阅读说明：本技术 一种洗发用硫化硒复合粉 (Selenium sulfide composite powder for hair washing ) 是由 郑小青 于 2021-07-14 设计创作，主要内容包括：本发明提供一种洗发用硫化硒复合粉,所述硫化硒以纳米形态均匀分散于纳米微球表面,可直接与洗发组合物混合使用,在组合物中不易发生沉降分离,无需在使用时再进行硫化硒与洗发水的混合,简单方便,碳球微粒可作为活性炭洗发水添加剂,能够减少头屑产生,降低油脂分泌,并对马拉色菌有明显的抑制作用。(The invention provides selenium sulfide composite powder for hair washing, wherein selenium sulfide is uniformly dispersed on the surface of a nano microsphere in a nano form, can be directly mixed with a hair washing composition for use, is not easy to settle and separate in the composition, does not need to be mixed with shampoo when in use, is simple and convenient, and carbon microsphere particles can be used as an active carbon hair washing additive, can reduce the generation of dandruff, reduce the secretion of grease, and have an obvious inhibiting effect on malassezia.)

1. The selenium sulfide composite powder for hair washing is characterized by being prepared by the following steps:

(1) preparing carbon spheres by a hydrothermal method;

(2) preparing electrolyte, and depositing nano selenium carbon sphere particles on the cathode of the surface of the carbon sphere through electrochemical treatment;

(3) vacuum drying the obtained nano selenium carbon sphere particles,

(4) preparing sulfur-doped selenium sulfide carbon sphere particles through vulcanization;

(5) purifying the selenium sulfide carbon sphere particles to obtain the selenium sulfide composite powder for washing and protecting.

2. The selenium sulfide composite powder for hair washing of claim 1, wherein the hydrothermal method is used for preparing carbon spheres as follows: dissolving 10-15g of glucose in 100ml of deionized water, adding 1-1.5g of formaldehyde, adjusting the pH concentration to 8-8.5 by using sodium hydroxide, stirring, transferring to a hydrothermal reaction kettle, adding 220 percent of formaldehyde in 200-220 percent of sodium hydroxide^oAnd C, carrying out hydrothermal treatment for 12-16h to obtain a tan suspension, and filtering, washing and drying to obtain carbon sphere particles.

3. The selenium sulfide composite powder for washing hair as set forth in claim 1, wherein the prepared electrolyte is composed of sodium selenite, sodium chloride, boric acid, surfactant, carbon sphere particles and deionized water, and the sodium selenite is sodium selenite17.3-51.9g/L, 10-12 g/L of sodium chloride, 20-25 g/L of boric acid, 0.05-0.1 g/L of surfactant and 15-25g/L of carbon sphere particles, wherein the current density of electrochemical treatment in the step (2) is 0.2-0.4 mA/cm²The electrochemical treatment time is 50-90 min.

4. The selenium sulfide composite powder for shampooing according to claim 1, wherein the electrochemical process in the step (2) comprises a cathode and an anode, the cathode is detachably attached to the inside of the electrolytic bath and is arranged around the anode, and the anode is arranged at the center of the electrolytic bath and is stirred during the electrochemical reduction of selenium.

5. The selenium sulfide composite powder for hair washing as claimed in claim 4, wherein the cathode material is preferably carbon material, the cathode is periodically cleaned and soaked in alkali solution, the elemental selenium on the surface of the cathode is recovered to prepare sodium selenite, and the stirring speed is 300-400 rpm.

6. The selenium sulfide composite powder for hair washing of claim 3, wherein the temperature of vacuum drying is 100-120-^oC, the time is 1-2 h.

7. The selenium sulfide composite powder for hair washing of claim 1, wherein the process for preparing the selenium sulfide carbon sphere particles by vulcanization comprises the following steps: placing the selenium sulfide carbon sphere particles obtained by drying in the step (3) into a reaction furnace, introducing sublimed sulfur powder gas,

continuously rotating the tumbling reaction furnace at 140-^oAnd C, fully reacting for 5-8h, and naturally cooling to form sulfur-doped selenium sulfide carbon sphere particles.

8. The selenium sulfide composite powder for hair washing of claim 1, wherein the process for purifying the selenium sulfide carbon sphere particles comprises: placing the sulfur-doped selenium sulfide carbon sphere particles prepared in the step (5) into a flowing gas drying furnace, wherein the flowing gas is nitrogen, and the drying temperature is 110-^oC, drying for 2-3 h.

9. The selenium sulfide composite powder for shampooing according to claim 1, wherein the sublimed sulfur powder gas comprises 95-98vol.% nitrogen.

10. The selenium sulfide composite powder for hair washing of any one of claims 1 to 9, wherein the selenium sulfide composite powder is used as an additive for anti-dandruff, anti-itching shampoo and conditioner agents such as shampoo, cream shampoo, soap shampoo, and the like.

Technical Field

The invention belongs to the field of daily chemicals, and particularly relates to selenium sulfide composite powder for hair washing.

Background

In daily life, under the influence of pressure and environmental pollution, more and more people are troubled by the problems of scurf, scalp itch, scalp inflammation and the like, most of the existing scurf removing products on the market adopt pyridine sulfate as the scurf removing agent, but the existing scurf removing agent has the defects that the pyridine sulfate is strong in irritation, insoluble in water and organic solvent, and is easy to appear poor in compatibility with other components, difficult to disperse, easy to precipitate and agglomerate when being applied to shampoo, so that the scurf removing effect is unstable. In the prior art, the plant extract is used as the anti-dandruff agent, and the anti-dandruff agent has the characteristics of mildness and no stimulation, but the plant extract has complex components, unclear effective components and beneficial effects, unobvious effects or even no claimed effect of a product, the effective components of the plant extract are easily influenced by an extraction process, and other components and shelf life in a system also easily influence the stability of the plant extract and the high activity of active substances, so that the anti-dandruff effect is unstable. The selenium disulfide lotion on the market is a medical lotion, the general content is 2.5%, and the lotion has a good curative effect on bacteria on the scalp and seborrheic dermatitis, the selenium disulfide is mainly externally used in a shampoo form, generally and mainly externally used on scalp parts and hair parts, has the main effects of resisting fungi and relieving itching, and has a certain effect of controlling grease, so the lotion is generally used for scalp seborrheic dermatitis, pityriasis capitis and the like in clinic, generally washes the head for 1 time in 3-4 days, and can play a certain role in removing fat, diminishing inflammation and relieving itching, but the irritation of the selenium disulfide to the skin is very strong, and the solid content in the lotion is too high to be used for a long time. In addition, the selenium disulfide has strong effect of inhibiting sebaceous gland secretion, and the high-content dosage form easily causes excessive dryness of scalp, and causes the problems of dandruff increase and scalp itching. Moreover, the selenium sulfide lotion has poor cleaning capability and needs to be matched with shampoo for use, which brings inconvenience to users.

In addition, medicinal selenium sulfide and shampoo in the market are usually purchased separately, and a user uses the shampoo and the selenium sulfide in a matched mode according to the ratio of 1:1 or 2:1 in the using process, mainly because the selenium sulfide is high in density, insoluble in water and oil and difficult to suspend in a shampoo system, the shampoo and the selenium sulfide are easily separated, the selenium sulfide is difficult to uniformly apply to the head of a human body, and the dandruff removing and itching relieving effects are poor.

At present, two main methods for preparing selenium disulfide are available.

The first method is a wet synthesis method: under the acidic condition, adding sodium sulfide (or ammonium sulfide, ammonium hydrogen sulfide) solution into selenious acid solution (selenium dioxide solution in water) to react with glacial acetic acid solution to generate selenium sulfide, and filtering, washing and drying to obtain the selenium sulfide product. The disadvantages are that: the purity of the selenium disulfide prepared by the method is low. Acetic acid is used in the synthesis process, so the production environment is relatively poor, and the requirement on equipment is high; and a large amount of sewage is generated in the synthesis and washing processes, so that the comprehensive production cost is high.

The second method comprises the following steps of pyrogenic synthesis: adding selenium and sulfur into a quartz tube according to a certain proportion, vacuumizing, sealing the tube, synthesizing at high temperature, and finally cooling, crushing the tube and sampling. The disadvantages are that: and (3) vacuumizing to seal the tube, wherein the quartz tube needs to be vacuumized to below 10-5Pa and then calcined and sealed, and the requirement on equipment is high. The quartz tube has small charging amount and low single-batch productivity; the quartz tube is a consumable, the produced quartz waste is more, and the comprehensive production cost is higher.

Disclosure of Invention

Based on the problems, the invention provides a method for preparing high-purity and high-water-solubility selenium sulfide composite powder, which comprises the following steps:

(1) preparing carbon spheres by a hydrothermal method;

(2) preparing electrolyte, and depositing nano selenium carbon sphere particles on the cathode of the surface of the carbon sphere through electrochemical treatment;

(3) vacuum drying the obtained nano selenium carbon sphere particles,

(4) preparing sulfur-doped selenium sulfide carbon sphere particles through vulcanization;

(5) purifying the selenium sulfide carbon sphere particles to obtain the selenium sulfide composite powder for washing and protecting.

Further, the hydrothermal method for preparing the carbon spheres comprises the following steps: dissolving 10-15g of glucose in 100ml of deionized water, adding 1-1.5g of formaldehyde, adjusting the pH concentration to 8-8.5 by using sodium hydroxide, stirring, transferring to a hydrothermal reaction kettle, adding 220 percent of formaldehyde in 200-220 percent of sodium hydroxide^oAnd C, carrying out hydrothermal treatment for 12-16h to obtain a tan suspension, and filtering, washing and drying to obtain carbon sphere particles.

Further, the prepared electrolyte consists of 17.3-51.9g/L of sodium selenite, 10-12 g/L of sodium chloride, 20-25 g/L of boric acid, 0.05-0.1 g/L of surfactant and 15-25g/L of carbon sphere particles and deionized water.

Further, the current density of the electrochemical treatment in the step (2) is 0.2-0.4 mA/cm²The electrochemical treatment time is 50-90 min.

Further, in the electrochemical process in the step (2), inert conductive materials are used as a cathode and an anode, the cathode is detachably attached to the inside of the electrolytic cell and is arranged around the anode, and the anode is arranged at the center of the electrolytic cell and is stirred in the electrochemical reduction process of selenium.

Furthermore, the cathode material is preferably a carbon material, the cathode is periodically cleaned and soaked in alkali liquor, the selenium simple substance on the surface of the cathode is recovered to prepare sodium selenite, and the stirring speed is 300-400 rpm.

Further, the temperature of the vacuum drying is 100-120-^oC, the time is 1-2 h.

Further, the process for preparing the selenium sulfide carbon sphere particles by vulcanization comprises the following steps: placing the selenium sulfide carbon sphere particles obtained by drying in the step (3) into a reaction furnace, introducing sublimed sulfur powder gas,

continuously rotating the tumbling reaction furnace at 140-^oAnd C, fully reacting for 5-8h, and naturally cooling to form sulfur-doped selenium sulfide carbon sphere particles.

Further, the process of purifying the selenium sulfide carbon sphere particles comprises the following steps: placing the sulfur-doped selenium sulfide carbon sphere particles prepared in the step (5) into a flowing gas drying furnace, wherein the flowing gas is nitrogen, and the drying temperature is 110-^oC, drying for 2-3 h.

Further, the sublimed sulfur powder gas comprises 95-98vol.% nitrogen.

Furthermore, the selenium sulfide composite powder is used as an additive of anti-dandruff itching-relieving washing and protecting reagents such as shampoo, cream shampoo, soap shampoo and the like.

The preparation process of the present invention is described in detail below.

(1) Preparation of carbon spheres by hydrothermal method: the process for preparing the carbon spheres by the hydrothermal method comprises the following steps: dissolving 10-15g of glucose in 100ml of deionized water, adding 1-1.5g of formaldehyde, adjusting the pH concentration to 8-8.5 by using sodium hydroxide, stirring, transferring to a hydrothermal reaction kettle, adding 220 percent of formaldehyde in 200-220 percent of sodium hydroxide^oAnd C, carrying out hydrothermal treatment for 12-16h to obtain a tan suspension, and filtering, washing and drying to obtain carbon sphere particles.

The invention adopts a hydrothermal method to prepare micron-sized carbon spheres, as shown in figure 1The micron-sized carbon spheres have low density and high specific surface area, and the main reason is that the carbon spheres obtained by hydrothermal treatment contain a large amount of polar functional groups, mainly a large amount of oxygen-containing functional groups, such as hydroxyl and carbonyl, and when the carbon spheres are taken as electrolyte additives, the carbon spheres can be uniformly distributed in the electrolyte, and a hydrothermal solution contains glucose, formaldehyde and a pH regulator, wherein the glucose is a carbon source, so that the size of the prepared carbon spheres is intensively distributed in a range of 2-4 μm, and when the particle size of the carbon spheres is closely related to the concentration of the glucose, the concentration of the glucose is increased within a certain range, and the size of the obtained carbon spheres is obviously increased; formaldehyde is an auxiliary agent or a stabilizing agent, wherein carbonyl can effectively react with hydroxyl or carbonyl on the surface of the carbon sphere, so that the polarity of the carbon sphere can be enhanced, and the stability of the carbon sphere in water can be improved; in addition, in addition to concentration and time, the key factors for hydrothermal process are temperature, when the hydrothermal temperature is low, the particles are small, the dispersion degree is high, but the uniformity of the particle size is low, carbon microspheres with uniform particle size cannot be effectively obtained, when the hydrothermal temperature is high, the particles are large, and are easy to agglomerate, so that the dispersion degree is low, and the hydrothermal temperature is limited to 200-^oC, the temperature section can obtain 2-4 μm big balls as shown in figure 2, and the dispersity is good, thus being beneficial to process production and control.

(2) Preparing electrolyte, and depositing nano selenium carbon sphere particles on the cathode of the surface of the carbon sphere through electrochemical treatment;

the invention does not put forward the means of electrodeposition for the first time, electrochemical reduction obtains nano-selenium particles, for example, CN102776524A discloses a preparation method of nano-selenium, comprising: a) adding electrolyte containing a selenium source and inorganic inert particles into an electrolytic cell, and introducing direct current into the electrolytic cell under the stirring state; b) and sequentially filtering, washing and drying the mixture in the electrolytic cell to obtain a mixture of selenium particles and inorganic inert particles.

In said patent, the following explanations are made:

as the reduction reaction proceeds, selenium is continuously formed on the cathode surface. In order to avoid that selenium particles are deposited on the surface of a cathode in a large quantity to form crystalline selenium and avoid that an excessively high polarization potential increases energy consumption in a reaction process, inorganic inert particles are added into an electrolytic cell and are electrolyzed in a stirring state, the inorganic inert particles continuously collide with the cathode under the driving of stirring force, the inorganic inert particles rub with the surface of the cathode and simultaneously drive selenium particles on the surface of the cathode to be separated from the surface of the cathode to enter an electrolyte system, then a mixture in the electrolytic cell is filtered, and solid particles obtained by filtering are sequentially washed and dried to obtain a mixture of amorphous selenium particles and inorganic inert particles.

The patent presents the following obvious problems:

(1) the patent precipitates selenium material on the surface of a cathode through electrochemical reduction treatment, and then physically collides and scrapes the selenium material on the surface of the cathode through the grinding action of inorganic inert particles to finally obtain a mixture of selenium and inorganic particles, and the surface of the inorganic particles cannot be electrodeposited with selenium particles due to the non-conductivity of the inorganic inert particles.

(2) The selenium finally prepared by the patent is in a nanometer scale, which represents a doubtful attitude of the present invention, and the skilled person knows that the particle size of the inorganic inert particles is 150-200 meshes, and the use of inert particles close to 70 microns cannot scrape the selenium particles in the nanometer scale on the surface of the cathode.

However, the electrochemical treatment provided by the patent is feasible to deposit nano-scale selenium on the surface of the cathode, and based on the above principle, the invention adopts the conductive carbon spheres and deposits the selenium nano-particles on the surface of the conductive carbon spheres, i.e. micron carbon spheres with selenium nano-particles attached to the surface can be obtained, which is specifically explained as follows:

firstly, preparing electrolyte, wherein the electrolyte consists of 17.3-51.9g/L of sodium selenite, 10-12 g/L of sodium chloride, 20-25 g/L of boric acid, 0.05-0.1 g/L of surfactant and 15-25g/L of carbon sphere particles, and the boric acid is boric acid, and the deionized water.

Wherein the sodium selenite is a selenium source and reacts with 6H under the acidic electrochemical condition⁺+SeO₃ ^2-+4e^-→3H₂O + Se; the chlorineSodium is dissolved as a conductive salt, so that the conductive capacity of the electrolyte is improved, and in addition, sodium sulfate and magnesium sulfate can also be used as conductive salts;

boric acid is used as a pH stabilizer, so that the pH stability of the electrolyte is effectively maintained; the surfactant is used for improving the dispersibility of the inorganic particles in the plating solution, and can be any surfactant in the prior art, such as sodium dodecyl sulfate, a nonionic surfactant P123, or a Tween surfactant.

In addition, because a large number of oxygen-containing polar groups exist on the surface of the carbon sphere, the groups can obviously adsorb SeO₃ ^2-Ions to form C-SeO₃ ^2-The carbon spheres strongly impact the surface of the cathode material in a disordered state under the stirring condition, and when the conductive carbon spheres are contacted with the cathode, the SeO on the surface of the carbon spheres₃ ^2-Electrochemical reduction on carbon spheres to form nano-selenium, and furthermore, if free SeO₃ ^2-Free SeO upon contact with conductive carbon spheres₃ ^2-Nano-selenium is deposited on the surface of the cathode, and in addition, the carbon spheres are likely to contact with the cathode under stirring to conduct electricity, which indicates that a part of free SeO exists₃ ^2-Cannot be contacted with the conductive carbon spheres, i.e. SeO inevitably occurs on the cathode surface₃ ^2-Electrochemically, so that after long-time electrochemical reduction treatment, selenium particles are formed on the surface of the cathode, namely at least three types of selenium exist in electrolysis, one type of selenium is selenium A attached to the surface of the carbon sphere, the other type of selenium B attached to the surface of the cathode, and the other type of selenium C falls into the electrolysis from the surface of the cathode due to stirring or friction, wherein in the process of recovering nano selenium carbon sphere particles, the particles comprise selenium A and selenium C which are mixtures and have obvious difference in morphology, the selenium A is nano-scale selenium particles attached to the surface of the micron carbon sphere, the size of the selenium A is 50-200nm, the selenium C is macroscopic particulate selenium obtained by physical collision friction and is a micron-scale or millimeter-scale simple selenium substance, and the selenium C is required to be recovered due to the shape and size of the selenium A and the selenium CThe selenium A can be micron-sized carbon spheres-nano selenium particles, the water solubility is good, the density is low, the selenium A can be suspended in an aqueous solution for a long time and cannot be precipitated, the selenium C is micron-sized amorphous simple substance particles which are mainly millimeter, the water solubility is poor, the density is high, and the precipitation is easy, so that the selenium A and the selenium C can be separated by a simple suspension separation method or a centrifugal separation method, and the obtained selenium A is treated in the step (3) to be dried in vacuum; soaking the obtained selenium C in alkali liquor, and recovering for the second time to prepare sodium selenite, wherein the reaction formula is as follows:

3Se+6NaOH=Na₂SeO₃+2Na₂Se+2H₂O。

in addition, inert conductive materials are used as a cathode and an anode in the electrochemical process, the cathode is detachably attached to the inside of the electrolytic cell and arranged around the anode, and the anode is arranged in the center of the electrolytic cell and is stirred in the electrochemical reduction process of selenium. And a large amount of selenium B is deposited on the surface of the cathode, and the selenium B and the selenium C are treated in the same way for secondary recovery, so that the detachable cathode needs to be cleaned regularly, the conductivity of the cathode can be improved, and the selenium C on the surface of the cathode can be recovered.

(3) And (3) drying the obtained nano selenium carbon sphere particles in vacuum: the temperature of the vacuum drying is 100-120 DEG C^oAnd C, the time is 1-2h, the vacuum drying is mainly aimed at removing liquid on the surface of the nano selenium carbon microsphere, and the nano selenium is required to be dried in vacuum due to high activity of the nano selenium, so that the drying temperature is not easy to be too high, and the phenomenon that the bonding force of the nano selenium and the micro carbon sphere is reduced due to too high temperature, so that heat transfer occurs and the particle size is increased finally is avoided.

(4) Preparing sulfur-doped selenium sulfide carbon sphere particles through vulcanization; placing the selenium sulfide carbon sphere particles obtained by drying in the step (3) in a reaction furnace, introducing sublimed sulfur powder gas, continuously rotating and rolling the reaction furnace in 140-^oAnd C, fully reacting for 5-8h, and naturally cooling to form sulfur-doped selenium sulfide carbon sphere particles.

As mentioned above, in the invention, by a mode similar to barrel plating, the conductive carbon microspheres are contacted with the cathode, so that the carbon microspheres are used as the cathode, selenium is electrochemically reduced on the surface of the carbon microspheres, the size of the obtained selenium A is 50-200nm, the particle size is small, the activity is higher, the distribution is uniform, and the reaction of sulfur gas and selenium nanoparticles can be realized at a certain temperature by a simple sulfur sublimation method to form selenium sulfide nanoparticles.

(5) Purifying the selenium sulfide carbon sphere particles to obtain selenium sulfide composite powder for washing and protecting: placing the sulfur-doped selenium sulfide carbon sphere particles prepared in the step (5) into a flowing gas drying furnace, wherein the flowing gas is nitrogen, and the drying temperature is 110-^oAnd C, drying for 2-3h, wherein the sublimed sulfur powder gas comprises 95-98vol.% nitrogen.

As mentioned above, because the loading of nano-selenium is limited, and the nano-selenium can react with the sulfur powder completely, the excess sulfur powder can exist in the following two forms: (1) sublimed sulfur does not deposit on the surface of the microsphere, moves along with the nitrogen gas and does not stay; (2) the sulfur is blocked, because the microporous ball has a certain specific surface area, the sulfur is blocked by the micropores or the nanopores, in the cooling process, sulfur powder is formed, based on the above, in order to improve the purity of the selenium sulfide on the surface of the micron carbon spheres, the sulfur-doped selenium sulfide carbon sphere particles obtained in the step (4) need to be subjected to surface treatment in a way of performing circulating heating by inert gas, then sulfur is retarded to perform secondary sublimation, and the sulfur is separated from the surface of the carrier, so that the high-purity selenium sulfide composite powder for washing and protecting is finally obtained, the loading capacity of the selenium sulfide on the surface of the carbon microsphere carrier is 1-3wt.%, the purity of the selenium sulfide is more than or equal to 95wt.%, and the size of the selenium sulfide is 200-300nm, as shown in figure 3, compared with the figure 2, the roughness of the selenium sulfide-carbon microsphere surface obtained by electrochemical reduction is obviously improved, and in the figure 4, the position of a dotted line square frame is selenium sulfide nano-particles.

The selenium sulfide composite powder obtained by the preparation method is used as an additive of anti-dandruff itching-relieving washing and protecting reagents such as shampoo, cream shampoo, soap shampoo and the like.

Advantageous technical effects

(1) According to the selenium sulfide composite powder for hair washing, the selenium sulfide is uniformly dispersed on the surface of the nano microsphere in a nano form.

(2) The selenium sulfide on the surface of the micron carbon ball has high purity, can be directly mixed with the shampoo composition for use, is not easy to precipitate and separate in the composition, does not need to be mixed with the shampoo when in use, and is simple and convenient.

(3) The carbon spheres prepared by the invention have good water solubility, and the carbon sphere particles can be used as an active carbon shampoo additive, can reduce dandruff, reduce grease secretion, and have obvious inhibiting effect on malassezia, namely, the carbon microspheres and the selenium sulfide are used as additives to enable the shampoo to have multiple functions.

Drawings

FIG. 1: the invention obtains SEM images of micron carbon spheres through hydrothermal treatment.

FIG. 2 is a drawing: the invention obtains SEM enlarged view of micron carbon spheres through hydrothermal treatment.

FIG. 3: SEM picture of the selenium sulfide composite powder prepared by the invention.

FIG. 4 is a drawing: SEM enlarged view of the selenium sulfide composite powder prepared by the invention.

Detailed Description

Example 1

The selenium sulfide composite powder for hair washing is prepared by the following steps:

(1) the carbon spheres were prepared by a hydrothermal method.

Dissolving 10% glucose in 100ml deionized water, adding 1-formaldehyde, adjusting pH to 8 with sodium hydroxide, stirring, transferring to hydrothermal reaction kettle, and reacting at 200 deg.C^oAnd C, carrying out hydrothermal treatment for 12h to obtain a tan suspension, and carrying out filtering, washing and drying treatment to obtain carbon sphere particles.

(2) Preparing electrolyte, and depositing nano selenium carbon sphere particles on the cathode of the surface of the carbon sphere through electrochemical treatment.

The prepared electrolyte consists of 17.3g/L of sodium selenite, 10 g/L of sodium chloride, 20g/L of boric acid, 0.05 g/L of surfactant and 15g/L of carbon sphere particles.

Inert conductive materials are used as a cathode and an anode in the electrochemical process, the cathode is detachably attached to the inside of the electrolytic cell and arranged around the anode, and the anode is arranged at the central position of the electrolytic cell and is stirred in the electrochemical reduction process of selenium.

The current density of the electrochemical treatment is 0.2 mA/cm²The electrochemical treatment time is 50 min.

(3) And (4) drying the obtained nano selenium carbon sphere particles in vacuum.

The temperature of the vacuum drying is 100 DEG C^oC, the time is 1 h.

(4) And (4) vulcanizing to prepare sulfur-doped selenium sulfide carbon sphere particles.

Placing the selenium sulfide carbon sphere particles obtained by drying in the step (3) in a reaction furnace, introducing sublimed sulfur powder gas, continuously rotating the reaction furnace in a rolling manner at 140 degrees, wherein the sublimed sulfur powder gas comprises 95vol.% of nitrogen^oAnd C, fully reacting for 5 hours, and naturally cooling to form sulfur-doped selenium sulfide carbon sphere particles.

(5) Purifying the selenium sulfide carbon sphere particles to obtain the selenium sulfide composite powder for washing and protecting.

Placing the sulfur-doped selenium sulfide carbon sphere particles prepared in the step (5) into a flowing gas drying furnace, wherein the flowing gas is nitrogen, and the drying temperature is 110 DEG^oC, drying for 2 h.

The cathode material is preferably carbon, the cathode is periodically cleaned and soaked in alkali liquor, the selenium simple substance on the surface of the cathode is recovered to prepare sodium selenite, and the stirring speed is 300 rpm.

Example 2

The selenium sulfide composite powder for hair washing is prepared by the following steps:

(1) the carbon spheres were prepared by a hydrothermal method.

Dissolving 12.5g of glucose in 100ml of deionized water, adding 1.25g of formaldehyde, adjusting the pH concentration to 8.25 by using sodium hydroxide, stirring, transferring to a hydrothermal reaction kettle, and performing reaction at 210^oAnd C, carrying out hydrothermal treatment for 14h to obtain a tan suspension, and carrying out filtering, washing and drying treatment to obtain carbon sphere particles.

(2) Preparing electrolyte, and depositing nano selenium carbon sphere particles on the cathode of the surface of the carbon sphere through electrochemical treatment.

The prepared electrolyte consists of 34.6g/L of sodium selenite, 11g/L of sodium chloride, 22.5 g/L of boric acid, 0.075 g/L of surfactant and 20/L of carbon sphere particles, wherein the sodium selenite, the sodium chloride, the boric acid, the surfactant, the carbon sphere particles and the deionized water are mixed together.

Inert conductive materials are used as a cathode and an anode in the electrochemical process, the cathode is detachably attached to the inside of the electrolytic cell and arranged around the anode, and the anode is arranged at the central position of the electrolytic cell and is stirred in the electrochemical reduction process of selenium.

The current density of the electrochemical treatment is 0.3 mA/cm²The electrochemical treatment time is 70 min.

(3) And (4) drying the obtained nano selenium carbon sphere particles in vacuum.

The temperature of the vacuum drying is 110 DEG C^oC, the time is 1.5 h.

(4) And (4) vulcanizing to prepare sulfur-doped selenium sulfide carbon sphere particles.

Placing the selenium sulfide carbon sphere particles obtained by drying in the step (3) in a reaction furnace, introducing sublimed sulfur powder gas, wherein the sublimed sulfur powder gas comprises 95-98vol.% of nitrogen, continuously rotating the reaction furnace, and turning at 155 DEG^oAnd C, fully reacting for 6.5 hours, and naturally cooling to form sulfur-doped selenium sulfide carbon sphere particles.

(5) Purifying the selenium sulfide carbon sphere particles to obtain the selenium sulfide composite powder for washing and protecting.

Placing the sulfur-doped selenium sulfide carbon sphere particles prepared in the step (5) in a flowing gas drying furnace, wherein the flowing gas is nitrogen, and the drying temperature is 115 DEG^oC, drying for 2.5 h.

The cathode material is preferably carbon, the cathode is periodically cleaned and soaked in alkali liquor, the selenium simple substance on the surface of the cathode is recovered to prepare sodium selenite, and the stirring speed is 350 rpm.

Example 3

The selenium sulfide composite powder for hair washing is prepared by the following steps:

(1) the carbon spheres were prepared by a hydrothermal method.

15g of the mixtureDissolving glucose in 100ml deionized water, adding 1.5g formaldehyde, adjusting pH to 8.5 with sodium hydroxide, stirring, transferring to hydrothermal reaction kettle, and reacting at 220 deg.C^oAnd C, carrying out hydrothermal treatment for 16h to obtain a tan suspension, and carrying out filtering, washing and drying treatment to obtain carbon sphere particles.

(2) Preparing electrolyte, and depositing nano selenium carbon sphere particles on the cathode of the surface of the carbon sphere through electrochemical treatment.

The prepared electrolyte consists of 51.9g/L of sodium selenite, 12 g/L of sodium chloride, 25g/L of boric acid, 0.1 g/L of surfactant and 25g/L of carbon sphere particles.

Inert conductive materials are used as a cathode and an anode in the electrochemical process, the cathode is detachably attached to the inside of the electrolytic cell and arranged around the anode, and the anode is arranged at the central position of the electrolytic cell and is stirred in the electrochemical reduction process of selenium.

The current density of the electrochemical treatment is 0.4 mA/cm²The electrochemical treatment time is 90 min.

(3) And (4) drying the obtained nano selenium carbon sphere particles in vacuum.

The temperature of the vacuum drying is 120 DEG C^oC, the time is 2 h.

(4) And (4) vulcanizing to prepare sulfur-doped selenium sulfide carbon sphere particles.

Placing the selenium sulfide carbon sphere particles obtained by drying in the step (3) into a reaction furnace, introducing sublimed sulfur powder gas, continuously rotating the reaction furnace to roll in 170, wherein the sublimed sulfur powder gas comprises 98vol.% of nitrogen^oAnd C, fully reacting for 8 hours, and naturally cooling to form sulfur-doped selenium sulfide carbon sphere particles.

(5) Purifying the selenium sulfide carbon sphere particles to obtain the selenium sulfide composite powder for washing and protecting.

Placing the sulfur-doped selenium sulfide carbon sphere particles prepared in the step (5) into a flowing gas drying furnace, wherein the flowing gas is nitrogen, and the drying temperature is 120 DEG^oC, drying for 3 h.

The cathode material is preferably carbon, the cathode is periodically cleaned and soaked in alkali liquor, the selenium simple substance on the surface of the cathode is recovered to prepare sodium selenite, and the stirring speed is 400 rpm.

The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.