WO2022012373A1

WO2022012373A1 - Active water preparation device, natural fiber dyeing and finishing treatment device and method

Info

Publication number: WO2022012373A1
Application number: PCT/CN2021/104687
Authority: WO
Inventors: 赵晋; 刘建勇; 朱若英; 杨文芳; 任海涛; 韩振邦; 石桂刚
Original assignee: 天津工业大学
Priority date: 2020-07-13
Filing date: 2021-07-06
Publication date: 2022-01-20
Also published as: JP2023525402A; CN113233692A; CN113233690A; CN113233691A; CN113429057B; CN113233691B; CN113233692B; JP7337421B2; CN113233690B; CN113277669B; CN113429057A; CN113277669A

Abstract

Provided are an active water preparation device, a natural fiber dyeing and finishing treatment device comprising an active water preparation device, and a method for dyeing and finishing natural fibers by using a natural fiber dyeing and finishing treatment device. The active water preparation device comprises a water tank, an electric field generating device and a magnetic field generating device. An active aqueous solution produced by the device is used for the pretreatment of natural fibers and textiles thereof.

Description

[Title of invention formulated by ISA pursuant to Rule 37.2] Active water preparation device and natural fiber dyeing and finishing treatment device and method

technical field

The invention relates to the technical field of environmental protection dyeing and finishing, in particular to an active water preparation device and a natural fiber dyeing and finishing treatment device and method.

Background technique

The purpose of pre-treatment of natural fibers and their textiles is to improve the whiteness of fabrics or fibers, remove various natural impurities, pulp, oil, etc. on the fabrics or fibers, so that the textiles have a clean, white appearance, soft feel and good water absorption. properties and wetting properties to facilitate subsequent dyeing and finishing.

In the current production, the pretreatment of textiles is a typical wet process, and the main chemicals used are alkaline agents such as sodium hydroxide, oxidants such as hydrogen peroxide, sodium hypochlorite, sodium chlorite, etc. Among them, the alkali agent, especially sodium hydroxide, has the function of swelling the fibers, cottonseed hulls and pulp and other substances and saponifying the related fat and wax substances, so that various impurities and pulp can be easily removed. At the same time, oxidants such as hydrogen peroxide and sodium hypochlorite are usually used under alkaline conditions. The oxidation of chemicals such as hydrogen peroxide, sodium hypochlorite, and sodium chlorite can destroy the chemical structure of pigments, pectin, pulp and other impurities, so that the whiteness, cleanliness and wettability of the treated textiles are improved, and subsequent dyeing is easy. Finishing.

The pretreatment of textiles generally includes alkaline boiling, oxygen bleaching, chlorine bleaching and other treatments, which have disadvantages such as long process, low efficiency, high energy consumption, large waste water discharge, and great damage to fibers.

SUMMARY OF THE INVENTION

The purpose of the present invention is to provide an active water preparation device and a natural fiber dyeing and finishing treatment device and method to solve at least one of the above technical problems existing in the prior art.

In order to solve the above technical problems, the present invention provides an active water preparation device, which includes: a water tank, an electric field generating device and a magnetic field generating device;

the water tank is used to accommodate the working fluid;

The electric field generating device includes: an electrode assembly for forming an electric field; the electrode assembly is arranged in the water tank for electric field treatment of the working fluid;

The magnetic field generating device includes a magnetic pole assembly for forming a magnetic field; the electrode assembly is arranged inside or outside the water tank for magnetizing the working fluid.

Further, the electrode assembly includes one or more pairs of positive electrodes and negative electrodes arranged at intervals.

Further, the magnetic pole assembly includes a positive magnetic pole and a negative magnetic pole; the positive magnetic pole and the negative magnetic pole are respectively arranged at opposite ends of the water tank.

Further, the water tank is made of insulating and corrosion-resistant materials such as glass, glass fiber reinforced plastics or high molecular polymer materials (polytetrafluoroethylene, pvc, etc.).

Further, the positive electrode and the negative electrode are flat plates; between the positive magnetic pole and the negative magnetic pole, the positive electrode and the negative electrode are alternately arranged at equal intervals;

Alternatively, the positive electrode and the negative electrode are cylindrical, and are alternately arranged in concentric circles at equal intervals in the radial direction.

Further, the positive magnetic pole and the negative magnetic pole are semi-enclosed magnetic poles, that is, the horizontal cross-sections of the positive magnetic pole and the negative magnetic pole are respectively semi-annular, respectively enclosing the water tank as much as possible from the opposite ends or both sides of the water tank, Thereby effectively increasing the strength of the magnetic field in the water tank.

Further, the magnetic pole assembly also includes an insulating electrode isolation plate and an insulating electrode isolation sand core plate; the upper and lower ends of the positive electrode and the negative electrode are respectively connected to the insulating electrode isolation plate and the insulating electrode isolation sand. on the core board, so that the space between the positive electrode and the negative electrode can be effectively maintained.

Further, the materials of the positive electrode and the negative electrode are 304, 321 and other stable stainless steel electrodes, pyrolytic graphite electrodes, graphene-coated composite graphite electrodes, phosphor copper electrodes, titanium electrodes, platinum titanium electrodes, and precious metal electrodes. , MMO ruthenium iridium titanium electrode, a mixture of one or more of carbon electrodes.

Further, the magnetic field strength of the magnetic pole assembly is adjustable. More preferably, the adjustment range of the magnetic field strength is 0-3T.

Further, the voltage between the two adjacent positive electrodes and the negative electrode can be adjusted, preferably, the adjustment range of the voltage between the two adjacent positive electrodes and the negative electrode is: 0-40V.

Further, the distance between two adjacent positive electrodes and negative electrodes is 5 millimeters to 1.5 meters.

Further, the working current between two adjacent positive electrodes and negative electrodes does not exceed 30A.

Further, an ozone generating device is also included, and the ozone output port of the ozone generating device is connected with the water tank through a pipeline, and is used for transporting ozone into the working fluid.

Further, an ultrasonic generating device is also included, and the ultrasonic vibrator (or ultrasonic transmitting unit) of the ultrasonic generating device is arranged in or outside the water tank, and is used for inputting ultrasonic waves to the working fluid in the water tank. The input of ultrasound can effectively further activate or activate the working fluid molecules, and accelerate the oxidation or activation of the working fluid.

Further, a power supply device is also included for supplying power to the electrode assembly, the magnetic pole assembly, the ozone generating device, the ultrasonic generating device and the control module.

Further, it also includes a gas recovery device for recovering gas (mainly ozone gas) overflowing from the working fluid. For example, the gas recovery device includes a gas collection cover and a recovery pipeline; the gas collection cover covers the upper opening of the water tank, the gas collection cover is provided with an exhaust port, and one end of the recovery pipeline is connected to the exhaust port; the other side of the recovery pipeline One end extends under the liquid level of the working fluid in the water tank, or the other end of the recovery pipeline is connected to the gas inlet of the ozone generating device to realize the collection and reuse of the overflowing gas. And an air pump can be added to the recovery pipeline to drive the flow of the overflowing gas.

Further, it also includes a water inlet device for inputting the working fluid into the water tank; and/or a water outlet device for exporting the working fluid in the water tank.

Under the synergistic effect of the magnetic field and the electric field, the finished working solution produced by the active water preparation device of the present application has oxidative properties and becomes active water, which can be used for desizing, scouring and bleaching of cotton-containing fibers and fabrics, or used in various Degumming and pre-bleaching of hemp fibers, or the degradation and decolorization of wastewater containing chromophores after the printing and dyeing process.

Compared with the traditional treatment method, the present application can only add an appropriate amount of environmentally friendly inorganic substances without additionally adding auxiliaries such as strong alkali, desizing agent, refining agent, bleaching agent, etc. ) After pre-treatment, there is no need for a lot of water washing, which greatly reduces the use of chemicals and greatly reduces the energy consumption of the overall process.

The invention also discloses a natural fiber dyeing and finishing treatment device, which comprises the oxidative active water preparation device and a pretreatment device;

The pretreatment device is connected to the oxidative active water preparation device, and the natural fibers are pretreated with the active water prepared by the oxidative active water preparation device.

Among them, there are various forms of pre-treatment devices, and the more common one is the soaking tank. The soaking tank is directly connected to the oxidative active water preparation device through pipelines, or connected to the active water storage tank through pipelines, and the storage tank is connected to the oxidative active water through pipelines. The water preparation unit is connected. The active water is input into the soaking tank, and then the natural fibers are soaked in the active water for a set time to complete the pre-treatment processes such as dyeing and finishing.

More preferably, the pretreatment device includes: a middle casing, an outer casing and a pump body;

Natural fibers are wound on the middle sleeve, and the outer sleeve is sleeved outside the middle sleeve; an annular working chamber for accommodating natural fibers is formed between the middle sleeve and the outer sleeve;

The outer circular side of the middle sleeve is provided with a plurality of through holes that communicate with the inside and outside of the middle casing cavity; the outer circular side of the outer sleeve is provided with a drain hole that communicates with the inside and outside of the annular working cavity;

The pump body is communicated with the lumen of the middle casing through the input pipeline, and is used to inject the working fluid (that is, the working fluid after activation treatment, that is, active water) into the lumen, and use the pressure to force the working fluid. The natural fibers in the annular working cavity are soaked through the through hole, the annular working cavity and the liquid drain hole in sequence.

Further, the middle sleeve and the outer sleeve are coaxially and horizontally arranged.

Further, the outer sleeve is assembled from the upper half shell and the lower half shell. After the natural fibers are wound on the middle sleeve, the upper half shell and the lower half shell can be fastened together, and the two are connected together with fasteners; a sealing gasket is preferably arranged between the upper half shell and the lower half shell .

Further, in the circumferential direction of the middle sleeve, the diameters of the plurality of through holes are the same and evenly spaced.

Wherein it is set: in the axial direction of the middle sleeve, the sum of the cross-sectional areas of the through holes per unit length is the unit hole area.

Further, one end of the middle casing is provided with a working fluid inlet; in the axial direction of the middle casing and in a direction gradually away from the working fluid inlet, the unit hole area gradually increases.

Further, both ends of the middle sleeve have working fluid inlets, and the working fluid inlets are connected with the outlet of the pump body through pipelines; the pipelines are provided with two working fluid inlets for alternately inputting into the lumen. Control valve for working fluid. Among them, the control valve is in the prior art, and details are not repeated here.

If the working fluid is input alternately from the working fluid inlets at both ends, the pipe resistance of the middle casing and other factors will cause uneven pressure in the middle casing in the axial direction; while the alternate input of the working fluid can reduce the Causes the problem of uneven soaking pressure of natural fibers.

Further, both ends of the middle casing are provided with working fluid inlets, and the area per unit hole gradually decreases in the axial direction of the middle casing and in the extending direction from the middle of the middle casing to its two ends.

Further, in the axial direction of the middle sleeve, the unit hole area is normally distributed.

Further, in the axial direction of the middle casing and in the extending direction from the middle of the middle casing to its two ends, the distribution of the unit hole area satisfies the following formula:

Among them, f(x)——is the distribution function of unit pore area;

Let the center point in the axial direction of the middle casing be the origin, and x be the coordinate value extending from the middle of the middle casing to its two ends;

π——pi; σ is 0.1L～0.3L.

Further, the sum of the cross-sectional areas of all the drainage holes on the outer sleeve is 1/4 to 2/3 of the sum of the cross-sectional areas of all the through holes on the middle sleeve, which is used to keep the work in the annular working cavity. The liquid is in a positive pressure state.

Further, the outer sleeve is provided with a working fluid collection cover, or the bottom of the outer sleeve is provided with a working fluid collection tank, and the working fluid collection cover or the working fluid collection tank is connected with the recovery pipeline and the oxidative active water. The water tank of the preparation device is connected for recycling and reusing the working fluid.

Adopt above-mentioned technical scheme, the present invention has following beneficial effect:

An oxidative active water preparation device provided by the present invention constructs a mixed action system of electric field, magnetic field and ozone, and uses pure water or aqueous electrolyte solution as a medium, and in the formed non-uniform electrode system, in-situ generation Aqueous solutions of a variety of highly chemically reactive particles. According to the change of the aqueous medium used and the parameters of the device, the in-situ generated particles can be ·OH, ·O, ·OH ₂ , ·O, ·Cl, ClO-, ClO ₂ -, OH-, H ₂ O ₂ , Several or all of O _3. All effective chemical components required for pretreatment can be generated in situ by using the device of the present invention, and each component has a beneficial synergistic effect due to being in a system at the same time. The active aqueous solution produced by the device is used for the pre-treatment of textiles, and the effect of conventional textile pre-treatment can be obtained by one or two immersion or padding treatments under normal temperature conditions, so it has the advantages of simplicity, energy saving and short process. , The advantages of less emission and no need for organic additives. At the same time, it avoids the insufficiency of hydrogen peroxide, sodium hypochlorite, and sodium hypochlorite that are unstable, easy to decompose, and difficult to store.

In addition, the present invention also discloses a method for dyeing and finishing natural fibers, comprising the following steps:

S10. Prepare active water;

S20. Pretreatment of natural fibers or textiles made of natural fibers;

Wherein, step S10 specifically includes the following steps:

S11. Configure inorganic salt solution;

S12. Use the magnetic pole assembly to apply a directional magnetic field to the inorganic salt solution; use the electrode assembly to ionize the inorganic salt solution to obtain oxidative active water (ie, the working solution during pretreatment);

Step S20 specifically includes the following steps:

S21. Pre-swollen natural fibers or their textiles;

S22. Immerse the pre-swelled natural fibers or their textiles in active water, the temperature of the active water is 20-100°C, and the soaking time is 10-90 minutes.

Further, step S21 specifically includes: soaking natural fibers or their textiles with an aqueous solution of inorganic sodium salt or potassium salt with a concentration of 5-15 g/l; the treatment temperature is 30-60 °C, and the treatment time is 10-90 min; further, the inorganic sodium The salt or potassium salt is one or more of sodium carbonate and potassium carbonate.

Further, the natural fibers are cotton fibers, the temperature of the active water in step S22 is 20-40° C., and the soaking time is 20-60 minutes.

Further, the natural fiber is hemp fiber, the temperature of the active water in step S22 is 20～100°C, and the soaking time is 10～90min.

Further, the natural fiber is wool fiber, and in step S21, the wool fiber or its fabric is immersed in a wetting agent (such as JFC, etc.) solution, the soaking time is not less than 30s, and then the excess aqueous solution is removed, and the rolling rate is not low. at 80%.

Further, in step S20, it also includes:

S23. Remove the excess aqueous solution of natural fibers or their fabrics, and the rolling rate is not less than 80%;

S24. Steps S22 and S23 are repeated, and the soaking and rolling are repeated 1-5 times continuously.

Further, step S20 also includes the steps of rinsing, opening, softening, and drying the natural fibers or their textiles treated with active water after washing with water.

Further, the inorganic salts in the inorganic salt solution in step S11 are inorganic sodium salts and/or inorganic potassium salts; further, the inorganic sodium salts are sodium sulfate, sodium hypochlorite, sodium hydrogen sulfate, sodium carbonate, chloride One or more of sodium and sodium perchlorate; inorganic potassium salt is one or more of potassium chloride, potassium carbonate and potassium sulfate.

Further, the concentration of the inorganic salt solution is 5-60 g/L.

Further, in step S12, the magnetic field strength is 0-3T, and the magnetization treatment time is 0-40min.

Further, in step S12, the temperature of the inorganic salt solution is 20-60°C;

Further, the pH value of the inorganic salt solution is 3-12; more preferably, the pH value is 7-9.

Further, the textiles are woven fabrics, knitted fabrics and the like.

Preferably, step S12 further includes the steps:

S12a. In the process of applying a directional magnetic field and an electric field to the inorganic salt solution, use an ozone generating device and a pipeline to transport ozone into the inorganic salt solution.

The input amount of ozone is set according to the saturation of ozone in the inorganic salt solution to avoid a large amount of ozone overflow.

Preferably, step S12 further includes the steps:

S12b. During the process of applying a directional magnetic field and an electric field to the inorganic salt solution, an ultrasonic wave generator is used to input ultrasonic waves into the inorganic salt solution. The input of ultrasound can effectively further activate or activate the working fluid molecules, and accelerate the oxidation or activation of the working fluid.

The present invention provides a brand-new natural fiber or its textile pretreatment process, which is different from traditional theory and practice. The production capacity is saved, the cost is saved, and the ecological pretreatment of natural fibers is realized.

Description of drawings

In order to more clearly illustrate the specific embodiments of the present invention or the technical solutions in the prior art, the following will briefly introduce the accompanying drawings that need to be used in the description of the specific embodiments or the prior art. Obviously, the accompanying drawings in the following description These are some embodiments of the present invention, and for those of ordinary skill in the art, other drawings can also be obtained from these drawings without any creative effort.

Fig. 1 is the schematic diagram of a kind of oxidative active water preparation device provided in the embodiment of the present invention;

FIG. 2 is a schematic structural diagram of the core component shown in FIG. 1;

Fig. 3 is the schematic diagram that the positive electrode and the negative electrode are arranged in concentric circles in the embodiment 1;

4 is a schematic structural diagram of an insulating electrode separator in Example 1;

5 is a schematic structural diagram of an insulating electrode isolation sand core board in Example 1;

Fig. 6 is a graph showing the effect of placing time on the redox potential of active water in Example 1;

Fig. 7 is the process curve diagram of dyeing treatment among the embodiment 3;

8 is a schematic structural diagram of a pre-processing device in Embodiment 7;

Fig. 9 is the structural representation of the middle casing in embodiment 7;

Fig. 10 is the structural representation of the natural fiber dyeing and finishing treatment device in Example 8;

Fig. 11 is the structural representation of the natural fiber dyeing and finishing treatment device in Example 9;

[Correction 20.07.2021 in accordance with Rule 91]
Fig. 12 is the structural representation of the natural fiber dyeing and finishing treatment device with ultrasonic generating device in Example 9;

Figure 13a is a photo of the sample before degumming in Example 18;

Figure 13b is a photo of the sample after degumming in Example 18;

Figure 14a is the SEM photograph of the sample before degumming in Example 19;

Figure 14b is the SEM photograph of the sample after degumming in Example 19;

Figure 15a is a photograph of wool scales after active water combined biological enzyme treatment in Example 24 of the present invention;

Figure 15b is a photograph of wool scales after active water combined biological enzyme treatment in Example 25 of the present invention;

Figure 15c is a photograph of wool scales after active water combined with biological enzymes in Example 26 of the present invention.

detailed description

The embodiments of the present invention will be described in detail below with reference to the examples, but those skilled in the art will understand that the following examples are only used to illustrate the present invention and should not be regarded as limiting the scope of the present invention. If the specific conditions are not indicated in the examples, it is carried out according to the conventional conditions or the conditions suggested by the manufacturer. The reagents or instruments used without the manufacturer's indication are conventional products that can be purchased from the market.

The present invention will be further explained below in conjunction with specific embodiments.

Example 1

As shown in FIG. 1 , a device for preparing oxidative active water provided in this embodiment includes: a power supply device, a core component, a water inlet device and a water outlet device.

As shown in FIG. 2 , the core assembly includes a water tank 4, an electric field generating device and a magnetic field generating device; the water tank 4 is used for accommodating the working fluid; the electric field generating device includes: an electrode assembly 3 for forming an electric field; the electrode assembly 3 is arranged in the water tank 4 It is used for electric field treatment of the working fluid; the magnetic field generating device includes a magnetic pole assembly 6 for forming a magnetic field; the electrode assembly 3 is arranged inside or outside the water tank 4 for magnetizing the working fluid.

The water tank 4 is made of insulating and corrosion-resistant materials such as glass, glass fiber reinforced plastics or high molecular polymer materials (polytetrafluoroethylene, pvc, etc.). The water inlet device is used to input the working fluid into the water tank 4; the water outlet device is used to export the working fluid in the water tank 4 to the storage tank or to the pretreatment device.

The electrode assembly 3 includes a plurality of pairs of positive electrodes 3a and negative electrodes 3b arranged at intervals. Referring to FIG. 2, the positive electrode 3a and the negative electrode 3b may be flat plates; between the positive magnetic pole and the negative magnetic pole, the positive electrode 3a and the negative electrode 3b are alternately arranged at equal intervals; or, as shown in FIG. 3, the positive electrode 3a The negative electrodes 3b and the negative electrodes 3b are cylindrical, and are alternately arranged at equal intervals in the shape of concentric circles in the radial direction.

2, 4 and 5, the magnetic pole assembly 6 further includes an insulating electrode isolation plate 3c and an insulating electrode isolation sand core plate 3d; the upper and lower ends of the positive electrode 3a and the negative electrode 3b are respectively connected to the insulating electrode isolation plate. 3c and the insulating electrode isolation sand core plate 3d, in this embodiment, the insulating electrode isolation plate 3c and the insulating electrode isolation sand core plate 3d are respectively provided with a clamping groove structure for clamping the positive electrode 3a and the negative electrode 3b, Thereby, the interval between the positive electrode 3a and the negative electrode 3b can be effectively maintained.

The materials of the positive electrode 3a and the negative electrode 3b are 304, 321 and other stable stainless steel electrodes, pyrolytic graphite electrodes, graphene-coated composite graphite electrodes, phosphor copper electrodes, titanium electrodes, platinum titanium electrodes, precious metal electrodes, MMO ruthenium A mixture of one or more of iridium titanium electrodes and carbon electrodes.

Preferably, the voltage between the two adjacent positive electrodes 3a and the negative electrode 3b is adjustable, and the adjustment range of the voltage between the two adjacent positive electrodes 3a and the negative electrode 3b is: 0-40V. And, the distance between two adjacent positive electrodes 3a and negative electrodes 3b is 5 mm to 1.5 meters. The working current between two adjacent positive electrodes 3a and negative electrodes 3b does not exceed 30A.

As shown in FIG. 2 , the magnetic pole assembly 6 includes a positive magnetic pole and a negative magnetic pole; the positive magnetic pole and the negative magnetic pole are respectively arranged at opposite ends of the water tank 4 . Preferably, the positive magnetic pole and the negative magnetic pole are semi-enclosed magnetic poles, that is, the horizontal cross-sections of the positive magnetic pole and the negative magnetic pole are respectively semi-annular, and surround the water tank 4 as much as possible from the opposite ends or both sides of the water tank 4, thereby The strength of the magnetic field in the water tank 4 is effectively increased.

Preferably, the magnetic field strength of the pole assembly 6 is adjustable. Among them, the adjustment range of the magnetic field strength is 0-3T.

In addition, as shown in FIG. 1 , another implementation of this embodiment is: an air supply device, the air supply device includes an ozone generating device and a conveying pipeline, and the ozone output port of the ozone generating device is connected to the water tank 4 through the conveying pipeline , used to transport ozone into the working fluid.

And, referring to FIG. 2 , the third embodiment of the present embodiment is: also includes an ultrasonic generating device 5, and the ultrasonic vibrator (or ultrasonic transmitting unit) of the ultrasonic generating device 5 is arranged at the bottom of the water tank 4, and is used to transmit to the water tank 4. The working fluid in the water tank 4 is input with ultrasonic waves. The input of ultrasound can effectively further activate or activate the working fluid molecules, and accelerate the oxidation or activation of the working fluid.

The power supply device is used to supply power to the electrode assembly 3, the magnetic pole assembly 6, the ozone generating device, the ultrasonic generating device and the control module.

And, this embodiment may further include a gas recovery device for recovering gas (mainly ozone gas) overflowing from the working fluid. For example, the gas recovery device includes a gas collection cover and a recovery pipeline; the gas collection cover covers the upper opening of the water tank 4, the gas collection cover is provided with an exhaust port, and one end of the recovery pipeline is connected to the exhaust port; the other end of the recovery pipeline Under the liquid level of the working liquid extending into the water tank 4, or the other end of the recovery pipeline is connected to the gas inlet of the ozone generating device, so as to realize the collection and reuse of the overflowed gas. And an air pump can be added to the recovery pipeline to drive the flow of the overflowing gas.

Under the synergistic action of the magnetic field and the electric field, the active water preparation device of the present application produces the finished working solution with oxidative properties to become active water, which can be used for desizing, scouring, and bleaching of cotton-containing fibers and fabrics, or used in various Degumming and pre-bleaching of hemp fibers, or the degradation and decolorization of wastewater containing chromophores after the printing and dyeing process.

The following is an example of active water preparation and performance using the active water preparation device of this embodiment.

(1) Preparation of active water:

a) Sodium chloride is mixed with water to form working solution (sodium chloride solution concentration is 10 g/L), and it is left to stand;

b) Inject the standing working fluid into the water tank, apply a 0.8T directional magnetic field around it, and keep the temperature of the working fluid in the water tank at 25°C.

c) Immerse the electrode assembly in the working solution, the electrode material is pyrolytic graphite electrode, the voltage between a pair of electrodes (positive electrode and negative electrode) in a single group is: 10V, and the distance between adjacent positive electrodes and negative electrodes (d) is set It is 5 mm, and the working current between a single set of electrodes is 3A. Simultaneously apply ultrasonic waves to the system;

d) Introduce ozone gas for 15s every 3min, in terms of per liter of working fluid, the ozone inflow rate is about 2g/hour;

e) After 1 hour, put the obtained active water in a container for later use.

(2) Determination of redox potential:

a) Use a redox potentiometer to test the working fluid produced in (1).

b) After placing the same batch of working solution (i.e. active water) produced in (1) for 1 day, 2 days, 3 days, 5 days, 7 days, 14 days, 28 days and 60 days, respectively, Its redox potential was tested. Test results: The redox potential of the prepared water is 975mV, and the results are shown in Figure 6 after being placed.

An oxidative active water preparation device provided by the present invention constructs a mixed action system of electric field, magnetic field and ozone, and uses pure water or aqueous electrolyte solution as a medium, and in the formed non-uniform electrode system, in-situ generation Aqueous solutions of a variety of highly chemically reactive particles. According to the change of the aqueous medium used and the parameters of the device, the in-situ generated particles can be ·OH, ·O, ·OH ₂ , ·O, ·Cl, ClO-, ClO ₂ -, OH-, H ₂ O ₂ , Several or all of O _3. All effective chemical components required for pretreatment can be generated in situ by using the device of the present invention, and each component has a beneficial synergistic effect due to being in a system at the same time. The active aqueous solution produced by the device is used for the pre-treatment of textiles, and the effect of conventional textile pre-treatment can be obtained by one or two immersion or padding treatments under normal temperature conditions, so it has the advantages of simplicity, energy saving and short process. , the advantages of less emissions. At the same time, it avoids the insufficiency of hydrogen peroxide, sodium hypochlorite, and sodium hypochlorite that are unstable, easy to decompose, and difficult to store.

Example 2:

(1) Pretreatment of pure cotton fibers (cotton fibers or fabrics made of cotton fibers)

The technological process is: preparation of active water → pre-swelling → active water treatment of fabrics → reduced water washing → water washing;

a) Pre-swelling: Immerse the pure cotton fabric fibers in a Na ₂ CO ₃ solution with a concentration of 30 g/l, and pre-soak for 60 min at 30°C;

b) Active water treatment: the pure cotton fiber after pre-swelling treatment is immersed in active water, the active water concentration is 2.42g/l, the treatment temperature is 40°C, the treatment time is 80min, and the liquor ratio is 1:30;

c) Reduction cleaning:

The pure cotton fiber after the active water treatment is reduced and cleaned with a sodium thiosulfate solution, the concentration of the sodium thiosulfate solution is 5g/l, the treatment temperature is room temperature, and the treatment time is 15min;

Test results: gross effect 12.7/30min (2.8cm/30min before treatment), CIE whiteness value 71.33 (CIE whiteness value before treatment 9.3), strong drop rate 28%.

(2) Reuse experiment of activated water after treatment

The active water after the cotton fabric is treated in (1) is used as the working solution for electrolysis and use.

1) Secondary electrolysis: put the used active water into the device described in Example 1 and continue electrolysis for 20min, and its redox potential increases, from 875mV to 954mV; the available chlorine concentration is increased from 2.1g/l to 2.5g/l. l.

2) Pre-treatment of pure cotton fabric with used active water:

The technological process is as follows: the active water (working solution) after pre-treatment in step (1) of this embodiment is filtered, and reused after secondary electrolysis in step 1)→fabric pre-swelling→active water treatment fabric→reduced water washing→water washing;

Specifically include:

d) Use 80-mesh nylon spun mesh to filter the pre-treated active water to obtain a clean and transparent high-oxidative active working solution; add a certain amount of new active water (for example, the new active water accounts for 5% of the filtered active water) to supplement the bath ratio .

e) The treatment process is the same as b) and c) in step (1)

Experimental results: gross effect 12.1/30min (2.8cm/30min before treatment), CIE whiteness value 69.31 (CIE whiteness value before treatment 9.3), strong drop rate 26%. It can be proved that the active water has good reusability and can be used continuously.

Example 3: Example of decolorization of active water

Prepare a piece of 5×5cm pure cotton fabric (pre-treated fabric, configure reactive red dye (reactive red 3BS) dye solution to dye the cotton fabric.

Its reactive dye dyeing prescription: reactive red 2.5% (owf), sodium chloride 30g/L, sodium carbonate 15g/L, dyeing temperature 60°C, bath ratio 1:30, the process curve is shown in Figure 7.

After dyeing, its test value is CIE L: 56.56; CIE a: -7.85; CIE b: -8.36; K/S value: 5.67. Collect the waste liquid for later use.

(S1) soak the active water prepared in step (1) in Example 1 with the above-mentioned dyed cotton fabric at a bath ratio of 1:30, at a constant temperature of 30°C, and stir with a magnetic stirrer, and the treatment time is 1h.

(S2) The cotton fabric was obviously discolored during the treatment, but the solution in the cup was still a colorless and transparent liquid. After the cotton fabric was taken out and washed with water, it was tested for CIE whiteness using Datecolo SF-600 colorimeter. The result was: 61.49, and the decolorization effect was remarkable.

(S3) Put the collected dyed waste liquid into a beaker, add the active water prepared in the step (1) of Example 1, stir with a magnetic stirrer, and the color disappears quickly.

Comparative Example 1: Preparation of active aqueous solution without ozone treatment

(1) a) sodium chloride and water are mixed to form an aqueous solution system (sodium chloride solution concentration is 50 grams per liter), leave standstill;

b) The aqueous solution after standing was injected into the treatment system, and a directional magnetic field of 0.5 T was applied to the periphery to keep the temperature in the system at 30°C.

c) Immerse the electrode assembly in the magnetized water body, the relevant composition and parameters of the electrode assembly: the counter electrode material is carbon electrode, the voltage between a single group of a pair of electrodes (positive and negative poles) is: 30V, and the distance between a single group of electrodes is 30V. (d) Set to 150 mm, the operating current between a single set of electrodes is 5 A. At the same time, ultrasonic waves are applied to the system for electrical treatment;

d) After 3 hours, put the obtained active water into the container for subsequent use;

(2) The redox potential of the activated water without ozone prepared in (1) was measured, and it was found that the redox potential values of different batches of solutions had a difference of about ±150mV, and the experiment repeatability was poor.

(3) Use the active aqueous solution prepared in (1) to carry out the pretreatment experiment of pure cotton fiber fabric, and the experimental process is the same as step (1) in Example 2. Test results: gross effect 9.8/30min (2.8cm/30min before treatment), CIE whiteness value 59.33 (CIE whiteness value before treatment 9.3), strong drop rate 11%. It can be seen that the reproducibility of the active water prepared without ozone is poor. Using the active water prepared without ozone to pre-treat pure cotton fiber fabrics, its whiteness and gross effect have a certain improvement compared with the untreated ones Compared with ozone, the gap is more obvious.

Comparative Example 2: Active aqueous solution without ultrasonication

(1) Prepare an active aqueous solution without ultrasonic treatment.

a) sodium chloride is mixed with water to form an aqueous solution system (sodium chloride solution concentration is 90 g/L), and it is left to stand;

b) The aqueous solution after standing was injected into the treatment system, and a directional magnetic field of 0.5 T was applied to the periphery to keep the temperature in the system at 25°C.

c) Immerse the electrode assembly into the magnetized water body, the relevant composition and parameters of the electrode assembly: the counter electrode material is a stable stainless steel electrode, the voltage between a single group of a pair of electrodes (positive and negative poles) is: 10V, a single group of electrode pair cells The spacing (d) is set to 500 mm, and the working current between a single group of electrodes is 1A;

d) In the process of electric treatment, ozone gas is fed for 15s every 3min, and the ozone feeding speed is about 1g/hour in terms of per liter of working fluid;

e) After 5 hours, put the obtained active water into the container for subsequent use;

(2) The redox potential of the activated water without ultrasonic treatment obtained in step (1) is measured, and it is found that the redox potential value is about 850mV, which is lower than the redox potential (about 950mV) after ultrasonic treatment.

(3) Use the active aqueous solution prepared in (1) to carry out the pretreatment experiment of pure cotton fiber fabric, and the experimental process is the same as step (1) in Example 2. Test results: gross effect 12/30min (2.8cm/30min before treatment), CIE whiteness value 62.36 (CIE whiteness value before treatment 9.3), strong drop rate 15%. The active aqueous solution without ultrasonic treatment has a certain effect on the pretreatment of cotton fabrics, but it is not ideal.

Comparative Example 3: Active aqueous solution without ultrasonic and ozone treatment

(1) Prepare an active aqueous solution without ultrasonic and ozone treatment.

a) sodium chloride is mixed with water to form an aqueous system (sodium chloride solution concentration is 25 g/L), and it is left to stand;

b) The aqueous solution after standing was injected into the treatment system, and a 1T-oriented magnetic field was applied around it, and the temperature in the system was kept at (15° C.).

c) Immerse the electrode assembly in the magnetized water body, the relevant composition and parameters of the electrode assembly: the counter electrode material is a graphene-coated composite graphite electrode, the voltage between a single group of a pair of electrodes (positive and negative poles) is: 20V, a single group The electrode pair unit spacing (d) is set to 15 mm, and the working current between a single group of electrodes is 2A;

d) After 2 hours, put the obtained active water into the container for subsequent use;

(2) The redox potential of the activated water prepared in (1) was measured, and it was found that the redox potential value was around 800mV, and the redox potential fluctuated within ±10mV in different batches of experiments.

(3) Use the active aqueous solution prepared in (1) to carry out the pretreatment experiment of pure cotton fiber fabric, and the experimental process is the same as step (1) in Example 2. Test results: gross effect 8/30min (2.8cm/30min before treatment), CIE whiteness value 51.2 (CIE whiteness value before treatment 9.3), strong drop rate 8%. The data of the active water prepared without ozone and ultrasonic treatment fluctuated obviously in repeated experiments, and in the process of pre-treatment of pure cotton fabrics, it was found that the pre-treatment effect was poor, and it was difficult to use alone.

In addition, this application also adopts different technical solutions. Different technical solutions use the same process parameters as possible (such as the same electric field strength, magnetic field strength and the same working fluid temperature and treatment time) to compare the same batch of cotton fibers. The test results are compared in Table 1 below.

Table 1 Comparison of cotton fiber treatment results with different technical schemes

In Comparative Example 1, on the basis of Example 2, the ultrasonic effect in the preparation of active water was omitted, that is, the active water was prepared by the method of "electric field + magnetic field + input ozone". Fabric pre-treatment process is the same as Example 2; Comparative Example 2 is based on Example 2, the ultrasonic wave effect in the preparation of active water is omitted, and the input ozone is omitted, i.e. "electric field+magnetic field" mode prepares active water. The fabric pretreatment process is the same as that in Example 2; when the active water is prepared in Comparative Example 3, only the electric field is used for treatment, and its parameters are the same as those in Example 2;

Through the comparison of the above experiments, the active water obtained by the combination of "electricity + magnetism + ozone + ultrasound" used in the invention can significantly improve the two main indicators of wool efficiency and whiteness of cotton fibers when used in the pretreatment of cotton fibers. , fully meet the requirements of subsequent handover, and has excellent technical effect; the combination of "electricity + magnetism + ozone", the treated fabric has good wool effect and whiteness index, and can meet the processing requirements of most light-colored fabrics; "Electric + Magnetic" combination, the treatment effect is acceptable, its wool effect and whiteness can meet the general requirements of the fabric, and the textiles of high-end finished products need further treatment; the separate electric or magnetic treatment technology basically cannot meet the subsequent processing. requirements, the feel, style, color, etc. of the end product will be greatly affected.

Example 7

This embodiment discloses a natural fiber dyeing and finishing treatment device, which includes the oxidative active water preparation device and the pretreatment device 100 as in the embodiment 1. The pretreatment device 100 is connected to the oxidative active water preparation device, and the natural fibers are pretreated with the active water prepared by the oxidative active water preparation device.

As shown in FIGS. 8 and 9 , the pretreatment device 100 includes: a middle sleeve 110 , an outer sleeve 120 and a pump body 130 ; natural fibers such as cotton fibers (not shown) are wound on the middle sleeve 110 , and the outer sleeve 120 The middle sleeve 110 is sleeved outside the middle sleeve 110; an annular working cavity for accommodating natural fibers is formed between the middle sleeve 110 and the outer sleeve 120; a plurality of lumens communicating with the middle sleeve 110 are arranged on the outer side of the middle sleeve 110 Through holes 111 inside and outside; the outer side of the outer sleeve 120 is provided with a drain hole 121 that communicates with the inside and outside of the annular working chamber; the pump body 130 is communicated with the lumen of the middle casing 110 through the input pipeline, for sending the liquid to the lumen Inject the working fluid (that is, the working fluid after activation treatment, that is, active water), and use the pressure to force the working fluid to pass through the through hole 111, the annular working cavity and the drain hole 121 in turn, so as to realize the soaking of the natural fibers in the annular working cavity deal with.

Wherein, the middle sleeve 110 and the outer sleeve 120 are coaxially and horizontally arranged. Specifically, the outer sleeve 120 is assembled from the upper half shell and the lower half shell. After the natural fibers are wound on the middle sleeve 110, the upper half shell and the lower half shell can be fastened together, and the two are connected together with fasteners; a seal is preferably provided between the upper half shell and the lower half shell washer.

More preferably, in the circumferential direction of the middle sleeve 110 , the diameters of the plurality of through holes 111 are the same and evenly spaced. In the axial direction of the middle casing 110, the sum of the cross-sectional areas of the through holes 111 per unit length is the unit hole area; one end of the middle casing 110 is provided with a working fluid inlet, and the middle casing 110 is axially and gradually away from the middle casing 110. In the direction of the working fluid inlet, the unit hole area gradually increases. Alternatively, both ends of the middle casing 110 are provided with working fluid inlets, and the working fluid inlets are connected to the outlet of the pump body 130 through a pipeline; a control valve 131 is provided on the pipeline, and the control valve 131 includes a water tank connected to the oxidative active water preparation device 4 connected inlets, and two liquid outlets, the two liquid outlets are respectively connected with the working fluid inlets at both ends of the middle casing 110 through pipelines, and the control valve 131 can control the working fluid to alternately pass through the two working fluid inlets in the middle casing. within the lumen of the tube 110 . Among them, the control valve 131 is in the prior art, and details are not repeated here.

If the working fluid is input alternately from the working fluid inlets at both ends, the pressure of the middle casing 110 in the axial direction will be uneven due to the pipeline resistance and other factors of the middle casing 110; The resulting problem of uneven soaking pressure of natural fibers.

Alternatively, both ends of the middle casing 110 are provided with working fluid inlets, and the working fluid is input into the lumen of the middle casing 110 through the two working fluid inlets at the same time. In the axial direction of the middle casing 110, the unit hole area is positive state distribution. In the axial direction of the middle sleeve 110 and in the extending direction from the middle of the middle sleeve 110 to its two ends, the distribution of the unit hole area satisfies the following formula:

Among them, f(x)——is the distribution function of unit pore area;

Let the center point in the axial direction of the middle casing 110 be the origin, and x be the coordinate value extending from the middle of the middle casing 110 to its two ends;

π——pi; σ is 0.1L～0.3L.

In the above technical solution, more preferably, the sum of the cross-sectional areas of all the drain holes 121 on the outer sleeve 120 is 1/4 to 2/3 of the sum of the cross-sectional areas of all the through holes 111 on the middle sleeve 110, for The working fluid in the annular working chamber is kept in a positive pressure state, thereby maintaining the working fluid in the annular working chamber to pre-treat the natural fibers in a positive pressure environment.

The outer sleeve 120 is provided with a liquid collecting device 140 such as a working fluid collection tank at the bottom of the outer sleeve 120 (or a relatively sealed working fluid collection cover is used), and the working fluid collection tank is connected with the recovery pipeline and the preparation of oxidative active water. The water tank connection of the device is used to recycle the working fluid.

The feature of the present invention is that the process of preparing oxidative active water does not need to add auxiliaries such as strong alkali, desizing agent, refining agent, bleaching agent, etc., but only needs to add an appropriate amount of environmentally friendly inorganic substances (preferably inorganic sodium salt and/or inorganic Potassium salt; Described inorganic sodium salt is one or more of sodium sulfate, sodium hypochlorite, sodium hydrogen sulfate, sodium carbonate, sodium chloride, sodium perchlorate; Inorganic potassium salt is potassium chloride, potassium carbonate, sulfuric acid One or several kinds of potassium), under the synergistic effect of magnetic field and electric field, only the water body is treated. The water is treated to form active water with strong oxidizing properties. Unlike traditional strong oxidizing liquids such as hydrogen peroxide, active water has no special requirements for the PH value of the reaction, and can play a corresponding role in acidic alkaline or neutral solutions. effect. Secondly, the water stability of this device is high. After testing, in the test with 60 days as the experimental period, no trend of decline in its performance was found. And the active water has a high safety factor. After heating and long-distance transportation, there is no gas release, so the storage container does not have the phenomenon of swelling the bottle body, and there is no danger of bursting. At the same time, after the dyeing process is finished, the wastewater containing color can also be decolorized directly with the active water, which not only has a fast decolorization speed, but also is not disturbed by the external environment such as the intensity of sunlight.

Example 8

The structure of this embodiment is basically the same as that of Embodiment 7, and the difference is:

As shown in FIG. 10 , in a natural fiber dyeing and finishing treatment device provided in this embodiment, the middle sleeve 110 is made of conductive material, and a plurality of connections between the inside and outside of the lumen of the middle sleeve 110 are provided on the outer side of the middle sleeve 110 At least one end of the middle casing 110 is provided with a working fluid inlet; the middle casing 110 may or may not be provided with an outer sleeve.

The through hole 111 and the working fluid inlet are connected to the liquid collecting device 140 through the circulation system 30, and the circulating system 30 is used to force the working fluid to circulate between the liquid collecting device 140 and the middle casing 110; specifically, the circulation system 30 includes a pump Body 31, delivery pipeline and control valve, etc. It is used to promote the circulating flow of the working fluid between the liquid collecting device 140 and the inner cavity of the middle casing 110 .

The core electrode 20 is inserted in the middle casing 110 along the direction of its central axis, and the core electrode 20 is connected to the DC power supply 21; The negative electrode is connected to the negative output end of the DC power supply 21 , and an electric field with a set voltage is formed therebetween for electric field treatment of the working fluid in the lumen of the middle casing 110 . In a simpler and safer implementation process, the middle sleeve 110 is directly grounded, and the middle sleeve 110 is indirectly connected to the DC power source 21 as a negative electrode.

In the above solution, more preferably, the positive magnetic pole 41 and the negative magnetic pole 42 oppositely arranged outside the middle sleeve 110 are used to magnetize the working fluid in the lumen of the middle sleeve 110 . The positive magnetic pole 41 and the negative magnetic pole 42 are preferably insulated from the middle sleeve 110 .

Wherein, this embodiment includes multiple pairs of positive magnetic poles 41 and negative magnetic poles 42 ; at least one pair of positive magnetic poles 41 and negative magnetic poles 42 are disposed between two adjacent through holes 111 . The positive magnetic pole 41 and the negative magnetic pole 42 are semi-enclosed magnetic poles, that is, the horizontal cross-sections of the positive magnetic pole 41 and the negative magnetic pole 42 are semi-annular, respectively, and surround the center as much as possible from the opposite ends or both sides of the middle sleeve 110 . the casing 110, thereby effectively increasing the magnetic field strength in the middle casing 110.

The natural fibers are wound outside the middle casing 110, and the working fluid treated by the electric field and the magnetic field in the lumen of the middle casing 110 is output through the through holes 111 to pre-treat the natural fibers.

More preferably, in this embodiment, the middle sleeve 110 and the magnetic pole assembly 40 can be sheathed with a protection sleeve 50, and the protection sleeve 50 is provided with a through hole for the passage of the working fluid. More preferably, the protective sleeve 50 is a cylindrical body made of mesh material or grid material.

The protective sleeve 50 is insulated from the middle sleeve 110 and the magnetic pole assembly 40 . More preferably, the protective sleeve 50 is made of magnetically conductive material. Therefore, it is beneficial to form a closed magnetic conduction channel, thereby reducing the leakage of the magnetic field and increasing the strength of the magnetic field at the same time.

Compared with Embodiment 7, this embodiment is more compact, and can continue to perform magnetization and ionization treatment on the working fluid during the pretreatment process, so as to maintain and further improve the activity and oxidizing property of the working fluid. In addition, it can also be used as the preparation and pretreatment equipment of the oxidative active working fluid to reduce the production cost.

Example 9

The structure of this embodiment is basically the same as that of Embodiment 8, and the difference is:

As shown in FIG. 11 , this embodiment includes an ozone generating device 70 , and the ozone output port of the ozone generating device 70 is connected to the gas input port at the end of the middle sleeve 110 through a pipeline, and an air pump 71 is arranged on the pipeline for supplying the middle sleeve The working fluid in the cavity of tube 110 delivers ozone. Preferably, the gas input port and the working fluid inlet are arranged on the same side to facilitate repeated mixing of ozone gas and working fluid. The liquid collecting device 140 adopts a box structure. The middle sleeve 10 is arranged in the middle and upper part of the box, and the working fluid discharged from the middle sleeve 10 finally drips and collects at the bottom of the box.

A more preferred implementation of this embodiment is that, as shown in FIG. 12 , an ultrasonic generating device 80 is further included, and the ultrasonic vibrator (or ultrasonic transmitting unit) of the ultrasonic generating device 80 is arranged at the end of the middle sleeve 110 for Ultrasonic waves are input into the working fluid in the organ cavity of the middle cannula 110 . The input of ultrasound can effectively further activate or activate the working fluid molecules, and accelerate the oxidation or activation of the working fluid.

This embodiment further includes a power supply device for supplying power to the electrode assembly, the magnetic pole assembly, the ozone generating device, the ultrasonic generating device and the control module.

Example 10

This embodiment discloses a dyeing and finishing method for hemp fibers or hemp textiles, specifically a degumming, refining and bleaching method for clean hemp fibers or hemp textiles. The process flow is: preparation of active water→swelling pretreatment →Activated water treatment →After-washing treatment.

1) Preparation of active water

a. Prepare 30g/L sodium chloride aqueous solution at room temperature, and place it in the active water preparation device. Immediately, the electrode is immersed in the water body, and the electrode is energized to apply an electric field for electrical treatment. The pyrolytic graphite electrode and the graphene-coated composite graphite electrode were used as the cathode and anode of the counter electrode, respectively. The voltage between the electrodes was 9 V, and the distance between the electrodes was adjusted to make the current in the water body 2.1 A.

b. After 50 minutes of electric treatment, the finished active water is obtained, which is put into an insulating container such as a glass container, and is ready for use.

2) Swelling pretreatment

Take an appropriate amount of flax fiber and immerse it in clear water, the bath ratio is 1:40, soak and turn the fiber properly under normal temperature and pressure, take out the flax fiber after 60 minutes, squeeze out the water and set aside.

3) Degumming treatment of active water

The hemp fiber treated in step 2) is immersed in active water, the bath ratio is 1:60, immersed at room temperature for 60 minutes, and stirred appropriately during the immersion.

4) After washing with water

The hemp fiber is taken out from the active water, and the hemp fiber is rinsed with clean water, then dehydrated, manually torn and loosened, and finally dried naturally at room temperature.

Example 11:

This embodiment is basically the same as Embodiment 10, except that:

1) Preparation of active water

a. Place a 30g/L mixed aqueous solution of sodium carbonate and sodium chloride (the mass ratio of the two components is 1:1) into the active water preparation device, and apply a stable magnetic field of 0.8T around it, and the system temperature is 35°C.

b. Immerse the electrode in the magnetized water body, apply electric field to electricity, and conduct electric treatment. The pyrolytic graphite electrode and the graphene-coated composite graphite electrode were used as the cathode and anode of the counter electrode, respectively. The voltage between the electrodes was 8V, and the distance between the electrodes was adjusted to make the current in the water body 1.9A.

c. After 60 minutes of electric treatment, the finished active water is obtained, which is put into an insulating container such as a glass container for use.

2) Swelling pretreatment

Immerse a certain mass of undegummed flax fiber in a 15g/L mixed aqueous solution of sodium carbonate and sodium chloride (the mass ratio of the two components is 1:1), and the immersion bath ratio is 1:30. After soaking for 4 hours, the hemp fibers were removed and the excess water was squeezed out.

3) Degumming treatment of active water

Immerse the swollen pretreated flax fiber in the finished active water, the bath ratio is 1:100, soak for 60 minutes at normal temperature and pressure, and stir properly during the soaking.

4) After washing with water

The hemp fiber was taken out from the active water, and the hemp fiber was rinsed with clean water, then dehydrated, manually torn and loosened, and finally dried in an oven at 85° C. to dryness.

Example 12:

This embodiment is basically the same as Embodiment 10, except that:

1) Preparation of active water: the same as the preparation of active water in Example 10.

2) Swelling pretreatment

Immerse a certain amount of flax fiber in a 20g/L sodium carbonate aqueous solution with a bath ratio of 1:30. After soaking for 4 hours, take out the flax fiber and squeeze out excess water.

3) Degumming treatment of active water

After the prepared active water is placed for 15 days, the flax fibers that have been swollen and pretreated are immersed in the finished active water at a liquor ratio of 1:60, soaked for 90 minutes at room temperature and pressure, and stirred appropriately during the soaking.

4) Post-treatment after washing: the same as the post-treatment part of degumming in Example 2.

Example 13:

This embodiment is basically the same as Embodiment 10, except that:

1) Preparation of active water

a. Place a 20g/L mixed aqueous solution of sodium carbonate and sodium chloride (the mass ratio of the two components is 1:1) into the active water preparation device, and apply a stable magnetic field of 0.8T around it, and the system temperature is 75°C.

b. An electric field is applied to the working solution, and the counter electrode material is a pyrolytic graphite electrode and a graphene-coated composite graphite electrode as the cathode and the anode, respectively. The voltage between the counter electrodes is 10V, and the current in the working fluid is maintained not exceeding 3A.

c. While applying the electric field, apply stable ultrasonic waves to the system through the ultrasonic generator.

d. During the electric treatment process, every 3 minutes, the ozone gas is introduced for 15 seconds, and the ozone injection rate in each liter of working fluid is about 2000 mg/hour within 15 seconds after the ozone generator is started. The overall treatment time is 50 minutes, and the obtained finished active water is put into a plastic bucket for use.

2) Swelling pretreatment: the same as the swelling pretreatment in Example 3, except that the treatment time was changed to 30 minutes.

3) Active water treatment: the same as the active water treatment part in Example 2.

Water washing post-treatment: the same as the water washing post-treatment part in Example 2.

Example 14:

This embodiment is basically the same as Embodiment 10, except that:

2) Swelling pretreatment: with the swelling pretreatment part in Example 2, only the sodium carbonate and the mixed aqueous solution of sodium chloride of 15g/L used in Example 2 are changed to the aqueous sodium chloride solution of 20g/L.

3) Degumming of active water: the same as the degumming part of active water in Example 2.

4) After-treatment of the water-washed glue: the same as the water-washed post-treatment part in Example 2.

In order to study the effect of degumming and refining and bleaching, the non-degummed hemp fibers and the CIE whiteness, pectin and lignin content of the samples after degumming in Examples 10-14 were tested. The results are listed in Table 2. As can be seen from Table 2, the content of pectin and lignin in the fiber samples of the five examples are significantly smaller than those of the untreated hemp samples, and the whiteness of the samples after degumming treatment is higher than that of the untreated hemp. significantly improved.

Table 2 Test results of degumming effect of different degumming schemes

Example 15: Degumming and bleaching of flax woven fabrics with active water

The process flow is: preparation of active water → swelling pretreatment → active water treatment → post-washing treatment

The degummed flax fibers in Example 12 were changed to undegummed flax woven fabrics, and the rest were the same as in Example 12. The properties of the treated textiles were characterized by CIE whiteness, pectin content, lignin content, and wool effect test values. The CIE whiteness of the untreated hemp fiber textile grey fabric is -33.5, the pectin content is 3.96%, the lignin content is 5.87%, and the gross value is 3.5; the CIE whiteness of the sample of this example after degumming treatment is 64 , the pectin content was 1.76%, the lignin content was 2.16%, and the gross value was 10.1.

Example 16: Degumming of flax roving with activated water

The degummed flax fibers in Example 10 were changed to undegummed flax rovings, and the rest were the same as those in Example 10. The CIE brightness of the untreated linen roving was –13.5, the pectin content was 3.16%, and the lignin content was 5.19%; the CIE brightness of the degummed linen roving was 48, and the pectin content was 1.36%. , the lignin content is 2.53%.

Example 17: Comparison of degumming effects of active water and traditional chemical degumming methods on hemp fibers

The hemp raw hemp fibers were degummed and leached by the alkaline-oxygen two-bath method, the alkaline-oxygen one-bath method and the active water of the present invention, which are commonly used in enterprises. The processing methods and results are as follows.

1) Alkali-oxygen two-bath degumming of hemp fiber

a. Process flow: sample preparation→hydrogen peroxide pretreatment→water washing→one-stage cooking→water washing→two-stage cooking→water washing→fiber→pickling→water washing→dehydration and opening→drying;

b. Process prescription

Hydrogen peroxide pretreatment: H ₂ O ₂ 5g/L, bath ratio 1:20, temperature 25℃, treatment time 25min

Head and said alkali _{cooking: NaOH 10g / L, NaSO 3} 1.5g / L, NaSiO 3 1.5g / L ,, bath ratio 1; 20, temperature 100 ℃, the processing time 60min

Two alkali _{cooking: NaOH 10g / L, NaSO 3} 1.5g / L, NaSiO 3 1.5g / L ,, bath ratio of 1: 20,100 ℃, treatment time 120min

Pickling: H ₂ SO ₄ 1g/L, bath ratio 1; 20, treatment time 2min

2) Alkali-oxygen one-bath degumming of hemp fibers

a. Process flow: hemp raw hemp → pickling pretreatment → water washing → alkaline oxygen one-bath treatment → fiberizing → water washing → pickling → water washing.

b. Process prescription:

Pickling pretreatment: H ₂ SO ₄ 1g/L, 45℃, time 45min, bath ratio 1:20

Alkali-oxygen one-bath treatment: NaOH 10g/L, H ₂ O ₂ 8g/L, NaSiO ₃ 1.5g/L,, bath ratio 1:30, 65℃, 120min

Pickling: H ₂ SO ₄ 1g/L, bath ratio 1:20, 2min

3) Degumming of hemp fibers by active water:

Only the substrate to be degummed in Example 14 was changed from flax fiber to hemp fiber, and other parts were completely the same as in Example 14. Table 3 below shows the degumming effect of three different degumming methods.

Table 3 Comparison of degumming effects of different degumming methods

Example 18: Reactivation of degumming wastewater and its degumming of flax fibers

1) Preparation of active water: All the waste water generated in each step in Example 11 was collected, and the solid impurities were removed by filtration. Use a salinity meter to test the salinity of the filtered wastewater, add sodium chloride to make the salinity of the filtered wastewater reach 30g/L, and use this water as the working solution to prepare active water. Among them, the pyrolytic graphite electrode was used as the cathode and the anode, the voltage between the electrodes was 9V, the distance between the electrodes was adjusted so that the water body current was 2.8A, and the electrolytic treatment was performed for 60 minutes to obtain the finished active water, which was placed in a glass container for use.

2) Swelling pretreatment: the same as the swelling pretreatment part of Example 11.

3) Degumming of active water: Immerse an appropriate amount of flax fiber in a container with active water at a liquor ratio of 1:90. The soaking time is 1h, with proper stirring during this period.

4) Degumming post-treatment: the same as the degumming post-treatment part of Example 11.

Figures 13a and 13b are digital photographs of flax fibers as-is and fibers after activated water degumming, respectively. The photos show that the whiteness of the flax fibers is significantly improved after degumming. The test results of pectin and lignin content showed that the pectin content of the degummed flax fiber treated with active water decreased from 4.16% before treatment to 2.51% after treatment, and the lignin content decreased from 5.18% before treatment to 2.75%. This example shows that the waste water produced by the degumming, refining and bleaching technology of the present invention can be recovered and reused.

Example 19: Reactivation of degumming wastewater and its degumming of hemp fibers

The method is the same as in Example 18, except that the substrate to be degummed is changed from flax fiber to hemp fiber.

Fig. 14a and Fig. 14b are electron microscope pictures of degummed hemp fibers of untreated hemp raw hemp fibers and active water prepared by reusing recovered wastewater, respectively. Figure 13 shows that the treated hemp fibers are well separated, and the fiber surface is clean and smooth, indicating a good degumming effect. This example shows that the wastewater produced by the degumming technology of the present invention can be recovered and reused.

In addition, this application also uses different technical solutions to carry out comparative tests on the same batch of flax fibers, and the process parameters in different technical solutions (such as the same electric field strength, magnetic field strength, and the same working fluid temperature and treatment time) are basically the same. , specifically: in the preparation of active water, a 30g/L sodium chloride aqueous solution is configured as the working solution; the pyrolytic graphite electrode and the graphene-coated composite graphite electrode are used as the cathode and anode of the counter electrode, respectively, and the cathode and the counter electrode are used. The voltage between the anode and the electrodes is 12V, and the distance between the electrodes is adjusted so that the current in the working fluid does not exceed 3A; the magnetic field treatment is achieved by uniformly applying a stable magnetic field of 0.8T around the working fluid; the ozone treatment is performed every 3 times during the electrolysis process. minutes, start the ozone generator for 15 seconds so that the working fluid is fed with ozone gas, and the ozone feeding rate is 2000 mg/hour per liter of working fluid; the system temperature is set to 75°C, and the overall treatment time is 50 minutes. The swelling pretreatment, active water treatment and post-washing treatment methods are the same as those of Example 10. The test results are compared in Table 4 below.

Table 4 Comparison of the treatment results of flax fiber with different technical schemes

Through the comparison of the above experiments, the active water obtained by the combination of "electricity + magnetism + ozone + ultrasound" used in the invention is used for the degumming treatment of flax fiber, and the two main indicators of lignin removal and whiteness of flax fiber are Significantly improved, fully meet the requirements of subsequent textile processing, with excellent technical effects; the combination of "electricity + magnetism + ozone", the treated hemp fiber has good lignin removal and whiteness index effects, which can meet the textile processing requirements of conventional linen fabrics ; For the "electric + magnetic" combination, the wool effect and whiteness can meet the general requirements of the fabric, and further processing is required for the high-end finished textile; the electrical treatment effect alone is acceptable and basically meets the subsequent processing requirements, but in order to make The feel, style and color of the end product meet the customer's requirements and still need further processing. Magnetic treatment alone cannot meet the requirements of subsequent processing and is not recommended.

Example 21

The present embodiment discloses a dyeing and finishing method for wool fibers, and the specific implementation cases are as follows:

(1) Pre-soak: Treat the 70s top in 1g/L JFC solution for 30s, one dip and one rolling, and the rolling rate is 80%.

(2) Electrolytic active water treatment: soak the wool in electrolytic active water for 90s, the pH value of the electrolytic active water is 8, the temperature is 30 ℃, and then the excess aqueous solution is removed by pressing rollers, the rolling rate is 80%, washed with water, and air-dried naturally .

(3) Test results of wool shrinkage resistance after electrolytic active water treatment: DFE is 19.66% (raw wool 29.99%), shrink ball diameter is 3.58cm (raw wool 3.34cm), and strength is reduced by 7.6%.

Example 22

(1) Pre-soak: 70s tops are treated in 1g/L JFC solution for 30s, one dip and one rolling, and the rolling rate is 80%.

(2) Electrolytic active water treatment: soak the wool in electrolytic active water for 90s, the pH value of the electrolytic active water is 5, the temperature is 50°C, and then the excess aqueous solution is removed by pressing rollers, and the rolling rate is 80%, and the above electrolytic active water is repeated. The treatment process is 1 time, then washed with water and air-dried naturally.

(3) Test results of anti-shrinkage performance of wool after electrolytically active water treatment: DFE is 15.68% (raw wool 29.99%), shrink ball diameter is 3.62cm (raw wool 3.34cm), and strength is reduced by 2.7%.

Example 23

(2) Electrolytic active water treatment: soak the wool in electrolytic active water for 90s, the pH value of the electrolytic active water is 8, the temperature is 50°C, and then the excess aqueous solution is removed by pressing rollers, and the rolling rate is 80%, and the above electrolytic active water is repeated. The treatment process is 2 times, then washed with water and air-dried naturally.

(3) Test results of wool shrinkage resistance after electrolytic active water treatment: DFE is 13.27% (raw wool 29.99%), shrink ball diameter is 3.75cm (raw wool 3.34cm), and strength is reduced by 13.5%.

Comparison of Examples 21-23 with the raw wool performance test results, as shown in Table 5.

Table 5 Comparison table of test results of active water-treated wool implementation sample and raw wool

Example 24

(1) Pre-dipping: 70s tops were treated in 1g/L JFC solution for 30s, the treatment temperature was 50°C, one dipping and one rolling, and the rolling ratio was 80%.

(2) Electrolytic active water treatment: soak the wool in electrolytic active water for 90s, the pH value of the electrolytic active water is 8, the temperature is 20 ℃, and then the excess aqueous solution is removed by pressing rollers, the rolling rate is 80%, and then the biological enzyme treatment is carried out .

(3) Soak in 2g/L biological enzyme for 90s, the pH value is 8, the temperature is 50℃, and then the excess aqueous solution is removed by a pressing roller, the rolling rate is 80%, the above biological enzyme treatment process is repeated again, and the biological enzyme is inactivated (80℃, one dipping and one rolling), washed with water, and dried.

(4) Test results of wool shrinkage resistance after active water combined with biological enzyme treatment: DFE was 8.66% (raw wool 29.99%), and shrinkage ball density was 0.0478g/cm ² (raw wool 0.08g/cm ² ).

Example 25

(1) Pre-dipping: Treat 70s tops in 1g/L JFC solution for 30s at a temperature of 50°C, one dipping and one rolling, and the rolling ratio is 80%.

(2) Electrolytic active water treatment: soak the wool in electrolytic active water for 90s, the pH value of the electrolytic active water is 8, and the temperature is 20°C, and then the excess aqueous solution is removed by pressing rollers, and the rolling rate is 80%, and the above electrolytic active water is repeated. The treatment process was carried out once, and then the biological enzyme treatment was carried out.

(3) Soak in 1g/L biological enzyme for 90s, the pH value is 8, the temperature is 50℃, and then the excess aqueous solution is removed by a pressing roller, the rolling rate is 80%, and the above biological enzyme treatment process is repeated 4 times, and the biological enzyme is inactivated. Live (80°C, one dip and one roll), washed with water, and dried.

(4) Test results of wool shrinkage resistance after active water combined with biological enzyme treatment: DFE was 8.07% (raw wool 29.99%), and shrinkage ball density was 0.0384 g/cm ² (raw wool 0.08 g/cm ² ).

Example 26

(3) Soak in 3g/L biological enzyme for 90s, the pH value is 8, the temperature is 50℃, and then the excess aqueous solution is removed with a pressing roller, the rolling rate is 80%, the above biological enzyme treatment process is repeated 4 times, the biological enzyme is inactivated Live (80°C, one dip and one roll), washed with water, and dried.

(4) Test results of wool shrinkage resistance after active water combined with biological enzyme treatment: DFE was 7.77% (raw wool 29.99%), and shrinkage ball density was 0.0402g/cm ² (raw wool 0.08g/cm ² ).

(5) After the shrinkage resistance test of machine-washable wool (TM31 5×5a), the area shrinkage of the treated sample was 2.18%.

Embodiment 24-26 is compared with raw wool performance test result, following table 6:

Table 6 Comparison table of test results of active water-treated wool implementation sample and raw wool

The wool treated with active water combined with biological enzymes is scanned by electron microscope, and the SEM of wool scales of wool fibers in Examples 24-26 are shown in Figure 15a, Figure 15b and Figure 15c, respectively.

In addition, this application also adopts different technical solutions. Different technical solutions use the same process parameters as possible (such as the same electric field strength, magnetic field strength, and the same working fluid temperature and treatment time) to compare the same batch of wool fibers. The test results are compared in the following table.

In Comparative Example 10, on the basis of Example 21, the ultrasonic effect in the preparation of active water was omitted, that is, the active water was prepared by the method of "electric field + magnetic field + input ozone". Graphite electrode, the voltage between the electrodes is 10V, and the current in the working solution is maintained not more than 3A, and the 70s top treatment process is the same as that of Example 1; Function, eliminating the need to input ozone, that is, "electric field + magnetic field" method to prepare active water. The 70s top treatment process is the same as that of Example 21; the active water in Comparative Example 12 was treated with an electric field only, and its parameters were the same as those in Example 21;

Through the comparison of the above experiments, the active water obtained by the combination of "electricity + magnetism + ozone + ultrasound" used in the invention has two effects on wool's directional friction effect (DFE) and shrinking ball diameter when it is used for 70s wool top shrinkage prevention treatment. The main indicators have been significantly improved, indicating that the shrinkage resistance of wool has been well improved and has excellent technical effects; the combination of "electricity + magnetism + ozone", the directional friction effect (DFE) of the treated 70s top and the shrinking ball The diameter index has a good effect and can improve the shrinkage resistance of wool fabrics; for the "electric + magnetic" combination, the treatment effect is acceptable, and its directional friction effect (DFE) and shrink ball diameter index show that it can meet the general shrinkage resistance requirements of fabrics. For high-end finished textiles, further processing is required; electrical or magnetic processing techniques alone cannot basically meet the requirements of wool shrink-resistance processing.

Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, but not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that: The technical solutions described in the foregoing embodiments can still be modified, or some or all of the technical features thereof can be equivalently replaced; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the technical solutions of the embodiments of the present invention. Scope.

Claims

An active water preparation device, characterized in that it comprises: a water tank, an electric field generating device and a magnetic field generating device;

the water tank is used to accommodate the working fluid;

The electric field generating device includes: an electrode assembly for forming an electric field; the electrode assembly is arranged in the water tank for electric field treatment of the working fluid;

The magnetic field generating device includes a magnetic pole assembly for forming a magnetic field; the electrode assembly is arranged inside or outside the water tank for magnetizing the working fluid.
The active water preparation device according to claim 1, wherein the electrode assembly comprises one or more pairs of positive electrodes and negative electrodes arranged at intervals.
The active water preparation device according to claim 2, wherein the magnetic pole assembly comprises a positive magnetic pole and a negative magnetic pole; the positive magnetic pole and the negative magnetic pole are respectively arranged at opposite ends of the water tank.
The active water preparation device according to claim 3, wherein the positive electrode and the negative electrode are flat plates; between the positive magnetic pole and the negative magnetic pole, the positive electrode and the negative electrode are alternately arranged at equal intervals;

Alternatively, the positive electrode and the negative electrode are cylindrical, and are alternately arranged in concentric circles at equal intervals in the radial direction.
The active water preparation device according to claim 3, wherein the positive magnetic pole and the negative magnetic pole are semi-enclosed magnetic poles, and the horizontal cross-sections of the positive magnetic pole and the negative magnetic pole are respectively semi-annular, and are respectively formed from opposite ends of the water tank. Or surround the sink as much as possible on both sides.
The active water preparation device according to claim 1, further comprising an ozone generating device, the ozone output port of the ozone generating device is connected to the water tank through a pipeline, and is used for transporting ozone into the working fluid.
The active water preparation device according to claim 1, further comprising an ultrasonic generating device, the ultrasonic vibrator of the ultrasonic generating device is arranged in or outside the water tank, and is used for inputting ultrasonic waves to the working fluid in the water tank.
A natural fiber dyeing and finishing treatment device with the active water preparation device according to any one of claims 1-7, characterized in that it comprises the oxidative active water preparation device and a pretreatment device;

The pretreatment device is connected to the oxidative active water preparation device, and the natural fibers are pretreated with the active water prepared by the oxidative active water preparation device.
The natural fiber dyeing and finishing treatment device according to claim 8, wherein the pretreatment device comprises: a middle casing, an outer casing and a pump body;

Natural fibers are wound on the middle sleeve, and the outer sleeve is sleeved outside the middle sleeve; an annular working cavity for accommodating natural fibers is formed between the middle sleeve and the outer sleeve;

The outer circular side of the middle sleeve is provided with a plurality of through holes that communicate with the inside and outside of the middle casing cavity; the outer circular side of the outer sleeve is provided with a drain hole that communicates with the inside and outside of the annular working cavity;

The pump body is communicated with the lumen of the middle casing through the input pipeline, and is used to inject the working fluid into the lumen, and use the pressure to force the working fluid to pass through the through hole, the annular working cavity and the Drainage hole for soaking the natural fibers in the annular working cavity.
The natural fiber dyeing and finishing treatment device according to claim 9, characterized in that, in the circumferential direction of the middle sleeve, the diameters of the plurality of through holes are the same and evenly spaced.
The natural fiber dyeing and finishing treatment device according to claim 10, wherein one end of the middle sleeve is provided with a working fluid inlet; in the axial direction of the middle sleeve and the direction gradually away from the working fluid inlet, the unit The pore area gradually increases.
The natural fiber dyeing and finishing treatment device according to claim 10, wherein the two ends of the middle sleeve are provided with a working fluid inlet, and the working fluid inlet is connected with the outlet of the pump body through a pipeline; A control valve for inputting working fluid into the lumen alternately through two working fluid inlets.
A method for dyeing and finishing natural fibers, comprising the steps of:

S10. Prepare active water;

S20. Pretreatment of natural fibers or textiles made of natural fibers;

Wherein, step S10 specifically includes the following steps:

S11. Configure inorganic salt solution;

S12. Use the magnetic pole assembly to apply a directional magnetic field to the inorganic salt solution; use the electrode assembly to ionize the inorganic salt solution to obtain oxidative active water;

Step S20 specifically includes the following steps:

S21. Pre-swollen natural fibers or their textiles;

S22. Immerse the pre-swelled natural fibers or their textiles in active water, the temperature of the active water is 20-100°C, and the soaking time is 10-90 minutes.
The method for dyeing and finishing natural fibers according to claim 13, wherein step S21 specifically comprises: soaking natural fibers or their textiles with an aqueous solution of inorganic sodium salt or potassium salt with a concentration of 5 to 15 g/l; 60° C., the treatment time is 10-90 min; further, the inorganic sodium salt or potassium salt is one or more of sodium carbonate and potassium carbonate.
The method for dyeing and finishing natural fibers according to claim 13, wherein the natural fibers are cotton fibers, the temperature of the active water in step S22 is 20-40°C, and the soaking time is 20-60 minutes.
The method for dyeing and finishing natural fibers according to claim 13, wherein the natural fibers are hemp fibers, the temperature of the active water in step S22 is 20-100°C, and the soaking time is 10-90 minutes.
The method for dyeing and finishing natural fibers according to claim 13, wherein the natural fibers are wool fibers, and in step S21, the wool fibers or their fabrics are soaked in a wetting agent solution for a soaking time of not less than 30s, and then Remove excess aqueous solution, and the rolling rate is not less than 80%.
The method for dyeing and finishing natural fibers according to claim 13, characterized in that, in step S20, further comprising:

S23. Remove the excess aqueous solution of natural fibers or their fabrics, and the rolling rate is not less than 80%;

S24. Steps S22 and S23 are repeated, and the soaking and rolling are repeated 1-5 times continuously.
The method for dyeing and finishing natural fibers according to claim 13, wherein the inorganic salt in the inorganic salt solution in step S11 is an inorganic sodium salt and/or an inorganic potassium salt; the inorganic sodium salt is sodium sulfate, One or more of sodium hypochlorite, sodium bisulfate, sodium carbonate, sodium chloride, sodium perchlorate; inorganic potassium salt is one or more of potassium chloride, potassium carbonate and potassium sulfate.
The method for dyeing and finishing natural fibers according to claim 13, characterized in that, in step S12, the magnetic field intensity is 0-3T, and the magnetization treatment time is 0-40min.
The method for dyeing and finishing natural fibers according to claim 13, wherein step S12 further comprises the steps:

S12a. In the process of applying a directional magnetic field and an electric field to the inorganic salt solution, use an ozone generating device and a pipeline to transport ozone into the inorganic salt solution.
The method for dyeing and finishing natural fibers according to claim 13, wherein step S12 further comprises the steps:

S12b. During the process of applying a directional magnetic field and an electric field to the inorganic salt solution, use an ultrasonic generating device to input ultrasonic waves into the inorganic salt solution.