CN114350860A - Non-chromium tanning process based on hydrotalcite and zirconium sulfate - Google Patents
Non-chromium tanning process based on hydrotalcite and zirconium sulfate Download PDFInfo
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- CN114350860A CN114350860A CN202210066790.8A CN202210066790A CN114350860A CN 114350860 A CN114350860 A CN 114350860A CN 202210066790 A CN202210066790 A CN 202210066790A CN 114350860 A CN114350860 A CN 114350860A
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- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C3/00—Tanning; Compositions for tanning
- C14C3/02—Chemical tanning
- C14C3/04—Mineral tanning
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Abstract
The invention relates to a chromium-free tanning process based on hydrotalcite and zirconium sulfate, which comprises the following steps: firstly, adding pickled Chinese wampee into a rotary drum, adding a certain amount of water, wherein the mass ratio of pickled Chinese wampee to water is 1: 1, then adding sodium chloride with the mass of 8 percent of the tare weight, and adjusting the pH of the solution to 2.0-3.5 by using a formic acid solution; adding hydrotalcite with the weight of 1-8% of the tare weight into the bath lotion, and rotating for 1-5 hours; adding Zr (SO) with the mass of 1-8% of the tare weight into the bath liquid4)2Rotating for 2-8 h, then adjusting the pH of the solution to 3.5-5.0 by using a sodium bicarbonate solution, and rotating for 30 min; standing overnight, rotating for 30 min the next day, and washing with water. The non-chrome tanning process avoids the use of heavy metal chromium, the shrinkage temperature of the obtained crust leather can reach more than 90 ℃, and the leather surface is white, flat and fine. In addition, the use of the hydrotalcite can promote the absorption and utilization of zirconium sulfate, reduce the zirconium content in waste liquid and improve the softness of leather.
Description
Technical Field
The invention belongs to the field of leather tanning technology, and relates to a chromium-free tanning technology based on hydrotalcite and zirconium sulfate.
Background
The most mature tanning process in the leather industry today is chrome tanning, which has been dominant in the global leather industry because of the good overall properties imparted to leather, but traditional chrome tanning is prone to oxidation of cr (iii) to cr (vi) with a potential carcinogenic risk during tanning and produces chromium-containing wastewater that is difficult to handle during tanning. Because of irreversible damage of chrome tanning to the environment and shortage of chrome resources in China, how to avoid the use of chrome tanning agents, reduce pollution caused by chrome tanning and realize clean tanning becomes one of research hotspots in the leather industry.
Chrome-free tanning agents currently under study can be divided into five major categories: chrome-free metal tanning agent, aldehyde tanning agent, synthetic organic tanning agent, plant tanning agent and organic-inorganic combined tanning agent. The zirconium tanned leather has good filling property, compact grain surface, good wear resistance, good storage property, sweat resistance and mildew resistance, and the shrinkage temperature of the zirconium tanned leather is second to that of the chrome tanned leather; but the poor penetration makes the finished leather compact plate hard and the softness poor. The hydrotalcite is a layered double-hydroxyl composite metal hydroxide formed by orderly assembling interlayer anions and laminates with positive charges, and has the characteristics of adjustable composition of metal ions of a main laminate, adjustable charge density and distribution of the main laminate and the like. It is worth noting that hydrotalcite has good adsorption capacity to heavy metals, and leather-making researchers have used hydrotalcite in combination with a small amount of chromium powder for leather tanning, and the adsorption capacity of hydrotalcite to heavy metals is utilized to reduce the chromium content in waste liquid. But does not completely solve the pollution problem of chrome tanning.
Disclosure of Invention
The invention aims to provide a chromium-free tanning process based on hydrotalcite and zirconium sulfate, which can improve the shrinkage temperature of leather to be more than 90 ℃ when being applied to leather tanning, avoid the use of a chromium tanning agent and realize clean tanning.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a non-chrome tanning process based on hydrotalcite and zirconium sulfate comprises the following steps:
step one, pretanning:
firstly, adding pickled Chinese wampee into a rotary drum, and adding water, wherein the mass ratio of pickled Chinese wampee to water is 1: 1, then adding sodium chloride with the mass of 8 percent of the tare weight, and adjusting the pH of the solution to 2.0-3.5 by using an acid solution; adding hydrotalcite into the bath lotion, and performing rotary pretanning;
step two, tanning:
adding Zr (SO) to the bath4)2Rotating and tanning, then adjusting the pH value of the solution to 3.5-5.0 by using a sodium bicarbonate solution, and rotating for 30 min; standing overnight, rotating for 30 min the next day, and washing with water.
The mass fraction of the acid solution in the first step is 10%.
The consumption of the hydrotalcite is 1% -8% of the mass of the acid skin.
The pre-tanning time in the first step is 1-5 h.
Zr (SO) in the tanning process4)2The dosage of the ZrO 2 zirconia ceramic is 1-8 percent of the mass of the pickled Chinese cabbage skin (by using ZrO)2Meter).
And the tanning time in the second step is 2-8 h.
The mass fraction of the sodium bicarbonate solution is 10%.
Compared with the prior art, the invention has the following advantages and effects:
the invention provides a chromium-free tanning process based on hydrotalcite and zirconium sulfate. The non-chrome tanning process avoids the use of heavy metal chromium, the shrinkage temperature of the obtained crust leather can reach more than 90 ℃, and the leather surface is white, flat and fine. The use of the hydrotalcite can promote the absorption and utilization of zirconium sulfate, reduce the zirconium content in waste liquid and improve the softness of leather.
Detailed Description
The present invention is further illustrated by the following specific examples. These examples are intended to illustrate the invention and are not intended to limit the scope of the invention. The implementation conditions used in the examples can be further adjusted according to the specific experimental environment, and the implementation conditions not mentioned are generally the conditions in routine experiments.
Example 1:
the method comprises the following steps:
pre-tanning: firstly, 100 g of pickled Chinese cabbage skin is added into a rotary drum, 100 g of water is added, then 8 g of sodium chloride is added, and formic acid solution (the mass fraction is 10%) is used for adjusting the pH value of the solution to 3; 5 g of hydrotalcite was added to the bath and rotated for 1 h.
Step two:
tanning: zr (SO) with a mass of 9.2 g tare was added to the bath4)2Rotating for 5 h, then adjusting the pH of the solution to 4 by using a sodium bicarbonate solution (the mass fraction is 10 percent), and rotating for 30 min; standing overnight, rotating for 30 min the next day, and washing with water.
Example 2:
the method comprises the following steps:
pre-tanning: firstly, 100 g of pickled Chinese cabbage skin is added into a rotary drum, 100 g of water is added, then 8 g of sodium chloride is added, and formic acid solution (the mass fraction is 10%) is used for adjusting the pH value of the solution to 3; 5 g of hydrotalcite was added to the bath and rotated for 1 h.
Step two:
tanning: zr (SO) with a mass of 11.5 g tare was added to the bath4)2Rotating for 4 h, then adjusting the pH of the solution to 4 by using a sodium bicarbonate solution (the mass fraction is 10 percent), and rotating for 30 min; standing overnight, rotating for 30 min the next day, and washing with water.
Example 3:
the method comprises the following steps:
pre-tanning: firstly, 100 g of pickled Chinese cabbage skin is added into a rotary drum, 100 g of water is added, then 8 g of sodium chloride is added, and formic acid solution (the mass fraction is 10%) is used for adjusting the pH value of the solution to 3; adding 4g of hydrotalcite into the bath solution, and rotating for 1 h.
Step two:
tanning: zr (SO) with a mass of 13.8 g tare was added to the bath4)2Rotating for 6 h, then adjusting the pH of the solution to 3.5 by using a sodium bicarbonate solution (the mass fraction is 10 percent), and rotating for 30 min; standing overnight, rotating for 30 min the next day, and washing with water.
Example 4:
the method comprises the following steps:
pre-tanning: firstly, 100 g of pickled Chinese cabbage skin is added into a rotary drum, 100 g of water is added, then 8 g of sodium chloride is added, and formic acid solution (the mass fraction is 10%) is used for adjusting the pH value of the solution to 3; 5 g of hydrotalcite was added to the bath and rotated for 1 h.
Step two:
tanning: zr (SO) with a mass of 13.8 g tare was added to the bath4)2Rotating for 4 h, then adjusting the pH of the solution to 3.5 by using a sodium bicarbonate solution (the mass fraction is 10 percent), and rotating for 30 min; standing overnight, rotating for 30 min the next day, and washing with water.
The properties of the leather are tested according to the national standard or standard test method (shrinkage temperature: GB 4689.8-1984; softness: GB/T39371-. With 11.5 g Zr (SO)4)2Tanning alone is a comparative example, and the properties of the tannage using a non-chrome tanning process based on hydrotalcite and zirconium sulphate are as follows:
| comparative example | Example 2 | |
| Shrinkage temperature (. degree.C.) | 82.3 | 90.2 |
| Softness (mm) | 3.6 | 5.4 |
In the above embodiments, embodiment 2 is the most preferred embodiment.
The invention is not limited to the examples, and any equivalent changes to the technical solution of the invention by a person skilled in the art after reading the description of the invention are covered by the claims of the invention.
Claims (7)
1. A non-chrome tanning process based on hydrotalcite and zirconium sulfate is characterized by comprising the following steps:
step one, pretanning:
firstly, adding pickled Chinese wampee into a rotary drum, and adding water, wherein the mass ratio of pickled Chinese wampee to water is 1: 1, then adding sodium chloride with the mass of 8 percent of the tare weight, and adjusting the pH of the solution to 2.0-3.5 by using an acid solution; adding hydrotalcite into the bath lotion, and performing rotary pretanning;
step two, tanning:
adding Zr (SO) to the bath4)2Rotational tanningThen, adjusting the pH of the solution to 3.5-5.0 by using a sodium bicarbonate solution, and rotating for 30 min; standing overnight, rotating for 30 min the next day, and washing with water.
2. The chrome-free tanning process based on hydrotalcite and zirconium sulfate according to claim 1, characterized in that:
the mass fraction of the acid solution in the first step is 10%.
3. The chrome-free tanning process based on hydrotalcite and zirconium sulfate according to claim 2, characterized in that:
the consumption of the hydrotalcite is 1% -8% of the mass of the acid skin.
4. A non-chrome tanning process based on hydrotalcite and zirconium sulphate according to claim 3, characterized in that:
the pre-tanning time in the first step is 1-5 h.
5. The chrome-free tanning process based on hydrotalcite and zirconium sulfate according to claim 4, characterized in that:
zr (SO) in the tanning process4)2The dosage of the ZrO 2 zirconia ceramic is 1-8 percent of the mass of the pickled Chinese cabbage skin (by using ZrO)2Meter).
6. A non-chrome tanning process based on hydrotalcite and zirconium sulphate according to claim 5, characterized in that:
and the tanning time in the second step is 2-8 h.
7. The chrome-free tanning process based on hydrotalcite and zirconium sulfate according to claim 6, characterized in that:
the mass fraction of the sodium bicarbonate solution is 10%.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116555500A (en) * | 2023-05-12 | 2023-08-08 | 陕西科技大学 | Chromium-free tanning process based on calcined hydrotalcite and zirconium sulfate |
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| CN113073159A (en) * | 2021-04-13 | 2021-07-06 | 陕西科技大学 | Layered hydrotalcite nano tanning agent with self-masking effect and preparation method thereof |
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- 2022-01-20 CN CN202210066790.8A patent/CN114350860A/en active Pending
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| CN110358877A (en) * | 2019-06-04 | 2019-10-22 | 陕西科技大学 | Acrylic/hydrotalcite-like nano tanning agent with layer structure and preparation method thereof and tannage |
| CN111118235A (en) * | 2019-12-27 | 2020-05-08 | 温州大学 | Method for tanning leather by external electric field |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116555500A (en) * | 2023-05-12 | 2023-08-08 | 陕西科技大学 | Chromium-free tanning process based on calcined hydrotalcite and zirconium sulfate |
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