CN103483403A - Circulating extraction method for extracting and purifying hesperidin from orange residues - Google Patents
Circulating extraction method for extracting and purifying hesperidin from orange residues Download PDFInfo
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- CN103483403A CN103483403A CN201310439872.3A CN201310439872A CN103483403A CN 103483403 A CN103483403 A CN 103483403A CN 201310439872 A CN201310439872 A CN 201310439872A CN 103483403 A CN103483403 A CN 103483403A
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Abstract
The invention discloses a circulating extraction method for extracting and purifying hesperidin from orange residues. The method comprises the steps of crude extraction and purification, breaks limitations of a raw material, solves problem of garbage produced in orange production and livelihood, successful changes waste into treasures and realizes recycled and economic use; through the research on the raw material, an alkali-acid extraction method is utilized and saturated lime water is used as a resolution solvent according to the characteristics of the raw material, the raw material source is stable, and the cost is relatively low; the precipitating action of the raw material on impurities such as pectin in the orange residues is utilized to further improve the treatment efficiency, so that the extraction, separation, purification and refining of the hesperidin are facilitated; according to the method, lime water wastewater subjected to resaturation through quicklime is further fully used to again extract the hesperidin, under the condition of not influencing the purification quality, the water source is saved, the sewage discharge amount is reduced, pollution to the surrounding environment is reduced, the production cost and sewage treatment cost of enterprises are reduced, and the product purity is relatively high.
Description
Technical field
The invention belongs to the Separation of Natural Products technical field, especially belong to a kind of isolation technique of effective ingredients in plant, particularly a kind of from the tangerine slag circulation utilization method of purification hesperidine.
Background technology
Oranges and tangerines are a kind of fruit of extensive plantation, contain hesperidine in oranges and tangerines, and existing method is extracted from dried orange peel or the dried immature fruit of citron orange, and extracting method mostly is water-ol extraction method and alkali-acid extraction method.
Hesperidine, have another name called Hesperidin, hesperidin, belongs to the natural flavone compounds, and its sterling is white needle-like crystals or pale yellow powder, and bitter is warm in nature, molecular formula C
28h
34o
15molecular weight 610.57, fusing point 258-262 ℃, be dissolved in hardly cold water, but larger solubleness is arranged in ethanol or hot water, dissolve in pyridine, glycerine, acetic acid or dilute alkaline soln, be insoluble in chloroform, acetone, ether or benzene, with iron trichloride, metallic salt reaction solution or generation precipitation, with hydrochloric acid-magnesium powder, react and be red-purple.
The Chinese patent that publication number is CN102276669A discloses the preparation method who extracts hesperidine from the dried immature fruit of citron orange, comprises the following steps: (1) prepares raw material is that dried immature fruit of citron orange fine powder is poured in extractor; (2) the configuration alkaline solution is made after immersion treatment emptying liquid stirring again to material in tank; (3) the configuration alkaline solution is done thermal treatment to material in tank; (4) the configuration alkaline solution is made for the first time after percolation treatment emptying liquid stirring again to material in tank; (5) the configuration alkaline solution is made for the second time after percolation treatment emptying liquid stirring again to material in tank; (6) pump into extracting solution and extract hesperidine; (7) the hesperidine crystallization of isolating; (8) to hesperidine crystallization be filtered dry, drying and processing.
In existing alkali-acid extraction method, the alkali lye that dissolves hesperidine by with discharge of wastewater, pollutes and wastes after acid is heavy.
Summary of the invention
The present invention according to the deficiencies in the prior art disclose a kind of from the tangerine slag circulation extracting method of purification hesperidine.The problem to be solved in the present invention is to provide a kind of method that takes full advantage of waste material tangerine slag purification hesperidine, and the present invention also provides alkali dissolution agent and the circulation utilization method thereof that has fine processing power for the tangerine slag.
The present invention is achieved through the following technical solutions:
The circulation utilization method of purification hesperidine from the tangerine slag, comprise slightly carry, purification step, it is characterized in that comprising the following steps:
Slightly carry
1) get the raw material citrus pulp and add the saturated limewater soaking and stirring 2 hours, adjusting PH with milk of lime in immersion process is 10.0-13.0, filters;
2) filter residue adds the saturated limewater soaking and stirring 2 hours again, filters;
3) merging filtrate, adjusting PH with acid is 2.0-5.0, places 12-24 hour, and throw out filters, and obtains crude product, and filtrate is stand-by;
Purifying
4) get above-mentioned crude product, add the sodium hydroxide solution that the bulking value specific concentration is 1.2%, be stirred to dissolving, filter; The sodium hydroxide solution that above-mentioned bulking value specific concentration is 1.2% is that the dissolution of sodium hydroxide of 1.2 gram weight is mixed with in 100 ml waters, or the volume of identical multiple increase sodium hydroxide weight and water prepares more 1.2% sodium hydroxide solution.
5) filtrate is 2.0-5.0 with nitric acid adjustment PH, and 60 ℃ of insulation 15-30 minute, take out, and filters, and solid 60-70 ℃ oven dry, obtain greyish white to faint yellow highly finished product;
The saturated limewater preparation
6) will in the stand-by filtrate of step 3), add excessive unslaked lime, stir, get saturated limewater stand-by;
7) repeating step 1) to 5), in each step, saturated liming is circulation saturated limewater prepared by step 6).
Above-mentionedly slightly carry filter residue in step 1) and add the saturated limewater of 2 times of volumes to soak, the described step 2 of slightly carrying) in filter residue add again the saturated limewater of 1.5 times of volumes to soak.
Further above-mentioned slightly carrying in step 3) adjusted PH with hydrochloric acid or nitric acid.
Above-mentioned purification step 4) sodium hydroxide solution added in is 12 to 1 with the part by weight of described crude product.
Above-mentioned each filtration step of slightly carrying in step adopts 200-400 mesh sieve squeeze and filter, and in purifying is rapid, each filtration step adopts 400 mesh sieves to filter.
Citrus pulp is oranges and tangerines remaining slags after the squeezing orange blossom.
Citrus pulp contains hesperidine, contains other impurity such as pectin simultaneously.The present invention adopts saturated limewater as dissolving alkali lye, and hesperidine is dissolved in basic solution, is insoluble to acidic solution; Its principle is after open loop, to dissolve in basic solution, regulates pH closed loop precipitation when acid; Adopt its alkalescence of saturated limewater gentle, can not cause because the pH of extracting solution in leaching process is inconsistent the change of hesperidine structure, because can not closed loop after the Hesperidin open loop, the extraction yield of pH de-stabilising effect Hesperidin.
Highly basic during saturated limewater (calcium hydroxide) belongs to, compare with oxygen sodium oxide, potassium hydroxide etc., and alkalescence is gentle, and when the hesperidine suitability for industrialized production, process for preparation is simple, convenient, less demanding to the preparation facility.Simultaneously, contain calcium ion in saturated limewater, calcium ion can with extracting solution or tangerine slag in pectin etc. form throw out, be conducive to hesperidine and extract, separate, purify and make with extra care.
By experimental study, the liming waste water that recycles is saturated again with unslaked lime after again for extracting Hesperidin, its yield and content do not reduce because of cycling utilization of wastewater.Adopt cycling utilization of wastewater, can save water source, reduce quantity of wastewater effluent, reduce the pollution to surrounding enviroment, and reduce production cost and the cost of sewage disposal of enterprise.
The present invention does not need raw material drying is pulverized, and can directly feed intake; In leaching process, do not need material and alkaline solution in tank are heated, can at room temperature carry out; Less demanding to extracting facility, as long as meet pH requirement in the raw material extracting solution, and stir and get final product.
Helpfulness of the present invention: the present invention adopts the tangerine slag as the raw material that extracts hesperidine, has broken through the raw material restriction, has solved the garbage problem that Orange Producing and life produce, and has successfully realized turning waste into wealth, the recycling economy utilization, through the research to raw material, the present invention is according to property of raw material, adopt alkali-acid extraction method and adopt saturated limewater as dissolution solvent, raw materials enjoy stable sources, cost is lower, and utilized raw material further to pass through processing efficiency to contamination precipitation effects such as pectin in the tangerine slag, being conducive to hesperidine extracts, separate, purify with refining, the present invention also further take full advantage of liming waste water saturated again with unslaked lime after again for extracting Hesperidin, in the situation that do not affect the purification quality, save water source, reduce quantity of wastewater effluent, the pollution of reduction to surrounding enviroment, production cost and the cost of sewage disposal of enterprise have been reduced, product purity is higher.
Embodiment
Below by embodiment, the present invention is conducted further description; the present embodiment is only for being further detailed the present invention; but can not be interpreted as limiting the scope of the invention, those skilled in the art's content according to the present invention makes some nonessential improvement and adjustment belongs to the scope of protection of the invention.
Embodiment 1
Utilize for the first time: get citrus pulp 1kg, add the saturated limewater of 2 times of volumes, soaking and stirring is after 2 hours, squeeze and filter (200-400 order), and it is 10.0-13.0 that the milk of lime of take in immersion process is adjusted PH; Add again 1.5 times of volume saturated limewater soaking and stirring 2 hours, squeeze and filter (200-400 order); Merging filtrate, adjusting PH with hydrochloric acid or nitric acid is 2.0-5.0, places 12-24 hour, gets the supernatant liquor I standby, throw out press filtration (400 order), obtain crude product 6-7g purity 65%-75%.
Get above-mentioned crude product, in the ratio of crude product and sodium hydroxide solution 1:12 weight ratio, add the sodium hydroxide solution that the bulking value specific concentration is 1.2%, be stirred to dissolving, filter in (400 order), remove insolubles, get filtrate, it is 2.0-5.0 that the salpeter solution that is 5% with weight percent content is adjusted PH, and 60 ℃ of insulation 15-30 minute, take out, filter in (400 order), 60-70 ℃ of oven dry, obtain greyish white to faint yellow highly finished product 3-4g, after testing, faint yellow highly finished product are hesperidine, and purity is greater than 90%.
Utilize for the second time: get citrus pulp 1kg, add 2 times of volume saturated limewaters, saturated limewater is by the preparation of supernatant liquor I and obtain, and soaking and stirring is after 2 hours, squeeze and filter (200-400 order), and the milk of lime of take in immersion process adjustment PH is 10.0-13.0; Add again 1.5 times of volume saturated limewater soaking and stirring 2 hours, squeeze and filter (200-400 order); Merging filtrate, adjusting PH with hydrochloric acid or nitric acid is 2.0-5.0, places 12-24 hour, gets supernatant liquor II standby, throw out press filtration (400 order), obtain crude product 6-7g, purity 65%-75%.
Get above-mentioned crude product, in the ratio of crude product and sodium hydroxide solution 1:12 weight ratio, add the sodium hydroxide solution that the bulking value specific concentration is 1.2%, be stirred to dissolving, filter in (400 order), remove insolubles, get filtrate, it is 2.0-5.0 that the salpeter solution that is 5% with weight percent content is adjusted PH, and 60 ℃ of insulation 15-30 minute, take out, filter in (400 order), 60-70 ℃ of oven dry, obtain greyish white to faint yellow highly finished product 3-4g, after testing, faint yellow highly finished product are hesperidine, and purity is greater than 90%.
Utilize for the third time: with utilizing for the second time, difference is that the saturated limewater that citrus pulp adds is obtained by supernatant liquor II preparation.With the preparation of citrus pulp 1kg raw material, obtain greyish white extremely faint yellow highly finished product 3-4g, after testing, faint yellow highly finished product are hesperidine, purity is greater than 90%.
Utilize for the 4th time: with utilizing for the third time, the difference gained supernatant liquor preparation that is the saturated limewater that adds of citrus pulp when utilizing for the third time and obtaining.With the preparation of citrus pulp 1kg raw material, obtain greyish white extremely faint yellow highly finished product 3-4g, after testing, faint yellow highly finished product are hesperidine, purity is greater than 90%.
The preparation of circulation saturated limewater: get above-mentioned each supernatant liquor, add excessive unslaked lime, stir, make it saturated, get the supernatant liquor saturated limewater stand-by.
Comparative example
Get citrus pulp 1kg, add the water of 2 times of volumes, with the 2mol/L sodium hydroxide solution, regulate pH to 12, soaking and stirring is after 2 hours, squeeze and filter (200-400 order); The water that adds again 1.5 times, regulate pH to 12 with the 2mol/L sodium hydroxide solution, and soaking and stirring is after 2 hours, squeeze and filter (200-400 order); Merging filtrate, adjusting PH with hydrochloric acid is 4.0-5.0, places 12-24 hour, gets supernatant liquor standby, throw out press filtration (400 order), obtain crude product 6.5-7.0g purity 60%-70%.Get above-mentioned crude product, press crude product and sodium hydroxide solution weight ratio 1:12 adds the sodium hydroxide solution that the bulking value specific concentration is 1.2%, be stirred to dissolving, filter in (400 order), remove insolubles, get filtrate, it is 4.0-5.0 that the hydrochloric acid soln with 5% is adjusted PH, 60 ℃ of insulation 15-30 minute, take out, filter in (400 order), 60-70 ℃ of oven dry, obtain greyish white to faint yellow highly finished product 4.0-4.8g.After testing, faint yellow highly finished product are hesperidine, and purity is 80-85%.
Utilize for the second time: get citrus pulp 1kg, add the water of 2 times of volumes, with the 2mol/L sodium hydroxide solution, regulate pH to 12, soaking and stirring is after 2 hours, squeeze and filter (200-400 order), and sodium hydroxide solution is that the supernatant liquor hydro-oxidation sodium utilized is for the first time made; The water that adds again 1.5 times, regulate pH to 12 with the 2mol/L sodium hydroxide solution, and soaking and stirring is after 2 hours, squeeze and filter (200-400 order); Merging filtrate, adjusting pH with hydrochloric acid is 4.0-5.0, places 12-24 hour, gets supernatant liquor standby, throw out press filtration (400 order), obtain crude product 7.5-8.5g, purity 45%-55%.Get above-mentioned crude product, by crude product and sodium hydroxide solution weight ratio 1:12, add the sodium hydroxide solution that the bulking value specific concentration is 1.2%, be stirred to dissolving, filter in (400 order), remove insolubles, get filtrate, it is 4.0-5.0 that the hydrochloric acid soln that is 5% with weight percent content is adjusted PH, 60 ℃ of insulation 15-30 minute, take out, filter in (400 order) 60-70 ℃ of oven dry, must be yellow to deep yellow highly finished product 3.5-4.5g, purity is 70-75%.
Result from embodiment 1 with comparative example, the present invention compares as the solvating agent extracting method with adopting other alkali, and repeatedly, and Hesperidin extracts the rate of transform to the waste water reusable edible and product purity is high.
Claims (5)
1. the circulation extracting method of a purification hesperidine from the tangerine slag is characterized in that comprising the following steps:
Slightly carry
1) get the raw material citrus pulp and add the saturated limewater soaking and stirring 2 hours, adjusting PH with milk of lime in immersion process is 10.0-13.0, filters;
2) filter residue adds the saturated limewater soaking and stirring 2 hours again, filters;
3) merging filtrate, adjusting PH with acid is 2.0-5.0, places 12-24 hour, and throw out filters, and obtains crude product, and filtrate is stand-by;
Purifying
4) get above-mentioned crude product, add the sodium hydroxide solution that the bulking value specific concentration is 1.2%, be stirred to dissolving, filter;
5) filtrate is 2.0-5.0 with nitric acid adjustment PH, and 60 ℃ of insulation 15-30 minute, take out, and filters, and solid 60-70 ℃ oven dry, obtain greyish white to faint yellow highly finished product;
The saturated limewater preparation
6) will in the stand-by filtrate of step 3), add excessive unslaked lime, stir, get saturated limewater stand-by;
7) repeating step 1) to 5), in each step, saturated liming is circulation saturated limewater prepared by step 6).
2. the circulation extracting method of purification hesperidine from the tangerine slag according to claim 1, it is characterized in that: describedly slightly carry filter residue in step 1) and add the saturated limewater of 2 times of volumes to soak, the described step 2 of slightly carrying) in filter residue add again the saturated limewater of 1.5 times of volumes to soak.
According to claim 1 or 2 described from the tangerine slag circulation extracting method of purification hesperidine, it is characterized in that: described slightly carrying in step 3) adjusted PH with hydrochloric acid or nitric acid.
4. the circulation extracting method of purification hesperidine from the tangerine slag according to claim 3, it is characterized in that: the sodium hydroxide solution added described purification step 4) is 12 to 1 with the weight ratio of described crude product.
5. the circulation extracting method of purification hesperidine from the tangerine slag according to claim 4, it is characterized in that: in slightly putting forward step, each filtration step adopts 200-400 mesh sieve squeeze and filter, and in purifying is rapid, each filtration step adopts 400 mesh sieves to filter.
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Cited By (5)
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| CN104610399A (en) * | 2014-12-16 | 2015-05-13 | 李玉山 | Method for controlling different colors of flavonoid compound |
| CN104656691A (en) * | 2015-01-04 | 2015-05-27 | 李玉山 | Method for controlling different stacking densities of compounds |
| CN105061532A (en) * | 2015-08-10 | 2015-11-18 | 厦门世达膜科技有限公司 | Production method for hesperidin |
| CN105779107A (en) * | 2014-12-24 | 2016-07-20 | 桂林电子科技大学 | Recycling and harmless treatment method for citrus peel |
| CN106520372A (en) * | 2016-11-02 | 2017-03-22 | 赣南师范大学 | Method for extracting essential oil and hesperidin by physiological fallen fruits of navel orange |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105779107A (en) * | 2014-12-24 | 2016-07-20 | 桂林电子科技大学 | Recycling and harmless treatment method for citrus peel |
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| CN105061532A (en) * | 2015-08-10 | 2015-11-18 | 厦门世达膜科技有限公司 | Production method for hesperidin |
| CN105061532B (en) * | 2015-08-10 | 2019-01-18 | 厦门世达膜科技有限公司 | A kind of production method of hesperidine |
| CN106520372A (en) * | 2016-11-02 | 2017-03-22 | 赣南师范大学 | Method for extracting essential oil and hesperidin by physiological fallen fruits of navel orange |
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Effective date of registration: 20191211 Address after: 210000 Shuizaogang 44, Gulou District, Nanjing City, Jiangsu Province Patentee after: Wei Deying Address before: 404300 Zhongxian Chongqing immigrant eco industrial park Patentee before: Chongqing main flow biological engineering company limited |
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Effective date of registration: 20200529 Address after: 546100 West Zone of Henan Industrial Park, Laibin Industrial Zone, Guangxi Zhuang Autonomous Region Patentee after: Guangxi TIANSHUNXIANG Pharmaceutical Co., Ltd Address before: 210000 Shuizaogang 44, Gulou District, Nanjing City, Jiangsu Province Patentee before: Wei Deying |