CN101386571B - Method for carbon dioxide supercritical continuous extraction of vanillic aldehyde and derivates thereof from acidic water solution - Google Patents
Method for carbon dioxide supercritical continuous extraction of vanillic aldehyde and derivates thereof from acidic water solution Download PDFInfo
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Abstract
The invention provides a carbon dioxide supercritical method for continuously extracting vanillin and derivatives thereof in acidic aqueous solution. The method is characterized in that glyoxylic acid and phenolic compounds are used as raw materials, condensed and oxidized so as to obtain an acidic aqueous solution containing 2 to 7 percent of the vanillin and the derivatives thereof; the acidic aqueous solution and carbon dioxide supercritical fluid are continuously and reversely mixed in an extraction column, enter separation tanks, and are decompressed and separated so as to obtain a product; the liquid flow rate of the acidic aqueous solution is between 2 and 6 Kg/h; the flow rate of the carbon dioxide fluid is between 10 and 25 Kg/h; the pressure is between 20 and 35 MPa; the temperature is between 40 and 65 DEG C; the separation pressures of the two separation tanks are between 5.5 and 7.0 MPa and between 4.5 and 5.5 MPa respectively; the temperatures of the two separation tanksare between 50 and 65 DEG C and between 30 and 45 DEG C respectively; and the method is simple to operate, improves product content, has the extraction efficiency over 95 percent, has the product content more than 95 percent, realizes the continuous feeding of supercritical extraction, and has good industrialization prospect.
Description
Technical field
The present invention relates to that a kind of to adopt oxoethanoic acid and phenolic compound with the CO 2 supercritical continuous countercurrent extraction be raw material, obtain containing the vanillin food grade,1000.000000ine mesh in the acidic aqueous solution of 2～7% vanillin food grade,1000.000000ine meshs and derivative thereof and the method for derivative thereof through condensation, oxidation.
Background technology
Its chemical name of vanillin food grade,1000.000000ine mesh (Vanillin) is 3-methoxyl group-4-hydroxy benzaldehyde, is the synthetic perfume of output maximum in the world, also is the important chemical intermediate, is widely used in aspects such as food, daily-use chemical industry, medicine is synthetic.In addition, vanillin food grade,1000.000000ine mesh is used as optical brightener in electroplating industry, is used as ripener in the agricultural.
Oxoethanoic acid and methyl catechol (or 2-thanatol or pyrocatechol) are advanced both at home and abroad at present synthesis techniques through condensation-oxidation route production vanillin food grade,1000.000000ine mesh and derivative thereof.That this technology has is simple to operation, " three wastes " less, easily handle the productive rate advantages of higher.To produce vanillin food grade,1000.000000ine mesh is example, and chemical equation (main reaction) is as follows:
Obtain containing 2～7% vanillin food grade,1000.000000ine mesh and derivative acidic aqueous solution thereof after this technology decarboxylation, general method is to adopt organic solvent to extract, and extracts wherein vanillin food grade,1000.000000ine mesh and derivative thereof, and stripping then or distilling organic solvent obtains product.This method exists energy consumption big, and solvent load is many, and deficiency such as polluted water.
External early stage patent has been introduced the method that the xylogen that adopts in the carbon dioxide upercritical fluid extraction oxidation wood pulp has obtained vanillin food grade,1000.000000ine mesh, this process stresses extracting pressure and variation of temperature, vanillin food grade,1000.000000ine mesh after the extraction contains impurity such as acetyl methyl catechol, methyl catechol, purity is about 90% only, has influenced back step purification procedures.
Summary of the invention
The objective of the invention is to adopt the method for vanillin food grade,1000.000000ine mesh in the CO 2 supercritical continuous countercurrent extraction acidic aqueous solution and derivative thereof, fluid flow rate, the residence time, extracting pressure and temperature that control is suitable, extraction back product content reaches more than 95.00%, and percentage extraction reaches more than 95%.
A kind of method of vanillin food grade,1000.000000ine mesh and derivative thereof in a kind of CO 2 supercritical continuous countercurrent extraction acidic aqueous solution, it is characterized in that: will be raw material with oxoethanoic acid and phenolic compound, the acidic aqueous solution that contains 2～7% vanillin food grade,1000.000000ine meshs and derivative thereof that obtains through condensation, oxidation, with Co 2 supercritical fluid continuous backmixing in column extractor, the vanillin food grade,1000.000000ine mesh and the derivative thereof of aqueous phase are dissolved in the CO 2 fluid, enter separating tank then, in two separating tanks, obtain product through twice decompression separation; The acidic aqueous solution liquid flow rate that contains 2～7% vanillin food grade,1000.000000ine meshs and derivative thereof is 2～6Kg/h, and the CO 2 fluid flow is 10～25Kg/h, and extracting pressure is 20～35MPa, when extraction temperature is 40～65 ℃; Twice separation decompression pressure in two separating tanks is controlled to be 5.5～7.0MPa respectively, 4.5～5.5MPa, and temperature is controlled to be 50～65 ℃ respectively, 30～45 ℃.
Above-mentioned method, its described liquid flow rate 3～4Kg/h that contains 2～7% vanillin food grade,1000.000000ine meshs and derivative thereof.
Above-mentioned method, its described CO 2 fluid flow is 15～20Kg/h.
Above-mentioned method, its described extracting pressure is 22～25MPa, extraction temperature is 55～60 ℃.
Vanillin food grade,1000.000000ine mesh and derivative thereof are 3-methoxyl group-4-hydroxy benzaldehyde, vanirom, 3-hydroxyl-4-methoxybenzaldehyde, 3,4-Dihydroxy benzaldehyde, 2-hydroxy 3-methoxybenzene formaldehyde, 2-hydroxyl-3-ethoxy-benzaldehyde.The general formula of vanillin food grade,1000.000000ine mesh and derivative thereof is (I)
In the formula
Y1 representative-H or-OH; Y2 representative-OH or-OCH
3Or OCH
2CH
3Y3 representative-H or-OH or-OCH
3Deng group.
Phenolic compound can be pyrocatechol, 2-methoxyphenol, 2-thanatol.Its general formula is
In the formula
Z1 representative-OH or-OCH3 or-groups such as OCH2CH3.
The present invention compared with prior art has obvious improvement and positively effect:
The present invention adopts carbonic acid gas that the vanillin food grade,1000.000000ine mesh and the derivative acidic aqueous solution thereof of content 2～7% are carried out continuous supercritical extraction, can obtain content greater than 95.00% product, obviously improve the content of vanillin food grade,1000.000000ine mesh and derivative thereof, realized the continuously feeding of supercritical extraction, simplified operation.
Embodiment
Now the present invention is further described as follows by embodiment:
Embodiment 1
The carbon dioxide of purity 99.5% is pressed into control extracting pressure 24MPa, 55 ℃ of extraction temperature from the column extractor bottom with the 15kg/h flow by high pressure plunger pump.Start liquid high pressure plunger pump then is dissolved with 3.3% vanillin food grade,1000.000000ine mesh acidic aqueous solution and enters the column extractor top by being pressed in the storage tank, and liquid flow rate is 4.0Kg/h, makes two fluids adverse current Continuous Contact in column extractor.The CO 2 fluid that has vanillin food grade,1000.000000ine mesh is by the column extractor top, reduce pressure separating tank 1 control pressure 6.0MPa, 55 ℃ of controlled temperature to separating tank 1, after the decompression, vanillin food grade,1000.000000ine mesh is stayed at the bottom of the separating tank, and carbon dioxide enters separating tank 2 again and reduces pressure, control pressure 5.3MPa, 32 ℃ of controlled temperature, isolating carbonic acid gas passes through drying chamber, compressor again, recycles, and water is discharged continuously from the column extractor bottom.Dynamic operation 16 hours stops extraction, is 95.03% with vanillin food grade,1000.000000ine mesh content in the efficient liquid phase chromatographic analysis separating tank 1, and aqueous phase vanillin food grade,1000.000000ine mesh content is 0.023%, extraction efficiency 96.8%.
Embodiment 2
Carry out according to embodiment 1.The carbon dioxide of purity 99.5% is pressed into control extracting pressure 22MPa, 60 ℃ of extraction temperature from the column extractor bottom with the 20kg/h flow by high pressure plunger pump.Start liquid high pressure plunger pump then is dissolved with 3.3% vanillin food grade,1000.000000ine mesh acidic aqueous solution and enters the column extractor top by being pressed in the storage tank, and liquid flow rate is 3.8Kg/h.The CO 2 fluid that has vanillin food grade,1000.000000ine mesh reduces pressure separating tank 1 control pressure 5.7MPa by the column extractor top to separating tank 1,55 ℃ of controlled temperature, after the decompression, vanillin food grade,1000.000000ine mesh is stayed at the bottom of the separating tank, carbon dioxide enters separating tank 2 again and reduces pressure, control pressure 5.0MPa, 30 ℃ of controlled temperature, dynamic operation 18 hours, stop extraction, with vanillin food grade,1000.000000ine mesh content in the efficient liquid phase chromatographic analysis separating tank 1 is 95.44%, and aqueous phase vanillin food grade,1000.000000ine mesh content is 0.019%, extraction efficiency 97.2%.
Embodiment 3
Carry out according to embodiment 1.The carbon dioxide of purity 99.5% is pressed into from the column extractor bottom with the 20kg/h flow by high pressure plunger pump, control extracting pressure 30MPa, extraction temperature is 45 ℃, liquid flow rate is 3.0Kg/h.Control separating tank 1 pressure 6.0MPa, 45 ℃ of controlled temperature, after the decompression, vanillin food grade,1000.000000ine mesh is stayed at the bottom of the separating tank, and carbon dioxide enters separating tank 2 again and reduces pressure, control pressure 5.0MPa, 30 ℃ of controlled temperature, dynamic operation 18 hours.With vanillin food grade,1000.000000ine mesh content in the efficient liquid phase chromatographic analysis separating tank 1 is 92.87%, and aqueous phase vanillin food grade,1000.000000ine mesh content is 0.063%, extraction efficiency 94.6%.
Embodiment 4
Carry out according to embodiment 1.The carbon dioxide of purity 99.5% is pressed into control extracting pressure 25MPa, 55 ℃ of extraction temperature from the column extractor bottom with the 20kg/h flow by high pressure plunger pump.Liquid flow rate is 5.0Kg/h.Control separating tank 1 pressure 6.0MPa, 55 ℃ of controlled temperature, after the decompression, vanillin food grade,1000.000000ine mesh is stayed at the bottom of the separating tank, and carbon dioxide enters separating tank 2 again and reduces pressure, control pressure 5.3MPa, 30 ℃ of controlled temperature, dynamic operation 10 hours.Vanillin food grade,1000.000000ine mesh content with efficient liquid phase chromatographic analysis separating tank 1 is 89.55%, and aqueous phase vanillin food grade,1000.000000ine mesh content is 0.087%, extraction efficiency 95.3%.
Embodiment 5
The carbon dioxide of purity 99.5% is pressed into control extracting pressure 22MPa, 60 ℃ of extraction temperature from the column extractor bottom with the 18kg/h flow by high pressure plunger pump.Start liquid high pressure plunger pump then is dissolved with 3.5% vanirone acidic aqueous solution and enters the column extractor top by being pressed in the storage tank, and liquid flow rate is 4.0Kg/h.The CO 2 fluid that has bourbonal is by the column extractor top, reduce pressure separating tank 1 control pressure 6.0MPa, 60 ℃ of controlled temperature to separating tank 1, after the decompression, vanirone is stayed at the bottom of the separating tank, and carbon dioxide enters separating tank 2 again and reduces pressure, control pressure 5.0MPa, 30 ℃ of controlled temperature, isolating carbonic acid gas passes through drying chamber, compressor again, recycles, and water is discharged continuously from the column extractor bottom.Dynamic operation 18 hours stops extraction, is 94.83% with vanirone content in the efficient liquid phase chromatographic analysis separating tank 1, and aqueous phase vanirone content is 0.037%, extraction efficiency 96.7%.
Embodiment 6
The carbon dioxide of purity 99.5% is pressed into control extracting pressure 25MPa, 60 ℃ of extraction temperature from the column extractor bottom with the 20kg/h flow by high pressure plunger pump.Start liquid high pressure plunger pump then is dissolved with 3.0% Isovanillin (3-hydroxyl-4-methoxybenzaldehyde) acidic aqueous solution and enters the column extractor top by being pressed in the storage tank, and liquid flow rate is 4.0Kg/h.The CO 2 fluid that has Isovanillin is by the column extractor top, reduce pressure to separating tank 1, separating tank 1 control pressure 6.0MPa, 55 ℃ of controlled temperature, after the decompression, Isovanillin is stayed at the bottom of the separating tank, and carbon dioxide enters separating tank 2 again and reduces pressure, control pressure 5.0MPa, 33 ℃ of controlled temperature.Isolating carbonic acid gas passes through drying chamber, compressor again, recycle, water is discharged continuously from the column extractor bottom, dynamic operation 18 hours, stop extraction, with Isovanillin content in the efficient liquid phase chromatographic analysis separating tank 1 is 94.41%, and aqueous phase vanillin food grade,1000.000000ine mesh content is 0.050%, extraction efficiency 95.5%.
Embodiment 7
The carbon dioxide of purity 99.5% is pressed into control extracting pressure 25MPa, 55 ℃ of extraction temperature from the column extractor bottom with the 18kg/h flow by high pressure plunger pump.Start liquid high pressure plunger pump then is dissolved with 2.8% veratryl aldehyde (3, the 4-Dihydroxy benzaldehyde) acidic aqueous solution and enters the column extractor top by being pressed in the storage tank, and liquid flow rate is 3.8Kg/h.The CO 2 fluid that has veratryl aldehyde is by the column extractor top, reduce pressure to separating tank 1, separating tank 1 control pressure 5.7MPa, 55 ℃ of controlled temperature, after the decompression, veratryl aldehyde is stayed at the bottom of the separating tank, and carbon dioxide enters separating tank 2 again and reduces pressure, control pressure 5.3MPa, 32 ℃ of controlled temperature, isolating carbonic acid gas passes through drying chamber again, compressor recycles, water is discharged continuously from the column extractor bottom, dynamic operation 14 hours stops extraction, is 95.07% with veratryl aldehyde content in the efficient liquid phase chromatographic analysis separating tank 1, aqueous phase veratryl aldehyde content is 0.027%, extraction efficiency 97.1%.
Claims (6)
1. the method for vanillin food grade,1000.000000ine mesh and derivative thereof in the CO 2 supercritical continuous extraction acidic aqueous solution, it is characterized in that: will be raw material with oxoethanoic acid and phenolic compound, the acidic aqueous solution that contains 2～7% vanillin food grade,1000.000000ine meshs and derivative thereof that obtains through condensation, oxidation, with Co 2 supercritical fluid continuous backmixing in column extractor, the vanillin food grade,1000.000000ine mesh and the derivative thereof of aqueous phase are dissolved in the CO 2 fluid, enter separating tank then, in two separating tanks, obtain product through twice decompression separation; The liquid flow rate that contains the acidic aqueous solution of 2～7% vanillin food grade,1000.000000ine meshs and derivative thereof is 2～6Kg/h, and the CO 2 fluid flow is 10～25Kg/h, and extracting pressure is 20～35MPa, and extraction temperature is 40～65 ℃; Twice separation decompression pressure in two separating tanks is controlled to be 5.5～7.0MPa respectively, 4.5～5.5MPa, and temperature is controlled to be 50～65 ℃ respectively, 30～45 ℃;
Described vanillin food grade,1000.000000ine mesh and derivative thereof are that general formula is the compound of (I):
In the formula:
Y1 representative-H or-OH; Y2 representative-OH or-OCH
3Or OCH
2CH
3Y3 representative-H or-OH or-OCH
3Group.
2. the method for vanillin food grade,1000.000000ine mesh and derivative thereof in the CO 2 supercritical continuous extraction acidic aqueous solution as claimed in claim 1 is characterized in that: phenolic compound is pyrocatechol, 2-methoxyphenol, 2-thanatol, and its general formula is (II)
In the formula:
Z1 representative-OH or-OCH3 or-the OCH2CH3 group.
3. the method for vanillin food grade,1000.000000ine mesh and derivative thereof in the CO 2 supercritical continuous extraction acidic aqueous solution as claimed in claim 1, it is characterized in that: described extracting pressure is 22～25MPa, extraction temperature is 55～60 ℃.
4. the method for vanillin food grade,1000.000000ine mesh and derivative thereof in the CO 2 supercritical continuous extraction acidic aqueous solution as claimed in claim 1 is characterized in that: the described liquid flow rate that contains the acidic aqueous solution of 2～7% vanillin food grade,1000.000000ine meshs and derivative thereof is 3～4Kg/h.
5. the method for vanillin food grade,1000.000000ine mesh and derivative thereof in the CO 2 supercritical continuous extraction acidic aqueous solution as claimed in claim 1, it is characterized in that: the flow of carbon dioxide gas amount is 15～20Kg/h.
6. the method for vanillin food grade,1000.000000ine mesh and derivative thereof in the CO 2 supercritical continuous extraction acidic aqueous solution as claimed in claim 1, it is characterized in that: vanillin food grade,1000.000000ine mesh and derivative thereof are 3-methoxyl group-4-hydroxy benzaldehyde, vanirom, 3-hydroxyl-4-methoxybenzaldehyde, 3,4-Dihydroxy benzaldehyde, 2-hydroxy 3-methoxybenzene formaldehyde or 2-hydroxyl-3-ethoxy-benzaldehyde.
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| CN2007101215443A CN101386571B (en) | 2007-09-10 | 2007-09-10 | Method for carbon dioxide supercritical continuous extraction of vanillic aldehyde and derivates thereof from acidic water solution |
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| CN2007101215443A CN101386571B (en) | 2007-09-10 | 2007-09-10 | Method for carbon dioxide supercritical continuous extraction of vanillic aldehyde and derivates thereof from acidic water solution |
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| CN101386571B true CN101386571B (en) | 2011-05-25 |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101987255A (en) * | 2009-07-30 | 2011-03-23 | 大连卓尔高科技有限公司 | Continuous countercurrent supercritical fluid extraction equipment and method applied to materials |
| CN103709021B (en) * | 2013-05-29 | 2015-05-13 | 浙江普洛康裕生物制药有限公司 | Vanillin extraction method |
| CN107941945B (en) * | 2017-11-23 | 2020-12-22 | 中山奕安泰医药科技有限公司 | Detection method of 3-ethoxy-4-methoxybenzonitrile |
| CN108008035B (en) * | 2017-11-23 | 2020-07-07 | 中山奕安泰医药科技有限公司 | Method for detecting purity of 3-ethoxy-4-methoxybenzaldehyde |
| CN112409146B (en) * | 2020-12-08 | 2023-07-07 | 南通亚香食品科技有限公司 | Continuous preparation process of vanillin |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4847422A (en) * | 1985-03-01 | 1989-07-11 | Yhtyneet Paperitehtaat Oy | Method for the production of vanillin |
| US4898990A (en) * | 1985-09-20 | 1990-02-06 | Fried. Krupp Gmbh | Process for the extraction of vanillin |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4847422A (en) * | 1985-03-01 | 1989-07-11 | Yhtyneet Paperitehtaat Oy | Method for the production of vanillin |
| US4898990A (en) * | 1985-09-20 | 1990-02-06 | Fried. Krupp Gmbh | Process for the extraction of vanillin |
Non-Patent Citations (1)
| Title |
|---|
| 符史良等.超临界CO2萃取香草兰的工艺研究和成分分析.食品与机械.2002,(2),12－14页. * |
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