CN103483403B - A kind of circulation extracting method of hesperidine of purifying from tangerine slag - Google Patents
A kind of circulation extracting method of hesperidine of purifying from tangerine slag Download PDFInfo
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- CN103483403B CN103483403B CN201310439872.3A CN201310439872A CN103483403B CN 103483403 B CN103483403 B CN 103483403B CN 201310439872 A CN201310439872 A CN 201310439872A CN 103483403 B CN103483403 B CN 103483403B
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- QUQPHWDTPGMPEX-QJBIFVCTSA-N hesperidin Chemical compound C1=C(O)C(OC)=CC=C1[C@H]1OC2=CC(O[C@H]3[C@@H]([C@@H](O)[C@H](O)[C@@H](CO[C@H]4[C@@H]([C@H](O)[C@@H](O)[C@H](C)O4)O)O3)O)=CC(O)=C2C(=O)C1 QUQPHWDTPGMPEX-QJBIFVCTSA-N 0.000 title abstract description 36
- QUQPHWDTPGMPEX-UHFFFAOYSA-N Hesperidine Natural products C1=C(O)C(OC)=CC=C1C1OC2=CC(OC3C(C(O)C(O)C(COC4C(C(O)C(O)C(C)O4)O)O3)O)=CC(O)=C2C(=O)C1 QUQPHWDTPGMPEX-UHFFFAOYSA-N 0.000 title abstract description 35
- 238000000034 method Methods 0.000 title abstract description 18
- 241000675108 Citrus tangerina Species 0.000 title abstract description 16
- 239000002893 slag Substances 0.000 title abstract description 15
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical class [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 abstract description 23
- 239000002994 raw material Substances 0.000 abstract description 17
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 abstract description 10
- 239000002351 wastewater Substances 0.000 abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 10
- 239000001100 (2S)-5,7-dihydroxy-2-(3-hydroxy-4-methoxyphenyl)chroman-4-one Substances 0.000 abstract description 8
- QUQPHWDTPGMPEX-UTWYECKDSA-N aurantiamarin Natural products COc1ccc(cc1O)[C@H]1CC(=O)c2c(O)cc(O[C@@H]3O[C@H](CO[C@@H]4O[C@@H](C)[C@H](O)[C@@H](O)[C@H]4O)[C@@H](O)[C@H](O)[C@H]3O)cc2O1 QUQPHWDTPGMPEX-UTWYECKDSA-N 0.000 abstract description 8
- APSNPMVGBGZYAJ-GLOOOPAXSA-N clematine Natural products COc1cc(ccc1O)[C@@H]2CC(=O)c3c(O)cc(O[C@@H]4O[C@H](CO[C@H]5O[C@@H](C)[C@H](O)[C@@H](O)[C@H]5O)[C@@H](O)[C@H](O)[C@H]4O)cc3O2 APSNPMVGBGZYAJ-GLOOOPAXSA-N 0.000 abstract description 8
- VUYDGVRIQRPHFX-UHFFFAOYSA-N hesperidin Natural products COc1cc(ccc1O)C2CC(=O)c3c(O)cc(OC4OC(COC5OC(O)C(O)C(O)C5O)C(O)C(O)C4O)cc3O2 VUYDGVRIQRPHFX-UHFFFAOYSA-N 0.000 abstract description 8
- 229940025878 hesperidin Drugs 0.000 abstract description 8
- ARGKVCXINMKCAZ-UHFFFAOYSA-N neohesperidine Natural products C1=C(O)C(OC)=CC=C1C1OC2=CC(OC3C(C(O)C(O)C(CO)O3)OC3C(C(O)C(O)C(C)O3)O)=CC(O)=C2C(=O)C1 ARGKVCXINMKCAZ-UHFFFAOYSA-N 0.000 abstract description 8
- 239000002253 acid Substances 0.000 abstract description 7
- 238000000605 extraction Methods 0.000 abstract description 7
- 238000000746 purification Methods 0.000 abstract description 6
- 239000000292 calcium oxide Substances 0.000 abstract description 5
- 235000012255 calcium oxide Nutrition 0.000 abstract description 5
- 229920006395 saturated elastomer Polymers 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 235000010987 pectin Nutrition 0.000 abstract description 4
- 229920001277 pectin Polymers 0.000 abstract description 4
- 239000001814 pectin Substances 0.000 abstract description 4
- 239000002699 waste material Substances 0.000 abstract description 4
- 238000004090 dissolution Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 239000010865 sewage Substances 0.000 abstract description 3
- 238000011109 contamination Methods 0.000 abstract description 2
- 238000001556 precipitation Methods 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract description 2
- 238000007670 refining Methods 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 61
- 239000000243 solution Substances 0.000 description 25
- 238000003756 stirring Methods 0.000 description 16
- 239000012043 crude product Substances 0.000 description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 14
- 239000000047 product Substances 0.000 description 14
- 239000000706 filtrate Substances 0.000 description 12
- 241000207199 Citrus Species 0.000 description 11
- 235000020971 citrus fruits Nutrition 0.000 description 11
- 238000002791 soaking Methods 0.000 description 10
- 239000006228 supernatant Substances 0.000 description 10
- 238000001914 filtration Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000012670 alkaline solution Substances 0.000 description 5
- 238000009413 insulation Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 239000000920 calcium hydroxide Substances 0.000 description 4
- 235000011116 calcium hydroxide Nutrition 0.000 description 4
- 235000013399 edible fruits Nutrition 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 240000004307 Citrus medica Species 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000003637 basic solution Substances 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 238000005325 percolation Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- GAMYVSCDDLXAQW-AOIWZFSPSA-N Thermopsosid Natural products O(C)c1c(O)ccc(C=2Oc3c(c(O)cc(O[C@H]4[C@H](O)[C@@H](O)[C@H](O)[C@H](CO)O4)c3)C(=O)C=2)c1 GAMYVSCDDLXAQW-AOIWZFSPSA-N 0.000 description 1
- FOGVNFMUZXDMTR-UHFFFAOYSA-N [Mg].Cl Chemical compound [Mg].Cl FOGVNFMUZXDMTR-UHFFFAOYSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 235000021050 feed intake Nutrition 0.000 description 1
- 229930003944 flavone Natural products 0.000 description 1
- -1 flavone compounds Chemical class 0.000 description 1
- 235000011949 flavones Nutrition 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- JBJWASZNUJCEKT-UHFFFAOYSA-M sodium;hydroxide;hydrate Chemical compound O.[OH-].[Na+] JBJWASZNUJCEKT-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- VHBFFQKBGNRLFZ-UHFFFAOYSA-N vitamin p Natural products O1C2=CC=CC=C2C(=O)C=C1C1=CC=CC=C1 VHBFFQKBGNRLFZ-UHFFFAOYSA-N 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
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- Coloring Foods And Improving Nutritive Qualities (AREA)
- Medicines Containing Plant Substances (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
The invention discloses a kind of circulation extracting method of hesperidine of purifying from tangerine slag.Comprise slightly carry, purification step.The present invention adopts tangerine slag as extracting the raw material of hesperidine, breaches raw material restriction, solves the garbage problem that Orange Producing and life produce, successfully achieve turn waste into wealth, recycling economy utilizes, 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 make use of raw material to contamination precipitation effects such as pectin in tangerine slag further by processing efficiency, be conducive to hesperidine to extract, be separated, purify with refining, the present invention also make full use of further liming waste water unslaked lime saturated again after again for extracting Hesperidin, when not affecting purification quality, save water source, reduce quantity of wastewater effluent, reduce the pollution to surrounding enviroment, reduce production cost and the cost of sewage disposal of enterprise, product purity is higher.
Description
Technical field
The invention belongs to Separation of Natural Products technical field, especially belong to a kind of isolation technique of effective ingredients in plant, particularly a kind of circulation utilization method of hesperidine of purifying from tangerine slag.
Background technology
Oranges and tangerines are a kind of fruit of extensive plantation, and containing hesperidine in oranges and tangerines, 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, has another name called Hesperidin, hesperidin, belongs to 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 DEG C, be dissolved in cold water hardly, but in ethanol or hot water, there is larger solubleness, dissolve in pyridine, glycerine, acetic acid or dilute alkaline soln, be insoluble in chloroform, acetone, ether or benzene, precipitate with iron trichloride, metallic salt reaction solution or generate, react in red-purple with hydrochloric acid-magnesium powder.
Publication number is that the Chinese patent of CN102276669A discloses the preparation method extracting hesperidine from the dried immature fruit of citron orange, comprises the following steps: (1) prepares raw material and dried immature fruit of citron orange fine powder is poured in extractor; (2) emptying liquid stirring again after configuration alkaline solution makes immersion treatment to material in tank; (3) configure alkaline solution and thermal treatment is done to material in tank; (4) alkaline solution is configured to emptying liquid stirring again after material work first time percolation treatment in tank; (5) alkaline solution is configured to emptying liquid stirring again after material work second time percolation treatment in tank; (6) pump into extracting solution and extract hesperidine; (7) to isolate hesperidine crystallization; (8) hesperidine crystallization is filtered dry, drying and processing.
In existing alkali-acid extraction method, the alkali lye dissolving hesperidine by with discharge of wastewater, pollutes and wastes after acid is heavy.
Summary of the invention
The present invention discloses a kind of circulation extracting method of hesperidine of purifying from tangerine slag according to the deficiencies in the prior art.The problem to be solved in the present invention is to provide a kind of method making full use of waste material tangerine slag purification hesperidine, present invention also offers alkali dissolution agent and the circulation utilization method thereof for tangerine slag with fine processing power.
The present invention is achieved through the following technical solutions:
To purify from tangerine slag the circulation utilization method of hesperidine, comprise slightly carry, purification step, it is characterized in that comprising the following steps:
Slightly carry
1) get raw citrus slag and add 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 saturated limewater soaking and stirring 2 hours again, filters;
3) merging filtrate, be 2.0-5.0 with acid adjustment PH, place 12-24 hour, throw out filters, and obtain crude product, filtrate is stand-by;
Purifying
4) get above-mentioned crude product, add the sodium hydroxide solution that bulking value specific concentration is 1.2%, be stirred to dissolving, filter; Above-mentioned bulking value specific concentration be 1.2% sodium hydroxide solution be the sodium hydroxide of 1.2 gram weight is dissolved in 100 ml waters be mixed with, or the identical multiple volume that increases sodium hydroxide weight and water prepares the sodium hydroxide solution of more 1.2%.
5) filtrate nitric acid adjustment PH is 2.0-5.0, and 60 DEG C of insulation 15-30 minute, take out, filter, solid 60-70 DEG C of oven dry, obtains greyish white to faint yellow highly finished product;
Prepared by saturated limewater
6) add excessive unslaked lime by stand-by for step 3) filtrate, stir, get saturated limewater stand-by;
7) repeating step 1) to 5), in each step, saturated limewater is circulation saturated limewater prepared by step 6).
Above-mentionedly slightly carry the saturated limewater that filter residue in step 1) adds 2 times of volumes and soak, describedly slightly put forward step 2) in the filter residue saturated limewater that adds 1.5 times of volumes again soak.
Further above-mentioned slightly carrying in step 3) adjusts PH with hydrochloric acid or nitric acid.
Above-mentioned purification step 4) in the sodium hydroxide solution that adds be 12 to 1 with the part by weight of described crude product.
Above-mentionedly slightly carry each filtration step in step and adopt 200-400 mesh sieve squeeze and filter, in purifying is rapid, each filtration step adopts 400 mesh screen.
Citrus pulp is oranges and tangerines remaining slags after squeezing orange blossom.
Citrus pulp contains hesperidine, simultaneously containing other impurity such as pectin.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 dissolved after open loop in basic solution, and when regulating pH extremely acid, then closed loop precipitates; Adopt its alkalescence of saturated limewater gentle, the change of hesperidine structure can not be caused because the pH of extracting solution in leaching process is inconsistent, because can not closed loop after Hesperidin open loop, the extraction yield of pH de-stabilising effect Hesperidin.
Highly basic during saturated limewater (calcium hydroxide) belongs to, compared with oxygen sodium oxide, potassium hydroxide etc., alkalescence is gentle, and when hesperidine suitability for industrialized production, process for preparation is simple, convenient, not high to preparation facility requirements.Meanwhile, containing calcium ion in saturated limewater, calcium ion can form throw out with the pectin etc. in extracting solution or tangerine slag, is conducive to hesperidine extracting and developing, purifies and refine.
By experimental study, be again used for extracting Hesperidin after the liming waste water unslaked lime recycled is saturated again, its yield and content do not reduce because of cycling utilization of wastewater.Adopt cycling utilization of wastewater, can water source be saved, 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 to pulverize, and can directly feed intake; In leaching process, do not need to heat material and alkaline solution in tank, can at room temperature carry out; Not high to extraction facility requirements, as long as meet pH requirement in raw material extracting solution, and stir.
Helpfulness of the present invention: the present invention adopts tangerine slag as extracting the raw material of hesperidine, breaches raw material restriction, solves the garbage problem that Orange Producing and life produce, successfully achieve turn waste into wealth, recycling economy utilizes, 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 make use of raw material to contamination precipitation effects such as pectin in tangerine slag further by processing efficiency, be conducive to hesperidine to extract, be separated, purify with refining, the present invention also make full use of further liming waste water unslaked lime saturated again after again for extracting Hesperidin, when not affecting purification quality, save water source, reduce quantity of wastewater effluent, reduce the pollution to surrounding enviroment, reduce production cost and the cost of sewage disposal of enterprise, 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
First time utilizes: get citrus pulp 1kg, add the saturated limewater of 2 times of volumes, and soaking and stirring is after 2 hours, and squeeze and filter (200-400 order), adjusts PH for 10.0-13.0 with milk of lime in immersion process; Add 1.5 times of volume saturated limewater soaking and stirring again 2 hours, squeeze and filter (200-400 order); Merging filtrate, be 2.0-5.0 with hydrochloric acid or nitric acid adjustment PH, place 12-24 hour, get supernatant liquor I for subsequent use, throw out press filtration (400 order), obtains crude product 6-7g purity 65%-75%.
Get above-mentioned crude product, add in the ratio of crude product and sodium hydroxide solution 1:12 weight ratio the sodium hydroxide solution that bulking value specific concentration is 1.2%, be stirred to dissolving, filter (400 order), removing insolubles, gets filtrate, adjusting PH with the salpeter solution that weight percent content is 5% is 2.0-5.0, and 60 DEG C of insulation 15-30 minute, take out, filter (400 order), 60-70 DEG C of oven dry, obtains 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%.
Second time utilizes: get citrus pulp 1kg, add 2 times of volume saturated limewaters, saturated limewater is prepared by supernatant liquor I and obtains, and soaking and stirring is after 2 hours, and squeeze and filter (200-400 order), adjusts PH for 10.0-13.0 with milk of lime in immersion process; Add 1.5 times of volume saturated limewater soaking and stirring again 2 hours, squeeze and filter (200-400 order); Merging filtrate, be 2.0-5.0 with hydrochloric acid or nitric acid adjustment PH, place 12-24 hour, get supernatant liquor II for subsequent use, throw out press filtration (400 order), obtains crude product 6-7g, purity 65%-75%.
Get above-mentioned crude product, add in the ratio of crude product and sodium hydroxide solution 1:12 weight ratio the sodium hydroxide solution that bulking value specific concentration is 1.2%, be stirred to dissolving, filter (400 order), removing insolubles, gets filtrate, adjusting PH with the salpeter solution that weight percent content is 5% is 2.0-5.0, and 60 DEG C of insulation 15-30 minute, take out, filter (400 order), 60-70 DEG C of oven dry, obtains 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%.
Third time utilizes: utilize with second time, difference is that the saturated limewater that citrus pulp adds is prepared by supernatant liquor II and obtains.With the preparation of citrus pulp 1kg raw material, 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 4th time: utilize with third time, difference is that the saturated limewater that citrus pulp adds is prepared by gained supernatant liquor when utilizing for the third time and obtains.With the preparation of citrus pulp 1kg raw material, 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%.
The preparation of circulation saturated limewater: get above-mentioned each supernatant liquor, add excessive unslaked lime, stirs, makes it saturated, get supernatant liquor saturated limewater stand-by.
Comparative example
Get citrus pulp 1kg, add the water of 2 times of volumes, regulate pH to 12 with 2mol/L sodium hydroxide solution, soaking and stirring is after 2 hours, squeeze and filter (200-400 order); Add the water of 1.5 times again, regulate pH to 12 with 2mol/L sodium hydroxide solution, soaking and stirring is after 2 hours, squeeze and filter (200-400 order); Merging filtrate, be 4.0-5.0 with hydrochloric acid adjustment PH, place 12-24 hour, get supernatant liquor for subsequent use, throw out press filtration (400 order), obtains 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 bulking value specific concentration is 1.2%, be stirred to dissolving, filter (400 order), removing insolubles, getting filtrate, is 4.0-5.0 with the hydrochloric acid soln adjustment PH of 5%, 60 DEG C of insulation 15-30 minute, take out, filter (400 order), 60-70 DEG C 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%.
Second time utilizes: get citrus pulp 1kg, add the water of 2 times of volumes, and regulate pH to 12 with 2mol/L sodium hydroxide solution, 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 first time is made; Add the water of 1.5 times again, regulate pH to 12 with 2mol/L sodium hydroxide solution, soaking and stirring is after 2 hours, squeeze and filter (200-400 order); Merging filtrate, be 4.0-5.0 with hydrochloric acid adjustment pH, place 12-24 hour, get supernatant liquor for subsequent use, throw out press filtration (400 order), obtains crude product 7.5-8.5g, purity 45%-55%.Get above-mentioned crude product, add by crude product and sodium hydroxide solution weight ratio 1:12 the sodium hydroxide solution that bulking value specific concentration is 1.2%, be stirred to dissolving, filter (400 order), removing insolubles, gets filtrate, is 4.0-5.0 with the hydrochloric acid soln adjustment PH that weight percent content is 5%, 60 DEG C of insulation 15-30 minute, take out, filter (400 order), 60-70 DEG C of oven dry, obtain yellow to deep yellow highly finished product 3.5-4.5g, purity is 70-75%.
From result with comparative example of embodiment 1, the present invention and other alkali of employing are as compared with solvating agent extracting method, and repeatedly, and Hesperidin extracts the rate of transform to waste water reusable edible and product purity is high.
Claims (4)
1. to purify from tangerine slag the circulation extracting method of hesperidine, it is characterized in that comprising the following steps:
Slightly carry:
1) get raw citrus slag and add 2 times of volume 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 1.5 times of volume saturated limewater soaking and stirring 2 hours again, filters;
3) merging filtrate, be 2.0-5.0 with acid adjustment pH, place 12-24 hour, throw out filters, and obtain crude product, filtrate is stand-by;
Purifying:
4) get above-mentioned crude product, add the sodium hydroxide solution that bulking value specific concentration is 1.2%, be stirred to dissolving, filter;
5) filtrate nitric acid adjustment pH is 2.0-5.0, and 60 DEG C of insulation 15-30 minute, take out, filter, solid 60-70 DEG C of oven dry, obtains greyish white to faint yellow highly finished product;
Prepared by saturated limewater:
6) by step 3) add excessive unslaked lime in stand-by filtrate, stir, get saturated limewater stand-by;
7) repeating step 1) to 5), in each step, saturated limewater is step 6) the circulation saturated limewater prepared.
2. to purify from tangerine slag according to claim 1 the circulation extracting method of hesperidine, it is characterized in that: described step 3) in hydrochloric acid or nitric acid adjustment pH.
3. to purify from tangerine slag according to claim 2 the circulation extracting method of hesperidine, it is characterized in that: described step 4) in the sodium hydroxide solution that adds be 12 to 1 with the weight ratio of described crude product.
4. to purify from tangerine slag according to claim 3 the circulation extracting method of hesperidine, it is characterized in that: adopt 200-400 mesh sieve squeeze and filter slightly carrying each filtration step in step, each filtration step adopts 400 mesh screen in purification step.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310439872.3A CN103483403B (en) | 2013-09-24 | 2013-09-24 | A kind of circulation extracting method of hesperidine of purifying from tangerine slag |
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| CN104610399A (en) * | 2014-12-16 | 2015-05-13 | 李玉山 | Method for controlling different colors of flavonoid compound |
| CN105779107A (en) * | 2014-12-24 | 2016-07-20 | 桂林电子科技大学 | Recycling and harmless treatment method for citrus peel |
| CN104656691A (en) * | 2015-01-04 | 2015-05-27 | 李玉山 | Method for controlling different stacking densities of compounds |
| 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 |
| CN115521346A (en) * | 2022-07-08 | 2022-12-27 | 李玉山 | A method for controlling bulk density of flavonoids |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101235062A (en) * | 2007-02-01 | 2008-08-06 | 湖南博特科技有限公司 | Preparation technique for extracting high pure hesperidin by cold impurity-removing one-step method |
| CN101747394A (en) * | 2009-12-31 | 2010-06-23 | 浙江工业大学 | Method for extracting hesperidin from tangerine peel |
| CN102250549A (en) * | 2011-04-24 | 2011-11-23 | 广州大学 | Method for extracting tangerine peel oil resin and hesperidin from tangerine peel |
| CN103113438A (en) * | 2013-01-30 | 2013-05-22 | 唐忠海 | Method for extracting hesperidin and orange peel uranidin from orange peel |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08188593A (en) * | 1995-01-10 | 1996-07-23 | Wakayama Agribio Kenkyu Center:Kk | Extraction and recovery of hesperidin contained in citrus fruits |
-
2013
- 2013-09-24 CN CN201310439872.3A patent/CN103483403B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101235062A (en) * | 2007-02-01 | 2008-08-06 | 湖南博特科技有限公司 | Preparation technique for extracting high pure hesperidin by cold impurity-removing one-step method |
| CN101747394A (en) * | 2009-12-31 | 2010-06-23 | 浙江工业大学 | Method for extracting hesperidin from tangerine peel |
| CN102250549A (en) * | 2011-04-24 | 2011-11-23 | 广州大学 | Method for extracting tangerine peel oil resin and hesperidin from tangerine peel |
| CN103113438A (en) * | 2013-01-30 | 2013-05-22 | 唐忠海 | Method for extracting hesperidin and orange peel uranidin from orange peel |
Non-Patent Citations (3)
| Title |
|---|
| 从柑桔皮同时制取乙醇和橙皮甙的新方法;饶志明，等;《漳州师范学院学报（自然科学版）》;20001130;第13卷(第4期);第56-60页 * |
| 柑橘果实加工废料资源化新技术研究;饶志明，等;《亚热带植物科学》;20011231;第30卷(第2期);第6-10页 * |
| 橙皮苷提取方法的研究;朱思明，等;《食品研究与开发》;20090731;第30卷(第7期);第17-20页 * |
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