization of reaction raw materials, catalyst
When additive amount is too low, the conversion ratio of cyclopentene compared with and glutaraldehyde selectivity it is lower, be unfavorable for the generation of glutaraldehyde.With in
Catalyst is that 8~17% additive amount of the quality of cyclopentene is compared in state patent CN1680032A, and the present invention uses 1~4%
Additive amount, the yield of the glutaraldehyde of acquisition is up to 87.1%, and the selectivity of glutaraldehyde is up to 87.1%, is better than Chinese patent
CN1680032A yield 76%, the data of selectivity 77%.By optimizing the additive amount of catalyst, glutaraldehyde is substantially increased
Yield favorably improves atom utilization, more economical environmental protection.
Reaction temperature is excessively high or too low, and the conversion ratio of cyclopentene and the selectivity of glutaraldehyde are lower, catalytic activity
It is lower；Reaction time needs to control at 24 hours or so, and the reaction time is shorter, and cyclopentene also unreacted is complete, conversion ratio mistake
Low, the reaction time is longer, product glutaraldehyde over-conversion, and the selectivity decline of glutaraldehyde also leads to the yield of final glutaraldehyde
It reduces, is unfavorable for Atom economy.
The tungsten based molecular sieve catalyst is to prepare after introducing tungsten oxide active component in situ during synthesis of molecular sieve
It obtains.
Specifically, the tungsten based molecular sieve catalyst the preparation method comprises the following steps:
Stock: raw material silicon source, silicon source, inorganic alkali source, template TPABr, water and tungsten source are weighed respectively；
Above-mentioned inorganic alkali source is added to the water, template machine TPABr is added, silicon source is added after dissolution, stirring and dissolving is added
Tungsten source, is stirred at room temperature, and adds silicon source, stirs the mixture for aging；
Mixture after aging is transferred to crystallization in ptfe autoclave；
Mixture after crystallization is filtered, is washed, dry, roasting goes template agent removing to obtain the tungsten based molecular sieve catalyst.
According to 100SiO in melting process2:1.0Al2O3:8.75Na2O:12TPABr:2600H2O:10~1.25WO3Rub
You weigh each raw material component by ratio；Silicon source in the raw material is SiO2, source of aluminium is Patent alum, the inorganic base
Source is sodium hydroxide, and the tungsten source is sodium tungstate.
In the ageing process, the aging temperature of mixture is 20~40 DEG C, and preferably 30 DEG C, ageing time is 8~12
Hour；
In the crystallization process, crystallization temperature is 150~220 DEG C, and preferably 180 DEG C, crystallization time is 30~40 hours,
Preferably 36 hours；
The maturing temperature of the roasting removal template machine is 450~600 DEG C, and preferably 550 DEG C, calcining time is 4~8 small
When, preferably 6 hours.
Compared with prior art, the invention has the following advantages that
(1) conversion ratio of preparation process, cyclopentene reaches 100%, reaches to the selectivity of target product glutaraldehyde
87.1%, the yield of glutaraldehyde reaches 87.1%, and reaction effect is good；
(2) catalyst activity in reaction process is high, and stability is good, by 3 test cycles, the activity data of catalyst
In, the yield of glutaraldehyde does not have sharp fall, shows that catalyst structure is stablized, reusable；And catalyst preparation mistake
Journey is simple, is easy expanding production.
Specific embodiment
The present invention is described in detail combined with specific embodiments below.Following embodiment will be helpful to the technology of this field
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill of this field
For personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made.These belong to the present invention
Protection scope.
Embodiment 1
A kind of tungsten based molecular sieve catalyst, preparation method includes the following steps:
(1) 36.715gH is added in 0.527gNaOH2In O, 2.5066gTPABr is added, is added after dissolution
0.5228gAl2(SO4)3·18H2O is stirred at room temperature to Quan Rong；
(2) 0.4438g Na is added2WO4, 30min is stirred at room temperature, adds 4.707gSiO2, mixture is stirred at 30 DEG C
Mix overnight aging；
(3) above-mentioned material, which is transferred in ptfe autoclave, reacts 36h at 180 DEG C, filter, washing, drying；
(4) by sample in Muffle furnace 550 DEG C of calcining 6h, obtain product.
Raw material in preparation process is as shown in table 1.
Source chemicals source in 1 preparation process of table
Embodiment 2
A kind of application method of tungsten based molecular sieve catalyst, the tungsten based molecular sieve catalyst is for being catalyzed cyclopentene catalysis oxygen
In the reaction of change value glutaraldehyde, the specific steps are as follows:
(1) in 100mL round-bottomed flask, the hydrogenperoxide steam generator of 3.89mL 30%wt is mixed with the 14mL tert-butyl alcohol, so
It is added afterwards and weighs the catalyst 0.1g prepared in embodiment 1, when three of the above substance is thoroughly mixed sufficiently and then is added
5.74mL cyclopentene, 35 DEG C of oil bath pan are stirred to react for 24 hours.
(2) after reaction, with GC-9790 gas chromatograph (FID, AE PEG-20M 30m × 0.32mm × 0.5um)
Mixed liquor after reaction is analyzed.
The conversion ratio of cyclopentene and the selectivity and yield of glutaraldehyde are calculated based on the analysis results, and the formation of catalyst is surveyed
Test result is as shown in table 2.
2 embodiment of table, 2 catalyst performance test result list
From table 2, it can be seen that using the catalyst in embodiment 1, the high conversion rate of cyclopentene conversion ratio up to 100%,
The selectivity of glutaraldehyde is 87.1%, yield 87.1%, due to the active number of the catalyst in Chinese patent CN1680032A
According to, show catalyst of the invention have better catalytic effect.
Embodiment 3
The present embodiment is to probe into catalytic oxidation of cyclopentene to prepare in glutaraldehyde reaction process, and reaction dissolvent is to reaction effect
It influences.
Specific step is as follows:
(1) the catalyst 0.1g for weighing the preparation of embodiment 1, in 100mL round-bottomed flask, by 3.89mL, the mistake of 30%wt
Hydrogen peroxide solution is mixed with 14mL alcoholic solvent, and weighed catalyst is then added, when three of the above substance be thoroughly mixed it is abundant it
Afterwards, 5.74mL cyclopentene is added, catalysis effect of the test catalyst in catalytic oxidation of cyclopentene for 24 hours is stirred to react at 35 DEG C
Fruit；
(2) under condition of different temperatures after reaction, with GC-9790 gas chromatograph (FID, AE PEG-20M 30m
× 0.32mm × 0.5um) mixed liquor after reaction is analyzed respectively.
Data analysis is carried out to the reaction effect obtained using different alcoholic solvents, as shown in table 3.
Catalyst performance test result list under the conditions of the different alcoholic solvent of table 3
From table 3 it is observed that being more advantageous to the progress of reaction using t-butanol solvent.
Embodiment 4
The present embodiment is to probe into catalytic oxidation of cyclopentene to prepare in glutaraldehyde reaction process, and catalyst amount is to reaction effect
Influence.
Specific step is as follows:
(1) catalyst 0.05,0.08,0.10,0.15g for weighing the preparation of embodiment 1 respectively, in 100mL round-bottomed flask,
The hydrogenperoxide steam generator of 3.89mL 30%wt is mixed with the 14mL tert-butyl alcohol, weighed catalyst is then added, works as three of the above
Substance is thoroughly mixed sufficiently and then is added 5.74mL cyclopentene, is stirred to react at 35 DEG C and tests catalyst for 24 hours in cyclopentene
Catalytic effect in catalysis oxidation；
(2) under condition of different temperatures after reaction, with GC-9790 gas chromatograph (FID, AE PEG-20M 30m
× 0.32mm × 0.5um) mixed liquor after reaction is analyzed respectively.
Data analysis is carried out to the reaction effect obtained using different catalysts dosage, as shown in table 4.
Influence result list of 4 catalyst amount of table to reaction effect
As can be seen from Table 4, the dosage of catalyst is excessively high or the too low yield for being unfavorable for glutaraldehyde, that is, is unfavorable for
Improve catalytic performance.
Embodiment 5
The present embodiment is to probe into catalytic oxidation of cyclopentene to prepare in glutaraldehyde reaction process, and reaction temperature is to reaction effect
It influences.
Specific step is as follows:
(1) the catalyst 0.1g for weighing the preparation of embodiment 1, in 100mL round-bottomed flask, by the peroxide of 3.89mL30%wt
Change hydrogen solution to mix with the 14mL tert-butyl alcohol, weighed catalyst is then added, after three of the above substance is thoroughly mixed sufficiently,
5.74mL cyclopentene is added, test catalyst for 24 hours is stirred to react at 25 DEG C, 35 DEG C, 45 DEG C, 55 DEG C respectively and is urged in cyclopentene
Change the catalytic effect in oxidation；
(2) under condition of different temperatures after reaction, with GC-9790 gas chromatograph (FID, AE PEG-20M 30m
× 0.32mm × 0.5um) mixed liquor after reaction is analyzed respectively.
Data analysis is carried out to using the reaction effect obtained under the conditions of differential responses temperature, as shown in table 5.
Catalyst performance test result list under the conditions of 5 differential responses temperature of table
As can be seen from Table 5, in reaction process, reaction temperature it is excessively high or it is too low be unfavorable for reaction go on smoothly,
When reaction temperature is 35 DEG C, catalyst activity is best.
Embodiment 6
The present embodiment is to probe into catalytic oxidation of cyclopentene to prepare in glutaraldehyde reaction process, and the reaction time is to reaction effect
It influences.
Specific step is as follows:
(1) the catalyst 0.1g for weighing the preparation of embodiment 1, in 100mL round-bottomed flask, by the peroxide of 3.89mL30%wt
Change hydrogen solution to mix with the 14mL tert-butyl alcohol, weighed catalyst is then added, after three of the above substance is thoroughly mixed sufficiently,
Add 5.74mL cyclopentene, be arranged 35 DEG C of reaction temperature, will control respectively in the reaction time in 12h, for 24 hours, 36h and 48h, compare
Catalytic effect of the catalyst in catalytic oxidation of cyclopentene；
(2) after reaction, with GC-9790 gas chromatograph (FID, AE PEG-20M 30m × 0.32mm × 0.5um)
The mixed liquor after reaction is analyzed respectively.
Data analysis is carried out to the reaction effect obtained using the differential responses time, as shown in table 6.
Catalyst performance test result list under 6 differential responses time conditions of table
As can be seen from Table 6, when reacted between when being 24 hours, the yield of glutaraldehyde reaches highest, terminates at this time anti-
It should can obtain best yield.
Embodiment 7
The present embodiment is to probe into catalytic oxidation of cyclopentene to prepare in glutaraldehyde reaction process, and the cycle-index of catalyst is to it
The stability of catalyst is probed into the influence of catalytic performance.
Specific step is as follows:
(1) the catalyst 0.1g for weighing the preparation of embodiment 1 is stand-by.
(2) in 100mL round-bottomed flask, the hydrogenperoxide steam generator of 3.89mL 30%wt is mixed with the 14mL tert-butyl alcohol, so
The catalyst 0.1g for weighing above-mentioned preparation is added afterwards, when three of the above substance is thoroughly mixed sufficiently and then is added 5.74mL ring
Amylene, 35 DEG C of oil bath pan are stirred to react for 24 hours.
(3) after reaction, with GC-9790 gas chromatograph (FID, AE PEG-20M 30m × 0.32mm × 0.5um)
Mixed liquor after reaction is analyzed.
(4) after each reaction, see that catalyst separates, then repeat the above steps (2), (3), (4) step.
Data analysis is carried out to the reaction effect that different cycle-index catalyst obtain, as shown in table 7.
The different number of repetition catalyst performance test result lists of table 7
As can be seen from Table 6, after catalyst 3 times circulations, it is still able to maintain good catalytic activity, catalyst is corresponding
Glutaraldehyde yield be 73.4%, show that the stability of catalyst of the invention is preferable.
Embodiment 8
A kind of tungsten based molecular sieve catalyst, W/Si molar ratio is 0.0125 in the catalyst, and preparation method includes following
Step:
(1) 36.715gH is added in 0.527gNaOH2In O, 2.5066gTPABr is added, is added after dissolution
0.5228gAl2(SO4)3·18H2O is stirred at room temperature to Quan Rong；
(2) 0.2878g Na is added2WO4, 30min is stirred at room temperature, adds 4.707gSiO2, mixture is stirred at 20 DEG C
Overnight aging is mixed, specific ageing time is 8 hours；
(3) above-mentioned material, which is transferred in ptfe autoclave, reacts 40h at 150 DEG C, filter, washing, drying；
(4) by sample in Muffle furnace 450 DEG C of calcining 8h, obtain product.
Raw material in preparation process is as shown in table 1.
The conversion ratio of cyclopentene and the selectivity and yield of glutaraldehyde are calculated based on the analysis results, and the formation of catalyst is surveyed
Test result is as shown in table 8.
8 embodiment of table, 2 catalyst performance test result list
Embodiment 9
A kind of tungsten based molecular sieve catalyst, W/Si molar ratio is 0.1 in the catalyst, and preparation method includes following step
It is rapid:
(1) 36.715gH is added in 0.527gNaOH2In O, 2.5066gTPABr is added, is added after dissolution
0.5228gAl2(SO4)3·18H2O is stirred at room temperature to Quan Rong；
(2) 0.2.302g Na is added2WO4, 30min is stirred at room temperature, adds 4.707gSiO2, mixture is stirred at 40 DEG C
Overnight aging is mixed, specific ageing time is 12 hours；
(3) above-mentioned material, which is transferred in ptfe autoclave, reacts 30h at 220 DEG C, filter, washing, drying；
(4) by sample in Muffle furnace 600 DEG C of calcining 8h, obtain product.
Raw material in preparation process is as shown in table 1.
The conversion ratio of cyclopentene and the selectivity and yield of glutaraldehyde are calculated based on the analysis results, and the formation of catalyst is surveyed
Test result is as shown in table 9.
9 embodiment of table, 2 catalyst performance test result list
Specific embodiments of the present invention are described above.It is to be appreciated that the invention is not limited to above-mentioned
Particular implementation, those skilled in the art can make various deformations or amendments within the scope of the claims, this not shadow
Ring substantive content of the invention.
Claims (10)
1. the process that a kind of catalytic oxidation of cyclopentene prepares glutaraldehyde, which comprises the following steps:
Hydrogenperoxide steam generator and reaction dissolvent are mixed, tungsten is added according to 1~4% additive amount that catalyst is cyclopentene quality
Based molecular sieve catalyst is uniformly mixed, and cyclopentene, stirring is added, and reaction system carries out catalytic oxidation, obtains glutaraldehyde production
Object.
2. the process that a kind of catalytic oxidation of cyclopentene according to claim 1 prepares glutaraldehyde, which is characterized in that institute
State the one or more that reaction dissolvent is selected from methanol, ethyl alcohol, isopropanol or the tert-butyl alcohol.
3. the process that a kind of catalytic oxidation of cyclopentene according to claim 1 prepares glutaraldehyde, which is characterized in that institute
The reaction temperature for stating catalytic oxidation is 20~50 DEG C, preferably 25~35 DEG C.
4. a kind of catalytic oxidation of cyclopentene according to claim 1 or 3 prepares the process of glutaraldehyde, feature exists
In the reaction time of the catalytic oxidation is 12~48 hours, preferably 24~36 hours.
5. the process that a kind of catalytic oxidation of cyclopentene according to claim 1 prepares glutaraldehyde, which is characterized in that institute
The molar ratio for stating cyclopentene and hydrogen peroxide is 1~2.
6. the process that a kind of catalytic oxidation of cyclopentene according to claim 1 prepares glutaraldehyde, which is characterized in that institute
The mass loading amount for stating tungsten oxide in tungsten based molecular sieve catalyst is 2~15%.
7. the process that a kind of catalytic oxidation of cyclopentene according to claim 1 prepares glutaraldehyde, which is characterized in that institute
Stating tungsten based molecular sieve catalyst is to be prepared after introducing tungsten oxide active component in situ during synthesis of molecular sieve.
8. the process that a kind of catalytic oxidation of cyclopentene according to claim 1 prepares glutaraldehyde, which is characterized in that should
Tungsten based molecular sieve catalyst the preparation method comprises the following steps:
Stock: raw material silicon source, silicon source, inorganic alkali source, template TPABr, water and tungsten source are weighed respectively；
Above-mentioned inorganic alkali source is added to the water, template machine TPABr is added, silicon source is added after dissolution, tungsten is added in stirring and dissolving
Source is stirred at room temperature, and adds silicon source, stirs the mixture for aging；
Mixture after aging is transferred to crystallization in ptfe autoclave；
Mixture after crystallization is filtered, is washed, dry, roasting goes template agent removing to obtain the tungsten based molecular sieve catalyst.
9. the process that a kind of catalytic oxidation of cyclopentene according to claim 8 prepares glutaraldehyde, which is characterized in that standby
According to 100SiO during material2:1.0Al2O3:8.75Na2O:12TPABr:2600H2O:10~1.25WO3Molar ratio weigh respectively
Raw material components；Silicon source in the raw material is SiO2, source of aluminium is Patent alum, and the inorganic alkali source is hydroxide
Sodium, the tungsten source are sodium tungstate.
10. a kind of preparation method of tungsten based molecular sieve catalyst according to claim 8, which is characterized in that the aging
In the process, the aging temperature of mixture is 20~40 DEG C, and preferably 30 DEG C, ageing time is 8~12 hours；
In the crystallization process, crystallization temperature is 150~220 DEG C, and preferably 180 DEG C, crystallization time is 30~40 hours, preferably
It is 36 hours；
The maturing temperature of the roasting removal template machine is 450~600 DEG C, and preferably 550 DEG C, calcining time is 4~8 hours,
Preferably 6 hours.
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| CN201910646190.7A CN110372483B (en) | 2019-07-17 | 2019-07-17 | Process method for preparing glutaraldehyde by catalytic oxidation of cyclopentene |
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| CN201910646190.7A CN110372483B (en) | 2019-07-17 | 2019-07-17 | Process method for preparing glutaraldehyde by catalytic oxidation of cyclopentene |
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| CN110372483A true CN110372483A (en) | 2019-10-25 |
| CN110372483B CN110372483B (en) | 2022-11-15 |
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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 |
| CN113603574A (en) * | 2021-09-23 | 2021-11-05 | 广东新华粤石化集团股份公司 | Method for catalyzing cyclopentene catalytic oxidation reaction by using vacancy silicotungstic heteropoly acid salt catalyst |
| CN113813986A (en) * | 2021-11-02 | 2021-12-21 | 烟台东化新材料有限公司 | Tungsten-based molecular sieve catalyst, preparation method thereof and method for preparing glutaraldehyde by catalytic oxidation of cyclopentene |
| CN113828253A (en) * | 2021-09-10 | 2021-12-24 | 天津渤化永利化工股份有限公司 | Reaction device and process method for continuously synthesizing glutaraldehyde |
| CN114192141A (en) * | 2021-11-26 | 2022-03-18 | 广东省科学院化工研究所 | Preparation method of glutaraldehyde |
| CN114426467A (en) * | 2020-10-29 | 2022-05-03 | 中国石油化工股份有限公司 | Method for preparing glutaraldehyde based on heterogeneous catalysis technology |
| 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 |
| CN114426467B (en) * | 2020-10-29 | 2024-05-10 | 中国石油化工股份有限公司 | Method for preparing glutaraldehyde based on heterogeneous catalysis technology |
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| CN114426467A (en) * | 2020-10-29 | 2022-05-03 | 中国石油化工股份有限公司 | Method for preparing glutaraldehyde based on heterogeneous catalysis technology |
| CN114426467B (en) * | 2020-10-29 | 2024-05-10 | 中国石油化工股份有限公司 | Method for preparing glutaraldehyde based on heterogeneous catalysis technology |
| CN113828253A (en) * | 2021-09-10 | 2021-12-24 | 天津渤化永利化工股份有限公司 | Reaction device and process method for continuously synthesizing glutaraldehyde |
| CN113603574A (en) * | 2021-09-23 | 2021-11-05 | 广东新华粤石化集团股份公司 | Method for catalyzing cyclopentene catalytic oxidation reaction by using vacancy silicotungstic heteropoly acid salt catalyst |
| 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 |
| CN113813986A (en) * | 2021-11-02 | 2021-12-21 | 烟台东化新材料有限公司 | Tungsten-based molecular sieve catalyst, preparation method thereof and method for preparing glutaraldehyde by catalytic oxidation of cyclopentene |
| CN113813986B (en) * | 2021-11-02 | 2024-04-02 | 烟台东化新材料有限公司 | Tungsten-based molecular sieve catalyst, preparation method thereof and method for preparing glutaraldehyde by catalytic oxidation of cyclopentene |
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