CN110358877B - Hydrotalcite-like nano tanning agent with layered structure and preparation method and tanning method thereof - Google Patents
Hydrotalcite-like nano tanning agent with layered structure and preparation method and tanning method thereof Download PDFInfo
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- C14—SKINS; HIDES; PELTS; LEATHER
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Abstract
The invention discloses a hydrotalcite-like nano tanning agent with a layered structure, a preparation method and a tanning method thereof, and the technical scheme is as follows: mixing nitrates of magnesium, aluminum and X with water to prepare a solution A, wherein X is one of chromium, iron, zirconium and zinc, mixing sodium carbonate with water to prepare a solution B, and mixing sodium hydroxide with water to prepare a solution C; and (3) simultaneously dripping the solution A and the solution C into the solution B under the stirring condition of 300 r/min, crystallizing at 80 ℃ for 10 hours after dripping is finished, and centrifuging and drying the obtained precipitate to obtain the hydrotalcite-like nano tanning agent with the layered structure. The shrinkage temperature of the leather tanned by the hydrotalcite-like nano tanning agent prepared by the invention can reach over 75 ℃, and the absorption and utilization of anionic dyeing and finishing chemicals such as dye, fatting agent and the like in wet operation after tanning can be promoted, so that the finished leather has good dyeing uniformity and softness.
Description
Technical Field
The invention belongs to the field of leather tanning technology, and particularly relates to a hydrotalcite-like nano tanning agent with a layered structure and a tanning method thereof.
Background
Chrome tanning is one of the most mature tanning methods in the tanning industry at present, can endow leather with good comprehensive performance, and is always dominant in the global tanning industry, but the traditional chrome tanning is easy to oxidize Cr (III) into Cr (VI) with potential carcinogenic risk in the processes of wet working procedures, storage and use after tanning, and certain treatment pressure exists in chromium-containing waste generated in the tanning process. Therefore, how to avoid or reduce the use of chrome tanning agents, reduce the pollution caused by chrome tanning and realize clean tanning becomes an important direction for sustainable development of leather industry.
In recent years, researchers have focused on the application of nanomaterials to leather making technologies to achieve clean tanning. According to the literature report, the layered nano clay can be combined with the collagen fibers to improve the damp-heat stability of the leather. However, the surface of natural or synthetic layered nano clay such as montmorillonite and laponite has negative charges, which is not beneficial to the absorption of anionic dyeing and finishing chemicals such as dye and fat-liquoring agent in the later stage of tanning. The hydrotalcite-like compound is a layered double-hydroxyl composite metal hydroxide formed by orderly assembling interlayer anions and laminates with positive charges, has the characteristics of adjustable composition of metal ions of main laminates, adjustable charge density and distribution of the main laminates and the like, and is widely applied to the aspects of biomedicine, photoelectric functional materials and the like. The literature reports that hydrotalcite-like compounds and biological macromolecules such as proteins can form an organic-inorganic nano hybrid material through hydrogen bonds, electrostatic interaction and the like, and skin collagen is a natural polymer with the property of amphoteric polyelectrolyte, so that the hydrotalcite-like compounds and collagen fibers can be combined to form a leather matrix.
Disclosure of Invention
The invention aims to provide a hydrotalcite-like nano tanning agent with a layered structure and a tanning method thereof, the raw materials of the tanning agent are cheap and easy to obtain, the preparation process is simple and easy to implement, and the shrinkage temperature of crust leather obtained by tanning with the tanning agent can reach over 75 ℃; can improve the thermal stability of finished leather, promote the absorption and utilization of anionic dyeing and finishing chemicals such as dye, fatting agent and the like in wet operation after tanning, and ensure that the finished leather has good dyeing uniformity and softness.
A preparation method of hydrotalcite-like nano tanning agent with layered structure comprises the steps of mixing nitrates of magnesium, aluminum and X with water to prepare a solution A, wherein the molar ratio of magnesium to aluminum to X is 20: 9-5: 1-5, wherein X is one of chromium, iron, zirconium and zinc, sodium carbonate is mixed with water to prepare a solution B, and sodium hydroxide is mixed with water to prepare a solution C; and (3) simultaneously dripping the solution A and the solution C into the solution B under the stirring condition of 300 r/min, crystallizing at 80 ℃ for 10 hours after dripping is finished, and centrifuging and drying the obtained precipitate to obtain the hydrotalcite-like nano tanning agent with the layered structure.
The amount concentration of the nitrate nitrogen substance in the solution A is 1 mol/L, the amount concentration of the substance in the solution B is 1 mol/L, and the amount concentration of the substance in the solution C is 2 mol/L.
The volume ratio of the solution A to the solution B to the solution C is 1: 1: 1.
a tanning method applying the tanning agent comprises the steps of firstly adding softened skins and water into a rotary drum, wherein the mass ratio of the softened skins to the water is 1: 1-1.5, then adding sodium chloride with the weight of 7% -8% of the skins, rotating for 30 min, then adjusting the pH value of bath liquid to 2.5-3.5 by using a formic acid solution, and continuing rotating for 30 min; then adding a hydrotalcite-like nano tanning agent with the weight of 0.5-8% of the tare weight, rotating for 3-8 hours, then adjusting the pH value of the bath liquid to 4.0-6.0 by using a sodium bicarbonate solution, and continuing rotating for 30 min; stopping the drum, standing for 24 h, rotating for 30 min the next day, and washing with water.
The tanning end point pH value of the tanning method is 4.0-6.0.
The mass ratio of formic acid to water in the formic acid solution is 1:10, and the mass ratio of sodium bicarbonate to water in the sodium bicarbonate solution is 1: 10.
Compared with the prior art, the invention has the beneficial effects that:
1) the invention introduces metal salt with certain tanning property, prepares hydrotalcite-like nano tanning agent by coprecipitation method under specific condition, provides hydrotalcite-like nano tanning agent with lamellar structure;
2) the shrinkage temperature of the obtained crust leather can reach over 75 ℃ by using the hydrotalcite-like nano tanning agent to tanne the leather;
3) the permanent electropositivity of the hydrotalcite-like plate layer endows leather fibers with positive charges, can promote the absorption and utilization of anionic dyeing and finishing chemicals such as dyes, fatting agents and the like in wet operation after tanning, and enables finished leather to have good dyeing uniformity and softness.
Drawings
FIG. 1 shows the shrinkage temperature of leather tanned by hydrotalcite-like nano tanning agent;
FIG. 2 shows the dye uptake of hydrotalcite-like nano-tanning agent with negatively charged natural clay and synthetic clay.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the embodiments of the present invention include, but are not limited to, the scope shown in the following examples.
Example 1:
preparing a hydrotalcite-like nano tanning agent:
respectively taking nitrates of magnesium, aluminum and zirconium, and mixing the nitrates with water to prepare a solution A, wherein the molar ratio of magnesium to aluminum to zirconium is 20: 8: 2, mixing sodium carbonate and water to prepare a solution B, and mixing sodium hydroxide and water to prepare a solution C; then under the condition of stirring at 300 r/min, simultaneously dropwise adding the solution A, C into a reaction container containing the solution B, crystallizing at 80 ℃ for 10 hours after dropwise adding is finished, and centrifuging and drying the obtained precipitate to obtain the hydrotalcite-like nano tanning agent with the layered structure;
the amount concentration of the nitrate nitrogen substance in the solution A is 1 mol/L, the amount concentration of the substance in the solution B is 1 mol/L, and the amount concentration of the substance in the solution C is 2 mol/L.
The volume ratio of the solution A to the solution B to the solution C is 1: 1: 1.
tanning:
firstly, adding softened skin and water into a rotary drum, wherein the mass ratio of the softened skin to the water is 1:1, adding sodium chloride with the weight of 8% of the weight of the skin, rotating for 30 min, then adjusting the pH value of bath liquid to 2.5 by using a formic acid solution, and continuing rotating for 30 min; then adding 3% of hydrotalcite-like nano tanning agent prepared according to the preparation method into the bath liquid, rotating for 3 h, then adjusting the pH value of the bath liquid to 4.5 by using sodium bicarbonate solution, and continuing rotating for 30 min; stopping the drum, standing for 24 h, rotating for 30 min the next day, and washing with water.
Example 2:
preparing a hydrotalcite-like nano tanning agent:
respectively mixing nitrates of magnesium, aluminum and chromium with water to prepare a solution A, wherein the molar ratio of magnesium to aluminum to chromium is 20: 7: 3, mixing sodium carbonate and water to prepare a solution B, and mixing sodium hydroxide and water to prepare a solution C; then under the condition of stirring at 300 r/min, simultaneously dropwise adding the solution A, C into a reaction container containing the solution B, crystallizing at 80 ℃ for 10 hours after dropwise adding is finished, and centrifuging and drying the obtained precipitate to obtain the hydrotalcite-like nano tanning agent with the layered structure;
the amount concentration of the nitrate nitrogen substance in the solution A is 1 mol/L, the amount concentration of the substance in the solution B is 1 mol/L, and the amount concentration of the substance in the solution C is 2 mol/L.
The volume ratio of the solution A to the solution B to the solution C is 1: 1: 1.
tanning:
firstly, adding softened skin and water into a rotary drum, wherein the mass ratio of the softened skin to the water is 1: 1.5, adding 8% of sodium chloride of the weight of the skin, rotating for 30 min, then adjusting the pH value of bath liquid to 3.0 by using a formic acid solution, and continuing rotating for 30 min; then adding hydrotalcite-like nano tanning agent which is 5 percent of the tare weight and is prepared according to the preparation method into the bath lotion, rotating for 8 hours, then adjusting the pH value of the bath lotion to 6.0 by using sodium bicarbonate solution, and continuing rotating for 30 min; stopping the drum, standing for 24 h, rotating for 30 min the next day, and washing with water.
Example 3:
preparing a hydrotalcite-like nano tanning agent:
respectively mixing nitrates of zinc, aluminum and zirconium with water to prepare a solution A, wherein the molar ratio of magnesium to aluminum to iron is 20: 6: 4, mixing sodium carbonate and water to prepare a solution B, and mixing sodium hydroxide and water to prepare a solution C; then under the condition of stirring at 300 r/min, simultaneously dropwise adding the solution A, C into a reaction container containing the solution B, crystallizing at 80 ℃ for 10 hours after dropwise adding is finished, and centrifuging and drying the obtained precipitate to obtain the hydrotalcite-like nano tanning agent with the layered structure;
the amount concentration of the nitrate nitrogen substance in the solution A is 1 mol/L, the amount concentration of the substance in the solution B is 1 mol/L, and the amount concentration of the substance in the solution C is 2 mol/L.
The volume ratio of the solution A to the solution B to the solution C is 1: 1: 1.
tanning:
firstly, adding softened skin and water into a rotary drum, wherein the mass ratio of the softened skin to the water is 1: 1.3, then adding 8% of sodium chloride of the tare weight, rotating for 30 min, then adjusting the pH value of bath liquid to 3.0 by using a formic acid solution, and continuing rotating for 30 min; adding hydrotalcite-like nano tanning agent with the weight of 8 percent of the tare weight prepared according to the preparation method into the bath lotion, rotating for 5 hours, then adjusting the pH value of the bath lotion to 5.0 by using sodium bicarbonate solution, and continuing rotating for 30 min; stopping the drum, standing for 24 h, rotating for 30 min the next day, and washing with water.
Referring to FIG. 1, 0 in FIG. 1#Is pure crust leather 1#Examples 1 and 2#Examples 2 and 3#In example 3, the shrinkage temperature of the leather tanned by the hydrotalcite-like nano tanning agent prepared in the example can reach over 75 ℃.
After pickled skins with the same mass and the same positions are tanned by a hydrotalcite-like nano tanning agent, natural clay with negative charges on the surface and synthetic clay respectively, the wet finishing procedure shown in the table 1 is firstly carried out, and then the absorbance of the dye before and after dyeing is measured, so that the dyeing rate of the pickled skins is calculated. The dye uptake can be obtained from the following formula:
R=C
0
-C/C
0
=A
0
-A/A
0
wherein R is the dye-uptake of the dye,C 0 is the concentration of the dye liquor before dyeing,Cis the concentration of the dye liquor after dyeing,A 0 is the absorbance of the dye solution before dyeing,Ais the absorbance of the dyed dye solution.
Table 1: hydrotalcite-like nano tanning agent, natural clay with negative charges on surface and wet finishing process of synthetic clay
| Procedure (ii) | Chemical material | Amount/% of | Temperature/. degree.C | Time/min | Remarks for note |
| Washing with water | Water (W) | 300 | At normal temperature | 10 | Liquid discharge |
| Retanning and dyeing | Water (W) | 150 | 30 | ||
| Acrylic acid retanning agent | 12 | 10 | |||
| |
3 | 90 | Liquid discharge | ||
| Fixing | Water (W) | 150 | 45 | 10 | |
| Formic acid | 1.5~2 | 20*3 | pH value of 4.0-4.5, and discharging liquid | ||
| Fatliquoring | Water (W) | 150 | 45 | ||
| NCS lecithin fatting agent | 12 | 90 | |||
| Fixation | Formic acid | 2.0 | 20*3 | pH is 3.5, and the product is washed out of the drum |
The data in figure 2 are obtained through calculation, and the dye uptake of the hydrotalcite-like nano tanning agent is 82.41%, which is higher than that of natural clay and synthetic clay with negative charges, so that the hydrotalcite-like nano tanning agent prepared by the invention can promote the absorption and utilization of anionic dyeing and finishing chemicals such as dye, fatting agent and the like in wet operation after tanning, and the finished leather has good dyeing uniformity and softness.
Claims (5)
1. A tanning method using a hydrotalcite-like nano-tanning agent having a layered structure, characterized in that:
firstly, adding softened skin and water into a rotary drum, wherein the mass ratio of the softened skin to the water is 1: 1-1.5, then adding 7% -8% of sodium chloride of the weight of the skin, rotating for 30 min, then adjusting the pH value of bath liquid to 2.5-3.5 by using a formic acid solution, and continuing rotating for 30 min; then adding a hydrotalcite-like nano tanning agent with the weight of 0.5-8% of the tare weight, rotating for 3-8 hours, then adjusting the pH value of the bath liquid to 4.0-6.0 by using a sodium bicarbonate solution, and continuing rotating for 30 min; stopping the drum, standing for 24 h, rotating for 30 min the next day, and washing with water;
the preparation method of the hydrotalcite-like nano tanning agent with the layered structure comprises the following steps:
respectively mixing nitrates of magnesium, aluminum and X with water to prepare a solution A, wherein X is one of chromium, iron, zirconium and zinc, and the molar ratio of magnesium to aluminum to X is 20: 9-5: 1-5, mixing sodium carbonate and water to prepare a solution B, and mixing sodium hydroxide and water to prepare a solution C; and (3) simultaneously dripping the solution A and the solution C into the solution B under the stirring condition of 300 r/min, crystallizing at 80 ℃ for 10 hours after dripping is finished, and centrifuging and drying the obtained precipitate to obtain the hydrotalcite-like nano tanning agent with the layered structure.
2. The tanning method using hydrotalcite-like nano-tanning agent having layered structure according to claim 1, characterized in that:
the quantity concentration of the nitrate radical material of the solution A is 1 mol/L, the quantity concentration of the material of the solution B is 1 mol/L, and the quantity concentration of the material of the solution C is 2 mol/L.
3. The tanning method using hydrotalcite-like nano-tanning agent having layered structure according to claim 2, characterized in that:
the volume ratio of the solution A to the solution B to the solution C is 1: 1: 1.
4. a tanning process using hydrotalcite-like nano-tanning agent with layered structure according to claim 3, characterized in that:
the tanning end point pH value of the tanning method is 4.0-6.0.
5. The tanning method using hydrotalcite-like nano-tanning agent having layered structure according to claim 4, characterized in that:
the mass ratio of formic acid to water in the formic acid solution is 1:10, and the mass ratio of sodium bicarbonate to water in the sodium bicarbonate solution is 1: 10.
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