CN1405211A - Method for preparing high-purity xanthohumic acid using supercritical CO2 - Google Patents
Method for preparing high-purity xanthohumic acid using supercritical CO2 Download PDFInfo
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- CN1405211A CN1405211A CN01141835A CN01141835A CN1405211A CN 1405211 A CN1405211 A CN 1405211A CN 01141835 A CN01141835 A CN 01141835A CN 01141835 A CN01141835 A CN 01141835A CN 1405211 A CN1405211 A CN 1405211A
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- xanthohumic acid
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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Abstract
There is a method of using super critical CO2 to produce high purity yellow rotten acid, it uses turves, lignite and wathering coal as raw materials, solid and liquid are separated after chemical reaction and extraction; the separated liquid is extracted by super critical CO2 again; the extracted liquid eliminates carrynig agent, then it is dried and produced into high purity yellow rotten acid.
Description
Technical field:
The invention belongs to a kind of preparation method of humic acids, be specifically related to a kind of method of producing high-purity xanthohumic acid with supercritical CO 2.
Background technology:
Xanthohumic acid is a kind of component of humic acids, except that the general feature that possesses humic acids, also has its special advantages, mainly shows as following several respects: the one, and its molecular weight is less and easily utilized by bio-absorbable; The 2nd, its functional group content is more, and is bigger than the physiologically active of general humic acids, also stronger to the complex ability of metal; The 3rd, humic acids can not direct water-soluble needs changes univalent metal salt such as potassium, sodium into or ammonium salt can be water-soluble, and the aqueous solution of these salt all is alkalescence, and xanthohumic acid can be directly water-soluble, and it is acid that its aqueous solution is.This three big feature makes xanthohumic acid that the effect of more purposes and Geng Jia be arranged at agricultural and field of medicaments.Therefore from humic acid material, extract xanthohumic acid and purifying, just become an important channel that utilizes cheap humic acid material to produce high value added product.The extracting and the purifying of xanthohumic acid mainly contain two kinds of methods, the one, solvent extraction process, i.e. sulfuric acid-acetone method at present; The 2nd, the resin extraction process.The former is the metal ion that replaces Xanthohumate in the coal with sulfuric acid, and the free xanthohumic acid is contained the acetone solution of less water, and the coal dust residue that forms and the vitriol of generation then do not dissolve, so just can obtain low grey xanthohumic acid after boiling off solvent.Second method is to discharge xanthohumic acid with the metal ion that strong acid ion exchange resin replaces sulfuric acid to replace Xanthohumate, and water extracts the xanthohumic acid that generates.Above-mentioned two kinds of methods have all been set up the Small Scale Industry production equipment, and as commodity selling.But,, therefore all there is the low excessively problem of extraction yield so its yield is subjected to the restriction of xanthohumic acid content in the raw material because these two kinds of methods all are to extract xanthohumic acid from raw material.And the more important thing is since after the extracting xanthohumic acid and other solvent or the thin slag of coal dust mix difficulty and separate, so the purity of product is difficult to improve.The product xanthohumic acid content of above-mentioned two kinds of methods preparation is 85% substantially, and purity reaches 95% above technology and all there is limitation in economy.Have not yet to see the patent report of high purity xanthohumic acid preparation.
Goal of the invention:
The present invention is intended to overcome the defective that above-mentioned two kinds of methods exist, and the preparation method of a kind of high yield, highly purified xanthohumic acid is provided.
It is raw material that the present invention adopts peat, brown coal and weathered coal, at first improves xanthohumic acid content through chemical modification, again through supercritical CO
2The extracting xanthohumic acid, product purity can reach more than 99%.Problems such as the solvent-free recovery of technological process are a kind of ideal high-purity xanthohumic acid preparation methods.
The preparation of high-purity xanthohumic acid of the present invention is carried out as follows:
(1) will be crushed to 40 order to 80 purpose feed coals, water, extractant, be 1 by weight: the mixed of 5-10: 0.08-0.2, slowly be warming up to 90--120 ℃, under this temperature, carry out the reaction of xanthohumic acid simultaneously and extracted 1--3 hour; Solid-liquid separation obtains thick xanthohumic acid solution;
(2) be raw material with thick xanthohumic acid solution, CO
2Be extractant, ethanol is entrainment agent, by thick xanthohumic acid and entrainment agent weight ratio is: 1: 2-8, and under 150-450Kg pressure, under 25-50 ℃ the super critical condition extracting 0.5-5 hour;
(3) through underpressure distillation entrainment agent is separated with xanthohumic acid, the spray-dried again high purity xanthohumic acid that obtains.
Aforesaid feed coal is that humic acids content should be peat, brown coal, the weathered coal more than 40%, and humic acids content is more preferably greater than 60%.
Aforesaid extractant is the mixture of sulfuric acid, nitric acid, hydrogen peroxide or wherein a kind of.
Compared with the prior art the present invention has following advantage:
(1) adopts chemical process that humic acid material is handled, not only make primary xanthohumic acid obtain activation and be easy to extracting, and produce a large amount of regenerated xanthohumic acids, make the xanthohumic acid extraction yield that by a relatively large margin raising be arranged;
(2) adopt supercritical CO first
2Abstraction technique carries out the refining of xanthohumic acid, and the pollution of having avoided other solvent to cause reaches the xanthohumic acid structural damage;
(3) the xanthohumic acid purity height of present method preparation can reach more than 99%.
The present invention adopts raw material sources in the low-grade coal that nature extensively distributes, and can be peat, brown coal, weathered coal, and its humic acids content will reach 40% (butt) at least, is preferably more than 60%.With the prepared high-purity xanthohumic acid of method of the present invention, its xanthohumic acid content can reach more than 99%.
Embodiment:
Embodiment 1
To be crushed to 60 purpose brown coal powders (containing humic acids 68.52%, xanthohumic acid 2.51%) 20g, with water 100ml, dense H
2SO
4With dense HNO
3Mixed solution (weight ratio is 1: 1) 3.8g, 80-90 ℃ of stirring reaction 2 hours, reactant was through centrifugation, supernatant liquor is thick xanthohumic acid goods 65g; Above-mentioned thick xanthohumic acid is added extractor, and add 200g ethanol, import the supercritical CO of purity 〉=99% behind the mixing
2, at 150 kilograms of pressure, 30 ℃ of following extractings 2.5 hours, decompression are steamed and are got entrainment agent, dryly must make with extra care xanthohumic acid, and its purity is 99.5%.
Embodiment 2
To be crushed to 60 purpose peat 20g, with water 200ml, mixed solution 5.28g (hydrogen peroxide 1.6g, dense H
2SO
43.68g), 90-100 ℃ of stirring reaction 3 hours, reactant was through centrifugation, and supernatant liquor is thick xanthohumic acid goods 110g; Above-mentioned thick xanthohumic acid is added extractor, and add 600g ethanol, import the supercritical CO of purity 〉=99% behind the mixing
2, at 200 kilograms of pressure, 50 ℃ of following extractings 5 hours, decompression are steamed and are got entrainment agent, dryly must make with extra care xanthohumic acid, and its purity is 99.95%.
Embodiment 3
To be crushed to 60 purpose weathering coal dust 20g, with water 150ml, dense H
2SO
47.4g 120 ℃ of stirring reactions 1 hour, reactant was through centrifugation, supernatant liquor is thick xanthohumic acid goods 80g; Above-mentioned thick xanthohumic acid is added extractor, and add 640g ethanol, import the supercritical CO of purity 〉=99% behind the mixing
2, at 450 kilograms of pressure, 40 ℃ of following extractings 0.5 hour, decompression are steamed and are got entrainment agent, dryly must make with extra care xanthohumic acid, and its purity is 99.1%.
Embodiment 4
To be crushed to 60 purpose brown coal powder 20g, with water 100ml, dense HNO
32.5g 120 ℃ of stirring reactions 2 hours, reactant was through centrifugation, supernatant liquor is thick xanthohumic acid goods 60g; Above-mentioned thick xanthohumic acid is added extractor, and add 300g ethanol, import the supercritical CO of purity 〉=99% behind the mixing
2, at 300 kilograms of pressure, 25 ℃ of following extractings 5 hours, decompression are steamed and are got entrainment agent, dryly must make with extra care xanthohumic acid, and its purity is 99.5%.
Embodiment 5
To be crushed to 60 purpose weathering coal dust 20g, with water 200ml, dense H
2SO
48g, 100 ℃ of stirring reactions 3 hours, reactant was through centrifugation, and supernatant liquor is thick xanthohumic acid goods 100g; Above-mentioned thick xanthohumic acid is added extractor, and add 200g ethanol, import the supercritical CO of purity 〉=99% behind the mixing
2, at 450 kilograms of pressure, 40 ℃ of following extractings 3 hours, decompression are steamed and are got entrainment agent, dryly must make with extra care xanthohumic acid, and its purity is 99.1%.
Embodiment 6
To be crushed to 60 purpose peat dust 20g, with water 100ml, dense H
2SO
44g, 90 ℃ of stirring reactions 2 hours, reactant was through centrifugation, and supernatant liquor is thick xanthohumic acid goods 50g; Above-mentioned thick xanthohumic acid is added extractor, and add 400g ethanol, import the supercritical CO of purity 〉=99% behind the mixing
2, at 450 kilograms of pressure, 50 ℃ of following extractings 5 hours, decompression are steamed and are got entrainment agent, dryly must make with extra care xanthohumic acid, and its purity is 99.9%.
Claims (4)
1. use supercritical CO for one kind
2Produce the method for high-purity xanthohumic acid, it is characterized in that preparation comprises the steps:
(1) will be crushed to 40 order to 80 purpose feed coals, water, extractant, be 1 by weight: the mixed of 5-10: 0.08-0.2, slowly be warming up to 90--120 ℃, under this temperature, carry out the reaction of xanthohumic acid simultaneously and extracted 1--3 hour; Solid-liquid separation obtains thick xanthohumic acid solution;
(2) be raw material with thick xanthohumic acid solution, CO
2Be extractant, ethanol is entrainment agent, by thick xanthohumic acid and entrainment agent weight ratio is: 1: 2-8, and under 150-450Kg pressure, under 25-50 ℃ the super critical condition extracting 0.5-5 hour;
(3) through underpressure distillation entrainment agent is separated with xanthohumic acid, the spray-dried again high purity xanthohumic acid that obtains.
2. a kind of supercritical CO of using as claimed in claim 1
2Produce the method for high-purity xanthohumic acid, it is characterized in that described feed coal is that humic acids content should be peat, brown coal, the weathered coal more than 40%.
3. the described a kind of supercritical CO of using of claim 1
2Produce the method for high-purity xanthohumic acid, it is characterized in that described extractant is the mixture of sulfuric acid, nitric acid, hydrogen peroxide or wherein a kind of.
4. claim 1 or 2 described a kind of supercritical COs of using
2Produce the method for high-purity xanthohumic acid, it is characterized in that humic acids content is greater than 60% in the described feed coal.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011418354A CN1159271C (en) | 2001-09-20 | 2001-09-20 | Method for preparing high-purity xanthohumic acid using supercritical CO2 |
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| CNB011418354A CN1159271C (en) | 2001-09-20 | 2001-09-20 | Method for preparing high-purity xanthohumic acid using supercritical CO2 |
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| CN1405211A true CN1405211A (en) | 2003-03-26 |
| CN1159271C CN1159271C (en) | 2004-07-28 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102584906A (en) * | 2012-01-15 | 2012-07-18 | 山西大学 | Extracting method of fulvic acid |
| CN104974356A (en) * | 2015-06-30 | 2015-10-14 | 昆明理工大学 | Method for extracting fulvic acid substances from diatomite |
| KR20150137532A (en) * | 2014-05-30 | 2015-12-09 | (주)코스메디션 | Method of isolation for humic substances using subcritical/supercritical water |
| CN108576058A (en) * | 2018-05-31 | 2018-09-28 | 中国矿业大学 | The extracting method of regenerated xanthohumic acid in a kind of low metamorphic lignite |
| CN109180743A (en) * | 2018-11-13 | 2019-01-11 | 安徽富里馨生物科技有限公司 | A kind of food-grade fulvic acid and preparation method thereof |
| CN110156506A (en) * | 2019-05-23 | 2019-08-23 | 黎进堂 | A kind of fulvic acid selenium foliar fertilizer and preparation method thereof |
-
2001
- 2001-09-20 CN CNB011418354A patent/CN1159271C/en not_active Expired - Lifetime
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102584906A (en) * | 2012-01-15 | 2012-07-18 | 山西大学 | Extracting method of fulvic acid |
| KR20150137532A (en) * | 2014-05-30 | 2015-12-09 | (주)코스메디션 | Method of isolation for humic substances using subcritical/supercritical water |
| KR101723813B1 (en) | 2014-05-30 | 2017-04-13 | (주)코스메디션 | Method of isolation for humic substances using subcritical/supercritical water |
| CN104974356A (en) * | 2015-06-30 | 2015-10-14 | 昆明理工大学 | Method for extracting fulvic acid substances from diatomite |
| CN104974356B (en) * | 2015-06-30 | 2017-07-28 | 昆明理工大学 | A kind of method that fulvic acid substance is extracted from diatomite |
| CN108576058A (en) * | 2018-05-31 | 2018-09-28 | 中国矿业大学 | The extracting method of regenerated xanthohumic acid in a kind of low metamorphic lignite |
| CN109180743A (en) * | 2018-11-13 | 2019-01-11 | 安徽富里馨生物科技有限公司 | A kind of food-grade fulvic acid and preparation method thereof |
| CN110156506A (en) * | 2019-05-23 | 2019-08-23 | 黎进堂 | A kind of fulvic acid selenium foliar fertilizer and preparation method thereof |
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| Publication number | Publication date |
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| CN1159271C (en) | 2004-07-28 |
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