阅读说明：本技术 一种有机植物染料的制备及其染色方法 (Preparation of organic plant dye and dyeing method thereof ) 是由 张永成 于 2020-06-28 设计创作，主要内容包括：本发明公开了一种有机植物染料的制备及其染色方法,制备方法包括以下步骤：(1)将提取原料和溶剂混合,保温,逆流提取；(2)将初提液离心分离,得到的第一滤液在超声下吸附处理；(3)将第一滤渣和第一流出液分别回送至逆流提取设备中进行逆流提取,然后按步骤(2)进行处理；(4)将第二滤渣和第二流出液按步骤(3)进行处理；将三个固相萃取柱分别脱附处理；(5)将色素提取液输送至真空反应釜中,加入矿物质和有机物,搅拌络合；(6)将络合初产物烘干,过筛,研磨3～10h。本发明制备方法具有高色素提取率、低溶剂消耗、低耗能、高收益、高品质的特点,所得染料可改善纺织品的色牢度,且染色方法能耗及生产成本低。(The invention discloses a preparation method of an organic plant dye and a dyeing method thereof, wherein the preparation method comprises the following steps: (1) mixing the extraction raw materials with a solvent, preserving heat, and performing countercurrent extraction; (2) performing centrifugal separation on the primary extract to obtain a first filtrate, and performing adsorption treatment on the first filtrate under ultrasonic waves; (3) respectively returning the first filter residue and the first effluent to countercurrent extraction equipment for countercurrent extraction, and then treating according to the step (2); (4) treating the second filter residue and the second effluent according to the step (3); respectively desorbing the three solid phase extraction columns; (5) conveying the pigment extracting solution into a vacuum reaction kettle, adding mineral substances and organic substances, and stirring and complexing; (6) and drying, sieving and grinding the complex primary product for 3-10 h. The preparation method has the characteristics of high pigment extraction rate, low solvent consumption, low energy consumption, high yield and high quality, the obtained dye can improve the color fastness of textiles, and the energy consumption and the production cost of the dyeing method are low.)

1. A preparation method of an organic plant dye is characterized by comprising the following steps: the method comprises the following steps:

(1) mixing the components in a mass ratio of 1: 3, mixing the extraction raw material and the solvent in a countercurrent extraction device, heating to 40-95 ℃, preserving heat for 1h, and then carrying out countercurrent extraction to obtain a primary extract;

(2) carrying out centrifugal separation on the primary extract to obtain a first filtrate and a first filter residue, and carrying out adsorption treatment on the first filtrate by a first solid-phase extraction column under an ultrasonic state to obtain a first effluent;

(3) respectively returning the first filter residue and the first effluent to a countercurrent extraction device, carrying out countercurrent extraction again at 40-95 ℃, then treating according to the method in the step (2) to obtain a second filter residue and a second effluent, and carrying out adsorption treatment by using a second solid-phase extraction column in the step;

(4) treating the second filter residue and the second effluent according to the method in the step (3) to obtain a third filter residue and a third effluent, wherein the third effluent is used as a solvent for next pigment extraction and is kept for standby application, and in the step, a third solid-phase extraction column is used for adsorption treatment; respectively carrying out desorption treatment on the first solid-phase extraction column, the second solid-phase extraction column and the third solid-phase extraction column by using petroleum ether, and then mixing liquids obtained by desorption to obtain a pigment extracting solution;

(5) conveying the pigment extracting solution into a vacuum reaction kettle, adding mineral substances and organic substances, uniformly stirring, complexing at 60-90 ℃ for 2 hours, vacuumizing to remove petroleum ether after complexing is finished, and obtaining a complex primary product, wherein the using amounts of the mineral substances and the organic substances are 0.1-10% and 10-30% of the mass of the pigment extracting solution respectively;

(6) and drying the complex primary product at 65-85 ℃, sieving the product by a 325-mesh sieve, and conveying the product to a nano grinder for grinding for 3-10 h to obtain the nano organic plant dye.

2. A process for the preparation of an organic vegetable dye according to claim 1, characterized in that: the first solid-phase extraction column, the second solid-phase extraction column and the third solid-phase extraction column are all prepared by mixing and filling alkaline alumina and kieselguhr according to the mass ratio of 1: 1.5.

3. A process for the preparation of an organic vegetable dye according to claim 1, characterized in that: the extraction raw material is plant root, stem, leaf, flower, fruit or rosewood sawdust.

4. A process for the preparation of an organic vegetable dye according to claim 1, characterized in that: the solvent is ethanol or deionized water or sodium bicarbonate solution with the concentration of 0.5 g/L.

5. A process for the preparation of an organic vegetable dye according to claim 1, characterized in that: the mineral is selected from one of alum, blue vitriol, titanium dioxide and magnesium oxide, and the organic is selected from one of tannin, peach gum, acetic acid and flavonoid compounds.

6. A process for the preparation of an organic vegetable dye according to claim 1, characterized in that: in the step (5), the pigment extracting solution is conveyed to a vacuum reaction kettle and then is subjected to heat preservation for 3-8 hours.

7. A method of dyeing an organic vegetable dye prepared according to any one of claims 1 to 7, characterized in that: and (3) mixing the fabric to be dyed according to the bath ratio of 1: 10 adding the mixture into a loose wool dyeing machine, heating to 60 ℃, adding the prepared organic plant dye and the auxiliary agent, and keeping the temperature for 20min, wherein the use amounts of the organic plant dye and the auxiliary agent are respectively 8% and 6% of the mass of the fabric to be dyed; adding organic acid to adjust pH to 5, heating to 95 deg.C at a rate of 1 deg.C/min, maintaining for 20min, adding softening agent, maintaining for 20min, and discharging deionized water when the temperature is increased to room temperature, wherein the amount of the softening agent is 1.8% of the amount of the dye.

8. A method of dyeing an organic plant dye as claimed in claim 7, characterized in that: the auxiliary agent is anhydrous sodium sulphate, and the organic acid is citric acid.

Technical Field

The invention relates to the technical field of dye extraction and dyeing, in particular to a preparation method and a dyeing method of an organic vegetable dye.

Background

At present, the application of dyes is very wide and is an indispensable part in modern life, but substances which cause serious harm to human bodies and the environment, such as chromium, arsenic, twenty-four aromatic amines and the like, exist in the chemical dye technology, and the dyes have the defects of complex synthesis process, high production cost, great environmental pollution and the like.

The organic plant dye is pigment extracted from flowers, grasses, trees, stems, leaves, fruits, seeds, peels, roots and the like in the nature, for example, leftover materials and wood chips after the production of redwood furniture are rich in a large amount of polyphenol pigment, has the advantages of no toxicity, no harm, no pollution, reproducibility and the like, is used for dyeing textiles, can improve the secondary and additional values, and realizes ecological protection on the environment, so that how to extract the natural plant pigment and obtain the organic plant dye which realizes zero emission, zero pollution and good color fastness is a problem which is urgently needed to be solved at present.

Disclosure of Invention

The invention aims to overcome the defects of the prior art and provides a preparation method of an organic vegetable dye and a dyeing method thereof, wherein the preparation method has the characteristics of high pigment extraction rate, low solvent consumption, low energy consumption, high yield and high quality, the obtained dye can obviously improve the color fastness of textiles when used for dyeing, and the dyeing method is practical and easy to implement, greatly reduces the energy consumption and saves the production cost.

In order to achieve the purpose, the invention adopts the following technical scheme:

a preparation method of an organic plant dye comprises the following steps:

(1) mixing the components in a mass ratio of 1: 3, mixing the extraction raw material and the solvent in a countercurrent extraction device, heating to 40-95 ℃, preserving heat for 1h, and then carrying out countercurrent extraction to obtain a primary extract;

(2) carrying out centrifugal separation on the primary extract to obtain a first filtrate and a first filter residue, and carrying out adsorption treatment on the first filtrate by a first solid-phase extraction column under an ultrasonic state to obtain a first effluent;

(3) respectively returning the first filter residue and the first effluent to a countercurrent extraction device, carrying out countercurrent extraction again at 40-95 ℃, then treating according to the method in the step (2) to obtain a second filter residue and a second effluent, and carrying out adsorption treatment by using a second solid-phase extraction column in the step;

(4) treating the second filter residue and the second effluent according to the method in the step (3) to obtain a third filter residue and a third effluent, wherein the third effluent is used as a solvent for next pigment extraction and is kept for standby application, and in the step, a third solid-phase extraction column is used for adsorption treatment; respectively carrying out desorption treatment on the first solid-phase extraction column, the second solid-phase extraction column and the third solid-phase extraction column by using petroleum ether, and then mixing liquids obtained by desorption to obtain a pigment extracting solution;

(5) conveying the pigment extracting solution into a vacuum reaction kettle, adding mineral substances and organic substances, uniformly stirring, complexing at 60-90 ℃ for 2 hours, vacuumizing to remove petroleum ether after complexing is finished, and obtaining a complex primary product, wherein the using amounts of the mineral substances and the organic substances are 0.1-10% and 10-30% of the mass of the pigment extracting solution respectively;

(6) and drying the complex primary product at 65-85 ℃, sieving the product by a 325-mesh sieve, and conveying the product to a nano grinder for grinding for 3-10 h to obtain the nano organic plant dye.

The first solid-phase extraction column, the second solid-phase extraction column and the third solid-phase extraction column are all prepared by mixing and filling alkaline alumina and kieselguhr according to the mass ratio of 1: 1.5.

The extraction raw material is plant root, stem, leaf, flower, fruit or rosewood sawdust. Wherein the plant root, stem, leaf, and fruit include folium Ilicis Pubescentis, folium Mori, folium Pini, folium Camelliae sinensis, fructus kaki, dragon fruit peel, pericarpium Granati, Carthami flos, stigma croci Sativi, flos Rosae Rugosae, radix Rubiae, radix Arnebiae, folium Isatidis, folium Nelumbinis, flos Jasmini sambac, caulis et folium Ipomoeae, and petiolus Citri Tangerinae.

The solvent is ethanol or deionized water or sodium bicarbonate solution with the concentration of 0.5 g/L.

The mineral is selected from one of alum, blue vitriol, titanium dioxide and magnesium oxide, and the organic is selected from one of tannin, peach gum, acetic acid and flavonoid compounds. Wherein the flavonoids include gardenia yellow pigment, chrysanthemum yellow pigment, coptisin, phellodendron amurense, quercetin, lutein, etc.

In the step (5), the pigment extracting solution is conveyed to a vacuum reaction kettle and then is subjected to heat preservation for 3-8 hours, so that the complexing rate of the pigment, mineral substances and organic substances can be improved.

The pigment extraction purity has an important influence on the subsequent pigment complexing yield, and the pigment extraction method comprises gel electrophoresis separation, resin separation and purification, membrane separation, countercurrent extraction and other methods, but the gel electrophoresis separation is suitable for the condition of small laboratory treatment capacity, and the industrial production can adopt the resin separation and purification and the membrane separation technology, but the resin separation and purification has the defects of difficult regeneration, more generated waste deionized water, and larger membrane separation investment in the early stage, while the traditional countercurrent extraction has the problems of large solvent consumption, low extraction rate, large energy consumption in the subsequent concentration process and the like. Therefore, the method adopts the method of combining countercurrent extraction and physical adsorption to extract the pigment, reduces the dosage of the solvent, improves the extraction rate of the pigment, omits the subsequent concentration process and reduces the energy consumption.

In the step (1), the solubility of the plant pigment is improved by heat preservation, particularly the solubility of lipophilic pigment in hot deionized water can be improved, and in addition, when sodium bicarbonate solution is used as a solvent, the sodium bicarbonate solution can promote the dissolution rate of the plant pigment, accelerate the extraction of the pigment and can also carry out extraction in a low-temperature environment.

Separating the filter residue containing impurities and the pigment dissolved in the solvent by the centrifugal separation operation in the step (2) because the initial extract obtained in the step (1) still contains the impurities such as fiber, protein and the like; the first solid phase extraction column can adsorb the pigment dissolved in the solvent, so that the solvent and the pigment are separated, the solvent can be recycled, and the dosage of the solvent is reduced; the first solid phase extraction column takes alkaline alumina and diatomite as fillers, so that the first solid phase extraction column can adsorb hydrophilic and lipophilic pigments at the same time, the pure pigments are collected in the solid phase extraction column completely and intensively, and the extraction method is favorable for reducing energy consumption; in addition, the adsorption capacity of the solid phase extraction column can be promoted by ultrasonic-assisted adsorption, because the activity of the adsorbent is increased by the interface effect of an ultrasonic field, and the diffusion of the pigment is enhanced.

Through the gradual operation of step (3) and step (4), can fully gather the pigment that remains in the filter residue in each step on the one hand, guarantee the purity of the pigment of adsorbing on the extraction column, improve the extraction yield, on the other hand, can retrieve the solvent again and use repeatedly, greatly reduced the consumption of solvent, also there is not the discharge problem of solvent, reduce environmental pollution.

In the step (5), the vegetable pigment is eluted by petroleum ether, on one hand, the vegetable pigment is eluted by the petroleum ether on the basis of the consideration that hydrophilic water pigment and lipophilic pigment can be eluted by the petroleum ether and the elution effect is good, on the other hand, the boiling point of the petroleum ether is 90-120 ℃ and is easy to volatilize, the liquid can still be kept when the pigment is complexed with mineral substances and organic substances, the complexing rate is ensured, and after the complexing, the vegetable pigment can be directly removed and recycled through extraction, so that the solvent concentration process in the traditional countercurrent extraction is omitted, and the energy consumption is greatly reduced.

A dyeing method of organic plant dye comprises the following steps of dyeing a fabric to be dyed according to a bath ratio of 1: 10 adding the mixture into a loose wool dyeing machine, heating to 60 ℃, adding the prepared organic plant dye and the auxiliary agent, and keeping the temperature for 20min, wherein the use amounts of the organic plant dye and the auxiliary agent are respectively 8% and 6% of the mass of the fabric to be dyed; adding organic acid to adjust pH to 5, heating to 95 deg.C at a rate of 1 deg.C/min, maintaining for 20min, adding softening agent, maintaining for 20min, and discharging deionized water when the temperature is increased to room temperature, wherein the amount of the softening agent is 1.8% of the amount of the dye.

The auxiliary agent is anhydrous sodium sulphate, and the organic acid is citric acid.

The bath ratio is 1: 10, dyeing cotton fabrics by using a traditional organic plant dye method, wherein the traditional organic plant dye method comprises the following steps: and (3) mixing the fabric to be dyed according to the bath ratio of 1: 10 adding the mixture into a loose wool dyeing machine, adding a dyeing pretreatment agent with the dosage of 20% of the fabric to be dyed, heating to 100 ℃, preserving the temperature for 90min, and discharging deionized water; washing with deionized water for 2 times, adding dye, dyeing auxiliary agent and deionized water with the same mass as that of the cotton fabric, wherein the use amounts of the dye and the auxiliary agent are respectively 8% and 10% of the mass of the fabric to be dyed, and discharging the deionized water after heat preservation at 100 ℃ for 60 min; then washing for 3-5 times by using deionized water, adding a color fixing agent, keeping the temperature at 65 ℃ for 20min, and discharging the deionized water, wherein the dosage of the color fixing agent is 1.6% of that of the dye; and finally adding a softening agent, keeping the temperature at 45 ℃ for 20min, discharging deionized water again, removing the deionized water, and drying to obtain the dyed fabric.

Compared with the traditional method, the dyeing method of the invention omits the repeated operations of temperature rise, heat preservation and water washing, thereby greatly reducing the energy consumption and saving the production cost. Like dyeing 100kg cotton fabric, the traditional method is adopted, deionized water is used for at least 1 ton, steam is used for 5 tons, electricity is used for 400 degrees, and labor cost is 700 yuan/ton, while the method of the invention is adopted, the dosage of the deionized water is about 150kg, steam is used for 2.6 tons, electricity is used for 150 degrees, and labor cost is 200 yuan/ton.

The invention has the beneficial effects that:

(1) the plant pigment is dissolved by alcohol, deionized water or sodium bicarbonate solution under heating, especially the sodium bicarbonate solution can accelerate extraction speed and can extract at low temperature, thus realizing primary extraction of the plant pigment.

(2) Through step-by-step repeated filter residue and steps such as filtrating centrifugal separation, phytochrome ultrasonic adsorption, dissolving reflux, countercurrent extraction, make the pigment that remains in the filter residue in each step carry out abundant collection on the one hand and get, guarantee the pigment purity of absorption on the extraction column, improved and extracted purity, and then improve the end product income, on the other hand can retrieve the solvent again and use repeatedly, the consumption of the solvent that has significantly reduced also does not have the discharge problem of solvent, does not have environmental pollution.

(3) The extracted plant pigment is complexed by mineral substances and organic substances, so that the stability of the product can be improved, and the color fastness of the textile fabric is improved.

(4) The petroleum ether is used for eluting the plant pigment, so that the complexing rate of the pigment, mineral substances and organic matters can be ensured, the complex can be directly removed by vacuumizing for recycling, the solvent concentration process in the traditional countercurrent extraction is omitted, and the energy consumption is greatly reduced.

(5) The dyeing process is improved, the plant pigment extracted from the plant is used for dyeing, the obtained textile does not harm human bodies, and meanwhile, the fabric can also have the performances of resisting bacteria and inflammation, resisting ultraviolet radiation, protecting skin and the like; in addition, the process can also greatly reduce energy consumption and save production cost.

Detailed Description

The invention is further described below with reference to specific embodiments: