CN113073159B - Layered hydrotalcite nano tanning agent with self-masking effect and preparation method thereof - Google Patents
Layered hydrotalcite nano tanning agent with self-masking effect and preparation method thereof Download PDFInfo
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- CN113073159B CN113073159B CN202110392476.4A CN202110392476A CN113073159B CN 113073159 B CN113073159 B CN 113073159B CN 202110392476 A CN202110392476 A CN 202110392476A CN 113073159 B CN113073159 B CN 113073159B
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- tanning agent
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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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
Abstract
The invention discloses a layered hydrotalcite nano tanning agent with a self-masking effect and a preparation method thereof, and solves the problem of low chromium absorption rate in the traditional chrome tanning. The technical scheme of the invention is as follows: a preparation method of a layered hydrotalcite nano tanning agent with a self-masking effect comprises the steps of using an organic intercalation agent solution and a mixed salt solution with a molar ratio of divalent metal ions to trivalent chromium metal ions being 2. The method utilizes a coprecipitation method to prepare the organic intercalation layered hydrotalcite nano tanning agent, can effectively improve chromium absorption, reduce the chromium content of the waste liquid, and can effectively solve the problem of environmental pollution caused by the chromium tanning waste liquid. The tanning agent has excellent tanning performance, the shrinkage temperature of tanned crust leather is not less than 85 ℃, and the tensile strength and the tearing strength are obviously improved.
Description
Technical Field
The invention belongs to the field of tanning agents, and particularly relates to a layered hydrotalcite nano tanning agent with a self-masking effect and a preparation method thereof.
Background
The chrome tanned leather has excellent extensibility, flexibility and plumpness, excellent resistance to heat and humidity, acid, alkali and water washing, high resistance to microbes, good raising property, light color, beautiful appearance, good dyeing property and good finishing property. Therefore, the chrome tanning agent is widely applied to leather tanning and is a main method for tanning leather light leather, but only 60% -70% of the conventional chrome tanning can be absorbed, the discharge of chrome tanning waste liquid has harm to the environment and can also cause chrome resource waste, and the chrome resource in China mainly depends on import. Therefore, the absorption and combination amount of chromium are effectively improved, and the preparation of the hydrotalcite nano tanning agent with the self-masking effect is an effective method for solving chromium pollution and effectively utilizing chromium resources.
Hydrotalcite is a Layered Double Hydroxide (LDH) with positive charges on the main layer plates and negative ions between the plates, and has the advantages of good quality, low cost, good thermal stability, environmental protection, etc., and thus has been widely used in the fields of adsorption, catalysis, flame retardation, etc. The chemical composition of the hydrotalcite main body layer, the internal space composition of the laminate, the internal grain size and distribution, and the species and quantity of the interlayer anions can be adjusted. The metal ions and the interlayer anions can be combined with amino groups and carboxyl groups of the collagen to generate ionic bonds or coordination, so that the shrinkage temperature and the humidity and heat resistance stability of the collagen are improved, and the collagen can be used as a tanning agent.
Disclosure of Invention
The invention aims to provide a layered hydrotalcite nano tanning agent with a self-masking effect and a preparation method thereof.
The specific technical scheme of the invention is as follows.
A preparation method of a layered hydrotalcite nano tanning agent with a self-masking effect is characterized in that an organic intercalation agent solution and a mixed salt solution with a molar ratio of divalent metal ions to trivalent chromium metal ions being 2.
The method specifically comprises the following steps:
the method comprises the following steps: weighing 2.0-4.4g of organic intercalator in a beaker, adding 10mL of distilled water, and stirring for dissolving to obtain an organic intercalator solution;
step two: weighing 0.75mol of chromium nitrate and 1.5mol of divalent metal salt powder in a beaker, adding 10mL of distilled water, stirring and dissolving to prepare a mixed salt solution with the molar ratio of divalent metal ions to trivalent chromium metal ions being 2;
step three: slowly dripping the salt solution obtained in the first step and the salt solution obtained in the second step into 300ml of deionized water, and continuously stirring in the process;
step four: after the dropwise addition is finished, adjusting the pH value of the solution to 9.0-10.0 by using 1mol/L NaOH solution, heating the solution to 80-90 ℃ in a water bath, and crystallizing the solution for 8-12 hours under the protection of nitrogen;
step five: washing with deionized water, vacuum-filtering, drying in a 60 deg.C constant temperature drying oven for 24h, and grinding to obtain organic intercalation layered hydrotalcite nano tanning agent.
In the first step, the organic intercalation agent is one or more of sodium citrate powder, itaconic acid powder, sodium tartrate powder and sodium dodecyl sulfate powder.
In the second step, the divalent metal salt is one or a mixture of magnesium nitrate powder, zinc nitrate powder, copper nitrate powder and calcium nitrate powder.
The layered hydrotalcite nano tanning agent with self-masking effect is prepared by the preparation method.
Compared with the prior art, the invention has the beneficial effects that:
1) The method for preparing the organic intercalated layered hydrotalcite nano tanning agent by using the coprecipitation method can effectively improve the chromium absorption, reduce the chromium content of the waste liquid and effectively solve the problem of environmental pollution caused by the chromium tanning waste liquid.
2) According to the invention, the organic intercalation agent is used for replacing the traditional anion intercalation agent, the coprecipitation method is used for preparing the organic intercalation layered hydrotalcite nano tanning agent, the self-masking effect is achieved, the chromium absorption rate is improved, the problem of low chromium absorption rate in the traditional chrome tanning is solved, the chromium resource consumption is reduced, and the biodegradability of the waste liquid is improved. The tanning agent has excellent tanning performance, the shrinkage temperature of tanned crust leather is not less than 85 ℃, and the tensile strength and the tearing strength are obviously improved.
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
The method comprises the following steps: 1.1g of sodium citrate is weighed into a beaker, 10mL of distilled water is added, and the solution is stirred and dissolved to obtain a sodium citrate solution.
Step two: 0.75mol of chromium nitrate and 1.5mol of divalent magnesium nitrate are weighed in a beaker, 10mL of distilled water is added, and the mixture is stirred and dissolved to prepare a mixed salt solution with the molar ratio of divalent metal ions to trivalent chromium metal ions being 2.
Step three: slowly dropping the salt solution in the first step and the salt solution in the second step into 300ml of deionized water, and continuously stirring in the process.
Step four: after the dropwise addition, the pH of the solution is adjusted to 9.0 by using 1mol/L NaOH solution, the solution is heated to 80 ℃ in a water bath, and crystallization is carried out for 8 hours under the protection of nitrogen.
Step five: washing with deionized water until the pH value of the supernatant is neutral, performing suction filtration, drying in a constant-temperature drying oven at 60 ℃ for 24h, and grinding to obtain the sodium citrate intercalated Mg-Cr hydrotalcite nano tanning agent.
Example 2
The method comprises the following steps: 3.1g of sodium tartrate is weighed into a beaker, 10mL of distilled water is added, and the solution is stirred and dissolved to obtain a sodium tartrate solution.
Step two: 0.75mol of chromium nitrate and 1.5mol of divalent magnesium nitrate are weighed in a beaker, 10mL of distilled water is added, and the mixture is stirred and dissolved to prepare a mixed salt solution with the molar ratio of divalent metal ions to trivalent chromium metal ions being 2.
Step three: slowly dropping the salt solution in the first step and the salt solution in the second step into 300ml of deionized water, and continuously stirring in the process.
Step four: after the dropwise addition, the pH of the solution is adjusted to 10.0 by using 1mol/L NaOH solution, the solution is heated to 85 ℃ in a water bath, and crystallization is carried out for 10 hours under the protection of nitrogen.
Step five: washing with deionized water until the pH value of the supernatant is neutral, performing suction filtration, drying in a constant-temperature drying oven at 60 ℃ for 24h, and grinding to obtain the sodium tartrate intercalation Mg-Cr hydrotalcite nano tanning agent.
Example 3
The method comprises the following steps: weighing 2.0g of itaconic acid in a beaker, adding 10mL of distilled water, and stirring to dissolve to obtain an itaconic acid solution.
Step two: 0.75mol of chromium nitrate and 1.5mol of divalent magnesium nitrate are weighed in a beaker, 10mL of distilled water is added, and the mixture is stirred and dissolved to prepare a mixed salt solution with the molar ratio of divalent metal ions to trivalent chromium metal ions being 2.
Step three: slowly dropping the salt solution in the first step and the salt solution in the second step into 300ml of deionized water, and continuously stirring in the process.
Step four: after the dropwise addition, the pH of the solution is adjusted to 9.0 by using 1mol/L NaOH solution, the solution is heated to 90 ℃ in a water bath, and crystallization is carried out for 12 hours under the protection of nitrogen.
Step five: washing with deionized water until the pH value of the supernatant is neutral, performing suction filtration, drying in a constant-temperature drying oven at 60 ℃ for 24h, and grinding to obtain the itaconic acid intercalated Mg-Cr hydrotalcite nano tanning agent.
Example 4
The method comprises the following steps: 3.1g of sodium tartrate is weighed into a beaker, 10mL of distilled water is added, and the mixture is stirred and dissolved to obtain a sodium tartrate solution.
Step two: 0.75mol of chromium nitrate and 1.5mol of copper nitrate trihydrate are weighed in a beaker, 10mL of distilled water is added, and the mixture is stirred and dissolved to prepare a mixed salt solution with the molar ratio of divalent metal ions to trivalent chromium metal ions being 2.
Step three: slowly dropping the salt solution obtained in the first step and the salt solution obtained in the second step into 300ml of deionized water, and continuously stirring in the process.
Step four: after the dropwise addition, the pH of the solution is adjusted to 9.0 by using 1mol/L NaOH solution, the solution is heated to 80 ℃ in a water bath, and crystallization is carried out for 8 hours under the protection of nitrogen.
Step five: washing with deionized water until the pH of the supernatant is neutral, performing suction filtration, drying in a constant-temperature drying oven at 60 ℃ for 24h, and grinding to obtain the sodium tartrate intercalated Cu-Cr hydrotalcite nano tanning agent.
In order to test the tanning performance of the layered hydrotalcite nano tanning agent prepared by the invention, the tanning performance of the layered hydrotalcite nano tanning agent prepared by the embodiment is judged by tanning application experiments. The shrinkage temperature of the sodium citrate intercalated Mg-Cr hydrotalcite nano tanning agent prepared in the embodiment 1 reaches 90 ℃; the shrinkage temperature of the sodium tartrate intercalation Mg-Cr hydrotalcite nano tanning agent prepared in the embodiment 2 and the shrinkage temperature of the itaconic acid intercalation Mg-Cr hydrotalcite nano tanning agent prepared in the embodiment 3 are both over 85 ℃; the shrinkage temperature of the sodium tartrate intercalated Cu-Cr hydrotalcite nano tanning agent prepared in the embodiment 4 is 85 ℃. The physical and mechanical properties of the tanned crust leather can meet the mechanical strength requirements of the leather industry standard QB/T1873-2010 for the vamp of the Chinese light industry and the leather industry standard QB/T1872-2004 for the clothing, and the tanned crust leather has certain practical application value.
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 (4)
1. A preparation method of a layered hydrotalcite nano tanning agent with a self-masking effect is characterized by comprising the following steps:
preparing a layered hydrotalcite nano tanning agent with a self-masking function by using an organic intercalation agent solution and a mixed salt solution with a molar ratio of divalent metal ions to trivalent chromium metal ions of 2;
the organic intercalation agent is one or more of sodium citrate powder, itaconic acid powder, sodium tartrate powder and sodium dodecyl sulfate powder.
2. The preparation method of the self-masking layered hydrotalcite nano-tanning agent according to claim 1, characterized in that:
the method specifically comprises the following steps:
the method comprises the following steps: weighing 2.0-4.4g of organic intercalator in a beaker, adding 10mL of distilled water, and stirring for dissolving to obtain an organic intercalator solution;
step two: weighing 0.75mol of chromium nitrate and 1.5mol of divalent metal salt powder in a beaker, adding 10mL of distilled water, stirring and dissolving to prepare a mixed salt solution with the molar ratio of divalent metal ions to trivalent chromium metal ions being 2;
step three: slowly dripping the salt solution obtained in the first step and the salt solution obtained in the second step into 300ml of deionized water, and continuously stirring in the process;
step four: after the dropwise addition is finished, adjusting the pH value of the solution to 9.0-10.0 by using 1mol/L NaOH solution, heating the solution to 80-90 ℃ in a water bath, and crystallizing the solution for 8-12 hours under the protection of nitrogen;
step five: washing with deionized water, vacuum-filtering, drying in a 60 deg.C constant temperature drying oven for 24h, and grinding to obtain organic intercalation layered hydrotalcite nano tanning agent.
3. The preparation method of the layered hydrotalcite nano tanning agent with self-masking effect according to claim 2, characterized in that:
in the second step, the divalent metal salt is one or more of magnesium nitrate powder, zinc nitrate powder, copper nitrate powder and calcium nitrate powder.
4. A layered hydrotalcite nano-tanning agent having self-masking effect prepared by the preparation method according to any one of claims 1 to 3.
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| CN114350860A (en) * | 2022-01-20 | 2022-04-15 | 陕西科技大学 | Non-chromium tanning process based on hydrotalcite and zirconium sulfate |
| CN116219086B (en) * | 2023-02-07 | 2024-01-19 | 陕西科技大学 | Flame-retardant ecological automobile leather and production process thereof |
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| CN110510607A (en) * | 2019-08-23 | 2019-11-29 | 陕西科技大学 | The polyamide modified scrap leather bits of amine-terminated hyperbrancedization are used as graphene oxide monolithic layer small size dispersing agent and its preparation method and application |
| CN111004877A (en) * | 2019-12-30 | 2020-04-14 | 陕西科技大学 | Nano tanning agent based on structure memory effect and preparation method and application thereof |
| CN112094962A (en) * | 2020-09-11 | 2020-12-18 | 陕西科技大学 | Method for preparing chromium-containing hydrotalcite nano tanning agent by using chrome tanning waste liquid |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110510607A (en) * | 2019-08-23 | 2019-11-29 | 陕西科技大学 | The polyamide modified scrap leather bits of amine-terminated hyperbrancedization are used as graphene oxide monolithic layer small size dispersing agent and its preparation method and application |
| CN111004877A (en) * | 2019-12-30 | 2020-04-14 | 陕西科技大学 | Nano tanning agent based on structure memory effect and preparation method and application thereof |
| CN112094962A (en) * | 2020-09-11 | 2020-12-18 | 陕西科技大学 | Method for preparing chromium-containing hydrotalcite nano tanning agent by using chrome tanning waste liquid |
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