CN102701944A - Method for preparing 2-ethyl hexanoic acid by catalytically oxidizing 2-ethylhexanal by molybdovanadophosphoric acid - Google Patents
Method for preparing 2-ethyl hexanoic acid by catalytically oxidizing 2-ethylhexanal by molybdovanadophosphoric acid Download PDFInfo
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- CN102701944A CN102701944A CN2012101973926A CN201210197392A CN102701944A CN 102701944 A CN102701944 A CN 102701944A CN 2012101973926 A CN2012101973926 A CN 2012101973926A CN 201210197392 A CN201210197392 A CN 201210197392A CN 102701944 A CN102701944 A CN 102701944A
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Abstract
The invention discloses a method for preparing 2-ethyl hexanoic acid by catalytically oxidizing 2-ethylhexanal by molybdovanadophosphoric acid, and relates to a method for preparing a chemical preparation. The method comprises the following steps: weighing molybdovanadophosphoric acid and dissolving the molybdovanadophosphoric acid in distilled water at first and then in hydrochloric acid to prepare a catalyst solution; adding 2-ethylhexanal and the prepared catalyst in an ordinary-pressure reaction device, slowly heating and stirring the mixture, regulating oxygen flux, and starting to introduce oxygen when the temperature rises to the reaction temperature; after the reaction is ended, separating out the aqueous phase solution on the lower layer to obtain organic phase matter on the upper layer; and depressurizing and distilling the organic phase matter to obtain colorless transparent and pungent oily liquid, 2-ethyl hexanoic acid. By changing the ratio of molybdenum to vanadium of the catalyst and optimizing the reaction condition, the conversion rate of the 2-ethylhexanal reaches above 99%, and the selection and yield of the 2-ethyl hexanoic acid reach above 98% respectively.
Description
Technical field
The present invention relates to a kind of preparation method of chemicals, particularly relate to the method that a kind of phosphorus molybdenum vanadium heteropolyacid catalyzed oxidation 2-ethyl hexanal prepares 2 ethyl hexanoic acid.
Background technology
The phosphorus molybdenum vanadium heteropolyacid of preparation has the Keggin structure, and unique stable molecular structure is arranged, and is easy on molecular level, design its characteristics acid and oxidation susceptibility of controlling.Preparing 2 ethyl hexanoic acid with phosphorus molybdenum vanadium heteropolyacid catalytic air oxidation 2-ethyl hexanal does not appear in the newspapers at present.As catalyzer, under certain reaction temperature and certain empty (oxygen) airshed, be used for atmospheric oxidation 2-ethyl hexanal preparation feedback with phosphorus molybdenum vanadium heteropolyacid, the transformation efficiency of 2-ethyl hexanal preferably can reach more than 96%, and the selectivity of 2 ethyl hexanoic acid preferably reaches 99%.Prepare 2 ethyl hexanoic acid with phosphorus molybdenum vanadium heteropolyacid catalyzed oxidation 2-ethyl hexanal, catalyst activity is high, consumption is little, reusable, compares transformation efficiency, gain in yield 10-15% with potassium permanganate, nitric acid etc., and does not corrode conversion unit.This preparation method, reaction conditions is gentle, easy and simple to handle, and reduces three-waste pollution.
Summary of the invention
The object of the present invention is to provide a kind of phosphorus molybdenum vanadium heteropolyacid catalyzed oxidation 2-ethyl hexanal to prepare the method for 2 ethyl hexanoic acid.Acidity and oxidisability performance through modulation vanadium atom ratio control catalyzer; The phosphorus molybdenum vanadium heteropolyacid catalyzer of the high catalytic activity that obtains; Have that catalyst levels is little, reaction conditions is gentle, easy and simple to handle, catalyzer is reusable, and equipment is not had characteristics such as corrosion.
The objective of the invention is to realize through following technical scheme:
Phosphorus molybdenum vanadium heteropolyacid catalyzed oxidation 2-ethyl hexanal prepares the method for 2 ethyl hexanoic acid, and said method comprises following process:
Take by weighing phosphorus molybdenum vanadium heteropolyacid, be dissolved in the zero(ppm) water, be dissolved in again and be mixed with catalyst solution in the hydrochloric acid, in the synthesis under normal pressure device; The catalyzer that adds the 2-ethyl hexanal and configure slowly heats up, stirs, and regulates oxygen flow; When temperature rises to temperature of reaction, begin aerating oxygen, reaction is isolated lower floor's aqueous phase solution after finishing; Obtain the organic phase material on upper strata, this organic phase material is carried out underpressure distillation, obtain the oily liquids that water white transparency has irritating smell---2 ethyl hexanoic acid.
Described phosphorus molybdenum vanadium heteropolyacid catalyzed oxidation 2-ethyl hexanal prepares the method for 2 ethyl hexanoic acid; Its said catalyzer for preparing 2 ethyl hexanoic acid with phosphorus molybdenum vanadium heteropolyacid as catalyzed oxidation 2-ethyl hexanal; And changing vanadium atom ratio control acidity of catalyst and oxidisability performance, expression formula is: H
3+nPMo
12-nV
nO
40XH
2O, 0.5≤n in the formula≤6,3≤x≤40.
Described phosphorus molybdenum vanadium heteropolyacid catalyzed oxidation 2-ethyl hexanal prepares the method for 2 ethyl hexanoic acid, and it prepares phosphorus molybdenum vanadium heteropolyacid: take by weighing molybdate, phosphoric acid salt and metavanadate by stoichiometric ratio, be dissolved in respectively in the deionized water; Aqueous phosphate solution is placed 80 ℃ water bath with thermostatic control, stir, then molybdate solution is slowly joined in the aqueous phosphate solution, in mixing solutions, slowly drip vitriol oil acidifying again, become faint yellow up to solution; Metavanadate solution is added in the mixing solutions that sulfuric acid acidation crosses, continue to drip the vitriol oil, become transparent orange-red solution, stop heating and stir, be cooled to room temperature until solution; At last, add ether, fully after the vibration, standing demix is told the orange-red oily solution of lower floor, steam ether after, promptly get orange red Powdered phosphorus molybdenum vanadium heteropolyacid.
Described phosphorus molybdenum vanadium heteropolyacid catalyzed oxidation 2-ethyl hexanal prepares the method for 2 ethyl hexanoic acid, and it prepares phosphorus molybdenum vanadium heteropolyacid: change the amount of metavanadate solution, prepare the phosphorus molybdenum vanadium heteropolyacid of different molybdenum vanadium ratios.
Described phosphorus molybdenum vanadium heteropolyacid catalyzed oxidation 2-ethyl hexanal prepares the method for 2 ethyl hexanoic acid, and its used molybdate is water-soluble molybdates such as ammonium, basic metal, magnesium, and metavanadate is water-soluble metavanadates such as sodium, potassium; And through adding metavanadate change molybdenum vanadium than changing acidity of catalyst and oxidisability performance.
Described phosphorus molybdenum vanadium heteropolyacid catalyzed oxidation 2-ethyl hexanal prepares the method for 2 ethyl hexanoic acid; Its catalyst system therefor is a phosphorus molybdenum vanadium heteropolyacid; Utilize deionized water and hydrochloric acid preparation catalyst solution, the amount of substance concentration of preparation catalyzer is 0.5-8mol/L, is preferably 2-5 mol/L; The massfraction of catalyzer is preferably in the 2-4% scope in the 1-10% scope; Range of reaction temperature is 40-120 ℃, is preferably in 50-70 ℃; Oxygen flow is 0-20mL/s, is preferably in 4-10mL/s; Reaction times is 2-8h, is preferably 4-6h.
Advantage of the present invention and effect are:
1. the present invention provides the phosphorus molybdenum vanadium heteropolyacid H of certain vanadium atom ratio
3+nPMo
12-nV
nO
40XH
2O, this heteropolyacid stable chemical performance and the good thermostability of tool, its acidity and oxidisability performance can transform through control vanadium atom ratio each other, have excellent catalytic activity to made 2 ethyl hexanoic acid by the oxidation of 2-ethyl hexanal.The phosphorus molybdenum vanadium heteropolyacid catalyzer that this invention provides reaches the preparation method who is made 2 ethyl hexanoic acid by the atmospheric oxidation of 2-ethyl hexanal, only needs under the reaction conditions of gentleness, can accomplish with simple technology, and in building-up process, has reduced three-waste pollution.
2. the present invention utilizes the phosphorus molybdenum vanadium heteropolyacid catalyzed oxidation 2-ethyl hexanal of suitable molybdenum vanadium ratio to prepare the preparation method of 2 ethyl hexanoic acid.Phosphorus molybdenum vanadium heteropolyacid solid catalyst H
3+nPMo
12-nV
nO
40XH
2O, the transformation efficiency of catalyzed oxidation 2-ethyl hexanal is high, selectivity is good, the 2 ethyl hexanoic acid productive rate is high.And through modulation vanadium atom ratio control acidity of catalyst and oxidisability performance, improve the selectivity and the productive rate of 2 ethyl hexanoic acid, obtain best catalytic effect, can reduce the production cost of 2 ethyl hexanoic acid.This flow preparation 2 ethyl hexanoic acid, reaction conditions is gentle, easy and simple to handle.
Description of drawings
Fig. 1 is catalyst system therefor phosphorus molybdenum vanadium heteropolyacid H of the present invention
4PMo
11VO
4032H
2The x-ray diffraction pattern of O;
Fig. 2 is catalyst system therefor phosphorus molybdenum vanadium heteropolyacid H of the present invention
4PMo
11VO
4032H
2The infrared spectrum of O;
Fig. 3 is the infrared spectrum of gained 2 ethyl hexanoic acid of the present invention.
Annotate: Fig. 1-Fig. 3 of the present invention is the analysis synoptic diagram of product state, figure Chinese words or the unintelligible understanding that does not influence technical scheme of the present invention of image.
Embodiment
Below in conjunction with embodiment the present invention is elaborated.
Fig. 1 is for taking by weighing the 20.00g Sodium orthomolybdate, 6.00g Sodium phosphate, dibasic, 1.85g sodium metavanadate, and disodium phosphate soln placed 80 ℃ water bath with thermostatic control, the H that makes by preceding method
4PMo
11VO
4032H
2The x-ray diffraction pattern of O catalyzer.
Fig. 2 is H
4PMo
11VO
4032H
2The O infrared spectrum.
Fig. 3 is for using H
4PMo
11VO
4032H
2O catalyzed oxidation 2-ethyl hexanal, temperature of reaction is 60 ℃, and the massfraction of catalyzer is 3%, is solvent with the dilute hydrochloric acid solution, and its amount of substance concentration is 2mol/L, and oxygen flow is 5mL/s, the reaction times is 5h, the infrared spectrum of the 2 ethyl hexanoic acid that makes.
Embodiment one: take by weighing the 20.00g Sodium orthomolybdate, the 6.00g Sodium phosphate, dibasic, the 1.85g sodium metavanadate is dissolved in the deionized water respectively.Disodium phosphate soln is placed 80 ℃ water bath with thermostatic control, then sodium molybdate solution is slowly joined in the disodium phosphate soln, in mixing solutions, slowly drip vitriol oil acidifying again, become faint yellow up to solution.Sodium metavanadate solution is added in the mixing solutions that sulfuric acid acidation crosses, under vigorous stirring, continue to drip the vitriol oil, become transparent orange-red solution until solution.Stop heating and stir, the mixing solutions of three kinds of solution is cooled to room temperature.At last, mixing solutions is transferred in the separating funnel, added a little ether again, fully after the vibration, standing demix is told the orange-red oily solution of lower floor.Repeated isolation also steams ether, promptly gets orange red Powdered phosphorus molybdenum vanadium heteropolyacid (H
4PMo
11VO
4032H
2O) catalyzer.
Embodiment two: H
4PMo
11VO
4032H
2O is a catalyzer, is solvent with the dilute hydrochloric acid solution, and amount of substance concentration is 2mol/L, and the massfraction in reaction system is 2%, and the flow of oxygen is 5mL/s, and the reaction times is 4h, and temperature of reaction is 40-120 ℃, makes 2 ethyl hexanoic acid by the oxidation of 2-ethyl hexanal.With this understanding, when temperature of reaction was 60 ℃, the transformation efficiency of 2-ethyl hexanal was 92.73%, the selectivity 92.64% of 2 ethyl hexanoic acid, and the yield of 2 ethyl hexanoic acid is 91.59%.
Embodiment three: H
4PMo
11VO
4032H
2O is a catalyzer; With the dilute hydrochloric acid solution is solvent, and amount of substance concentration is 2mol/L, and the massfraction in reaction system is 2%; The flow of oxygen is 5mL/s; Temperature of reaction is respectively 60 ℃, and the reaction times is 1h, 2h, 3h, 4h, 5h, 6h, 7h, makes 2 ethyl hexanoic acid by the oxidation of 2-ethyl hexanal.With this understanding, the reaction times, the transformation efficiency of 2-ethyl hexanal was 95.57% when being 7h, the selectivity 95.44% of 2 ethyl hexanoic acid.
Embodiment four: H
4PMo
11VO
4032H
2O is a catalyzer, is solvent with the dilute hydrochloric acid solution, and amount of substance concentration is 2mol/L, and the flow of oxygen is 5mL/s, and temperature of reaction is 60 ℃, and the reaction times is 4h, H
4PMo
11VO
4032H
2The massfraction of O in reaction system is 0.5%-10%, makes 2 ethyl hexanoic acid by the oxidation of 2-ethyl hexanal.With this understanding, H
4PMo
11VO
4032H
2The massfraction of O in reaction system is 3% o'clock, and the transformation efficiency of 2-ethyl hexanal is 96.73%, the selectivity 95.44% of 2 ethyl hexanoic acid, and the yield of 2 ethyl hexanoic acid is 95.59%.
Embodiment five: H
4PMo
11VO
4032H
2O is a catalyzer, is solvent with the dilute hydrochloric acid solution, and amount of substance concentration is 2mol/L; Massfraction in reaction system is 3%, and temperature of reaction is respectively 60 ℃, and the reaction times is 5h; The flow of oxygen is 1-20 mL/s, makes 2 ethyl hexanoic acid by the oxidation of 2-ethyl hexanal.With this understanding, when the flow of oxygen was 10 mL/s, the transformation efficiency of 2-ethyl hexanal was 99.83%, the selectivity 98.34% of 2 ethyl hexanoic acid, and the yield of 2 ethyl hexanoic acid is 98.79%.
Claims (6)
1. phosphorus molybdenum vanadium heteropolyacid catalyzed oxidation 2-ethyl hexanal prepares the method for 2 ethyl hexanoic acid, it is characterized in that, said method comprises following process:
Take by weighing phosphorus molybdenum vanadium heteropolyacid, be dissolved in the zero(ppm) water, be dissolved in again and be mixed with catalyst solution in the hydrochloric acid, in the synthesis under normal pressure device; The catalyzer that adds the 2-ethyl hexanal and configure slowly heats up, stirs, and regulates oxygen flow; When temperature rises to temperature of reaction, begin aerating oxygen, reaction is isolated lower floor's aqueous phase solution after finishing; Obtain the organic phase material on upper strata, this organic phase material is carried out underpressure distillation, obtain the oily liquids that water white transparency has irritating smell---2 ethyl hexanoic acid.
2. phosphorus molybdenum vanadium heteropolyacid catalyzed oxidation 2-ethyl hexanal according to claim 1 prepares the method for 2 ethyl hexanoic acid; It is characterized in that; The said catalyzer for preparing 2 ethyl hexanoic acid with phosphorus molybdenum vanadium heteropolyacid as catalyzed oxidation 2-ethyl hexanal; And changing vanadium atom ratio control acidity of catalyst and oxidisability performance, expression formula is: H
3+nPMo
12-nV
nO
40XH
2O, 0.5≤n in the formula≤6,3≤x≤40.
3. phosphorus molybdenum vanadium heteropolyacid catalyzed oxidation 2-ethyl hexanal according to claim 1 prepares the method for 2 ethyl hexanoic acid; It is characterized in that; Preparation phosphorus molybdenum vanadium heteropolyacid: take by weighing molybdate, phosphoric acid salt and metavanadate by stoichiometric ratio, be dissolved in respectively in the deionized water; Aqueous phosphate solution is placed 80 ℃ water bath with thermostatic control, stir, then molybdate solution is slowly joined in the aqueous phosphate solution, in mixing solutions, slowly drip vitriol oil acidifying again, become faint yellow up to solution; Metavanadate solution is added in the mixing solutions that sulfuric acid acidation crosses, continue to drip the vitriol oil, become transparent orange-red solution, stop heating and stir, be cooled to room temperature until solution; At last, add ether, fully after the vibration, standing demix is told the orange-red oily solution of lower floor, steam ether after, promptly get orange red Powdered phosphorus molybdenum vanadium heteropolyacid.
4. phosphorus molybdenum vanadium heteropolyacid catalyzed oxidation 2-ethyl hexanal according to claim 3 prepares the method for 2 ethyl hexanoic acid, it is characterized in that the preparation phosphorus molybdenum vanadium heteropolyacid: change the amount of metavanadate solution, prepare the phosphorus molybdenum vanadium heteropolyacid of different molybdenum vanadium ratios.
5. phosphorus molybdenum vanadium heteropolyacid catalyzed oxidation 2-ethyl hexanal according to claim 3 prepares the method for 2 ethyl hexanoic acid, it is characterized in that, used molybdate is water-soluble molybdates such as ammonium, basic metal, magnesium, and metavanadate is water-soluble metavanadates such as sodium, potassium; And through adding metavanadate change molybdenum vanadium than changing acidity of catalyst and oxidisability performance.
6. phosphorus molybdenum vanadium heteropolyacid catalyzed oxidation 2-ethyl hexanal according to claim 1 prepares the method for 2 ethyl hexanoic acid; It is characterized in that; Catalyst system therefor is a phosphorus molybdenum vanadium heteropolyacid; Utilize deionized water and hydrochloric acid preparation catalyst solution, the amount of substance concentration of preparation catalyzer is 0.5-8mol/L, is preferably 2-5 mol/L; The massfraction of catalyzer is preferably in the 2-4% scope in the 1-10% scope; Range of reaction temperature is 40-120 ℃, is preferably in 50-70 ℃; Oxygen flow is 0-20mL/s, is preferably in 4-10mL/s; Reaction times is 2-8h, is preferably 4-6h.
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| CN109438216A (en) * | 2018-12-06 | 2019-03-08 | 万华化学集团股份有限公司 | A kind of preparation method of high-purity isooctyl acid |
| CN109482211A (en) * | 2017-09-09 | 2019-03-19 | 中国石油化工股份有限公司 | A kind of catalyst and preparation method thereof for synthesizing 2 cyano pyrazine |
| CN110372488A (en) * | 2019-07-25 | 2019-10-25 | 润泰化学（泰兴）有限公司 | A kind of preparation method of methyl methacrylate |
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Cited By (8)
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| CN109438216A (en) * | 2018-12-06 | 2019-03-08 | 万华化学集团股份有限公司 | A kind of preparation method of high-purity isooctyl acid |
| CN109438216B (en) * | 2018-12-06 | 2021-07-23 | 万华化学集团股份有限公司 | Preparation method of high-purity isooctanoic acid |
| CN110372488A (en) * | 2019-07-25 | 2019-10-25 | 润泰化学（泰兴）有限公司 | A kind of preparation method of methyl methacrylate |
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Application publication date: 20121003 |