CN1560014A - Process for synthesizing amyl acid by catalyzing oxidizing amyl aldehyde of environmental pretection - Google Patents
Process for synthesizing amyl acid by catalyzing oxidizing amyl aldehyde of environmental pretection Download PDFInfo
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- CN1560014A CN1560014A CNA200410016887XA CN200410016887A CN1560014A CN 1560014 A CN1560014 A CN 1560014A CN A200410016887X A CNA200410016887X A CN A200410016887XA CN 200410016887 A CN200410016887 A CN 200410016887A CN 1560014 A CN1560014 A CN 1560014A
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- acid
- glutaraldehyde
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- hydrogen peroxide
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Abstract
The invention is a method of synthesizing glutaric acid by environmental catalytic oxidation of glutaraldehyde. It uses tungstenic acid as catalyst, uses 25%-50% of hydrogen peroxide water solution as oxidant at 60-100 deg.C, and making catalytic oxidization on glutaraldehyde to synthesize the glutaric acid. Its character: it uses glutaraldehyde commodity as raw material, and on relatively moderate conditions, the yield of glutaric acid can reach 97-98% and the purity >=99.0%. It provides a new glutaric acid preparing route able to be used in industrialized production. It is low-cost, and adopts hydrogen peroxide water solution as the oxidant, eliminates the environmental protection problem caused by traditional nitric acid oxidizing method, and implements the purpose of environmental catalytic oxidation process.
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 catalyzed oxidation glutaraldehyde 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.What part producer adopted at present is that raw material is serious owing to environmental pollution via the synthetic route of cyclopentanol or cyclopentanone nitric acid oxidation method with the pentamethylene, is difficult to be applied to large-scale commercial production.Consider that from the angle of protection environment the eco-friendly catalytic selective oxidation synthesizing glutaric acid of research and development method seems necessary.
The cyclopentenes route of our development in laboratory provides the industrialized route of cheap preparation glutaraldehyde, with this product is the problem that the raw material synthesizing glutaric acid has not only solved the exploitation of novel glutaraldehyde derived product, and a kind of industrial route of novel synthesizing glutaric acid cheaply is provided.If but be that oxygenant oxidation glutaraldehyde prepares pentanedioic acid with the concentrated nitric acid, there is the serious problem of environmental pollution equally.This patent has disclosed a kind of mild condition, environmental protection be the variation route of oxygenant oxidation glutaraldehyde synthesizing glutaric acid with the aqueous hydrogen peroxide solution, have significant industrial value.
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 catalyzed oxidation glutaraldehyde synthesizing glutaric acid.So that realize the large-scale industrial production of pentanedioic acid.
The method of catalyzed oxidation glutaraldehyde synthesizing glutaric acid provided by the invention, with the commodity glutaraldehyde is raw material, use wolframic acid, tungstophosphoric acid or the tungstosilicic acid of toxicological harmless to be catalyzer, aqueous hydrogen peroxide solution with 25%--50% is an oxygenant, direct catalyzed oxidation glutaraldehyde under 60～100 ℃, reacted 6～24 hours, the mol ratio of hydrogen peroxide and glutaraldehyde is 2～2.5.
Catalyzer generally is directly to add or adopt in-situ synthetic method directly to obtain in reaction system in when beginning reaction.Tungstic acid catalyst is mainly yellow wolframic acid H
2WO
4NH
2O, wherein, n=0～4.With H
2WO
42H
2O and H
2WO
43H
2O is for well.Original position obtains in reaction system also can to pass through equimolar sodium wolframate and strong acid (hydrochloric acid, nitric acid or sulfuric acid), and the pH value that importantly makes reaction back system is less than 3, preferably less than 2.The amount ranges of tungstic acid catalyst is 0.2～5% of a benchmark with raw material glutaraldehyde mole number.When tungstophosphoric acid and tungstosilicic acid or its hydrate were made catalyzer, amount ranges was 0.01～2% of a benchmark with raw material glutaraldehyde mole number.Certainly, also can use its heteropolyacid salt by obtaining tungstophosphoric acid or tungstosilicic acid catalyzer with strong acid (hydrochloric acid, nitric acid, phosphoric acid or sulfuric acid) original position in reaction system, same, importantly make the pH value of reacting the back system less than 3, preferably less than 2, but must be greater than 0.
The present invention's concentration is that the aqueous hydrogen peroxide solution of 25%--50% (as 27.5%, 30% or 50%) is an oxygenant, need not to use any organic solvent to make reaction medium.The mol ratio of hydrogen peroxide and glutaraldehyde is 2～2.5.
Detailed process of the present invention is: add the wolframic acid or the heteropoly acid containing tungsten catalyzer of calculated amount earlier, add the aqueous hydrogen peroxide solution of whole consumptions again, stirred under the room temperature 0.5～1 hour, make catalyst dissolution.Thereafter, stirring velocity rises to about 1000 ± 200R.P.M., begins to drip the aqueous solution that contains glutaraldehyde.By oil bath heating, control is bathed temperature and is risen to 100 ℃ since 60 ℃ about 3～4 hours, keeps reactant and refluxes 8～24 hours.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 the part pentanedioic acid through evaporation, and total yield of products can reach 90～98%, and purity surpasses 99%, and fusing point is 97～99 ℃.
Embodiment
The invention is further illustrated by the following examples.
Embodiment 1:
In 250 milliliter of three neck round-bottomed flask of stirring, reflux condensation mode and thermometer is housed, add 2.15 gram (7.5 mmole) wolframic acid dihydrate H respectively
2WO
42H
2O and concentration stirred 10 minutes PH ≈ 1 after being 27.5% hydrogen peroxide 83 milliliters (0.75 mole) under the room temperature.Stirring velocity rises to about 1000R.P.M. after dripping 50% aqueous solution that contains glutaraldehyde 30g (0.3 mole) again.By oil bath heating, control is bathed temperature and is risen to 100 ℃ since 60 ℃ about 3～4 hours, keeps reactant and refluxes.React sampling analysis after 8 hours.
Analytical results: pentanedioic acid, 98.6%; Succinic Acid, 1.0%; Other products 0.4%.The reaction mixture cooling, 0 ℃ of placement is spent the night, and filters.A small amount of cold wash once gets pentanedioic acid 31.7g (yield 80%).M.p.=97～99 ℃, purity (pressing GC analyzes) 〉=99.0%.Further evaporate residual filtrate, recyclable pentanedioic acid 7.2 grams.
Embodiment 2～4:
Two tungstic acid hydrate, wolframic acid, the consumption difference of three tungstic acid hydrate and four tungstic acid hydrate: 4.03g (15 mmole) and 1.27g (4.5 mmole), 0.19g (0.6 mmole).Adopt 0.8 mole 27.5%, 0.6 mole 30% respectively, and 0.9 mole 50% aqueous hydrogen peroxide solution is made oxygenant.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:
12-tungstophosphoric acid consumption is respectively 0.009g (0.003 mmole); (1.79g 0.6 mmole); 12-tungstosilicic acid consumption is respectively 0.009g (0.003 mmole); (1.79g 0.6 mmole).All adopt 0.6～0.75 mole 50% aqueous hydrogen peroxide solution to make oxygenant.In 8～24 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: tungstenic catalyst series catalyzed oxidation glutaraldehyde system pentanedioic acid performance is * relatively
| Embodiment | Catalyzer | Catalyst levels **??(mol％) | Reaction times (h) | Product is formed (%) | |||
| Superpolymer | Glutaraldehyde acid | Succinic Acid | Pentanedioic acid | ||||
| ??1 | ??H 2WO 4·2H 2O | ????2.5 | ????10 | ????0 | ????0.4 | ????1.0 | ????98.6 |
| ??2 | ??H 2WO 4 | ????5.0 | ????8 | ????0.2 | ????0 | ????0.9 | ????98.9 |
| ??3 | ??H 2WO 4·3H 2O | ????1.5 | ????18 | ????0 | ????0.6 | ????3.1 | ????96.3 |
| ??4 | ??H 2WO 4·4H 2O | ????0.2 | ????24 | ????1.0 | ????6.7 | ????3.3 | ????89.0 |
| ??5 | ??H 3PW 12O 40· ????6H 2O | ????0.01 | ????24 | ????5.0 | ????5.2 | ????2.5 | ????87.3 |
| ??6 | ??H 3PW 12O 40· ????6H 2O | ????2.0 | ????16 | ????0.3 | ????0.1 | ????2.8 | ????96.8 |
| ??7 | ??H 4SiW 12O 40· ????6H 2O | ????0.01 | ????24 | ????2.0 | ????6.3 | ????3.0 | ????88.7 |
| ??8 | ??H 4SiW 12O 40· ????6H 2O | ????2.0 | ????14 | ????2.5 | ????0.2 | ????4.3 | ????93.0 |
*Glutaraldehyde 30g (300 mmole), 0.6～0.75 mole of 27.5%, 30% or 50% aqueous hydrogen peroxide solution (in pure hydrogen peroxide, embodiment 1～4 is adopted 0.6 mole, embodiment 5～8 is adopted 0.75 mole), 60 ℃～100 ℃ reflux temperature reactions.
*Catalyst levels is by the glutaraldehyde molecular fraction.
Claims (8)
1, a kind of environmental friendliness catalyzed oxidation glutaraldehyde prepares the method for pentanedioic acid, it is characterized in that with wolframic acid, tungstophosphoric acid or tungstosilicic acid are catalyzer, aqueous hydrogen peroxide solution with 25%--50% is an oxygenant, 60～100 ℃ of catalyzed oxidation glutaraldehyde, reacted 6～24 hours, the mol ratio of hydrogen peroxide and glutaraldehyde is between 2～2.5.
2, by the described method of claim 1, it is characterized in that the tungstic acid catalyst structure of using is H
2WO
4NH
2O, wherein n=0～4.
3, by the described method of claim 1, it is characterized in that the tungstophosphoric acid catalyst structure of using is H
3PW
12O
40NH
2O, wherein n=2～10.
4, by the described method of claim 1, it is characterized in that the tungstosilicic acid catalyst structure that uses is H
4SiW
12O
40NH
2O, wherein n=2～10.
5,, it is characterized in that tungstic acid catalyst adopts sodium wolframate and hydrochloric acid original position under reaction conditions synthetic by the described method of claim 1.
6, by the described method of claim 1, it is characterized in that the amount ranges of tungstic acid catalyst is 0.2～5% of a benchmark with raw material glutaraldehyde mole number.
7, by the described method of claim 1, it is characterized in that the amount ranges of tungstophosphoric acid catalyst is 0.01～2% of a benchmark with raw material glutaraldehyde mole number.
8, by the described method of claim 1, it is characterized in that tungstosilicic acid catalyst consumption scope is 0.01～2% of a benchmark with raw material glutaraldehyde mole number.
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| CN 200410016887 CN1238328C (en) | 2004-03-11 | 2004-03-11 | Process for synthesizing amyl acid by catalyzing oxidizing amyl aldehyde of environmental pretection |
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|---|---|---|---|
| CN 200410016887 CN1238328C (en) | 2004-03-11 | 2004-03-11 | Process for synthesizing amyl acid by catalyzing oxidizing amyl aldehyde of environmental pretection |
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| CN1560014A true CN1560014A (en) | 2005-01-05 |
| CN1238328C CN1238328C (en) | 2006-01-25 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101570479B (en) * | 2009-06-15 | 2013-04-03 | 上海华谊丙烯酸有限公司 | Method for preparing glutaric acid through oxidation of glutaral pentanedial |
| CN103450004A (en) * | 2013-08-13 | 2013-12-18 | 复旦大学 | Environment-friendly high-efficiency method for synthesizing adipic acid by catalytically oxidating adipic dialdehyde |
| CN107353314A (en) * | 2016-05-10 | 2017-11-17 | 江苏福锌雨医药科技有限公司 | A kind of synthetic method of 5- deoxidations-L-arabinose |
| 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 |
-
2004
- 2004-03-11 CN CN 200410016887 patent/CN1238328C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101570479B (en) * | 2009-06-15 | 2013-04-03 | 上海华谊丙烯酸有限公司 | Method for preparing glutaric acid through oxidation of glutaral pentanedial |
| CN103450004A (en) * | 2013-08-13 | 2013-12-18 | 复旦大学 | Environment-friendly high-efficiency method for synthesizing adipic acid by catalytically oxidating adipic dialdehyde |
| CN107353314A (en) * | 2016-05-10 | 2017-11-17 | 江苏福锌雨医药科技有限公司 | A kind of synthetic method of 5- deoxidations-L-arabinose |
| 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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| Publication number | Publication date |
|---|---|
| CN1238328C (en) | 2006-01-25 |
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