A micro-nano interface coupling construction preparation method of lees biochar powder and tourmaline powder and functional fiber prepared therefrom

Abstract

The present invention combines for the first time the porous carbon powder derived from micro-nano-scale distiller's grains biomass with the characteristics of tourmaline powder, functionally integrates the special properties of the two, and designs the interface bonding mode of the two from a microscopic perspective. Under specific process conditions, the two powders react chemically at the interface to combine, so that the performance of the two can be synergistically enhanced and the structure can fully exert its functions. The composite material has been successfully applied to textiles, giving it more excellent functions (mildew resistance, warmth retention), while also having partial antibacterial, deodorizing and negative ion release functions. In addition, the present invention takes into account the richness and stability of raw materials. For example, tourmaline is a natural ore, and distiller's grains come from the residual biomass resources of the brewing industry. Through ingenious design, the two are combined to realize fiber functionalization, which not only produces healthy and comfortable functional fibers, but also provides high added value for the utilization of biomass waste, achieving the purpose of turning waste into treasure and improving the economic benefits of enterprises.

Description

Technical Field

[0001] The invention relates to a functional fiber, in particular to a preparation method for micro-nano interface coupling construction of vinasse biochar powder and tourmaline powder and the functional fiber prepared therefrom. Background Art

[0002] "Functional fibers" refer to ordinary fibers that have been endowed with specific functions beyond their basic properties. Common added functions include antibacterial, mildew-proof, mite-repellent, temperature and humidity control, moisture absorption and quick-drying, high far-infrared emissivity, negative ion generation, deodorization, conductivity, flame retardancy, oil and dirt resistance, and radiation protection. There are generally two methods for producing functional textiles: one is to directly use these functional fibers to develop and design functional textiles with the corresponding functions; the other is to apply functional finishing to ordinary fibers or textiles. The former method of directly producing functional fibers often involves modifying conventional synthetic fiber materials, such as by introducing functional additives through blending and composite spinning. In addition to meeting environmental and physiological safety requirements, these additives must be uniformly dispersed in the fibers and form a stable and compatible interface with the fiber material, imparting specific and stable functions to the fibers. Compared to the latter method of using finishing agents to functionalize the fibers, the direct introduction of functional additives to prepare fibers offers advantages such as a simpler process, less pollutants and waste generation, and more stable and long-lasting functions. "Healthy functional fibers" are typically based on polyester, nylon, polypropylene, cotton, and other fibers, and come in both filament and staple fibers. In recent years, with the development of society and improvements in living standards, demand for these fibers has grown. The emergence of emerging nanoscience and technology, including the development of various nanomaterials, has provided strong support for the development of various functional fibers, and the industry is showing positive momentum.

[0003] my country is a major wine producer with a diverse range of liquor varieties, producing over 10 million tons of baijiu (white liquor) annually. While striving to produce rich, flavorful baijiu, the production process inevitably generates a significant amount of distiller's grains biomass waste. Besides a significant amount of water, distiller's grains are primarily composed of organic matter such as cellulose, hemicellulose, lignin, and protein, as well as components such as enzymes, alcohols, acids, and esters. Consequently, distiller's grains are prone to decay and deterioration, not only polluting the environment but also wasting solid waste resources. Therefore, resource recycling of distiller's grains is essential. Traditional methods include landfill composting, fermentation to produce biogas, and processing into low-value products such as animal feed. Because distiller's grains are rich in organic matter and oxygen and nitrogen groups, physical or chemical treatments can produce highly porous distiller's grains biochar, which can be used to improve soil quality and develop high-value materials such as catalysts and adjuvants. However, compared to high-value carbon nanomaterials, the value of distiller's grains biochar still has significant room for improvement.

[0004] Tourmaline, also known as tourmaline or tourmaline, is a ring-shaped silicate mineral containing elements such as boron, aluminum, sodium, iron, magnesium, and lithium. Its composition is diverse, and its surface is rich in hydrophilic groups such as hydroxyl groups. Tourmaline permanently emits far-infrared light with a wavelength of 4 to 14 μm. Its far-infrared emissivity exceeds 0.88, matching the human body's resonant absorption, producing resonance and thermal effects. Furthermore, due to its excellent pyroelectric and piezoelectric properties, it undergoes spontaneous polarization in response to changes in temperature or pressure, possessing natural electrical polarity and the ability to release negative ions.

[0005] The prior art with publication number CN 106400158 A (a kind of hygroscopic and breathable polyester filament with cool feeling and antistatic and its preparation method) discloses a kind of hygroscopic and breathable polyester filament with cool feeling and antistatic, and its raw materials include 3-15 parts of bamboo activated carbon powder and 2-6 parts of nano-level tourmaline powder, which can obtain a kind of hygroscopic and breathable polyester filament with cool feeling and antistatic, endowing the polyester filament with the effects of moisture absorption and mildew resistance, air purification, antibacterial and insecticide removal, cooling and skin care, and antistatic, while having UV protection and protective effect, can further enhance the tensile strength of the polyester filament, improve elongation at break, and extend the service life of the polyester filament. However, the invention directly uses various powders to mix and stir evenly, and no interfacial chemical reaction can occur between the various powders, and it is also impossible to form a strong micro-nano interface region that can interact with each other, that is, it cannot achieve the effect of mutual reinforcement. Summary of the Invention

[0006] In response to the above problems, the present invention combines the porous carbon powder derived from micro-nano-scale liquor lees biomass with the characteristics of tourmaline powder for the first time, functionally integrates the special properties of the two, and designs the interface bonding mode of the two from a microscopic perspective. Under specific process conditions, the two powders react chemically at the interface to combine, so that the two can synergize in performance and fully exert their functions in structure. The composite material has been successfully applied to textiles, making it have more excellent functions (mildew proof, warm keeping), while also having partial antibacterial, deodorizing and negative ion release functions. In addition, the present invention takes into account the richness and diversity of raw materials, such as tourmaline is a natural ore, and liquor lees comes from the residual biomass resources of the brewing industry. Through ingenious design, the two are combined to realize fiber functionalization, which not only produces healthy and comfortable functional fibers, but also provides high added value for the utilization of biomass waste, achieves the purpose of turning waste into treasure and improving the economic benefits of enterprises, and makes a positive contribution to alleviating environmental pressure.

[0007] The present invention first provides a preparation method for the micro-nano interface coupling construction of white wine lees biochar powder and tourmaline powder. The wine lees biochar powder and tourmaline powder are respectively pretreated and modified to form pretreated and modified wine lees biochar powder and pretreated and modified tourmaline powder, which are further mixed with a dispersant and vacuum dried. The pretreated and modified wine lees biochar powder is obtained by mixing white wine lees dry powder with an activator, carbonizing the obtained biomass carbon powder, grinding and modifying it with a surface modifier, and spray drying it. The pretreated and modified tourmaline powder is obtained by grinding and modifying tourmaline powder with a surfactant, and spray drying it. The vacuum drying forms a micro-nano interface connection area between the white wine lees biochar and tourmaline powder particles.

[0008] The present invention secondly provides a functional fiber with both mildew resistance and antibacterial properties, which is spun from a functional masterbatch, wherein the functional masterbatch contains a white wine lees biochar-tourmaline mixed functional powder. The white wine lees biochar-tourmaline mixed functional powder is prepared by mixing raw materials including pretreated and modified white wine lees biochar powder, pretreated and modified tourmaline powder and a dispersant, and vacuum drying to form a micro-nano interface connection area between the white wine lees biochar and the tourmaline powder particles. The pretreated and modified white wine lees biochar powder is prepared by mixing white wine lees dry powder with an activator, carbonizing the obtained biomass carbon powder, grinding and modifying it with a surface modifier, and spray-drying it. The pretreated and modified tourmaline powder is prepared by grinding and modifying tourmaline powder with a surfactant, and spray-drying it.

[0009] The activator is NaHCO3 or ZnCl2, the surfactant is one of KH550 (APTES), KH570, and dimethyldiethoxysilane (DEDMS); the dispersant is selected from one of stearamide, N,N'-methylbisstearamide, N,N'-ethylbisstearamide, hydroxyethylethylenebisstearamide, and N,N'-ethylenebis-12-hydroxystearamide, or a mixture of two or more thereof.

[0010] The white wine lees biochar-tourmaline mixed functional powder comprises 10 to 20 parts of pretreated and modified wine lees biochar powder, 10 to 20 parts of pretreated and modified tourmaline powder and 1 to 6 parts of a dispersant.

[0011] Finally, the present invention provides a method for preparing the functional fiber having both mildew resistance and antibacterial properties according to claim 1, the method comprising the following steps:

[0012] Step 1: Pretreatment and surface modification of lees biochar powder and tourmaline powder

[0013] The vinasse dry powder and the activator are mixed in an appropriate proportion to obtain a biochar preparation precursor, and the precursor is carbonized at a high temperature in an inert gas atmosphere to obtain biomass carbon powder, wherein the carbonization temperature is 400-900° C. and the carbonization time is 0.5-3 hours; the obtained biomass carbon powder is mixed with a surface modifier, and the mixture is fully ground and modified in a sand mill, and spray-dried to obtain a pretreated and modified vinasse biochar powder; tourmaline powder is fully ground and modified in the surface modifier, and spray-dried to obtain a pretreated and modified tourmaline powder;

[0014] Step 2: Mixing of lees biochar and tourmaline powder and their interface connection

[0015] The pretreated and modified vinasse biochar powder, the pretreated and modified tourmaline powder and the dispersant are mixed in a certain mass ratio and then dried under vacuum conditions to form a micro-nano interface connection area between the vinasse biochar and the tourmaline powder particles, thereby preparing a white vinasse biochar-tourmaline mixed functional powder. The vacuum drying temperature is 100-200° C., the vacuum degree is 0.05-0.1 torr, and the drying time is 2-6 hours.

[0016] Step 3: Preparation of functional masterbatch and functional fiber

[0017] The anti-mildew and antibacterial masterbatch is prepared by mixing and extruding white wine lees biochar-tourmaline mixed functional powder, slices and a wetting agent; and the anti-mildew and antibacterial masterbatch is melt-spun to obtain functional fibers with both anti-mildew and antibacterial properties.

[0018] The vinasse dry powder in the first step is obtained by drying and crushing fresh vinasse with a water content of 50-65%, and the tourmaline powder is 6000-12000 mesh.

[0019] In the first step, the solid content of the grinding material in the sand mill is 5-50wt%, preferably 10-30% (solid: water solvent = 5 / 95-50 / 50), and the grinding time is 0.5-4h, preferably 1-2h; the spray drying setting temperature is 120-160°C, the fan speed is 80-90%, the peristaltic pump speed is 30-70%, and the needle is passed for 5-20s.

[0020] In the second step, the particle size of the surface-modified vinasse biochar powder is in the range of 50 to 200 nm, and the particle size of the surface-modified tourmaline powder is in the range of 50 to 300 nm.

[0021] In the third step, 21 to 46 parts of white wine lees biochar-tourmaline mixed functional powder, 2 to 6 parts of wetting agent, and 48 to 87 parts of slices are used; the slices include but are not limited to nylon, polypropylene, and polyester slices; the wetting agent is preferably one or a mixture of two or more of liquid paraffin, polyethylene wax, oxidized polyethylene wax, polypropylene wax, stearic acid, stearyl alcohol, calcium stearate, and ethyl bisstearamide polar modifiers.

[0022] In the third step, the extrusion granulation is carried out by using one of a single-screw extrusion granulator, a twin-screw extrusion granulator, a single-screw extrusion granulator with internal mixing, a twin-screw extrusion granulator with internal mixing, and a two-stage extrusion granulator. The granulation temperature is set in the range of 150-280°C.

[0023] Compared with the prior art, the present invention has the following effects:

[0024] 1. The present invention utilizes biochar from white wine lees to weave functional fibers, which is a recycling of surplus biomass resources, improves economic benefits, fully recovers carbon-containing resources, and “turns waste into treasure” to contribute to the dual carbon policy.

[0025] 2. The present invention connects and compounds white wine lees biochar and tourmaline at the interfacial atomic or molecular level, which not only gives full play to the porosity and adsorption of the carbon material, but also synergizes with the functions of tourmaline powder to prepare a mildew-proof and warm fiber with better performance. The rich oxygen-containing groups on the surface of white wine lees biochar and the hydrophilic groups on the surface of tourmaline are easy to graft and modify. The modified coupling agent reacts under specific vacuum and temperature conditions to form an interfacial chemical bond connection, so that the two powders are in close contact and enhance each other's functions. The high specific surface area and porosity of white wine lees biochar, and the specific surface area and porosity are adjustable, can increase the contact area with tourmaline while contributing to the emission of far-infrared wavelengths of tourmaline and the release of negative ions, thereby synergistically improving the performance of the tourmaline itself.

[0026] 3. The wet grinding and modification of distiller's grains carbon and tourmaline, followed by spray drying to obtain a powder, results in a smaller and more uniform powder particle size and more complete surface modifier incorporation compared to dry ball milling.

[0027] 4. The process of the present invention improves the mixing uniformity of the product. High-proportion nanopowders have the problem of agglomeration during the melt spinning process. The present invention uses a suitable dispersant and dispersion process to evenly mix the functional powders, and the functional powders are evenly distributed in the masterbatch and the fiber. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1a is the isothermal adsorption-desorption curve of N2 by the vinasse biochar obtained in Example 1; Figure 1b This is the pore distribution curve of the vinasse biochar obtained in Example 1.

[0029] Figure 2a is the isothermal adsorption-desorption curve of N2 by the vinasse biochar obtained in Example 2; Figure 2b This is the pore distribution curve of the vinasse biochar obtained in Example 2.

[0030] Figure 3a is the isothermal adsorption-desorption curve of N2 by the vinasse biochar obtained in Example 3; Figure 3b This is the pore distribution curve of the vinasse biochar obtained in Example 3.

[0031] Figure 4a This is the SEM image of “micron-scale” white wine lees biochar; Figure 4b This is the SEM image of “micro-nano-scale” white wine lees biochar.

[0032] Figure 5a This is a SEM image of “micron-sized” tourmaline powder; Figure 5b This is an SEM image of "micro-nano-level" tourmaline powder. DETAILED DESCRIPTION

[0033] Example 1: Preparation of Liquor Grains Biochar-Tourmaline Composite "Nylon Filament"

[0034] Step 1: Dry the fresh white wine lees and grind them into dry wine lees powder through conventional drying and crushing process. Mix the dry wine lees powder and activator NaHCO3 in appropriate proportions to obtain the precursor for biochar preparation. Carbonize the precursor in N2 atmosphere at T6=600℃ for 2h to obtain wine lees biochar powder. Figure 1a It can be seen from the isothermal adsorption-desorption curve that there is an obvious hysteresis loop between the relative partial pressure P / P0 of 0.4 and 0.9, indicating that the white wine lees biochar has a mesoporous structure. Figure 1b It can be seen that the pore size of the prepared white wine lees biochar is concentrated in the range of 3 to 4 nm, and the pore size distribution range is very narrow. The obtained white wine lees biochar has a large specific surface area and pore volume.

[0035] The obtained biochar was ground and surface modified. The obtained biochar powder was mixed with the surface modifier DEDMS in a certain proportion using a sand mill and fully ground and modified. The solid content in the ground material was 20wt% (solid: water solvent = 1:4), and the grinding time was 2h. The 10000 mesh tourmaline powder was surface modified using the same material ratio and grinding conditions. The ground material suspension was spray dried to obtain a powder. The spray dryer was set at a temperature of 150°C, a fan speed of 80%, a peristaltic pump speed of 65%, and the needle was passed for 10s. The dry powder was then dried in a conventional oven at 80°C for 24h.

[0036] Step 2: Preparation of the Functional Masterbatch: Calculate the raw materials by absolute dry weight to obtain 100 parts each of modified white wine lees biochar, 10 parts modified 10,000-mesh tourmaline powder, and 3 parts dispersant N,N'-methylbisstearamide. Stir the mixture in a low-speed mixer at 100 rpm for 20 minutes to obtain a white wine lees biochar-tourmaline mixed functional powder. This powder is then dried under vacuum conditions, preferably at a vacuum level of 0.08 torr to 0.1 torr, for 4 hours at a temperature of 120°C.

[0037] Step 3: Weigh 23 parts of dried white wine lees biochar-tourmaline mixed functional powder, 3 parts of polyethylene wax, and 74 parts of spinning-grade nylon chips with an intrinsic viscosity of 2.40 dL / g, use a low-speed mixer to stir at 150 rpm for 30 minutes, and obtain the raw materials for preparing the functional masterbatch.

[0038] Step 4: Add the raw materials for preparing the functional masterbatch into the twin-screw extruder granulator, set the temperature of each zone of the mixer to 250℃ for the head, 220℃ for zone 1, 250℃ for zone 2, 250℃ for zone 3, and 250℃ for zone 4, and obtain the white wine lees biochar-tourmaline composite nylon masterbatch after screw stirring, extrusion, water cooling, pelletizing and drying.

[0039] Step 5: The white wine lees biochar-tourmaline composite nylon masterbatch and nylon chips are evenly mixed in a mass ratio of 4:96, and produced according to conventional nylon filament production process and production conditions to obtain white wine lees biochar-tourmaline composite nylon filament with a filament specification of 75D / 72F.

[0040] Example 2: Preparation of white wine lees biochar-tourmaline composite "polyester staple fiber"

[0041] Step 1: Dry the fresh white wine lees by conventional drying and crushing process to obtain dry wine lees powder. Mix the dry wine lees powder with the activator NaHCO3 in appropriate proportions to obtain the precursor for biochar preparation. Carbonize the precursor in N2 atmosphere at T5=500℃ for 2h to obtain wine lees biochar powder. Figure 2a It can be seen from the isothermal adsorption-desorption curve that there is an obvious hysteresis loop between the relative partial pressure P / P0 of 0.45 and 0.9, indicating that the white wine lees biochar has a mesoporous structure. Figure 2b It can be seen that the pore size of the prepared white wine lees biochar is concentrated in the range of 3.5-4 nm, the pore size distribution range is very narrow, and the obtained white wine lees biochar has a large specific surface area and pore volume.

[0042] The obtained biochar was ground and surface modified. The obtained biochar powder was mixed with the surface modifier DEDMS in a certain proportion using a sand mill and fully ground and modified. The solid content in the ground material was 20wt% (solid: water solvent = 1:4), and the grinding time was 2h. The 10000 mesh tourmaline powder was surface modified using the same material ratio and grinding conditions. The ground material suspension was spray dried to obtain a powder. The spray drying temperature was set at 150°C, the fan speed was 80%, the peristaltic pump speed was 65%, and the needle was passed for 10s. The dry powder was then dried in a conventional oven at 80°C for 24h.

[0043] Step 2: Preparation of the Functional Masterbatch: Calculate the raw materials by absolute dry weight to obtain 100 parts each of 10 parts white wine lees biochar powder, 10 parts 12000 mesh tourmaline powder, and 2 parts N,N'-ethylenebis-12-hydroxystearamide (dispersant). Stir the mixture in a low-speed mixer at 100 rpm for 20 minutes to obtain a white wine lees biochar-tourmaline mixed functional powder. This powder is then dried under vacuum conditions, preferably at a vacuum level of 0.08 torr to 0.1 torr, for 4 hours at a temperature of 120°C.

[0044] Step 3: Weigh 22 parts of dried white wine lees biochar-tourmaline mixed functional powder, 4 parts of polyethylene wax, and 74 parts of PET chips with an intrinsic viscosity of 0.65 dL / g, use a low-speed mixer to stir at 150 rpm for 30 minutes to obtain the raw materials for preparing functional masterbatch.

[0045] Step 4: Add the raw materials for preparing the functional masterbatch into the twin-screw extruder granulator, set the temperature of each zone of the mixer to 250℃ for the head, 250℃ for zone 1, 265℃ for zone 2, 265℃ for zone 3 and 265℃ for zone 4, and obtain the white wine lees biochar-tourmaline composite polyester masterbatch after screw stirring, extrusion, water cooling, pelletizing and drying.

[0046] Step 5: The white wine lees biochar-tourmaline composite polyester masterbatch and the spinning-grade polyester chips are evenly mixed in a mass ratio of 5:95, and produced according to the conventional polyester staple fiber production process and production conditions to obtain the white wine lees biochar-tourmaline composite polyester staple fiber with a staple fiber specification of 3.33dtex*64mm.

[0047] Example 3: Preparation of Liquor Grains Biochar-Tourmaline Composite "Polypropylene Staple Fiber"

[0048] Step 1: Dry the fresh white wine lees by conventional drying and crushing process to obtain dry wine lees powder. Mix the dry wine lees powder with the activator NaHCO3 in appropriate proportions to obtain the precursor for biochar preparation. Carbonize the precursor in N2 atmosphere at T4=400℃ for 2h to obtain wine lees biochar powder. Figure 3aIt can be seen from the isothermal adsorption-desorption curve that there is an obvious hysteresis loop between the relative partial pressure P / P0 of 0.45 and 0.9, indicating that the white wine lees biochar has a mesoporous structure. Figure 3b It can be seen that the pore size of the prepared white wine lees biochar is concentrated in the range of 3.5-4 nm, the pore size distribution range is very narrow, and the obtained white wine lees biochar has a large specific surface area and pore volume.

[0049] The obtained biochar was ground and surface modified. The obtained biochar powder was mixed with the surface modifier DEDMS in a certain proportion using a sand mill and fully ground and modified. The solid content in the ground material was 20wt% (solid: water solvent = 1:4), and the grinding time was 2h. The 10000 mesh tourmaline powder was surface modified using the same material ratio and grinding conditions. The ground material suspension was spray dried to obtain a powder. The spray drying temperature was set at 150°C, the fan speed was 80%, the peristaltic pump speed was 65%, and the needle was passed for 10s. The dry powder was then dried in a conventional oven at 80°C for 24h.

[0050] Step 2: Preparation of the Functional Masterbatch: Calculate the raw materials by absolute dry weight to obtain 12 parts of distillers' grains biochar powder, 12 parts of 10,000-mesh tourmaline powder, and 3 parts of the dispersant N,N'-ethylenebis-12-hydroxystearamide. Stir the mixture in a low-speed mixer at 100 rpm for 20 minutes to obtain a mixed functional powder of distillers' grains biochar and tourmaline. This mixture is then dried (reacted) under vacuum conditions, preferably at a vacuum level of 0.08 torr to 0.1 torr, for 4 hours at a temperature of 120°C.

[0051] Step 3: Weigh 27 parts of dried white wine lees biochar-tourmaline mixed functional powder, 4 parts of calcium stearate, and 69 parts of PP chips with a melt index of 40g / 10min, use a low-speed mixer to stir at 150 rpm for 30 minutes to obtain the raw materials for preparing functional masterbatch.

[0052] Step 4: Add the raw materials for preparing the functional masterbatch into the twin-screw extruder granulator, set the temperature of each zone of the mixer to 215°C for the head, 190°C for zone 1, 240°C for zone 2, 240°C for zone 3, and 240°C for zone 4, and obtain the white wine lees biochar-tourmaline composite polypropylene masterbatch after screw stirring, extrusion, water cooling, pelletizing and drying.

[0053] Step 5: The white wine lees biochar-tourmaline composite polypropylene masterbatch and the spinning-grade polypropylene chips are evenly mixed in a mass ratio of 4:96, and produced according to the conventional polypropylene staple fiber production process and production conditions to obtain the white wine lees biochar-tourmaline composite polypropylene staple fiber with a staple fiber specification of 3.33dtex*32mm.

[0054] Comparative Example 1: Preparation of "nylon filaments" containing only white wine lees biochar

[0055] Step 1: Prepare modified vinasse biochar powder by comparing with Example 1.

[0056] Step 2: Take 10 parts of white wine lees biochar and 2 parts of dispersant N,N'-methylbisstearamide respectively, use a low-speed mixer to stir at 100 rpm for 20 minutes to obtain white wine lees biochar functional powder.

[0057] Step 3: Weigh 12 parts of dried white wine lees biochar functional powder, 2 parts of polyethylene wax, and 86 parts of spinning-grade nylon chips with an intrinsic viscosity of 2.40 dL / g, and use a low-speed mixer to stir at 150 rpm for 30 minutes to obtain the raw materials for preparing the functional masterbatch.

[0058] Step 4: Add the raw materials for preparing functional masterbatch into the twin-screw extruder granulator, set the temperature of each zone of the mixer to 250℃ for the head, 220℃ for zone 1, 250℃ for zone 2, 250℃ for zone 3, and 250℃ for zone 4, and obtain the white wine lees biochar nylon masterbatch after screw stirring, extrusion, water cooling, pelletizing and drying.

[0059] Step 5: The white wine lees biochar nylon masterbatch and nylon chips were evenly mixed in a mass ratio of 4:96, and produced according to conventional nylon filament production process and production conditions to obtain white wine lees biochar nylon filament with a filament specification of 75D / 72F.

[0060] Comparative Example 2: Preparation of polyester staple fiber containing only tourmaline

[0061] Step 1: Comparing with Example 2, the functional masterbatch was prepared by taking 100 parts of the raw materials for the preparation of the functional masterbatch, and taking 10 parts of the modified tourmaline powder and 2 parts of the dispersant N,N'-ethylenebis-12-hydroxystearamide. The mixture was stirred at 100 rpm in a low-speed mixer for 20 minutes to obtain a functional tourmaline powder.

[0062] Step 2: Weigh 12 parts of dried tourmaline mixed functional powder, 2 parts of polyethylene wax, and 86 parts of PET chips with an intrinsic viscosity of 0.65 dL / g, and use a low-speed mixer to stir at 150 rpm for 30 minutes to obtain the raw materials for preparing the functional masterbatch.

[0063] Step 3: Add the raw materials for preparing functional masterbatch into the twin-screw extruder granulator, set the temperature of each zone of the mixer to 250℃ for the head, 250℃ for zone 1, 265℃ for zone 2, 265℃ for zone 3 and 265℃ for zone 4, and obtain the tourmaline polyester masterbatch after screw stirring, extrusion of strands, water cooling, pelletizing and drying.

[0064] Step 4: The tourmaline polyester masterbatch and the spinning-grade polyester chips are evenly mixed in a mass ratio of 5:95, and produced according to the conventional polyester staple fiber production process and production conditions to obtain the tourmaline polyester staple fiber with a staple fiber specification of 3.33dtex*64mm.

[0065] Comparative Example 3: Preparation of white wine lees biochar-tourmaline composite "nylon filament" without vacuum drying (reaction)

[0066] In contrast to Example 1, the modified powders were directly mixed in a low-speed mixer without vacuum drying (reaction), and no micro-nano interface connection region was formed between the lees carbon powder and the tourmaline powder. The mixed powders were then granulated and subsequently filamented.

[0067] Comparative Example 4: No modification of white wine lees carbon powder and tourmaline powder

[0068] The unmodified powder has a strong surface hydrophilicity and poor compatibility with the surface of the polymer chips, and cannot be used directly for spinning.

[0069] Below are the test results of mildew resistance and heat preservation functions.

[0070] The anti-mildew properties of the white wine lees biochar-tourmaline composite fibers obtained in Examples 1, 2, and 3 were tested according to the national standard "GB / T 24346-2009 Evaluation of Anti-mildew Properties of Textiles." The test results are detailed in Table 1 below. Comparative Example 1 is a nylon filament containing only white wine lees biochar. Comparative Example 3 is a nylon filament composite of white wine lees biochar and tourmaline powder that has not undergone vacuum drying (reaction).

[0071] Table 1 Anti-mildew test results

[0072]

[0073] As can be seen from Table 1, the mildew resistance of the white wine lees biochar-tourmaline composite fibers obtained in Examples 1, 2, and 3 was higher than that of Comparative Examples 1 and 2, reaching a mildew resistance level of 0. These results indicate that the fibers obtained in the Examples have a better mildew resistance than the white wine lees biochar fibers and the white wine lees biochar-tourmaline composite fibers that have not been vacuum dried (reacted).

[0074] illustrate:

[0075] 1. "GB / T 24346-2009 Evaluation of Anti-mildew Properties of Textiles", as shown in Table 2 below.

[0076] Table 2 Evaluation criteria for anti-mildew performance

[0077] Mold growth Mildew resistance level No obvious mold growth under a magnifying glass 0 Mold growth is sparse or localized, covering less than 10% of the sample surface area 1 The mold coverage area on the sample surface is less than 30% 2 The coverage area of ​​mold on the sample surface is less than 60% (30% to 60%) 3 The mold coverage area on the sample surface reaches or exceeds 60% 4

[0078] Far infrared rays resonate and warm the human body, raising the perceived ambient temperature, maintaining warmth and storing heat, improving blood microcirculation, and boosting overall activity. The present invention tested the thermal insulation effect in accordance with the national standard "GB / T 30127-2013 Testing and Evaluation of Far-Infrared Properties of Textiles." The test results are detailed in Table 3 below. Examples 1, 2, and 3 are white wine lees biochar-tourmaline composite fibers, while Comparative Example 2 is a polyester staple fiber containing only tourmaline. Comparative Example 3 is a white wine lees biochar-tourmaline powder composite "nylon filament" that has not undergone a vacuum drying (reaction) step.

[0079] Table 3 Far infrared test results

[0080]

[0081]

[0082] As can be seen from Table 3, the far-infrared radiation temperature rise and far-infrared emissivity of the white wine lees biochar-tourmaline composite fibers obtained in Examples 1, 2, and 3 were all higher than those in Comparative Example 2, and the far-infrared emissivity was higher than that in Comparative Example 3. These results indicate that compared to tourmaline fibers, the white wine lees biochar-tourmaline composite fibers obtained in the Examples have better far-infrared emission effects than the tourmaline fibers that have not been vacuum dried (reacted).

[0083] illustrate:

[0084] 1. "GB / T 30127-2013 Textiles - Testing and Evaluation of Far-Infrared Properties", the evaluation criteria for the far-infrared properties of fiber samples are shown in Table 4 below.

[0085] Table 4 Evaluation criteria for far infrared performance of fiber samples

[0086] Standard value Single judgment Far infrared radiation temperature rise (℃) ≥1.7 conform to Far infrared emissivity ≥0.83 conform to

Claims

1. A functional fiber with both mildew resistance and antibacterial properties, which is spun from functional masterbatch, characterized in that: The functional masterbatch comprises a white wine lees biochar-tourmaline mixed functional powder, which is prepared by mixing raw materials including pretreated and modified wine lees biochar powder, pretreated and modified tourmaline powder, and a dispersant, and vacuum drying. The pretreated and modified wine lees biochar powder is prepared by mixing wine lees dry powder with an activator, carbonizing the obtained biomass carbon powder, grinding and modifying it with a surface modifier, and spray drying it. The pretreated and modified tourmaline powder is prepared by grinding and modifying tourmaline powder with a surface modifier, and spray drying it. The method for preparing the functional fiber comprises the following steps: Step 1: Pretreatment and surface modification of lees biochar powder and tourmaline powder The vinasse dry powder and the activator are mixed in an appropriate proportion to obtain a biochar preparation precursor, and the precursor is carbonized at a high temperature in an inert gas atmosphere to obtain biomass carbon powder, wherein the carbonization temperature is 400-900° C. and the carbonization time is 0.5-3 hours; the obtained biomass carbon powder is mixed with a surface modifier, and the mixture is fully ground and modified in a sand mill, and spray-dried to obtain a pretreated and modified vinasse biochar powder; tourmaline powder is fully ground and modified with the surface modifier, and spray-dried to obtain a pretreated and modified tourmaline powder; Step 2: Mixing of lees biochar and tourmaline powder and their interface connection The pretreated and modified vinasse biochar powder, the pretreated and modified tourmaline powder and the dispersant are mixed in a certain mass ratio and then dried under vacuum conditions to form a micro-nano interface connection area between the vinasse biochar and the tourmaline powder particles, thereby preparing a white vinasse biochar-tourmaline mixed functional powder. The vacuum drying temperature is 100-200° C., the vacuum degree is 0.05-0.1 Torr, and the drying time is 2-6 hours. Step 3: Preparation of functional masterbatch and functional fiber The anti-mildew and antibacterial masterbatch is prepared by mixing and extruding a mixture of white wine lees biochar and tourmaline functional powder, slices, and a wetting agent; and the anti-mildew and antibacterial masterbatch is melt-spun to obtain a functional fiber with both anti-mildew and antibacterial properties. The activator is NaHCO3 or ZnCl2, and the surface modifier is one of KH550, KH570 and dimethyldiethoxysilane.

2. The preparation method according to claim 1, wherein the functional component is characterized in that the dispersant is selected from one or a mixture of two or more of stearamide, N,N'-methylbisstearamide, N,N'-ethylbisstearamide, hydroxyethylethylenebisstearamide, and N,N'-ethylenebis-12-hydroxystearamide.

3. The preparation method according to claim 1, characterized in that The white wine lees biochar-tourmaline mixed functional powder comprises 10 to 20 parts of pretreated and modified wine lees biochar powder, 10 to 20 parts of pretreated and modified tourmaline powder and 1 to 6 parts of a dispersant.

4. The preparation method according to claim 1, characterized in that The vinasse dry powder in the first step is obtained by drying and crushing fresh vinasse with a moisture content of 50-65%, and the tourmaline powder is 6000-12000 mesh.

5. The preparation method according to claim 1, characterized in that In the first step, the solid content of the grinding material in the sand mill is 5-50wt%, and the grinding time is 0.5-4h; the spray drying setting temperature is 120-160°C, the peristaltic pump speed is 30-70%, and the needle is passed for 5-20s.

6. The preparation method according to claim 1, characterized in that In the second step, the particle size of the surface-modified vinasse biochar powder ranges from 50 to 200 nm, and the surface-modified tourmaline fraction is further ground to 50 to 300 nm.

7. The preparation method according to claim 3, characterized in that In the third step, 21 to 46 parts of white wine lees biochar-tourmaline mixed functional powder, 2 to 6 parts of wetting agent, and 48 to 87 parts of slices are used; the slices include nylon, polypropylene, and polyester slices; the wetting agent is one or a mixture of two or more of liquid paraffin, polyethylene wax, oxidized polyethylene wax, polypropylene wax, stearic acid, stearyl alcohol, calcium stearate, and ethyl bisstearamide polar modifiers.

8. The preparation method according to claim 1, characterized in that In the third step, the granulation temperature is set in the range of 150-280°C.

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