CN112094962B - Method for preparing chromium-containing hydrotalcite nano tanning agent by using chrome tanning waste liquid - Google Patents
Method for preparing chromium-containing hydrotalcite nano tanning agent by using chrome tanning waste liquid Download PDFInfo
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- CN112094962B CN112094962B CN202010953082.7A CN202010953082A CN112094962B CN 112094962 B CN112094962 B CN 112094962B CN 202010953082 A CN202010953082 A CN 202010953082A CN 112094962 B CN112094962 B CN 112094962B
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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
- C14C3/06—Mineral tanning using chromium compounds
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Abstract
The invention discloses a method for preparing a chromium-containing hydrotalcite nano tanning agent by using chrome tanning waste liquid, and aims to solve the problem that the chrome tanning waste liquid pollutes the environment. The technical scheme of the invention is as follows: a method for preparing chromium-containing hydrotalcite nano tanning agent by using chromium tanning waste liquid is characterized in that the chromium tanning waste liquid is used, a coprecipitation method is adopted, and the molar ratio of divalent metal ions to chromium ions is controlled to prepare the chromium-containing hydrotalcite nano tanning agent. The chrome-containing hydrotalcite nano tanning agent prepared by the invention has excellent tanning performance, the shrinkage temperature of tanned crust leather is not less than 85 ℃, the tensile strength and the tearing strength are both increased, and the biodegradability of tanning waste liquid using chrome-containing hydrotalcite is improved.
Description
Technical Field
The invention belongs to the field of tanning agents, and particularly relates to a method for preparing a chromium-containing hydrotalcite nano tanning agent by using chrome tanning waste liquid.
Background
The chrome tanning agent is widely applied to the tanning industry due to excellent tanning performance, but the chrome tanning waste liquid has harm to the environment, so that the effective utilization of the chrome tanning waste liquid is one of the research hotspots in the tanning industry. The chrome tanning waste liquid has complex components and contains a large amount of heavy metal Cr3 +And contains various inorganic ions and organic acids, e.g. SO4 2-、Cl-、Na+、K+Formic acid, acetic acid and the like, and proteins, animal fats and oils and the like decomposed from the collagen skin, have high treatment difficulty and high cost.
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. The amount of the wastewater containing chromium generated by the tanning industry of China is about 5000-2O3In terms of) 1000-5000mg/L, and the existing chromium recycling method has the defects of high cost, complex operation, secondary pollution and the like.
Disclosure of Invention
The invention mainly aims to provide a method for preparing a chromium-containing hydrotalcite nano tanning agent by using chrome tanning waste liquid, which solves the problem that the chrome tanning waste liquid pollutes the environment.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a method for preparing a chromium-containing hydrotalcite nano tanning agent by using chromium tanning waste liquid adopts a coprecipitation method to control the molar ratio of divalent metal ions to chromium ions, so as to prepare the chromium-containing hydrotalcite nano tanning agent.
The method specifically comprises the following steps:
the method comprises the following steps: weighing 0.02mol of anhydrous sodium carbonate into a beaker, adding 100mL of distilled water, and stirring for dissolving to obtain a sodium carbonate solution;
step two: weighing 45.6-228mL of the chrome tanning waste liquid after suction filtration, adding 0.2-9g of divalent nitrate, stirring and dissolving to prepare a mixed salt solution with the molar ratio of divalent metal ions to trivalent chromium metal ions being 2: 1;
step three: slowly dripping the mixed salt solution obtained in the step two into a beaker filled with a sodium carbonate solution at the temperature of 30 ℃, 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, stirring the solution for 1 hour, stopping stirring the solution, and heating and refluxing the solution for 8 hours;
step five: and then 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 chromium-containing hydrotalcite nano tanning agent.
In the second step, the chromium content in the chrome tanning waste liquid is Cr2O3The concentration is 1000-5000 mg/L.
In the second step, the divalent nitrate is one or more of zinc nitrate hexahydrate powder, magnesium nitrate hexahydrate powder, calcium nitrate tetrahydrate powder and copper nitrate trihydrate powder.
Compared with the prior art, the invention has the beneficial effects that:
the method for preparing the chromium-containing hydrotalcite nano tanning agent by using the chrome tanning waste liquid can effectively solve the problem of environmental pollution caused by the chrome tanning waste liquid. The hydrotalcite tanning agent prepared by using the chrome tanning waste liquid can reduce the chromium pollution and effectively recover the chromium. The prepared chromium-containing hydrotalcite nano tanning agent has excellent tanning performance, the shrinkage temperature of tanned crust leather is not less than 85 ℃, the tensile strength and the tearing strength are both increased, and the biodegradability of tanning waste liquid using chromium-containing hydrotalcite is 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.
A method for preparing chromium-containing hydrotalcite nano tanning agent by using chromium-containing waste liquid specifically comprises the following steps:
the method comprises the following steps: weighing 0.02mol of anhydrous sodium carbonate into a beaker, adding 100mL of distilled water, and stirring for dissolving to obtain a sodium carbonate solution;
step two: weighing 45.6-228mL of the chrome tanning waste liquid after suction filtration, adding 0.2-9g of divalent metal ions, stirring and dissolving to prepare a mixed salt solution with the molar ratio of the divalent metal ions to the trivalent metal ions being 2: 1;
step three: at 30 ℃, respectively and slowly dripping the mixed salt solution into a beaker filled with a sodium carbonate solution in sequence, 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, stirring the solution for 1 hour, stopping stirring the solution, and heating and refluxing the solution for 8 hours;
step five: and then 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 for later use.
Preferably, in the second step, the concentration of the chrome tanning waste liquid is 1000-2O3Meter).
Preferably, in step three, the divalent metal ions are: zinc nitrate hexahydrate powder, magnesium nitrate hexahydrate powder, calcium nitrate tetrahydrate powder and copper nitrate trihydrate powder.
Example 1
The method comprises the following steps: 0.02mol of anhydrous sodium carbonate is weighed in a beaker, 100mL of distilled water is added, and the solution is stirred and dissolved to obtain a sodium carbonate solution.
Step two: measuring 100mL (Cr) of the chrome tanning waste liquid after suction filtration2O31500 mg/L), 1.17g of zinc nitrate hexahydrate is addedAnd stirring and dissolving the powder to prepare a mixed salt solution with the molar ratio of the divalent metal ions to the trivalent metal ions being 2: 1.
Step three: at 30 ℃, the mixed salt solution is slowly dropped into a beaker filled with sodium carbonate solution, and is continuously stirred in the process.
Step four: after the dropwise addition, the pH of the solution was adjusted to 9.0 with 1mol/L NaOH solution, heated to 80 ℃ in a water bath, stirred for 1h, stopped stirring, and heated under reflux for 8 h.
Step five: and then 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 for later use.
Example 2
The method comprises the following steps: 0.02mol of anhydrous sodium carbonate is weighed in a beaker, 100mL of distilled water is added, and the solution is stirred and dissolved to obtain a sodium carbonate solution.
Step two: measuring 100mL (Cr) of the chrome tanning waste liquid after suction filtration2O33500 mg/L), adding 2.23g of copper nitrate trihydrate powder, stirring and dissolving to prepare a mixed salt solution with the molar ratio of the divalent metal ions to the trivalent metal ions being 2: 1.
Step three: at 30 ℃, the mixed salt solution is slowly dropped into a beaker filled with sodium carbonate solution, and is continuously stirred in the process.
Step four: after the dropwise addition, the pH of the solution was adjusted to 10.0 with 1mol/L NaOH solution, heated to 85 ℃ in a water bath, stirred for 1h, stopped stirring, and heated under reflux for 8 h.
Step five: and then 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 for later use.
Example 3
The method comprises the following steps: 0.02mol of anhydrous sodium carbonate is weighed in a beaker, 100mL of distilled water is added, and the solution is stirred and dissolved to obtain a sodium carbonate solution.
Step two: measuring 100mL (Cr) of the chrome tanning waste liquid after suction filtration2O32500 mg/L), adding 1.69g of magnesium nitrate hexahydrate powder, stirring and dissolving to prepare the molar ratio of divalent metal ions to trivalent metal ionsIs a mixed salt solution of 2: 1.
Step three: at 30 ℃, the mixed salt solution is slowly dropped into a beaker filled with sodium carbonate solution, and is continuously stirred in the process.
Step four: after the dropwise addition, the pH of the solution was adjusted to 9.0 with 1mol/L NaOH solution, heated to 90 ℃ in a water bath, stirred for 1h, stopped stirring, and heated under reflux for 8 h.
Step five: and then 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 for later use.
In order to test the tanning performance of the chromium-containing hydrotalcite nano tanning agent prepared by the invention, the inventor conducts tanning application experiments on the chromium-containing hydrotalcite nano tanning agent and judges the tanning performance of the chromium-containing hydrotalcite nano tanning agent. The shrinkage temperature of the Cu-Cr-LDH reaches 91.5 ℃; Zn-Cr-LDH and Mg-Cr-LDH, wherein the shrinkage temperature is over 85 ℃; Ca-Cr-LDH is relatively low with a shrinkage temperature of 66.0 ℃. 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 and the leather industry standard QB/T1872-2004 for the clothing in the China light industry, 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 (3)
1. A method for preparing chromium-containing hydrotalcite nano tanning agent by using chrome tanning waste liquid is characterized by comprising the following steps:
controlling the molar ratio of divalent metal ions to chromium ions by adopting a coprecipitation method to prepare the chromium-containing hydrotalcite nano tanning agent;
the method specifically comprises the following steps:
the method comprises the following steps: weighing 0.02mol of anhydrous sodium carbonate into a beaker, adding 100mL of distilled water, and stirring for dissolving to obtain a sodium carbonate solution;
step two: weighing 45.6-228mL of the chrome tanning waste liquid after suction filtration, adding 0.2-9g of divalent nitrate, stirring and dissolving to prepare a mixed salt solution with the molar ratio of divalent metal ions to trivalent chromium metal ions being 2: 1;
step three: slowly dripping the mixed salt solution obtained in the step two into a beaker filled with a sodium carbonate solution at the temperature of 30 ℃, 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, stirring the solution for 1 hour, stopping stirring the solution, and heating and refluxing the solution for 8 hours;
step five: and then 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 chromium-containing hydrotalcite nano tanning agent.
2. The method for preparing the chromium-containing hydrotalcite nano tanning agent by using the chrome tanning waste liquid according to the claim 1, which is characterized in that:
in the second step, the chromium content in the chrome tanning waste liquid is Cr2O3The concentration is 1000-5000 mg/L.
3. The method for preparing the chromium-containing hydrotalcite nano tanning agent by using the chrome tanning waste liquid according to the claim 2, which is characterized in that:
in the second step, the divalent nitrate is one or more of zinc nitrate hexahydrate powder, magnesium nitrate hexahydrate powder, calcium nitrate tetrahydrate powder and copper nitrate trihydrate powder.
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| CN113073158B (en) * | 2021-04-13 | 2022-06-03 | 陕西科技大学 | Method for preparing organic intercalation chromium-containing hydrotalcite nano tanning agent by using chrome tanning waste liquid |
| CN113073159B (en) * | 2021-04-13 | 2023-02-14 | 陕西科技大学 | Layered hydrotalcite nano tanning agent with self-masking effect and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104152599A (en) * | 2014-08-01 | 2014-11-19 | 河南博奥皮业有限公司 | Recycling method of chrome tanning waste liquor and matching device thereof |
| CN104498648A (en) * | 2014-12-17 | 2015-04-08 | 四川大学 | Method for preparing chrome tanning agent from waste chrome tanning liquid |
| 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 |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104152599A (en) * | 2014-08-01 | 2014-11-19 | 河南博奥皮业有限公司 | Recycling method of chrome tanning waste liquor and matching device thereof |
| CN104498648A (en) * | 2014-12-17 | 2015-04-08 | 四川大学 | Method for preparing chrome tanning agent from waste chrome tanning liquid |
| 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 |
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