CN101033231B - Method of preparing high-purity medical xanthonumic acid - Google Patents
Method of preparing high-purity medical xanthonumic acid Download PDFInfo
- Publication number
- CN101033231B CN101033231B CN200710097275A CN200710097275A CN101033231B CN 101033231 B CN101033231 B CN 101033231B CN 200710097275 A CN200710097275 A CN 200710097275A CN 200710097275 A CN200710097275 A CN 200710097275A CN 101033231 B CN101033231 B CN 101033231B
- Authority
- CN
- China
- Prior art keywords
- acid
- liquid
- resin
- coal
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Abstract
FA is a type of natural biological activity preparation with wide usage in animal growth, disease resistance, promoting blood circulation, and immunization. The technology to produce medical FA with high purity is the method to use low-grade coal as raw material for purification through acid extraction and resin adsorption - desorption. The preparation process includes four steps: (1) using the low concentration of HCl or H2SO4 to extract the low-grade coal to get FA solution, (2) using the specific resin to adsorb FA, and then using desorption to absorb the FA, (3) using cation exchange resinto conduct desalination and purification, (4) desalting and drying the FA solution to get the medical FA with purity more than 95%.
Description
1, technical field product of the present invention belongs to the fine chemistry preparation, is specifically related to extraction and the purification process of medical xanthonumic acid (Fulvic Acid, code name FA).
2, background technology FA is a class natural bioactive preparation, mainly extracts from low level coal (peat, brown coal, weathered coal) or other humic organic matters.Once announced the patent that much relates to the FA preparation method, but majority is the agricultural thick product without any purifying procedure.Minority relates to the patent of FA process for purification, nearly all is loaded down with trivial details chemical means.As European patent EP 00117223A1 (1984) (publication number, down together) method that provides is: extract total humic acid with alkali lye from peat or other humic substances, through acidifying, repeated precipitation and separate, classification, etc. step, obtain being used for the FA of fertilizer, with similar CN1117036 (1996), CN1211392 (1999), the CN1456539 (the also prior oxidation or the sulfonation that have) such as (2003) in addition of this method.CN1070568 (1993) extracts FA with HCl from weathered coal, add alkali neutralization, with high-valency metal salt precipitation, again with the resin cation (R.C.) mechanically mixing, through washing, separate, concentrate, evaporation, drying, make medicinal oral FA, but do not report preparation purity; CN1213665 (1999) extracts total humic acid with alkali lye from peat, again with extraction using alcohol ulmic acid+FA wherein, then with HCl, water dissolve repeatedly, backflow, cooling, precipitation, evaporation, drying etc., products therefrom is still the sodium salt of FA.All there are tediously long numerous and diverse, the drawbacks such as loss of material is many, product purity is low, production cost height of process in above method.
3, summary of the invention method provided by the invention, the method that mainly adopts resin absorption to separate and purify has effectively overcome above-mentioned defective, has clear superiority in raising work efficiency, assurance FA purity with aspect reducing cost especially.
Raw material required for the present invention mainly is:
(1) low-grade coal: comprise weathered coal, brown coal, peat, also the coal that can adopt the artificial oxidation to cross.FA content should at least 10% in the various raw materials.
(2) extraction agent: HCl or H
2SO
4
(3) sorbent material: a) storng-acid cation exchange resin (001 * 7,001 * 4,002 * SC etc.);
B) anionite-exchange resin (strong basicity 201 * 7, IRA-401S, IRA-900; Macropore D201, D202 etc.);
C) macroporous adsorbent resin XAD-4, XAD-8, YJX-01, the A101 etc. of middle polarity (strong or).
(4) desorbing agent: inorganic alkali solution (5～10%NaOH or 5～10%KOH solution), water-containing organic solvent (20～30% methyl alcohol, 50～70% acetone, 10～20% Virahols);
(5) pure water: all waters of this preparation process are the deionized water that ion exchange treatment is crossed, its specific conductivity≤μ Ω.
Products obtained therefrom FA content of the present invention 〉=95% (butt), all the other components are inorganic salts (mainly be Ca, Mg, Fe, Al, Si, S etc., be harmless element).
This FA product preparation step is as follows:
1, extraction: will be crushed to-80 purpose feed coals, acid, water mixed by 1: 0.5～1: 5～10 (weight), centrifugal or filter at 60～80 ℃ of reaction 1h down to material, wash residue with water 2～3 times.Filtrate and washings are merged, be transferred to pH=2～3, get A liquid with NaOH or KOH.
2, absorption-desorption: anionite-exchange resin or macroporous adsorbent resin are contained in glass or synthetic glass post (among about Φ 100mm * h1000mm), handle with the method in common pre-activated, by the flow of air speed (S)=0.2～0.3 (L/Lh) with A liquid by resin column, then with water rinse resin to effluent liquid colourless till.Carry out desorption with the NaOH of normality or KOH solution or organic solvent with the air speed of S=0.3～0.5, till elutriant is colourless.All elutriants are merged, get B liquid.
3, desalination: Zeo-karb is adorned post (material and size are with 2), by the universal method pre-treatment.Press the air speed of S=0.2～0.3 B liquid is passed through resin column, water washes pillar then, till washing lotion is colourless.Filtrate and washing lotion merge, and get C liquid.
4, concentrate-drying: C liquid is put into vacuum rotary evaporator, is being evaporated to FA concentration about 10% under≤70 ℃, then in vacuum rake dryer in≤60 ℃ of dry down powdery FA products, reclaim organic solvent and water simultaneously.As with inorganic alkali lye desorption, also available spray-drier drying (not reclaiming solvent).
Various resins are regenerated and repair by method in common.
4, embodiment
Example 1:
In the 1M3 reactor, put into water 500L, 30%HCl100L ,-80 order weathering hard coal 50kg are warming up to 80 ℃, extracting 1h under stirring.Emit material, vacuum filtration, and washing filter residue.Filtrate and washing lotion merge, and with the D202 type macroporous resin column of air speed by having handled well of S=0.2, water fully washes then.With the air speed of S=0.4, use the 5%NaOH desorption.The air speed of elutriant being pressed S=0.3 washes resin with water again by 001 * 7 type sun resin.Filtrate and washing lotion merge, and obtain powdery FA product after concentrated-drying, and its purity is 97.65%.
Example 2:
Basic step is with embodiment 1, but uses A101 type macroporous adsorbent resin instead, carries out desorption with 20% methyl alcohol, and gained FA product purity is 95.8%.
Claims (2)
1. the preparation method of a high-purity medical xanthonumic acid, it is characterized in that: used raw material is to contain weathered coal, brown coal, peat or the artificial oxidation coal of xanthohumic acid more than 10% among this preparation method; And carry out as follows:
(1) extraction:, handled 1 hour down at 60～80 ℃ with the mixed of feed coal, acid, water 1: 0.5 by weight～1: 5～10; Centrifugal or the filtration to above-mentioned blended material, and wash residue with water; Washings after filtrate filtered and the washing is mixed the formation mixed solution, and this mixed solution is transferred to pH=2～3, obtain A liquid with sodium hydroxide or potassium hydroxide;
(2) adsorption-desorption: A liquid is adsorbed xanthohumic acid by sorbent material, obtain B liquid with the desorbing agent desorb again; Described sorbent material is anionite-exchange resin or macroporous adsorbent resin; Described anionite-exchange resin is 201 * 7, IRA-401S, IPA-900, D201, D202; Described macroporous adsorbent resin is XAD-4, XAD-8, YJX-01, A101; Described desorbing agent is a kind of in 5～10% sodium hydroxide solution, 5～10% potassium hydroxide solution, 20～30% methyl alcohol, 50～70% acetone and 10～20% Virahols;
(3) desalination: to B liquid desalting and purifying, and wash resin with water with resin cation (R.C.), the filtrate and the washing lotion that merge in the demineralising process obtain C liquid;
(4) concentrate-drying: above-mentioned C liquid is concentrated down in≤70 ℃ under vacuum condition, dry down at≤60 ℃.
2. the method for claim 1 is characterized in that: extracting the used acid of xanthohumic acid is hydrochloric acid or sulfuric acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710097275A CN101033231B (en) | 2007-04-29 | 2007-04-29 | Method of preparing high-purity medical xanthonumic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710097275A CN101033231B (en) | 2007-04-29 | 2007-04-29 | Method of preparing high-purity medical xanthonumic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101033231A CN101033231A (en) | 2007-09-12 |
| CN101033231B true CN101033231B (en) | 2010-05-26 |
Family
ID=38729994
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200710097275A Expired - Fee Related CN101033231B (en) | 2007-04-29 | 2007-04-29 | Method of preparing high-purity medical xanthonumic acid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101033231B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101744844B (en) * | 2009-12-14 | 2012-05-30 | 昆明理工大学 | Fulvic acid or sodium fulvate substance with hypoglycemic function |
| CN103073732A (en) * | 2012-11-09 | 2013-05-01 | 沈阳农业大学 | Preparation method of fulvic acid in peat |
| CN104939050A (en) * | 2014-03-24 | 2015-09-30 | 黄志恒 | Preparation of fulvic acid or zinc fulvate oral granule |
| CN105085935B (en) * | 2015-09-16 | 2017-05-10 | 中国环境科学研究院 | XAD-8 resin grading method of alga fulvic acid |
| CN105777819A (en) * | 2016-05-10 | 2016-07-20 | 上海晶宇环境工程股份有限公司 | Process for extracting fulvic acid from garbage leachate membrane concentrated liquid and special device thereof |
| CN107998686B (en) * | 2017-11-28 | 2020-06-26 | 中国科学院南京土壤研究所 | Extracting agent for extracting humate with high antibacterial activity, and extraction method and application thereof |
| 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 |
| CN115651034A (en) * | 2022-10-26 | 2023-01-31 | 山西农业大学 | Preparation method and application of active small-molecule selenium fulvate chelate |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1070568A (en) * | 1992-10-28 | 1993-04-07 | 巩义市制药厂 | The production method of oral xanthogenic acid as medicine |
| JP2004325425A (en) * | 2003-04-28 | 2004-11-18 | Silk Kogei:Kk | Method of manufacturing standard powder sample of in-water fulvic acid |
-
2007
- 2007-04-29 CN CN200710097275A patent/CN101033231B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1070568A (en) * | 1992-10-28 | 1993-04-07 | 巩义市制药厂 | The production method of oral xanthogenic acid as medicine |
| JP2004325425A (en) * | 2003-04-28 | 2004-11-18 | Silk Kogei:Kk | Method of manufacturing standard powder sample of in-water fulvic acid |
Non-Patent Citations (8)
| Title |
|---|
| 徐莉英等.应用XAD系列高聚物吸附剂分离和纯化土壤富里酸溶液.土壤 5.1991,(5),278-280. |
| 徐莉英等.应用XAD系列高聚物吸附剂分离和纯化土壤富里酸溶液.土壤 5.1991,(5),278-280. * |
| 成绍鑫等.黄腐酸制剂开发中有关问题的思考及工作进展.腐植酸 2.2000,(2),1-7. |
| 成绍鑫等.黄腐酸制剂开发中有关问题的思考及工作进展.腐植酸 2.2000,(2),1-7. * |
| 折步国等.从天祝褐煤中提取黄腐酸的研究.腐植酸 1.2000,(1),15-17,14. |
| 折步国等.从天祝褐煤中提取黄腐酸的研究.腐植酸 1.2000,(1),15-17,14. * |
| 焦元刚等.风化煤中黄腐酸的提取研究.化工时刊21 1.2007,21(1),30-32. |
| 焦元刚等.风化煤中黄腐酸的提取研究.化工时刊21 1.2007,21(1),30-32. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101033231A (en) | 2007-09-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101033231B (en) | Method of preparing high-purity medical xanthonumic acid | |
| CN103041787B (en) | Preparation method of crosslinked chitosan-manganese dioxide composite adsorbing material | |
| CN103301803A (en) | Preparation method of attapulgite-modified clay for ammonia-nitrogen wastewater treatment | |
| US20170233301A1 (en) | Method, system and a process for producing fertilizers from seawater | |
| CN104046805B (en) | A kind of method that weathered superficial leaching rare-earth ore leach liquor Rare Earth Ion reclaims | |
| CN102489241B (en) | Preparation and regeneration method of water treatment defluoridation material | |
| CN100564276C (en) | A kind of preparation method who removes the modified hydrotalcite of Trace Mercury in the water, cadmium ion | |
| CN101805037A (en) | Method for removing humic acid pollutants in water by magnetic chitosan particle | |
| CN101804330A (en) | Heavy metal ion adsorbent and preparation and application method thereof | |
| CN102060398A (en) | Method for treating dimethylamine waste water by using weakly acidic cation exchange resin | |
| CN103073732A (en) | Preparation method of fulvic acid in peat | |
| CN105289562B (en) | Heavy metal wastewater thereby recoverying and utilizing method | |
| CN101961645B (en) | Adsorbing agent for eliminating S4O2<-> in acid mine wastewater and preparation method thereof | |
| CN100366337C (en) | Method for preparing absorbent with phosphor concentration and phosphor reclaim function | |
| CN207734649U (en) | Weathered coal extracts the device of pharmaceutical grade fulvic acid | |
| CN106432752A (en) | Preparing method of coal fulvic acid with high purity | |
| CN103059083A (en) | Process for purifying troxerutin crystallization mother liquor | |
| CN102974319A (en) | Drinking water cleaning agent with arsenic-removal function and preparation method thereof | |
| CN103253686A (en) | Method for producing vegetalitas fulvic acid/potassium sulfate concentrated solution/vegetalitas organic bacterial manure by utilizing alcohol biologic wastewater | |
| CN109126734A (en) | A kind of high efficiency, low cost adsorbent and preparation method for heavy metal containing wastewater treatment | |
| CN103071456B (en) | Organic amine iodine ion adsorbent as well as preparation method and application thereof | |
| CN105214621A (en) | A kind of preparation method of novel straw cellulose adsorbent | |
| CN103193800B (en) | A kind of method of each component of separation and purification from cefaclor enzymatic reaction liquid | |
| CN105521768A (en) | Drinking water purifying agent with arsenic removing function and preparation method thereof | |
| RU2506331C1 (en) | Method for obtaining ammonium tungstate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20100526 Termination date: 20170429 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |