CN102757663A - Chestnut shell pigment grading method - Google Patents
Chestnut shell pigment grading method Download PDFInfo
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- CN102757663A CN102757663A CN2011101053267A CN201110105326A CN102757663A CN 102757663 A CN102757663 A CN 102757663A CN 2011101053267 A CN2011101053267 A CN 2011101053267A CN 201110105326 A CN201110105326 A CN 201110105326A CN 102757663 A CN102757663 A CN 102757663A
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- 239000000049 pigment Substances 0.000 title claims abstract description 156
- 241001070941 Castanea Species 0.000 title claims abstract description 93
- 235000014036 Castanea Nutrition 0.000 title claims abstract description 93
- 238000000034 method Methods 0.000 title claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000003960 organic solvent Substances 0.000 claims abstract description 24
- 239000000287 crude extract Substances 0.000 claims abstract description 23
- 239000011347 resin Substances 0.000 claims abstract description 15
- 229920005989 resin Polymers 0.000 claims abstract description 15
- 238000001179 sorption measurement Methods 0.000 claims abstract description 15
- 238000001556 precipitation Methods 0.000 claims abstract description 11
- 239000001058 brown pigment Substances 0.000 claims abstract description 10
- 230000008569 process Effects 0.000 claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- 238000000638 solvent extraction Methods 0.000 claims abstract description 3
- 230000020477 pH reduction Effects 0.000 claims abstract 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 58
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 42
- 239000000243 solution Substances 0.000 claims description 41
- 239000007864 aqueous solution Substances 0.000 claims description 28
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 17
- 238000000605 extraction Methods 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 10
- 239000002244 precipitate Substances 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 7
- 240000004957 Castanea mollissima Species 0.000 claims description 6
- 235000018244 Castanea mollissima Nutrition 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 235000006667 Aleurites moluccana Nutrition 0.000 claims description 5
- 239000000284 extract Substances 0.000 claims description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 239000006228 supernatant Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims 2
- 208000032400 Retinal pigmentation Diseases 0.000 claims 1
- 150000007522 mineralic acids Chemical class 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 238000007873 sieving Methods 0.000 claims 1
- 230000007935 neutral effect Effects 0.000 abstract description 22
- 101000623895 Bos taurus Mucin-15 Proteins 0.000 abstract description 7
- 235000013305 food Nutrition 0.000 abstract description 6
- 238000012545 processing Methods 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract description 5
- 230000002378 acidificating effect Effects 0.000 abstract description 4
- 231100000252 nontoxic Toxicity 0.000 abstract description 4
- 230000003000 nontoxic effect Effects 0.000 abstract description 4
- 239000002778 food additive Substances 0.000 abstract 1
- 235000013373 food additive Nutrition 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 238000010521 absorption reaction Methods 0.000 description 22
- 210000002659 acromion Anatomy 0.000 description 18
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 18
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 18
- 150000003254 radicals Chemical class 0.000 description 18
- 238000001228 spectrum Methods 0.000 description 18
- 239000002253 acid Substances 0.000 description 15
- 239000008367 deionised water Substances 0.000 description 14
- 229910021641 deionized water Inorganic materials 0.000 description 14
- 238000000227 grinding Methods 0.000 description 10
- 238000011084 recovery Methods 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- 230000008021 deposition Effects 0.000 description 7
- 241000628997 Flos Species 0.000 description 6
- 238000010828 elution Methods 0.000 description 6
- 230000001476 alcoholic effect Effects 0.000 description 5
- 241000219428 Fagaceae Species 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 235000013361 beverage Nutrition 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 235000013399 edible fruits Nutrition 0.000 description 2
- 239000000989 food dye Substances 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000002916 wood waste Substances 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 1
- 235000011511 Diospyros Nutrition 0.000 description 1
- 244000236655 Diospyros kaki Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- 208000034189 Sclerosis Diseases 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- 240000008866 Ziziphus nummularia Species 0.000 description 1
- -1 acidic drinks Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 235000019789 appetite Nutrition 0.000 description 1
- 230000036528 appetite Effects 0.000 description 1
- 238000013475 authorization Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 235000005911 diet Nutrition 0.000 description 1
- 230000000378 dietary effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 235000002864 food coloring agent Nutrition 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 231100000957 no side effect Toxicity 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 230000035764 nutrition Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 230000035807 sensation Effects 0.000 description 1
- 235000019615 sensations Nutrition 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
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- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
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- Coloring Foods And Improving Nutritive Qualities (AREA)
- Medicines Containing Plant Substances (AREA)
- Cosmetics (AREA)
Abstract
本发明涉及食品添加剂中天然食用色素生产加工技术，具体说是一种板栗壳天然棕色素的分级方法。将板栗壳色素粗提液经酸化沉淀、亲水性有机溶剂萃取以及大孔树脂吸附等方法将板栗壳色素分级得到3个溶解性不同的组分。组分I溶于亲水性有机溶剂和碱性、中性以及酸性的水中；组分II溶于碱性水和亲水性有机溶剂；组分III仅溶于碱性水中。在应用过程中可以根据具体情况选用合适的板栗壳色素分级组分，拓展了板栗壳色素的应用范围。本项发明所提供的方法安全无毒、生产成本低、工艺简单易于工业化生产。The invention relates to a production and processing technology of natural food pigment in food additives, in particular to a method for grading natural brown pigment of chestnut shells. The crude extract of chestnut shell pigment was subjected to acidification precipitation, hydrophilic organic solvent extraction, and macroporous resin adsorption to fractionate chestnut shell pigment to obtain three components with different solubility. Component I is soluble in hydrophilic organic solvents and alkaline, neutral and acidic water; component II is soluble in alkaline water and hydrophilic organic solvents; component III is only soluble in alkaline water. In the application process, suitable graded components of the chestnut shell pigment can be selected according to specific conditions, which expands the application range of the chestnut shell pigment. The method provided by the invention is safe and non-toxic, has low production cost, simple process and easy industrial production.
Description
Technical field
The present invention relates to the process for processing technology of natural food colour, is a kind of stage division to the chestnut shell pigment specifically.
Background technology
Color is one of important factor that constitutes the food aesthetic quality.The color of food can not only make people produce appetite, and is an important Oranoleptic indicator who differentiates that food quality is good and bad, also influences the sensation of people to local flavor simultaneously.Therefore, keeping or give the good color and luster of food is a major issue in the foodstuffs industry.Chemosynthesis food dye is bright in colour, good stability, but the security of the synthetic colour of People more and more concern in recent years, and synthetic colour is fewer and feweri as the consumption of foodstuff additive, even the use that is under an embargo.And natural pigment has and has no side effect, and human body is had certain health care dietary function, as foodstuff additive, enjoys people to favor it, thereby becomes the focus of countries in the world food dye research and development.Chinese chestnut (
Castanea mollissima) genus Fagaceae (Fagaceae) plant.Its fruit is enjoyed the laudatory title of " king of dry fruit ", with jujube, persimmon and be called " iron crops ", " woody grain ", is a kind of food of cheap and tasty, being rich in nutrition and nourishing function.China is the largest production state of Chinese chestnut, accounts for global ultimate production about 75%.Owing to reasons such as kernel sclerosis, insect pest make not storage endurance of Chinese chestnut, thereby consumption such as traditional marrons glaces of China and boiling chestnut receive the restriction of season and storage requirement, and consumption is very limited, must in time carry out deep processing.Chestnut shell is the industrial wood waste that produces in the Chinese chestnut deep-processing process.Shenyang Inst. of Applied Ecology, Chinese Academy of Sciences is with the raw material of this industrial wood waste as extraction and processing natural brown pigment; 2 of national inventing patents have successively been declared; And obtain the authorization; These 2 patents are respectively a kind of process for extracting (ZL 03133730.9) of Brown Pigment in Chestnut Shells and a kind of working method (ZL 200410050753.X) of Brown Pigment in Chestnut Shells, have set up the extraction and the working method of chestnut shell brown pigment.Though these 2 patents of invention have very strong novelty and important use is worth and commercial promise; But part also comes with some shortcomings; As: the chestnut shell pigment that extracts or produce according to these 2 methods that patent provided can dissolve in alkalescence and neutral water fully; But in sour water with in the ethanol, have only part to dissolve, limited the range of application of pigment.This invention is intended to overcome above-mentioned deficiency; The component that solvability is different in the chestnut shell pigment is carried out fractional separation, aborning can be according to concrete needs, solubility property and working conditions that the reference plate chestnut color is plain; Select suitable colour component, expand its range of application.
Summary of the invention
The object of the present invention is to provide a kind of stability strong, safety non-toxic, the stage division of the Brown Pigment in Chestnut Shells that technology is simple, cost is low.
To achieve these goals, the technical scheme of the present invention's employing is:
1) in chestnut shell pigment crude extract, adds rare mineral acid, regulate the pH value, make the pigment that is insoluble to acid be able to deposition to 1-3.
2) adopt centrifugal or filtering method will precipitate and solution separating.
3) with above-mentioned steps 2) the middle solution that obtains is through macroporous resin column, and enrichment is pigment wherein, washs adsorption column with acidic aqueous solution earlier then, to remove the organic impurity of non-pigmented, again with the deionized water wash adsorption column, to remove mineral acid; Use the ethanol elution pigment at last, the ethanolic soln that drying contains pigment obtains chestnut shell pigment classification component I, and this colour component is dissolved in alkalescence, neutrality and the tart water, also is dissolved in common hydrophilic organic solvent, like methyl alcohol, ethanol, acetone etc.; Pigment yield 1.4-3.2g/100g chestnut shell, molecular weight 500-10000Da, carboxyl-content are 1.2-1.8 mmol/g, and content of phenolic hydroxyl groups is 5.9-7.1 mmol/g, and the semiquinone number of free radical is 9 * 10
15-2 * 10
17Spin/g, ultraviolet-visible light spectrum does not have absorption peak in the 200-800nm scope, only at the 270-290nm place one acromion is arranged, look valency in the neutral aqueous solution
Be 52-66.
4) with step 2) in separate the deposition obtain with the hydrophilic organic solvent repetitive scrubbing, separate elutant and pigment residue with centrifugal or filtering method, closely colourless until elutant.Dry elutant of difference and residue.Obtain chestnut shell pigment classification component II after the elutant drying, this colour component is dissolved in alkaline aqueous solution and hydrophilic organic solvent, is insoluble in neutral and the sour water; Pigment yield 4.3-5.2g/100g chestnut shell, molecular weight 10000-100000Da, carboxyl-content are 0.9-1.5 mmol/g, and content of phenolic hydroxyl groups is 7.8-9.1 mmol/g, and the semiquinone number of free radical is 7 * 10
16-6 * 10
19Spin/g, ultraviolet-visible light spectrum does not have absorption peak in the 200-800nm scope, only at the 270-290nm place one acromion is arranged, look valency in the neutral aqueous solution
Be 64-73; Obtain chestnut shell pigment classification component III after the residue drying, this colour component is dissolved in alkaline aqueous solution, but is insoluble to neutrality and acidic aqueous solution; Also be insoluble to common organic solvent; Pigment yield 6.3-8.1g/100g chestnut shell, molecular weight are greater than 100000Da, and carboxyl-content is 1.9-2.5 mmol/g; Content of phenolic hydroxyl groups is 3.6-4.3 mmol/g, and the semiquinone number of free radical is 8 * 10
15-9 * 10
16Spin/g, ultraviolet-visible light spectrum does not have absorption peak in the 200-800nm scope, only at the 270-290nm place one acromion is arranged, look valency in the neutral aqueous solution
Be 41-48.
The present invention has following advantage:
1. the chestnut shell pigment has been carried out classification according to deliquescent difference; Obtain 3 kinds of components that solvability is different, in application process, can select suitable chestnut shell pigment classification component as the case may be for use, component III is adapted at using under the alkaline condition; Component I I all can use under alkaline condition and in the beverage; The component I use range is the widest, except being suitable for alkaline condition and beverage, also can under neutral and acid (like acidic drinks, vinegar etc.) condition, use; Can select suitable classification component according to demands of different aborning, thereby expand the range of application of chestnut shell pigment;
2. safety non-toxic, each processing link does not have any chemical treating process, so the product that makes is tasteless, safety non-toxic and without any side effects to human body.
3. technology is simple, cost is low.Simple process steps of the present invention and operational condition can make suitability for industrialized production acceptant.
Embodiment
Obtaining of pigment crude extract can be carried out with reference to following patent: 1) ZL 03133730.9, a kind of process for extracting of Brown Pigment in Chestnut Shells. or 2) ZL 200410050753.X, a kind of working method of Brown Pigment in Chestnut Shells.
The concrete acquisition process of raw material (pigment crude extract) is following:
Chestnut shell is pulverized; After removing floss; (the alkali concentration expressed in percentage by weight is for O.03%-0.1% with the aqueous solution of sodium hydroxide, yellow soda ash, sodium hydrogencarbonate one matter or dilute alcohol solution; The alcohol concentration expressed in percentage by volume is 30%-70%) and the aqueous solution of their arbitrary combination or dilute alcohol solution obtain chestnut shell pigment vat liquor for extracting solvent extraction (extracting temperature is 50-90 ℃, extraction time 1-12 hour).Vat liquor filters or thick to consider the back centrifugal, filtrating or centrifuged supernatant as crude extract directly get into pigment classification link or dry for the pigment crude extract so that be in store for.Classification is preceding to be that solvent and regulation system pH dissolve pigment pigment crude extract greater than 9 fully with water, regains the pigment crude extract.
Embodiment 1
It is particle diameter 3 ~ 5mm that the 500g chestnut shell is pulverized, and sieves, after employing is sieved and removed floss; It is dropped in the lixiviate jar, and with the 6L aqueous sodium hydroxide solution lixiviate of concentration expressed in percentage by weight 0.03 %, extraction temperature is 85 ℃; 3 hours time, filter the filtrating obtain according to the further classification of following steps:
(1) regulates pH value of filtrate to 2 with 4mol/L hydrochloric acid.Leave standstill 12 hours, fully precipitate so that be insoluble to the pigment of acid.
(2) cf-with 1 0000 g separates pigementation and pigment solution, and difference collecting precipitation and solution.
(3) the gained pigment solution is through being equipped with XAD-8 macroporous resin adsorption post; Wherein contained pigment is adsorbed on the resin; With deionized water (regulating pH) the flushing adsorption column of the pH 2 of 2 times of column volumes, use the deionized water rinsing adsorption column again, Cl in effluent then with HCl
-Detect negative (adding the constant muddiness of Silver Nitrate), at last with 95% ethanol elution pigment.Dry under 60 ℃ behind the elutriant recovery ethanol, the gained solid obtains chestnut shell pigment classification component I through grinding.This part pigment is dissolved in acidity, neutrality and the alkaline water, also is dissolved in common hydrophilic organic solvent, like methyl alcohol, ethanol, acetone etc.Pigment yield 3.2g/100g chestnut shell, molecular weight 500-10000Da, carboxyl-content are 1.2 mmol/g, and content of phenolic hydroxyl groups is 5.9 mmol/g, and the semiquinone number of free radical is 9 * 10
15Spin/g, ultraviolet-visible light spectrum does not have absorption peak in the 200-800nm scope, only at the 270-290nm place one acromion is arranged, look valency in the neutral aqueous solution
Be 66.
(4) resulting deposition in the step (2) is put in people's 1000 mL beakers, add 800 mL, 95% ethanol, adopted magnetic stirrer 6 hours, the cf-with 1 0000 g separates pigment residue and pigment solution then.
(5) the pigment residue is put in people's beaker, repeating step (4), approaching colourless until elutant.
(6) collect the ethanolic soln that contains pigment that produces in the step (4) and (5), dry under 60 ℃ behind the recovery ethanol, the gained solid obtains chestnut shell pigment classification component II through grinding.Pigment yield 5.2g/100g chestnut shell, molecular weight 10000-100000Da, carboxyl-content are 0.9 mmol/g, and content of phenolic hydroxyl groups is 7.8 mmol/g, and the semiquinone number of free radical is 7 * 10
16Spin/g, ultraviolet-visible light spectrum does not have absorption peak in the 200-800nm scope, only at the 270-290nm place one acromion is arranged, look valency in the neutral aqueous solution
Be 73.
(7) with the drying under the alcoholic acid pigment residue room temperature that is insoluble to that obtains in the step (5), grind and obtain chestnut shell pigment classification component III.Pigment yield 8.1g/100g chestnut shell, molecular weight are greater than 100000Da, and carboxyl-content is 1.9 mmol/g, and content of phenolic hydroxyl groups is 3.6 mmol/g, and the semiquinone number of free radical is 8 * 10
15Spin/g, ultraviolet-visible light spectrum does not have absorption peak in the 200-800nm scope, only at the 270-290nm place one acromion is arranged, look valency in the neutral aqueous solution
Be 41.
Embodiment 2
It is particle diameter 3 ~ 5mm that the 500g chestnut shell is pulverized, and sieves, after employing is sieved and removed floss; It is dropped in the lixiviate jar, and with the 6L yellow soda ash liquid lixiviate of concentration expressed in percentage by weight 0.05 %, extraction temperature is 75 ℃; 3 hours time, filter the filtrating obtain according to the further classification of following steps:
(1) regulates pH value of filtrate to 3 with the acid of 0.5mol/L hydrochloric acid.Leave standstill 12 hours, fully precipitate so that be insoluble to the pigment of acid.
(2) cf-with 10000g separates pigementation and pigment solution, and difference collecting precipitation and solution.
(3) the gained pigment solution is through being equipped with XAD-8 macroporous resin absorption post; Wherein contained pigment is adsorbed on the resin; With the deionized water rinsing adsorption column of the pH 2 of 2 times of column volumes, use the deionized water rinsing adsorption column again, then at last with 95% ethanol elution pigment.Dry under 60 ℃ behind the elutriant recovery ethanol, the gained solid obtains chestnut shell pigment classification component I through grinding.This part pigment is dissolved in acidity, neutrality and the alkaline water, also is dissolved in common hydrophilic organic solvent, like methyl alcohol, ethanol, acetone etc.Pigment yield 1.9 g/100g chestnut shells, molecular weight 500-10000Da, carboxyl-content are 1.6 mmol/g, and content of phenolic hydroxyl groups is 6.1 mmol/g, and the semiquinone number of free radical is 4 * 10
16Spin/g, ultraviolet-visible light spectrum does not have absorption peak in the 200-800nm scope, only at the 270-290nm place one acromion is arranged, look valency in the neutral aqueous solution
Be 56.
(4) resulting deposition in the step (2) is put in people's 1000 mL beakers, add 800 mL methyl alcohol, adopted magnetic stirrer 6 hours, the cf-with 1 0000 g separates pigment residue and pigment solution then.
(5) the pigment residue is put in people's beaker, repeating step (4), approaching colourless until elutant.
(6) collect the methanol solution that contains pigment that produces in the step (4) and (5), dry under 60 ℃ behind the recovery methyl alcohol, the gained solid obtains chestnut shell pigment classification component II through grinding.Pigment yield 4.5g/100g chestnut shell, molecular weight 10000-100000Da, carboxyl-content are 0.9 mmol/g, and content of phenolic hydroxyl groups is 7.9 mmol/g, and the semiquinone number of free radical is 9 * 10
16, ultraviolet-visible light spectrum does not have absorption peak in the 200-800nm scope, only at the 270-290nm place one acromion is arranged, look valency in the neutral aqueous solution
Be 72.
(7), grind and obtain chestnut shell pigment classification component III with dry under the pigment residue room temperature that is insoluble to methyl alcohol that obtains in the step (5).Pigment yield 7.5g/100g chestnut shell, molecular weight are greater than 100000Da, and carboxyl-content is 2.4 mmol/g, and content of phenolic hydroxyl groups is 3.9 mmol/g, and the semiquinone number of free radical is 3 * 10
16Spin/g, ultraviolet-visible light spectrum does not have absorption peak in the 200-800nm scope, only at the 270-290nm place one acromion is arranged, look valency in the neutral aqueous solution
Be 46.
Embodiment 3
It is particle diameter 3 ~ 5mm that the 500g chestnut shell is pulverized; Sieve, after employing is sieved and removed floss, it is dropped in lixiviate jar; 6L sodium hydroxide ethanolic soln (with the preparation of 50% aqueous ethanolic solution) lixiviate with concentration expressed in percentage by weight 0.03 %; Extraction temperature is 65 ℃, 8 hours time, filters the filtrating obtain according to the further classification of following steps:
(1) regulates pH value of filtrate to 2 with 1mol/L nitric acid.Leave standstill 12 hours, fully precipitate so that be insoluble to the pigment of acid.
(2) cf-with 10000g separates pigementation and pigment solution, and difference collecting precipitation and solution.
(3) the gained pigment solution adds equal-volume deionized water dilution back through XAD-8 macroporous resin absorption post is housed; Wherein contained pigment is adsorbed on the resin; Then with the deionized water rinsing adsorption column of the pH 2 of 2 times of column volumes; Use the deionized water rinsing adsorption column again, at last with 95% ethanol elution pigment.Dry under 60 ℃ behind the elutriant recovery ethanol, the gained solid obtains chestnut shell pigment classification component I through grinding.This part pigment is dissolved in acidity, neutrality and the alkaline water, also is dissolved in common hydrophilic organic solvent, like methyl alcohol, ethanol, acetone etc.Pigment yield 1.4 g/100g chestnut shells, molecular weight 500-10000Da, carboxyl-content are 1.7 mmol/g, and content of phenolic hydroxyl groups is 6.9 mmol/g, and the semiquinone number of free radical is 1 * 10
17Spin/g, ultraviolet-visible light spectrum does not have absorption peak in the 200-800nm scope, only at the 270-290nm place one acromion is arranged, look valency in the neutral aqueous solution
Be 54.
(4) resulting deposition in the step (2) is put in people's 1000 mL beakers, add 800 mL methyl alcohol and 95% alcoholic acid equal-volume mixed solution, adopted magnetic stirrer 6 hours, the cf-with 10000g separates pigment residue and pigment solution then.
(5) the pigment residue is put in people's beaker, repeating step (4), approaching colourless until elutant.
(6) collect the solution that contains pigment that produces in the step (4) and (5), dry under 60 ℃ behind the recovery solvent, the gained solid obtains chestnut shell pigment classification component II through grinding.Pigment yield 4.8g/100g chestnut shell, molecular weight 10000-100000Da, carboxyl-content are 1.4 mmol/g, and content of phenolic hydroxyl groups is 9.0 mmol/g, and the semiquinone number of free radical is 6 * 10
19Spin/g, ultraviolet-visible light spectrum does not have absorption peak in the 200-800nm scope, only at the 270-290nm place one acromion is arranged, look valency in the neutral aqueous solution
Be 67.
(7) with the drying under the alcoholic acid pigment residue room temperature that is insoluble to that obtains in the step (5), grind and obtain chestnut shell pigment classification component III.Pigment yield 7.1g/100g chestnut shell, molecular weight are greater than 100000Da, and carboxyl-content is 2.3 mmol/g, and content of phenolic hydroxyl groups is 4.3 mmol/g, and the semiquinone number of free radical is 9 * 10
15Spin/g, ultraviolet-visible light spectrum does not have absorption peak in the 200-800nm scope, only at the 270-290nm place one acromion is arranged, look valency in the neutral aqueous solution
Be 46.
Embodiment 4
It is particle diameter 3 ~ 5mm that the 500g chestnut shell is pulverized, and sieves, after employing is sieved and removed floss; It is dropped in the lixiviate jar, and with the 6L caustic lye of soda lixiviate of concentration expressed in percentage by weight 0.03 %, extraction temperature is 50 ℃; 12 hours time, filter the filtrating obtain according to the further classification of following steps:
(1) regulates pH value of filtrate with 1mol/L hydrochloric acid, make it reach 2.5.Leave standstill 12 hours, fully precipitate so that be insoluble to the pigment of acid.
(2) cf-with 10000g separates pigementation and pigment solution, and difference collecting precipitation and solution.
(3) the gained pigment solution is through being equipped with XAD-8 macroporous resin absorption post, and wherein contained pigment is adsorbed on the resin, with the deionized water rinsing adsorption column of the pH 2 of 2 times of column volumes, uses the deionized water rinsing adsorption column again, Cl in effluent then
-Detect negative, at last with 95% ethanol elution pigment.Dry under 60 ℃ behind the elutriant recovery ethanol, the gained solid obtains chestnut shell pigment classification component I through grinding.This part pigment is dissolved in acidity, neutrality and the alkaline water, also is dissolved in common hydrophilic organic solvent, like methyl alcohol, ethanol, acetone etc.Pigment yield 1.4 g/100g chestnut shells, molecular weight 500-10000Da, carboxyl-content are 1.8 mmol/g, and content of phenolic hydroxyl groups is 7.1 mmol/g, and the semiquinone number of free radical is 2 * 10
17Spin/g, ultraviolet-visible light spectrum does not have absorption peak in the 200-800nm scope, only at the 270-290nm place one acromion is arranged, look valency in the neutral aqueous solution
Be 52.
(4) resulting deposition in the step (2) is put in people's 1000 mL beakers, add 800 mL, 95% ethanol, adopted magnetic stirrer 6 hours, the cf-with 10000 g separates pigment residue and pigment solution then.
(5) the pigment residue is put in people's beaker, replaced 95% ethanol with acetone, repeating step (4), approaching colourless until elutant.
(6) collect the organic solvent solution that contains pigment that produces in the step (4) and (5), dry under 60 ℃ behind the recovery solvent, the gained solid obtains chestnut shell pigment classification component II through grinding.Pigment yield 4.3 g/100g chestnut shells, molecular weight 10000-100000Da, carboxyl-content are 1.5 mmol/g, and content of phenolic hydroxyl groups is 9.1 mmol/g, and the semiquinone number of free radical is 6 * 10
19Spin/g, ultraviolet-visible light spectrum does not have absorption peak in the 200-800nm scope, only at the 270-290nm place one acromion is arranged, look valency in the neutral aqueous solution
Be 64.
(7), grind and obtain chestnut shell pigment classification component III with dry under the pigment residue room temperature that is insoluble to organic solvent that obtains in the step (5).Pigment yield 6.3g/100g chestnut shell, molecular weight are greater than 100000Da, and carboxyl-content is 2.5 mmol/g, and content of phenolic hydroxyl groups is 4.3 mmol/g, and the semiquinone number of free radical is 9 * 10
16Spin/g, ultraviolet-visible light spectrum does not have absorption peak in the 200-800nm scope, only at the 270-290nm place one acromion is arranged, look valency in the neutral aqueous solution
Be 48.
Embodiment 5
It is particle diameter 3 ~ 5mm that the 500g chestnut shell is pulverized, and sieves, after employing is sieved and removed floss; It is dropped in the lixiviate jar, and with 6L sodium hydroxide ethanolic soln (with the preparation of the 50% methanol aqueous solution) lixiviate of concentration expressed in percentage by weight 0.03 %, extraction temperature is 65 ℃; 8 hours time; Slightly consider with cotton, the centrifugal 20min of filtrating 10000g, the supernatant spraying drying obtains the pigment crude extract.The pigment crude extract is added in the deionized water of 6L, stir and make the pigment suspension evenly, regulation system pH to 9, with magnetic stirrer, 40 ℃ of following incubation 12h make the pigment crude extract dissolve the crude extract that obtains again, then according to the further classification of following steps:
(1) regulates pH value of filtrate with 0.5mol/L nitric acid, make it reach 2.Leave standstill 12 hours, fully precipitate so that be insoluble to the pigment of acid.
(2) cf-with 10000g separates pigementation and pigment solution, and difference collecting precipitation and solution.
(3) the gained pigment solution adds equal-volume deionized water dilution back through XAD-8 macroporous resin absorption post is housed; Wherein contained pigment is adsorbed on the resin; Then with the deionized water rinsing adsorption column of the pH 2 of 2 times of column volumes; Use the deionized water rinsing adsorption column again, at last with 95% ethanol elution pigment.Dry under 60 ℃ behind the elutriant recovery ethanol, the gained solid obtains chestnut shell pigment classification component I through grinding.This part pigment is dissolved in acidity, neutrality and the alkaline water, also is dissolved in common hydrophilic organic solvent, like methyl alcohol, ethanol, acetone etc.Pigment yield 1.4 g/100g chestnut shells, molecular weight 500-10000Da, carboxyl-content are 1.7 mmol/g, and content of phenolic hydroxyl groups is 6.9 mmol/g, and the semiquinone number of free radical is 1 * 10
17Spin/g, ultraviolet-visible light spectrum does not have absorption peak in the 200-800nm scope, only at the 270-290nm place one acromion is arranged, look valency in the neutral aqueous solution
Be 54.
(4) resulting deposition in the step (2) is put in people's 1000 mL beakers, add 800 mL acetone and 95% alcoholic acid equal-volume mixed solution, adopted magnetic stirrer 6 hours, the cf-with 10000g separates pigment residue and pigment solution then.
(5) the pigment residue is put in people's beaker, repeating step (4), approaching colourless until elutant.
(6) collect the solution that contains pigment that produces in the step (4) and (5), dry under 60 ℃ behind the recovery solvent, the gained solid obtains chestnut shell pigment classification component II through grinding.Pigment yield 4.8g/100g chestnut shell, molecular weight 10000-100000Da, carboxyl-content are 1.4 mmol/g, and content of phenolic hydroxyl groups is 9.0 mmol/g, and the semiquinone number of free radical is 6 * 10
19Spin/g ultraviolet-visible light spectrum does not have absorption peak in the 200-800nm scope, only at the 270-290nm place one acromion is arranged, look valency in the neutral aqueous solution
Be 67.
(7) with the drying under the alcoholic acid pigment residue room temperature that is insoluble to that obtains in the step (5), grind and obtain chestnut shell pigment classification component III.Pigment yield 7.1g/100g chestnut shell, molecular weight are greater than 100000Da, and carboxyl-content is 2.3 mmol/g, and content of phenolic hydroxyl groups is 4.3 mmol/g, and the semiquinone number of free radical is 9 * 10
15Spin/g, ultraviolet-visible light spectrum does not have absorption peak in the 200-800nm scope, only at the 270-290nm place one acromion is arranged, look valency in the neutral aqueous solution
Be 46.
Claims (9)
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| CN103042023A (en) * | 2012-12-20 | 2013-04-17 | 菏泽瑞璞牡丹产业科技发展有限公司 | Comprehensive utilization method of peony shells |
| CN103214643A (en) * | 2013-04-28 | 2013-07-24 | 西南林业大学 | Method for performing two-step catalyzed synthesis on basic resin by using natural melanin |
| CN103232582A (en) * | 2013-04-28 | 2013-08-07 | 西南林业大学 | Catalyzed synthesis method of base resin by utilizing natural melanin |
| CN103232725A (en) * | 2013-04-24 | 2013-08-07 | 湖北紫鑫生物科技有限公司 | High-stability chestnut shell brown pigment as well as refining method and application thereof |
| CN104250456A (en) * | 2014-05-20 | 2014-12-31 | 东北林业大学 | Method for purifying hazelnut shell brown pigment |
| CN106146770A (en) * | 2015-03-30 | 2016-11-23 | 西南林业大学 | A kind of method of radical polymerization natural melanin synthesized base resin |
| CN107173810A (en) * | 2017-06-19 | 2017-09-19 | 镇雄滇龙生态科技有限公司 | A kind of method that tannin, polysaccharide and Chestnut shell pigment are extracted from chestnut shell |
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| CN104250456B (en) * | 2014-05-20 | 2016-03-30 | 东北林业大学 | A kind of purification method of hazelnut shell brown pigment |
| CN106146770A (en) * | 2015-03-30 | 2016-11-23 | 西南林业大学 | A kind of method of radical polymerization natural melanin synthesized base resin |
| CN107173810A (en) * | 2017-06-19 | 2017-09-19 | 镇雄滇龙生态科技有限公司 | A kind of method that tannin, polysaccharide and Chestnut shell pigment are extracted from chestnut shell |
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