CN1021573C - Pentendial prodn. from cyclopentene by hydroperoxide single-step-method - Google Patents
Pentendial prodn. from cyclopentene by hydroperoxide single-step-method Download PDFInfo
- Publication number
- CN1021573C CN1021573C CN 89109401 CN89109401A CN1021573C CN 1021573 C CN1021573 C CN 1021573C CN 89109401 CN89109401 CN 89109401 CN 89109401 A CN89109401 A CN 89109401A CN 1021573 C CN1021573 C CN 1021573C
- Authority
- CN
- China
- Prior art keywords
- glutaraldehyde
- cyclopentene
- industrial
- hydrogen peroxide
- wolframic acid
- 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.)
- Expired - Fee Related
Links
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims abstract description 18
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 title claims abstract description 15
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 title claims abstract description 13
- NEOPYIBVKJWHMN-UHFFFAOYSA-N pent-2-enedial Chemical compound O=CCC=CC=O NEOPYIBVKJWHMN-UHFFFAOYSA-N 0.000 title description 2
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims abstract description 19
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims abstract description 14
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000007800 oxidant agent Substances 0.000 claims abstract description 9
- 230000001590 oxidative effect Effects 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 150000001941 cyclopentenes Chemical class 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 4
- GJEZBVHHZQAEDB-UHFFFAOYSA-N 6-oxabicyclo[3.1.0]hexane Chemical compound C1CCC2OC21 GJEZBVHHZQAEDB-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 10
- 239000003054 catalyst Substances 0.000 abstract description 6
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 abstract 1
- 230000003647 oxidation Effects 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- BHTJEPVNHUUIPV-UHFFFAOYSA-N pentanedial;hydrate Chemical compound O.O=CCCCC=O BHTJEPVNHUUIPV-UHFFFAOYSA-N 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- -1 phosphorus compound Chemical class 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 2
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000001143 conditioned effect Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- UDKYUQZDRMRDOR-UHFFFAOYSA-N tungsten Chemical compound [W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W] UDKYUQZDRMRDOR-UHFFFAOYSA-N 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention provides a new method for preparing glutaraldehyde from cyclopentene by one-step oxidization by using a water solution of industrial H2O2 as oxidant with industrial significance, which is characterized in that the method uses cyclopentadiene of industrial products as raw material, and the cyclopentadiene is prepared into cyclopentene by catalytic hydrogenation; the glutaraldehyde is obtained in one-step oxidization at a temperature between 30 and 40DEGC by using the water solution of industrial H2O2 as oxidant, tungstic acid as catalyst and tertiary butyl alcohol as solvent, and the yield is from 65 to 70%. Additionally, the method has the advantages of easy operation and low cost, and is suitable for industrialization.
Description
The invention belongs to a kind of method of producing glutaraldehyde.
The method of producing at present glutaraldehyde is to get by being hydrolyzed after methacrylaldehyde and the EVE condensation again.This method raw material sources difficulty, complicated operation, the glutaraldehyde cost that makes is higher.The someone sets about studying the C that uses cheapness in the world in recent years
5One of fraction cyclopentadiene through simple hydrogenation step, makes cyclopentene as raw material, produces glutaraldehyde by the cyclopentene oxidation step then, and a rear step is to utilize C
5Key, also be research emphasis.Produce glutaraldehyde by the cyclopentene oxidation step, what formed patent report has acetyl acetone catalytic oxidation (Ger.Offen.2,201,456), an acetyl acetone～B
2O
3Catalytic oxidation (Ger.Offen.2,252,674), tungstic acid～B
2O
3Catalytic oxidation (JP8295921) and molybdenum～phosphorus compound or molybdenum～tungsten～phosphorus compound catalytic oxidation (JP86289051).These method Main Problems are: (1) will react in anhydrous system, uses anhydrous H
2O
2Make oxidant; (2) yield is low, generally about 30%, and no industrial value.Have in the recent period report to make catalyst with molybdenum～tungsten～phospha polyacid, the glutaraldehyde yield reaches 61%(notes: as to the cyclopentene meter, yield is 20%), still in anhydrous system, react, use anhydrous H
2O
2Make oxidant (CHEN.LETT.1988(5), 877).Anhydrous hydrogen peroxide preparation difficulty costs an arm and a leg.
The purpose of this invention is to provide the method that a kind of cost is low, yield is high, technology is simply produced glutaraldehyde with industrial aqueous hydrogen peroxide solution oxidation step.
The method of producing glutaraldehyde that the present invention proposes is a raw material with the cyclopentenes behind the cyclopentadiene hydrogenating, and the trimethyl carbinol is a solvent, in the solution of cyclopentenes, add catalyzer, be dropping oxidizing agent under 30～40 ℃ of conditions in normal pressure, temperature then, stir, make glutaraldehyde.Wherein the solvent of Cai Yonging is the trimethyl carbinol, and the volume ratio of the cyclopentenes and the trimethyl carbinol is 1: 1～1: 10, is a phase to keep reaction system, helps the carrying out of oxidizing reaction.The catalyst that adopts is wolframic acid, and oxidant is the industrial hydrogen peroxide aqueous solution, about 6 hours reaction time.After reaction finishes, destroy the peroxide (peroxide wolframic acid) in the reactant liquor, and the filtering recovering catalyst wolframic acid.Process according to a conventional method filtrate, concentrate and decompression distillation, namely get 25% or 50% glutaraldehyde water solution product, yield 65～70%.
Present method selects for use wolframic acid to make catalyzer, and its amount ranges that comparatively is fit to is 1～20% of a cyclopentenes weight.
The industrial H of this method
2O
2The aqueous solution is made oxidant, the H that drips when reaction
2O
2It is comparatively suitable that the aqueous solution should make in the system concentration be not more than 4M, to avoid wolframic acid catalysis H
2O
2Decompose.Like this, take full advantage of H
2O
2The effect of cyclopentene oxide can make again reaction carry out under condition of normal pressure.H
2O
2The consumption of the aqueous solution is the stoichiometry that cyclopentene oxide becomes glutaraldehyde.
The present invention has been owing to selected wolframic acid to make catalyst, the restriction that becomes glutaraldehyde under anhydrous condition, to carry out from the cyclopentene oxidation step that has broken through that tradition is thought on the document, and also yield obviously improves, and makes method have industrial significance.
The inventive method is simple, easy to operate, and catalyst system therefor, oxygenant and solvent are the common industrial industrial chemicals, realizes industrialization easily.
Embodiment one
In 40 milliliters of tert-butyl alcohols (SILVER REAGENT) solution, add 0.25 gram wolframic acid and 3.09 gram cyclopentene (SILVER REAGENT), conditioned reaction temperature to 35 ℃, in 2 hours with 10 milliliters of 30%H
2O
2The aqueous solution dropwises, and constantly stirs.Stopped reaction after 6 hours destroys the superoxide in the reaction solution (peroxide wolframic acid), and removes by filter wolframic acid, boils off uncle's butyraldehyde, gets the glutaraldehyde dilute solution, and underpressure distillation more promptly gets 25% or 50% glutaraldehyde water solution product, yield 70.3%.
Embodiment two
The cyclopentenes that obtains behind hydrogenation with the cyclopentadiene of technical grade is a raw material, include a small amount of cyclopentadiene (＜%) and pentamethylene (＜3%).In 100 milliliters of t-butanol solvent, add 0.25 gram wolframic acid and 15 milliliters of these cyclopentene raw materials, conditioned reaction temperature to 35 ℃, in 2～3 hours with 40 milliliter 30% H
2O
2The aqueous solution dropwises, and constantly stirs.Finish until 6 hours afterreactions.Reaction solution is pressed embodiment one same treatment method to be handled.Get 25% or 50% glutaraldehyde water solution product, yield 69%.
Claims (3)
1, a kind of method of producing glutaraldehyde is a raw material with the cyclopentenes behind the cyclopentadiene hydrogenating, adds solvent, catalyzer, is dropping oxidizing agent under the 30-40 ℃ of condition in normal pressure, temperature then, stirs, and makes glutaraldehyde, it is characterized in that:
(1) oxidant that adopts is the industrial hydrogen peroxide aqueous solution;
(2) catalyzer is a wolframic acid;
(3) solvent is the tert-butyl alcohol, and consumption is 1-10 times of cyclopentene volume, to keep reaction system as a phase.
2, the method for producing glutaraldehyde according to claim 1 is characterized in that above-mentioned catalyzer wolframic acid consumption is the 1-20% of cyclopentenes weight.
3, the method for producing glutaraldehyde according to claim 1 is characterized in that in reaction process, and hydrogen peroxide concentration in reaction system is controlled at below the 4M, and the hydrogen peroxide consumption is the stoichiometry that cyclopentene oxide becomes glutaraldehyde.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 89109401 CN1021573C (en) | 1989-12-14 | 1989-12-14 | Pentendial prodn. from cyclopentene by hydroperoxide single-step-method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 89109401 CN1021573C (en) | 1989-12-14 | 1989-12-14 | Pentendial prodn. from cyclopentene by hydroperoxide single-step-method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1044454A CN1044454A (en) | 1990-08-08 |
| CN1021573C true CN1021573C (en) | 1993-07-14 |
Family
ID=4857991
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 89109401 Expired - Fee Related CN1021573C (en) | 1989-12-14 | 1989-12-14 | Pentendial prodn. from cyclopentene by hydroperoxide single-step-method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1021573C (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IN191721B (en) | 2000-01-28 | 2003-12-20 | Sumitomo Chemical Co | |
| CN1107666C (en) * | 2000-05-19 | 2003-05-07 | 中国科学院广州化学研究所 | Synthesis process of alpha, alpha-dihalogen pentaneldial, dihalogen acid and their derivative |
| CN1107664C (en) * | 2000-05-19 | 2003-05-07 | 中国科学院广州化学研究所 | Synthesis process of a compound |
| CN101792423B (en) * | 2010-03-25 | 2012-03-21 | 江苏大学 | Method for catalytically oxidizing cyclopentene |
| CN102603500A (en) * | 2011-11-07 | 2012-07-25 | 常州大学 | Method for preparing glutaraldehyde by utilizing microchannel reactor |
| 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 |
| 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 |
-
1989
- 1989-12-14 CN CN 89109401 patent/CN1021573C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1044454A (en) | 1990-08-08 |
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|---|---|---|---|
| C06 | Publication | ||
| C10 | Entry into substantive examination | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |