CN1903823A - Method of large scale synthesizing glutaric acid by environment friendly catalyzing and oxidizing cyclopentene - Google Patents
Method of large scale synthesizing glutaric acid by environment friendly catalyzing and oxidizing cyclopentene Download PDFInfo
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- CN1903823A CN1903823A CN 200610029713 CN200610029713A CN1903823A CN 1903823 A CN1903823 A CN 1903823A CN 200610029713 CN200610029713 CN 200610029713 CN 200610029713 A CN200610029713 A CN 200610029713A CN 1903823 A CN1903823 A CN 1903823A
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Abstract
The present invention relates to a large-scale industrial production method for synthesizing pentandioic acid by using catalyst friendly to environment to catalytically oxidate cyclopentene. It is characterized by that it uses tungstic acid as catalyst, uses chelate organic ligand as cocatalyst, under the condition of 46-110deg.C uses hydrogen peroxide aqueous solution as oxidant to catalytically oxidate cyclopentene so as to synthesize pentandioic acid. Its yield can be up to 93-95% and its purity is greater than or equal to 99.0%.
Description
Technical field
The invention belongs to chemical technology field, be specifically related to a kind of eco-friendly method of utilizing aqueous hydrogen peroxide solution catalytically oxidizing cyclopentene heavy industrialization to prepare pentanedioic acid.
Background technology
Pentanedioic acid is extremely important industrial chemicals, has at aspects such as chemistry, building, medicine, agriculturals widely to use.In plastics industry, pentanedioic acid and glutaric acid alky ester class thereof also can be used as the composition of the polyester plasticizer of polyvinyl chloride as the intermediate of softening agent such as polyvinyl chloride, polyester, polymeric amide.Polyester glutarate has the weather resistance plastification as softening agent, is used for the manufacturing of polyvinyl chloride.Aspect medical,, be used to prepare each sterilization and disinfection washing lotion and medicine because it has broad-spectrum bactericidal capacity.Pentanedioic acid not only has killing action to the bacterium on the zooparasite bodily tissue, to planting disease and pest also is agent for killing preferably, as being raw material with the pentanedioic acid, kill the virus washing lotion and sterilization foam and other killing agents that are mixed with, can kill the bacterium that parasitizes on animal, the plant, insect etc., also can be used for insect protected.In addition, pentanedioic acid also can be used for the synthesizing liquid polyester, the molecular structure of improvement PET fiber, thus the dyeability of improvement ET fiber improves dye uptake.Utilize tackiness agent that pentanedioic acid makes can extensive bonding textiles, metal etc.In addition, pentanedioic acid or its ester also can be used for the washing of stack gases such as the preparation of synthetic, scale remover of polyester polyol and sulfur-bearing etc.
Pentanedioic acid generally obtains by separating among the byproduct dicarboxylic acid mixture in the hexanodioic acid production process.Because the improvement of adipic acid, the pentanedioic acid of its by-product is fewer and feweri.Therefore, press for the route of synthesis of development of new pentanedioic acid.Traditional cyclopentanol or cyclopentanone nitric acid oxidation method generally are not used further to large-scale commercial production because environmental pollution is serious.Consider that from the angle of protection environment the eco-friendly catalytic selective oxidation synthesizing glutaric acid of research and development method seems necessary.
Recently, people such as K.Sato report (Science 1998,281 (5383), 1646) is at consisting of phase-transferring agent tricaprylmethylammonium hydrosulfate [(n-C
8H
17)
3N (CH
3)] HSO
4When existing, with Na
2WO
42H
2O is a catalyzer, and under the condition of organic solvent-free, the yield of the hydrogen peroxide oxidation cyclopentenes with 30% reaches about 90%.Can directly obtain the highly purified pentanedioic acid of 80% yield after the reaction mixture cooling.Yet tricaprylmethylammonium hydrosulfate price is very expensive, and suitability for industrialized production both at home and abroad all is unrealized.The more important thing is that quaternary ammonium salt has certain toxicity, thereby also can pollute.The Chinese patent (CN 1087012C) that people such as Deng Youquan disclose has been introduced a kind of cleaning method that is prepared hexanodioic acid by the tetrahydrobenzene catalyzed oxidation, because this method only has laboratory scale lab scale data (consumption of tetrahydrobenzene only is about 25 grams), and the hydrogen peroxide concentration that uses is 30%, the hydrogen peroxide of not test (N.T.) greater concn.And when this condition is used for making pentanedioic acid by cyclopentenes, pentanedioic acid yield not high (having only 80%), and when reaction owing to be at first to add hydrogen peroxide, add cyclopentenes then, the material spray accident promptly often takes place in the extremely difficult control of temperature of reaction under the condition of 25 gram magnitudes.More massive experiment in addition cause the blast.Therefore, for safety factors, in fact this method does not have IP prospecting.
Summary of the invention
The object of the present invention is to provide the method for a kind of more environmental friendliness, efficient and practical catalytically oxidizing cyclopentene large-scale industry synthesizing glutaric acid.
The method of the catalytically oxidizing cyclopentene large scale synthesizing glutaric acid that the present invention proposes, the wolframic acid that is to use toxicological harmless is a catalyzer, chelating class organic ligand is a promotor, with concentration is that the aqueous hydrogen peroxide solution of 30%-70% is an oxygenant, catalytically oxidizing cyclopentene in 46-100 ℃ of scope, reacted 24-48 hour, and made pentanedioic acid; Wherein, the molar ratio of hydrogen peroxide and cyclopentenes is 4-5, and catalyst levels is the 02-5% of cyclopentenes mole number, and the mol ratio of catalyzer and promotor is 0.1-2.
The maximum characteristics of composite catalyst involved in the present invention are that the negatively charged ion catalytic center contains chelating class organic ligand, thereby make catalytic active center when having oxidation susceptibility, have certain oleophylic performance again.Therefore make the oxidation and the hydrolysis reaction that occur in the two-phase system in the water be easy to carry out, and no longer need to use the quaternary ammonium salt, the quaternary alkylphosphonium salt that cost an arm and a leg and might produce environmental pollution to make consisting of phase-transferring agent, acquisition pentanedioic acid that simultaneously can high yield.
The catalyzer that the present invention uses generally is that original position is synthetic when the reaction beginning.Main raw material is yellow wolframic acid H
2WO
4NH
2O, wherein, n=1,2,3,4.With H
2WO
42H
2O and H
2WO
43H
2O is for well.The amount ranges of tungstic acid catalyst is for being 0.2～5% of benchmark with raw material cyclopentenes mole number.
The present invention especially usable concentration is that the aqueous hydrogen peroxide solution of 35%-70% (as 35%, 50%, 70%) is an oxygenant, does not re-use any organic solvent and makes reaction medium.The mol ratio of hydrogen peroxide and cyclopentenes is 4～5.
Among the present invention, used promotor can be oxalic acid, Succinic Acid or tartrate, perhaps is nicotinic acid or pyridine-2,6 dicarboxylic acid, perhaps is oxine or 2-hydroxyquinoline, perhaps is Whitfield's ointment.The mol ratio of catalyzer and promotor consumption is 0.1-2.
The more excellent step that pentanedioic acid is made in large-scale industry is: add the tungstic acid catalyst of calculated amount earlier, add the cyclopentenes of whole consumptions again, stir under the room temperature, add the organic ligand promotor then, under the room temperature restir 20-40 minute; Thereafter, begin to drip aqueous hydrogen peroxide solution, by steam heat supply and chuck cooling water temperature, control still temperature rises to 70 ℃ gradually since 46 ℃ at 6～16 hours, keeps reaction mass and refluxes 12～24 hours; After treating that cyclopentenes runs out of, temperature is elevated to 90～110 ℃, reacted again 6-8 hour; Reacted liquid is cooled off down and places and spend the night in putting 0 ℃, separate out crystal in the process.Leach crystallization,, directly obtain the white crystals product through washing, drying.Remaining filtrate can further be obtained pentanedioic acid through evaporation, and total yield of products can reach 90～95%, and fusing point is 97～99 ℃.
The method that the present invention discloses not only can be used 30% hydrogen peroxide, even can use 35%, 50% and 70% hydrogen peroxide, through the large-scale industry test, do not find any potential safety hazard, and pentanedioic acid yield very high (more than 95%), the industrial Succinic Acid that produces of not wishing does not appear, purify through simple, can sell, have higher prospects for commercial application.In addition, the present invention finds also that in test the hydrogen peroxide of use high density is product yield height not only, the purity height, and also the rate of utilization of production equipment is also high, greatly reduces the equipment use cost, has improved throughput.This is because when preparing diacid by the cycloolefin oxidation, one mole alkene need consume 4 moles hydrogen peroxide, consider the decomposition and consumption of hydrogen peroxide, the actual amount of using is also bigger, if use 30% hydrogen peroxide, to one 5 tons reactor, the actual cyclopentenes that can only bear 600 kilograms; And use 50% hydrogen peroxide instead, then can bear 900 kilograms cyclopentenes; Use 70% hydrogen peroxide instead, then can bear 1200 kilograms cyclopentenes.
The present invention can be under relatively mild condition, 500 kilograms of the cyclopentenes of once can feeding intake, and obtaining pentanedioic acid is 910 kilograms.The pentanedioic acid yield can reach 93～95%, purity 〉=99.0%.This method provides a kind of novel pentanedioic acid that can be used for large-scale industrial production to prepare route, has realized the purpose of environmental friendliness catalytic conversion process simultaneously.
Embodiment
The invention is further illustrated by the following examples.
Embodiment 1:
In 5000 liters of enamel reaction stills of stirring, reflux condensation mode and thermometer are housed, add 52.7 kilograms of wolframic acid dihydrate H respectively
2WO
42H
2O and 500 kilograms of cyclopentenes stirred 30 minutes under the room temperature, added 23.2 kilograms of oxalic acid (C
4H
2O
42H
2O), continue to stir 30 minutes, drip 2200 kilogram of 50% hydrogen peroxide again.By the cooling of steam-heated cal(l)andria and chuck, control still temperature rises to 70 ℃ since 46 ℃ about 6～16 hours, keep reactant and refluxed 12～24 hours, treat that cyclopentenes runs out of after, temperature is elevated to 90～110 ℃.React sampling analysis after 6-8 hour again.
Analytical results: pentanedioic acid, 94.8%; 1,2-encircles pentanediol, 0.4%; Glutaraldehyde, 2.1%; Other is 2.7% years old.The reaction mixture distillation concentrates postcooling, and 0 ℃ of placement is spent the night, and filters.A small amount of cold wash once gets 776 kilograms of pentanedioic acids (yield 80%).M.p.=97～99 ℃, purity (pressing GC analyzes) 〉=99.0%.Further the evaporation residual filtrate can continue to obtain 145 kilograms of pentanedioic acids.
Embodiment 2～4:
One tungstic acid hydrate, the consumption difference of three tungstic acid hydrate and four tungstic acid hydrate: 42.2 kilograms and 31.6 kilograms; Corresponding oxalic acid add-on: 18.6 kilograms, 13.9 kilograms; 14.0 kilogram.Other feeding quantity, operating process and time are all with embodiment 1.Reaction is finished post analysis and be the results are shown in subordinate list 1.
Embodiment 5～8:
Two tungstic acid hydrate consumptions are respectively 4.2 kilograms; 8.4 kilogram; 84 kilograms; 105 kg.
The organic ligand promotor is respectively:
Oxalic acid: 1.9 kilograms
Nicotinic acid: 41 kilograms
Oxine: 21.8 kilograms
Whitfield's ointment: 5.4 kilograms
In 24 hours reaction times, other feeding quantity, operating process are all with implementation example 1.Reaction is finished post analysis and be the results are shown in subordinate list 1.
Table 1: wolframic acid-different organic ligand promotor catalytically oxidizing cyclopentene system pentanedioic acid performances relatively
*
| Embodiment | Organic ligand promotor and consumption (with the wolframic acid mol ratio) | The tungstic acid catalyst consumption ** (mol％) | Reaction times (h) | Product is formed (%) | ||||
| Cyclopentanone | 1,2-encircles pentanediol | Glutaraldehyde | Other *** | Pentanedioic acid | ||||
| 1 | Oxalic acid (1: 1) | 2.5 | 24 | 0 | 0.4 | 2.1 | 2.7 | 94.8 |
| 2 | Oxalic acid (1: 1) | 2.0 | 24 | 0.1 | 0.7 | 1.9 | 2.8 | 94.5 |
| 3 | Oxalic acid (1: 1) | 1.5 | 24 | 0.1 | 2.6 | 3.3 | 2.0 | 92.0 |
| 4 | Oxalic acid (1: 1) | 1.5 | 36 | 0.2 | 1.7 | 0.1 | 3.0 | 95.0 |
| 5 | Oxalic acid (1: 1) | 0.2 | 48 | 0.3 | 2.2 | 0.5 | 9.7 | 87.3 |
| 6 | Nicotinic acid (2: 1) | 0.4 | 48 | 0.7 | 0.7 | 0.2 | 16.6 | 81.8 |
| 7 | 8. hydroxyquinoline (0.5: 1) | 4.0 | 40 | 0.4 | 0.3 | 2.0 | 2.6 | 94.7 |
| 8 | Whitfield's ointment (0.2: 1) | 5.0 | 36 | 0 | 0.7 | 1.0 | 3.3 | 95.0 |
*500 kilograms of cyclopentenes, 1100 kilograms of 35%, 50% or 70% aqueous hydrogen peroxide solutions (in pure hydrogen peroxide), 46 ℃～110 ℃ reflux temperature reactions.
*Catalyst levels is by the cyclopentenes molecular fraction, and the ratio of organic ligand promotor and wolframic acid is in mole.
* *Other products comprise cyclopentenone, oxalic acid, cyclopentanol etc.
Claims (4)
1, a kind of method of large scale synthesizing glutaric acid by environment friendly catalyzing and oxidizing cyclopentene, it is characterized in that with the wolframic acid being catalyzer, chelating class organic ligand is a promotor, with weight concentration is that 30～70% aqueous hydrogen peroxide solution is an oxygenant, at 46～100 ℃ of catalytically oxidizing cyclopentenes, reacted 24～48 hours, and made pentanedioic acid; Wherein, the molar ratio of hydrogen peroxide and cyclopentenes is 4～5, and the consumption of tungstic acid catalyst is for being 0.2～5% of benchmark with raw material cyclopentenes mole number, and the mol ratio of wolframic acid and chelating class organic ligand catalyzer is 0.1～2.
2, method according to claim 1 is characterized in that the tungstic acid catalyst structure of using is H
2WO
4NH
2O, n=1 wherein, 2,3,4.
3, method according to claim 1 is characterized in that described promotor is oxalic acid or Succinic Acid or tartrate, perhaps is nicotinic acid or pyridine-2,6 dicarboxylic acid, perhaps is oxine or 2-hydroxyquinoline, perhaps is Whitfield's ointment.
4, method according to claim 1 is characterized in that adding earlier the tungstic acid catalyst of calculated amount, adds the cyclopentenes of whole consumptions again, stirs under the room temperature, adds the organic ligand promotor then, under the room temperature restir 20-40 minute; Thereafter, begin to drip aqueous hydrogen peroxide solution, by steam heat supply and chuck cooling water temperature, control still temperature rises to 70 ℃ gradually since 46 ℃ at 6～16 hours, keeps reaction mass and refluxes 12～24 hours; After treating that cyclopentenes runs out of, temperature is elevated to 90～110 ℃, reacted again 6-8 hour; Reacted liquid is cooled off down in putting 0 ℃, and place and spend the night, separate out crystal in the process, be required pentanedioic acid product.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101696162A (en) * | 2009-10-30 | 2010-04-21 | 华南理工大学 | Method for preparing glutaric acid from dimethyl glutarate |
| CN107537564A (en) * | 2016-06-24 | 2018-01-05 | 中国科学院大连化学物理研究所 | Han quaternary alkylphosphonium salts phosphorus part Porous-Organic copolymer heterogeneous catalyst and its preparation and application |
| CN108355703A (en) * | 2018-02-09 | 2018-08-03 | 青岛科技大学 | A kind of glutaraldehyde oxidation functional mesoporous molecular sieve catalyst of glutaric acid tungstenic processed and preparation method thereof |
-
2006
- 2006-08-03 CN CN 200610029713 patent/CN1903823A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101696162A (en) * | 2009-10-30 | 2010-04-21 | 华南理工大学 | Method for preparing glutaric acid from dimethyl glutarate |
| CN101696162B (en) * | 2009-10-30 | 2013-01-02 | 华南理工大学 | Method for preparing glutaric acid from dimethyl glutarate |
| CN107537564A (en) * | 2016-06-24 | 2018-01-05 | 中国科学院大连化学物理研究所 | Han quaternary alkylphosphonium salts phosphorus part Porous-Organic copolymer heterogeneous catalyst and its preparation and application |
| CN107537564B (en) * | 2016-06-24 | 2020-04-07 | 中国科学院大连化学物理研究所 | Heterogeneous catalyst containing quaternary phosphonium salt-phosphorus ligand organic porous copolymer and preparation and application thereof |
| CN108355703A (en) * | 2018-02-09 | 2018-08-03 | 青岛科技大学 | A kind of glutaraldehyde oxidation functional mesoporous molecular sieve catalyst of glutaric acid tungstenic processed and preparation method thereof |
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