A kind of method of utilizing discarded hickory nut epicarp to prepare pigment
Technical field
The invention belongs to pigment preparation method technical field, be specially a kind of method of utilizing discarded hickory nut epicarp to prepare pigment.
Background technology
Pigment is divided into synthetic colour and natural pigment two classes according to its source difference, synthetic colour lovely luster, strong coloring force, not less, the stable performance of fugitive color, consumption, but mainly belong to the phenyl amines pigment with carcinogenesis due to synthetic colour, and people find that successively a lot of synthetic colours have serious chronic toxicity and carinogenicity, and the advantages such as the pigment of plant origin is nontoxic with it, safety, color and luster are naturally bright-coloured, good stability are subject to popular favor all the time.The plant resources of China is abundant, replaces with natural pigment the development trend that synthetic colour has become following food, makeup and dyestuffs industries.
Be oxidized to very soon tannic red tannin and quinones after containing a large amount of tannic acids, polyatomic phenol and anthraquinone analog compound, particularly condensed tannin and polyphenol components ingress of air in hickory nut epicarp, these compounds often have darker color.The tannic red element is water-fast red-brown or sorrel pigment, and not only self color is unique, but also has converging action, can make the skin hardening, thereby protects mucous membrane, reduces skin pain and prevent that bacterium from infecting.Hickory nut epicarp is the food-processing waste at present, enormous amount.But so far there are no utilizing discarded hickory nut epicarp to prepare the report of pigment.
Summary of the invention
For the above-mentioned problems in the prior art, the object of the invention is to design provides a kind of technical scheme of utilizing discarded hickory nut epicarp to prepare the method for pigment, the extraction purification technique that adopts is advanced, preparation technology is simple, easy to operate, raw material sources are abundant, extraction yield is high, stable performance, environment-friendly high-efficiency, easy suitability for industrialized production, and the pigment that obtains can be used as the pigment applications of Ran Fa treatment oil, drawing, clothes dyeing.
A kind of described method of utilizing discarded hickory nut epicarp to prepare pigment is characterized in that comprising the following steps:
1) raw material is processed: naturally dry after hickory nut epicarp is cleaned, put in 35 ℃ of-45 ℃ of baking ovens dry 20-30 hour, and taking-up, standby;
2) the broken extraction: raw material is put in smashing extractor, add the broken extraction of 50~100% aqueous ethanols or 50~100% aqueous acetone 1~2 time at every turn, raw material is broken into 20~60 purpose granularities, if raw material weight be 1kg aqueous ethanol or aqueous acetone consumption be 6~10 liters, each extraction time is 1~3 minute;
3) filtration under diminished pressure: with the extracting solution suction filtration, discard filter residue, merge suction filtration liquid;
4) flash concentration: the extracting solution after filtering is at 40 ℃-55 ℃, and vacuum tightness is to adopt Reduced Pressure Concentration Device to carry out flash concentration under 0.090Mpa~0.095 Mpa condition, regulates the feed liquor speed of solution to be concentrated, with 150~300 mLmin
-1Flow repeatedly concentrated, reclaim ethanol, obtain amounting to the concentrated solution that every milliliter of concentrated solution contains 0.5~1.0 gram crude drug;
5) macroporous resin purification: by the macroporous adsorbent resin separation and concentration, first use H
2The O wash-out, then carry out gradient elution with 10~80% aqueous ethanol successively, use at last 70% acetone wash-out, the flow velocity of elutriant is 5~15 mLmin
-1, each wash-out position of collecting respectively 3 times of column volumes;
6) continue flash concentration: 20~70% alcohol elutions are merged, at 45 ℃-55 ℃, vacuum tightness is to adopt Reduced Pressure Concentration Device to carry out flash concentration under 0.090Mpa~0.095 Mpa condition, regulates the feed liquor speed of solution to be concentrated, with 150~300 mLmin
-1Flow repeatedly concentrated, get concentrated solution;
7) vacuum-drying: concentrated solution is dry at 45 ℃-55 ℃ lower vacuum concentration, make hickory nut epicarp sorrel pigment product.
A kind of described method of utilizing discarded hickory nut epicarp to prepare pigment is characterized in that in step 1), oven temperature is 40 ℃-42 ℃, and be 23-25 hour time of drying.
A kind of described method of utilizing discarded hickory nut epicarp to prepare pigment is characterized in that step 2) in: aqueous ethanol concentration is 60-90%, preferred 70-80%; Aqueous acetone concentration is 60-90%, preferred 70-80%.
A kind of described method of utilizing discarded hickory nut epicarp to prepare pigment is characterized in that in step 4): the flash concentration temperature is 45 ℃-50 ℃, and feed liquor speed is 200~250 mLmin
-1, every milliliter of concentrated solution contains 0.6-0.8 gram crude drug.
A kind of described method of utilizing discarded hickory nut epicarp to prepare pigment is characterized in that step 5), 6) in: H adopted successively
2O, 10% ethanol, 20% ethanol, 40% ethanol, 60% ethanol, 80% ethanol, 70% acetone carry out gradient elution; Elution flow rate is 10~12 mLmin
-1, merging 20% ethanol, 40% ethanol and 60% ethanol alcohol elution, the flash concentration temperature is 50 ℃-52 ℃, feed liquor speed is 200~250mLmin
-1
A kind of described method of utilizing discarded hickory nut epicarp to prepare pigment is characterized in that in step 7): drying temperature is 50 ℃-54 ℃.
Described smashing extractor can directly be buied from the market, and Reduced Pressure Concentration Device (flash concentration device) also can directly be buied from the market for the designed, designed assembling.
A kind of above-mentioned method of utilizing discarded hickory nut epicarp to prepare pigment has following beneficial effect:
1, utilize discarded plant material to extract pigment, turn waste into wealth, reduced the waste of resource, improved using value and the utilization ratio of hickory nut epicarp, also the exploitation for natural pigment provides new source.
2, hickory nut epicarp is adopted the broken extraction of water-containing solvent, keying action by high-speed stirring, vibration, mixing, infiltration, dipping, make composition in raw material be transferred to solvent within the extremely short time in and reach the stripping balance, complete when having realized pulverizing and leaching process, room temperature is extracted and is avoided the thermo-sensitivity composition to destroy simultaneously, have quick, complete, energy-efficient, easy and simple to handle, the more high advantage of working efficiency of extraction, improved pigment composition extraction yield.Extracting solution adopts vacuum flashing concentrated, has that the concentrated solution heating temperature is low, heated time is short, effectively protect the thermo-sensitivity composition not to be destroyed, and concentrated speed is fast, efficient is high, the advantages such as simple to operate, easy to use, energy-conserving and environment-protective.
3, the extraction purification technique that adopts is advanced, and preparation technology is simple, easy to operate, non-toxic and safe, pollution-free, and production cost is low, and raw material sources are abundant, extraction yield is high, and product performance are stable, easy suitability for industrialized production.By comprehensive development and utilization hickory nut epicarp waste, can increase the added value of agricultural byproducts, therefore have certain economic worth and realistic meaning.
4, this pigment is a kind of natural environmental-friendly pigment, can be applicable to dye send out in treatment oil, drawing, clothes dyeing, has well upper chromatic effect, and the pigment color and luster is unique, stable, does not fade for a long time.After measured, utilize pigment dry powder that the present invention obtains through the colorimetric method for determining absorbancy, the look valency is more than 80.
The percentage composition that relates in present specification unless otherwise indicated all refers to weight percentage.
Embodiment
Now in conjunction with embodiments of the invention and correlation test, the invention will be further described.
1) raw material is processed: naturally dry after hickory nut epicarp is cleaned, put in 40 ℃ of baking ovens dry 24 hours, and taking-up, standby;
2) the broken extraction: raw material is put in smashing extractor, is added at every turn that 70% aqueous ethanol or 70% aqueous acetone are broken to be extracted 2 times, if raw material weight be 1kg aqueous ethanol or aqueous acetone consumption be 8 liters, each extraction time is 2 minutes;
3) filtration under diminished pressure: with the extracting solution suction filtration, discard filter residue, merge suction filtration liquid;
4) flash concentration: the extracting solution after filtering is at 50 ℃, and vacuum tightness is to adopt Reduced Pressure Concentration Device to carry out flash concentration under 0.095 Mpa condition, regulates the feed liquor speed of solution to be concentrated, with 230 mLmin
-1Flow repeatedly concentrated, reclaim ethanol, obtain amounting to the concentrated solution that every milliliter of concentrated solution contains 0.6 gram crude drug;
5) macroporous resin purification: concentrated solution by Diaion HP-20 macroporous adsorbent resin separation and concentration, is adopted H
2O, 10% ethanol, 20% ethanol, 40% ethanol, 60% ethanol, 80% ethanol, 70% acetone carry out gradient elution, and the flow velocity of elutriant is 10 mL min
-1, each wash-out position of collecting respectively 3 times of column volumes;
6) continue flash concentration: 20% ethanol, 40% ethanol and 60% alcohol elution are merged, and at 50 ℃, vacuum tightness is to adopt Reduced Pressure Concentration Device to carry out flash concentration under 0.095 Mpa condition, regulates the feed liquor speed of solution to be concentrated, with 250 mLmin
-1Flow repeatedly concentrated, reclaim ethanol, get concentrated solution;
7) vacuum-drying: concentrated solution is dry at 50 ℃ of lower vacuum concentration, make hickory nut epicarp sorrel pigment product.
In above-mentioned steps 1) in oven temperature be 35 ℃, 42 ℃, 45 ℃, be 20 hours, 25 hours, 30 hours time of drying.Step 2) in: aqueous ethanol concentration 50%, 60%, 80%, 90%, 100%; Aqueous acetone concentration is 50%, 60%, 80%, 90%, 100%, the broken extraction 1 time, if raw material weight be 1kg aqueous ethanol or aqueous acetone consumption be 6 liters, 7 liters, 9 liters, 10 liters, each extraction time is 1 minute, 3 minutes.In step 4): the flash concentration temperature is 45 ℃, 48 ℃; Feed liquor speed is 150 mLmin
-1, 200 mLmin
-1, 250 mLmin
-1, 300 mLmin
-1, every milliliter of concentrated solution contains 0.6 or 0.8 gram crude drug.In step 5) and step 6): first use H
2The O wash-out, then carry out gradient elution with 15% ethanol, 25% ethanol, 35% ethanol, 45% ethanol, 55% ethanol, 70% ethanol, 70% acetone; The flow velocity of elutriant is 5 mL min
-1, 8 mL min
-1, 10 mL min
-1, 12 mL min
-1, 15 mL min
-1Merge 25% ethanol, 35% ethanol, 45% ethanol, 55% ethanol and 70% alcohol elution, the flash concentration temperature is 45 ℃ or 48 ℃.Also can first use H
2The O wash-out, then carry out gradient elution with 20% ethanol, 30% ethanol, 50% ethanol, 60% ethanol, 70% ethanol, 70% acetone, merge 30% ethanol, 50% ethanol, 60% alcohol elution.In step 7): drying temperature is 45 ℃ or 55 ℃.Other processing step is the same, also can obtain beneficial effect of the present invention.Adopt the yield of the pigment product that above-mentioned preparation method makes 8.5%~18.8%.This pigment is sorrel or red-brown pulvis, and the product of making can be solid pigment, dissolves with polar organic solvent during use, makes paste after can also adding the blenders such as dispersion agent and wetting agent.
For further illustrating beneficial effect of the present invention, describe below by corresponding correlation data.
1. the impact of broken extraction conditions on extraction efficiency.
The amount and the yield that obtain pigment in this table refer to that raw material through amount of pigment and yield that fragmentation extraction, flash concentration, macroporous resin adsorption enrichment, continuation flash concentration, vacuum-drying obtain after becoming dry powder, has omitted macroporous resin purification and flash concentration drying process in table.By table 1 data as can be known: adopt the extraction conditions of embodiment 1 and embodiment 6, namely adopt 70% acetone and 70% ethanol to extract, the extraction efficiency of pigment is the highest, shows that acetone has stronger penetration power than ethanol to plant tissue.Consider that ethanol compares with acetone, have advantage safer, inexpensive, that be easy to get, therefore 70% ethanol is preferred embodiment.
2. in order to determine the quality of Smashing extraction method, adopt broken extraction conditions and the conventional extracting method of embodiment 6 to compare test, the extraction conditions of conventional extracting method is as far as possible consistent aspect solvent strength, solvent load, the results are shown in Table 2.
As shown in Table 2: thermal backflow is extracted and need to be heated at higher temperature, makes polyphenol components be subject to heat collapse, and bothers during operational cost, and the extraction yield of pigment is minimum.Though supersound extraction, cold soaking extraction are that room temperature is extracted with the diacolation extraction, need not heating, bother when the time length that extraction needs, operational cost, extraction yield is not high.Compare with conventional extracting method, adopt Smashing extraction method to extract rapidly and efficiently, the pigment that obtains is stable, extraction yield is high.
3. the Color of pigment and stability test, test-results such as following table 3.
Test-results shows: the pigment product of the present invention's preparation is red-brown or sorrel, tries out the pigment of Yu dyeing hair, the damp look of clothes, drawing, and color and luster is unique, satisfactory for result, colour-fast for a long time.Observed colour stable, lasting eight months.