CN114426468A - Method for preparing glutaraldehyde by taking cyclopentene as raw material - Google Patents
Method for preparing glutaraldehyde by taking cyclopentene as raw material Download PDFInfo
- Publication number
- CN114426468A CN114426468A CN202011110335.0A CN202011110335A CN114426468A CN 114426468 A CN114426468 A CN 114426468A CN 202011110335 A CN202011110335 A CN 202011110335A CN 114426468 A CN114426468 A CN 114426468A
- Authority
- CN
- China
- Prior art keywords
- cyclopentene
- catalyst
- reaction
- hydrogen peroxide
- glutaraldehyde
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 title claims abstract description 112
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 title claims abstract description 59
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 35
- 239000002994 raw material Substances 0.000 title claims abstract description 28
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 68
- 239000003054 catalyst Substances 0.000 claims abstract description 50
- 238000006243 chemical reaction Methods 0.000 claims abstract description 50
- 238000007254 oxidation reaction Methods 0.000 claims description 30
- 230000003647 oxidation Effects 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 14
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 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
- 230000035484 reaction time Effects 0.000 claims description 8
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-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
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052721 tungsten Inorganic materials 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
- 239000002638 heterogeneous catalyst Substances 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 abstract description 2
- 230000008569 process Effects 0.000 description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 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
- 239000003795 chemical substances by application Substances 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
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000002360 preparation method Methods 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
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000007210 heterogeneous catalysis Methods 0.000 description 2
- 239000010985 leather Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-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
- 230000001413 cellular effect Effects 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
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 238000010586 diagram Methods 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
- 239000011964 heteropoly acid Substances 0.000 description 1
- 238000007172 homogeneous catalysis Methods 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
- 230000000813 microbial effect Effects 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
- 239000004848 polyfunctional curative Substances 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
- 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
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 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
- 229910001868 water Inorganic materials 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/56—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
Landscapes
- 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. The method adopts a segmented experiment, uses tungsten-based heterogeneous catalysts with different acid strengths, and controls the reaction process and improves the reaction selectivity by adjusting the addition 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 yield of glutaraldehyde is over 80%. The method has the advantages of high substrate conversion rate, environment-friendly reaction system, less by-products 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 particularly relates to a heterogeneous catalysis process technology for preparing glutaraldehyde by selective oxidation with cyclopentene as a raw material.
Background
Glutaraldehyde (GA for short) is an important fine chemical product and intermediate, and has the function of crosslinking and solidifying protein. Can be used as high-efficiency low-toxicity sterilization disinfectant, excellent leather tanning agent, color kinescope film hardener, organic synthesis agent and the like, and is widely applied to the fields of biomedical engineering, cellular immunology, biochemistry, leather chemistry, histochemistry, microbial industry, environmental protection and the like. Currently, the main synthesis methods of glutaraldehyde 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. Although the reaction route of the pentanediol oxidation method is short, the oxidation depth is not easy to control, the yield is low, the raw materials are in short supply, the production cost is high, and the possibility of realizing industrialization is not high. Therefore, the method for preparing glutaraldehyde by selective oxidation by using cyclopentene as a raw material is favored, and 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 and heterogeneous 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 mostly adopted for synthesizing glutaraldehyde by oxidizing cyclopentene at present, and the catalyst is usually a solid-phase catalyst containing tungsten elements. For example, CN1425498 introduces a tungsten-containing catalyst prepared by preparing TiO2 microsphere as a carrier through closed crystallization, and the yield of glutaraldehyde is 69.4% at most, 60.3% at least, and 65.4% on average. CN1380138 is a catalyst for oxidation reaction prepared by introducing tungsten component in situ in the process of synthesizing MCM-41 type full-silicon mesoporous molecular sieve, and the yield of glutaraldehyde is up to 72%, the yield is 50% at the lowest, and the average yield is 66.5%. CN1446631 is a catalyst for oxidation reaction prepared by in-situ introducing tungsten oxide component in the process of synthesizing SBA-15 type all-silicon mesoporous molecular sieve, and the yield of glutaraldehyde is 47.0% at the lowest, 78.9% at the highest and 63.1% on average. The technology disclosed in CN107652170A is to use [ C6H5CH2N (CH3)2(CH2)3SO3H ] Ti0.5PW4O16 as a catalyst, acetone as a solvent, the volume of the solvent is 56 times that of cyclopentene, and the reaction is carried out for 3H under the condition that the temperature is 35 ℃, and the yield of glutaraldehyde is 70%.
In summary, the existing proprietary technology focuses on the preparation and modification of catalysts, and cyclopentene can obtain a more ideal conversion rate by using these catalysts, but the defects are that the selectivity of the target product is relatively low, the average yield of glutaraldehyde is generally below 70%, the boiling points of the main byproducts, i.e. 1, 2-cyclopentanediol, cyclopentene epoxy compound, glutaric acid, etc., are higher than that of glutaraldehyde, and the glutaraldehyde is active in chemical property and easy to polymerize, and is easy to react in the separation process, so that it is difficult to prepare a glutaraldehyde product suitable for medical use.
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 provided by the invention is adjusted on the basis of the prior art, the supported heteropoly acid is used as the catalyst, and a step-by-step oxidation method is adopted, so that the control of the reaction is enhanced, and the selectivity of the reaction is improved on the premise of ensuring good conversion rate, so as to make up for 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 cyclopentene, a solvent, a catalyst and hydrogen peroxide as raw materials, then feeding the mixture into a first oxidation reactor for pre-oxidation reaction, and oxidizing the cyclopentene into cyclopentane epoxide at the reaction temperature of 30-45 ℃ for 4-10 hours; wherein the dosage of the catalyst is 2.0-8.0 wt% 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 feeding the mixture into a second oxidation reactor for reaction, wherein the reaction temperature is 45-60 ℃, and the reaction time is 8-16 hours; wherein the dosage of the catalyst is 2.0-8.0 wt% of cyclopentene, and the feeding 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 feeding 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 materials 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%.
Furthermore, the dosage of the catalyst in the step 1) is 3.0-6.0 wt% of cyclopentene, the feeding mass ratio of the cyclopentene to hydrogen peroxide is 1: 0.7-1.3, the mass ratio of the cyclopentene to the solvent tert-butyl alcohol 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 amount of the catalyst in the step 2) is 3.0-6.0 wt% of cyclopentene, the feeding mass ratio of the materials 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 amount of the catalyst in the step 3) is 3.0-6.0 wt% of cyclopentene, the feeding mass ratio of the materials 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 tert-butyl alcohol, tert-amyl alcohol or isopropanol, etc.
Further, the concentration of hydrogen peroxide in the steps 1), 2) and 3) is 30-50 wt%.
The process of synthesizing glutaraldehyde by oxidizing cyclopentene with hydrogen peroxide is that cyclopentene reacts first to generate cyclopentene epoxide, then cyclopentene epoxide is converted into intermediate product of beta-hydroxycyclopentyl hydrogen peroxide, and the beta-hydroxycyclopentyl hydrogen peroxide is rearranged and converted into glutaraldehyde. Through a great deal of experimental research, the inventor finds that the oxidation reaction is influenced by the interaction of the peroxytungstic acid and the cyclopentene and the intermediate process of the series reaction, and particularly the concentration of the hydrogen peroxide on the surface of the catalyst has a very significant influence on the reaction process and the yield of the glutaraldehyde. By adopting a segmented experiment, catalysts with different acid strengths are used, and the adding amount of hydrogen peroxide and the concentration of hydrogen peroxide on the surface of the catalyst are adjusted, so that the reaction process is controlled, and the aim of improving the selectivity can be fulfilled.
The method adopts a segmented experiment, uses tungsten-based heterogeneous catalysts with different acid strengths, and controls the reaction process and improves the reaction selectivity by adjusting the addition 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 yield of glutaraldehyde is over 80%. The invention has the advantages of high substrate conversion rate, environment-friendly reaction system, less by-products and convenient separation to obtain qualified products.
Drawings
FIG. 1 is a process flow diagram for preparing glutaraldehyde from cyclopentene according to the present invention.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that it would be apparent to those skilled in the art that several modifications and improvements can be made without departing from the inventive concept. All falling within the scope of the present invention.
[ examples 1 to 10 ]
The W-SBA-15 mesoporous molecular sieve catalyst is prepared by an in-situ synthesis method under an acidic condition by using sodium tungstate as a tungsten source, polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (P123) as a template agent and tetraethyl orthosilicate (TEOS) as a silicon source, and comprises the following specific steps:
sequentially mixing raw materials P123, TEOS, HCl, H2O and W according to a molar ratio of 1.0: 60: 350: 900: 6 to 0.75, transferring the solution into a reaction kettle, crystallizing for 3 days at 95 ℃, washing with absolute ethyl alcohol and deionized water for three times respectively, drying at 80 ℃ overnight, and finally roasting at 550 ℃ for 6 hours to obtain the W-SBA-15 molecular sieve (WO)310-30% of mass fraction).
The method for preparing glutaraldehyde by taking cyclopentene as a raw material comprises the following specific steps:
1) mixing cyclopentene, a solvent, a catalyst and hydrogen peroxide as raw materials, and then feeding the mixture into a first oxidation reactor for pre-oxidation reaction to oxidize the cyclopentene into cyclopentane epoxide;
2) mixing the material obtained after the reaction in the step 1) with hydrogen peroxide and a catalyst, and feeding 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 feeding the mixture into a third oxidation reactor for reaction to prepare glutaraldehyde.
In each example, the types and specifications of the reaction raw materials are shown in Table 1. The technological process of the embodiments 1-10 is shown in figure 1, and the raw material W1 and the solvent are sequentially reacted by three oxidation reactors to obtain a glutaraldehyde product W2, wherein each reactor adopts different catalysts and is added with hydrogen peroxide in a certain proportion. The raw material W1 was high-purity cyclopentene, and the process conditions of the first oxidation reactor, the second oxidation reactor, and the third oxidation reactor in each example were shown in tables 2, 3, and 4, respectively, and the composition analysis of the product by gas chromatography after the reaction was completed, and the selectivity and yield of glutaraldehyde were shown in table 5. The yield and selectivity of glutaraldehyde are defined as:
TABLE 1 reaction raw materials selected in the examples
TABLE 2 reaction conditions in the first oxidation reactor of each example
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 yields and selectivities obtained in the 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 invention have been described in detail, it will be understood by those skilled in the art that the invention is not limited thereto, and that various changes and modifications may be made without departing from the spirit of the invention, and the scope of the appended claims is to be accorded the full scope of the invention.
Claims (9)
1. A method for preparing glutaraldehyde by taking cyclopentene as a raw material comprises the following steps:
1) mixing cyclopentene, a solvent, a catalyst and hydrogen peroxide as raw materials, then feeding the mixture into a first oxidation reactor for pre-oxidation reaction, and oxidizing the cyclopentene into cyclopentane epoxide at the reaction temperature of 30-45 ℃ for 4-10 hours; wherein the dosage of the catalyst is 2.0-8.0 wt% 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 feeding the mixture into a second oxidation reactor for reaction, wherein the reaction temperature is 45-60 ℃, and the reaction time is 8-16 hours; wherein the dosage of the catalyst is 2.0-8.0 wt% of cyclopentene, and the feeding 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 feeding 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 materials to hydrogen peroxide is (5-10) to 1.
2. The method for preparing glutaraldehyde by using cyclopentene as a raw material according to claim 1, wherein: the catalyst in the step 1) is a W-SBA-15 mesoporous molecular sieve catalyst, and the mass fraction of WO3 is 20-25%.
3. The method for preparing glutaraldehyde by using cyclopentene as a raw material according to claim 1, wherein: the amount of the catalyst 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-butyl alcohol is 1: 4-8, the reaction temperature is 35-41 ℃, and the reaction time is 5-8 hours.
4. The method for preparing glutaraldehyde by using cyclopentene as a raw material according to claim 1, wherein: the catalyst in the step 2) is a W-SBA-15 mesoporous molecular sieve catalyst, and the mass fraction of WO3 is 15-20%.
5. The method for preparing glutaraldehyde by using cyclopentene as a raw material according to claim 1, wherein: the dosage of the catalyst in the step 2) is 3.0-6.0 wt% of cyclopentene, the feeding mass ratio of the materials to hydrogen peroxide is (6-8) to 1, the reaction temperature is 50-56 ℃, and the reaction time is 10-14 hours.
6. The method for preparing glutaraldehyde by using cyclopentene as a raw material according to claim 1, wherein: the catalyst in the step 3) is a W-SBA-15 mesoporous molecular sieve catalyst, and the mass fraction of WO3 is 10-15%.
7. The method for preparing glutaraldehyde by using cyclopentene as a raw material according to claim 1, wherein: the amount of the catalyst in the step 3) is 3.0-6.0 wt% of cyclopentene, the feeding mass ratio of the materials to hydrogen peroxide is (6-8) to 1, the reaction temperature is 50-56 ℃, and the reaction time is 5-8 hours.
8. The method for preparing glutaraldehyde by using cyclopentene as a raw material according to claim 1, wherein: the solvent in the steps 1), 2) and 3) is tert-butyl alcohol, tert-amyl alcohol or isopropanol.
9. The method for preparing glutaraldehyde by using 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%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011110335.0A CN114426468B (en) | 2020-10-16 | 2020-10-16 | Method for preparing glutaraldehyde by taking cyclopentene as raw material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011110335.0A CN114426468B (en) | 2020-10-16 | 2020-10-16 | Method for preparing glutaraldehyde by taking cyclopentene as raw material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114426468A true CN114426468A (en) | 2022-05-03 |
| CN114426468B CN114426468B (en) | 2024-05-28 |
Family
ID=81309683
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011110335.0A Active CN114426468B (en) | 2020-10-16 | 2020-10-16 | Method for preparing glutaraldehyde by taking cyclopentene as raw material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114426468B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116003236A (en) * | 2023-02-14 | 2023-04-25 | 山东京博石油化工有限公司 | Production method of glutaraldehyde |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4587057A (en) * | 1982-09-13 | 1986-05-06 | Nippon Oil Co., Ltd. | β-Hydroxycyclopentylperoxide compounds and the use thereof |
| CN1446631A (en) * | 2003-01-30 | 2003-10-08 | 复旦大学 | Molecular sieve catalyst containing pores in tungsten media utilized for synthesizing glutaraldehyde and its preparation method |
| CN1911889A (en) * | 2005-08-09 | 2007-02-14 | 中国石化上海石油化工股份有限公司 | Method of synthesizing glutaraldehyde by oxidation of cyclo amylene |
| CN101564686A (en) * | 2009-05-27 | 2009-10-28 | 广东工业大学 | Catalyst for oxidizing-synthesizing glutaric dialdehyde with cyclopentene and preparation method thereof |
| CN110372483A (en) * | 2019-07-17 | 2019-10-25 | 上海应用技术大学 | A kind of catalytic oxidation of cyclopentene prepares the process of glutaraldehyde |
-
2020
- 2020-10-16 CN CN202011110335.0A patent/CN114426468B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4587057A (en) * | 1982-09-13 | 1986-05-06 | Nippon Oil Co., Ltd. | β-Hydroxycyclopentylperoxide compounds and the use thereof |
| CN1446631A (en) * | 2003-01-30 | 2003-10-08 | 复旦大学 | Molecular sieve catalyst containing pores in tungsten media utilized for synthesizing glutaraldehyde and its preparation method |
| CN1911889A (en) * | 2005-08-09 | 2007-02-14 | 中国石化上海石油化工股份有限公司 | Method of synthesizing glutaraldehyde by oxidation of cyclo amylene |
| CN101564686A (en) * | 2009-05-27 | 2009-10-28 | 广东工业大学 | Catalyst for oxidizing-synthesizing glutaric dialdehyde with cyclopentene and preparation method thereof |
| CN110372483A (en) * | 2019-07-17 | 2019-10-25 | 上海应用技术大学 | A kind of catalytic oxidation of cyclopentene prepares the process of glutaraldehyde |
Non-Patent Citations (2)
| Title |
|---|
| 戴维林, 俞宏坤, 邓景发, 蒋安仁: "过氧化氢水溶液催化氧化环戊烯制备戊二醛机理研究", 化学学报, no. 02 * |
| 王建华, 丁文光, 周建平, 菅秀君: "环戊烯催化氧化合成戊二醛", 化工进展, no. 04, pages 259 - 261 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116003236A (en) * | 2023-02-14 | 2023-04-25 | 山东京博石油化工有限公司 | Production method of glutaraldehyde |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114426468B (en) | 2024-05-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110372483B (en) | Process method for preparing glutaraldehyde by catalytic oxidation of cyclopentene | |
| EP1072600B2 (en) | Process for the preparation of Epoxides | |
| CN114426468B (en) | Method for preparing glutaraldehyde by taking cyclopentene as raw material | |
| CN107602358B (en) | Method for preparing methoxy acetone by using micro-reaction device | |
| CN113603574B (en) | Method for catalyzing catalytic oxidation reaction of cyclopentene by using short-site silicotungstic heteropolyacid salt catalyst | |
| CN103212437A (en) | Method for preparing titanium-based catalyst and synthesizing epoxypropane and dicumyl peroxide | |
| CN111808054A (en) | Preparation method of ionic liquid and application of ionic liquid in cyclohexanone synthesis | |
| CN110498778B (en) | Method for preparing cyclohexene oxide by epoxidation of cyclohexene | |
| CN101279892B (en) | Method for preparing 1,2-cyclohexanediol by catalytic oxidation of cyclohexene | |
| JP2007533608A (en) | Method for preparing alkylene oxide | |
| CN113956150B (en) | Preparation method of glyceric acid | |
| KR20110101691A (en) | Improved method for producing catechol and hydroquinone from phenol and hydrogen peroxide | |
| CN115894194A (en) | Method for preparing glutaraldehyde by taking cyclopentane epoxide as raw material | |
| CN112480059A (en) | Method for directly synthesizing cyclic carbonate from olefin under catalysis of metalloporphyrin | |
| CN111004091A (en) | Method for preparing 4,4,5,5, 5-penta-fluoropentanol | |
| CN112574024A (en) | Method for preparing succinic acid | |
| CN101279957A (en) | Method for preparing epoxypropane by epoxidation of propene | |
| CN113908828B (en) | Bismuth molybdate catalyst for preparing cyclohexene oxide by cyclohexene epoxidation, and preparation method and application thereof | |
| KR102055927B1 (en) | Process for preparing acrolein | |
| CN118079896A (en) | Tungsten bismuth composite oxide catalyst, preparation and application | |
| CN112939766B (en) | Method for preparing glutaric acid | |
| CN114890966B (en) | Catalyst for limonene epoxidation reaction | |
| CN111253343B (en) | Method for preparing styrene oxide by using metal-free catalyst | |
| CN113952948A (en) | Molybdenum oxide catalyst for preparing cyclohexanediol by oxidizing cyclohexene and preparation method and application thereof | |
| CN118079946A (en) | Composite oxide supported catalyst, preparation and application thereof in preparing glutaraldehyde from cyclopentene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |