CN109628662B - Preparation and application of modified tannic acid chromium tanning auxiliary - Google Patents

Preparation and application of modified tannic acid chromium tanning auxiliary Download PDF

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CN109628662B
CN109628662B CN201811613224.4A CN201811613224A CN109628662B CN 109628662 B CN109628662 B CN 109628662B CN 201811613224 A CN201811613224 A CN 201811613224A CN 109628662 B CN109628662 B CN 109628662B
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alkaline substance
rotating
modified
tannic acid
water
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CN109628662A (en
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张辉
陈博
强西怀
俞力栋
王新科
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Shaanxi University of Science and Technology
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Shaanxi University of Science and Technology
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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
    • C14C1/00—Chemical treatment prior to tanning
    • 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
    • C14C1/00—Chemical treatment prior to tanning
    • C14C1/08—Deliming; Bating; Pickling; Degreasing
    • 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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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Treatment And Processing Of Natural Fur Or Leather (AREA)

Abstract

A preparation and application of a modified tannic acid chrome tanning auxiliary agent are disclosed, wherein the preparation method comprises the steps of dissolving a polyhydroxy phenolic compound in a first solvent, and neutralizing with an alkaline substance; then dissolving chloroacetic acid in a second solvent, and neutralizing with an alkaline substance; adding the two solutions into a flask simultaneously, and dropwise adding an alkaline substance aqueous solution in several times until the pH value is 7 to obtain a modified tannic acid chrome tanning auxiliary agent; the application method comprises the steps of firstly putting delimed, softened and washed liming leather into a rotary drum, adding water and the modified chromium tannate tanning auxiliary agent, and then rotating; adjusting pH to 8.5-9.0 with alkaline substance, and rotating; adding acidic substance to adjust pH of the bath liquid to 2.5-3.0, and rotating; then adding chromium powder for rotation; adding sodium bicarbonate into water solution, adjusting pH to 3.8-4.0, rotating, and adding hot water; stopping the drum for one night, taking out the drum the next day, and setting up and standing; the invention improves the absorptivity of the chrome tanning agent and has little harm to the environment.

Description

Preparation and application of modified tannic acid chromium tanning auxiliary
Technical Field
The invention relates to the technical field of chrome tanning auxiliary agents, in particular to a preparation method and application of a modified tannic acid chrome tanning auxiliary agent.
Background
The chrome tanning can endow leather with good physical and mechanical properties, such as smooth and fine grain surface of finished leather, high Ts, high tensile strength, soft finished leather and water washing resistance. The operation process is simple, the cost is low, and the chrome tanning agent is favored by a plurality of tanneries, but the absorption rate of chrome is low, a large part of chrome is not utilized and is directly discharged in the environment, trivalent chromium ions are easily oxidized into hexavalent chromium ions in the natural environment, the environment is seriously polluted, and only 3000 tons of chrome are discharged along with waste water every year in China, so the chrome tanning agent is produced at will.
However, most of the current research on chrome tanning aids is based on the aldehyde series, and the use of such chrome tanning aids is limited due to environmental pollution. The tannin belongs to a natural product, and the chrome tanning auxiliary developed based on the tannin belongs to an environment-friendly reagent, so that the harm to the environment is small, and no related literature is disclosed at present.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide the preparation and the application of the modified tannic acid chrome tanning auxiliary, improve the absorptivity of the chrome tanning agent and have small harm to the environment.
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of a modified tannic acid chrome tanning auxiliary agent comprises the following steps:
1) dissolving 25-34 parts of polyhydroxy phenolic compound in 120-160 parts of first solvent, and neutralizing with alkaline substance X at 0-5 ℃ to ensure that the pH value is 7 +/-0.5;
2) dissolving 11-22 parts of chloroacetic acid in 25-35 parts of second solvent, and neutralizing with an alkaline substance X at 0-5 ℃ to ensure that the pH value is 7 +/-0.5;
3) and (2) adding the two solutions into a 500mL four-neck flask, heating to 50 ℃, dropwise adding an alkaline substance Y aqueous solution with the same mole as chloroacetic acid for 5 times, wherein the mass fraction of the alkaline substance Y aqueous solution is 30%, dropwise adding the alkaline substance Y aqueous solution once every 30min, heating the system to 60 ℃ after the last dropwise adding is finished, carrying out heat preservation reaction, testing the pH, and stopping the reaction until the pH is 7 to obtain the modified tannic acid chrome tanning aid, wherein the parts are parts by mass.
The polyhydroxy phenolic compound is tannic acid.
The chloroacetic acid is monochloroacetic acid.
The first solvent and the second solvent are deionized water.
The alkaline substance X is anhydrous sodium carbonate.
The alkaline substance Y is sodium hydroxide.
The application method of the modified tannic acid chrome tanning auxiliary agent comprises the following steps:
1) pre-tanning: putting the delimed and softened water washed liminated leather into a rotary drum, adding water accounting for 100 percent of the weight of the liminated leather and a modified tannic acid chromium tanning auxiliary agent accounting for 15 percent of the weight of the liminated leather, and rotating for 1 to 2 hours at the temperature of between 20 and 25 ℃; adjusting the pH value to 8.5-9.0 within 1h by using an alkaline substance Z diluted by 10 times of water, and continuously rotating for 1-2 h;
2) pickling: adding acidic substances diluted by 10 times of water into the bath liquid in the step 1), adjusting the pH value of the bath liquid to 2.5-3.0 within 1h, and continuously rotating for 1-2h at 20-25 ℃;
3) chrome tanning: adding chromium powder accounting for 5-6% of the weight of the ash soaking skin, wherein Cr is contained in the chromium powder2O3The content is 25 percent, and the temperature is changed for 2 hours at 20-25 ℃; adding baking soda 1.8-2.2% of the weight of the ash soaking skin and preparing into 10% aqueous solution, adding at 6 times at intervals of 20min, adjusting pH to 3.8-4.0, rotating for 1h, adding 150% hot water at 40 deg.C, and rotating for 2 h; stopping the drum, standing overnight, rotating for 0.5h the next day, taking out the drum, and standing.
The ash dipping skin is sheepskin, cowhide or pigskin.
The alkaline substance Z is baking soda or sodium carbonate.
The acidic substance is formic acid or sulfuric acid.
The invention has the beneficial effects that:
the method adopts polyhydroxy phenolic compound tannic acid to react with monochloroacetic acid to obtain the chrome tanning auxiliary agent of the modified tannic acid; the chrome tanning auxiliary agent using the modified tannic acid is added during pickling, so that the adjustment of a tanning process can be omitted, and the absorption of collagen on the chrome tanning agent can be greatly improved. The shrinkage temperature of the prepared wet blue leather can reach more than 110 ℃, and Cr in waste liquid2O3The content of (a) is reduced to below 0.65 g/L. The modified tannic acid chrome tanning auxiliary agent can improve the absorptivity of a chrome tanning agent and has small harm to the environment.
Detailed Description
The present invention is described in detail below with reference to examples, which are provided for further illustration of the present invention and are not to be construed as limiting the scope of the present invention.
Embodiment one, a preparation method of a modified tannic acid chrome tanning auxiliary agent, comprising the following steps:
1) dissolving 25g tannic acid in 120g deionized water, and neutralizing with anhydrous sodium carbonate at 0 deg.C to pH 6.5;
2) 11g of monochloroacetic acid are dissolved in 25g of deionized water and neutralized to pH 6.5 with anhydrous sodium carbonate at 0 ℃;
3) and (2) adding the two solutions into a 500mL four-neck flask, heating to 50 ℃, dropwise adding a sodium hydroxide aqueous solution (the mass fraction is 30%) with the same mole as chloroacetic acid for 5 times, dropwise adding the aqueous solution once every 30min, heating the system to 60 ℃ after the last dropwise adding is finished, carrying out heat preservation reaction, testing the pH, stopping the reaction until the pH is 7, and obtaining the modified tannic acid chrome tanning aid, wherein the pH of the modified tannic acid chrome tanning aid is 7 and the reddish brown liquid.
The application of the modified chrome tannate tanning aid of the embodiment comprises the following steps:
1) pre-tanning: putting the delimed, softened and washed grey sheepskin into a rotary drum, adding water accounting for 100 percent of the weight of the grey sheepskin and a modified tannic acid chromium tanning auxiliary agent accounting for 15 percent of the weight of the grey sheepskin, and rotating for 1 hour at the temperature of 20 ℃; adjusting the pH to 8.5 within 1h by using baking soda diluted by 10 times of water, and continuing rotating for 1 h;
2) pickling: adding 10 times of water diluted formic acid into the bath liquid in the step 1), adjusting the pH of the bath liquid to 2.5 within 1h, and continuously rotating for 1h at 20 ℃;
3) chrome tanning: adding chromium powder (Cr) 5 wt% of the grey sheepskin2O3Content of 25%), 20 ℃ and 2 h; adding baking soda 1.8% of the weight of the grey sheepskin into 10% aqueous solution for 6 times at intervals of 20min, adjusting pH to 3.8, rotating for 1h, supplementing hot water at 40 ℃ of 150% of the weight of the grey sheepskin, and rotating for 2 h; stopping the drum, standing overnight, rotating for 0.5h the next day, taking out the drum, and standing.
The shrinkage temperature of the wet blue leather measured by using the modified chrome tannate tanning additive of the embodiment is 115 ℃, and the waste liquid Cr2O3The content was 0.61 g/L.
Embodiment two, a preparation method of a modified tannic acid chrome tanning auxiliary agent comprises the following steps:
1) dissolving 30g tannic acid in 140g deionized water, and neutralizing with anhydrous sodium carbonate at 3 deg.C to pH 7;
2) 16g of monochloroacetic acid are dissolved in 30g of deionized water and neutralized to pH 7 with anhydrous sodium carbonate at 3 ℃;
3) and (2) adding the two solutions into a 500mL four-neck flask, heating to 50 ℃, dropwise adding a sodium hydroxide aqueous solution (the mass fraction is 30%) with the same mole as chloroacetic acid for 5 times, dropwise adding the aqueous solution once every 30min, heating the system to 60 ℃ after the last dropwise adding is finished, carrying out heat preservation reaction for 3h, and discharging to obtain the modified tannic acid chrome tanning aid, wherein the pH value of the modified tannic acid chrome tanning aid is 7, and the modified tannic acid chrome tanning aid is a reddish brown liquid.
The application method of the modified tannic acid chrome tanning auxiliary agent comprises the following steps:
1) pre-tanning: putting the delimed, softened and washed pigskin into a rotary drum, adding water accounting for 100 percent of the weight of the pigskin soaked pigskin and a modified tannic acid chrome tanning auxiliary agent accounting for 15 percent of the weight of the pigskin soaked pigskin, and rotating for 1.5 hours at 23 ℃; adjusting the pH value to 8.7 within 1h by using 10 times of the calcined soda diluted by water, and continuously rotating for 1.5 h;
2) pickling: adding sulfuric acid diluted by 10 times of water into the bath liquid in the step 1) in several times, adjusting the pH value of the bath liquid to 2.8 within 1 hour, and continuously rotating for 1-2 hours at 23 ℃;
3) chrome tanning: adding chromium powder (Cr) 5.5 wt% of pigskin2O3Content of 25 percent), and rotating for 2 hours at 23 ℃; adding baking soda 2.0% of pigskin weight into 10% aqueous solution at intervals of 20min for 6 times, adjusting pH to 3.9, rotating for 1 hr, supplementing hot water at 40 deg.C 150% of pigskin weight, and rotating for 2 hr; stopping the drum, standing overnight, rotating for 0.5h the next day, taking out the drum, and standing.
The shrinkage temperature of the wet blue leather measured by using the modified chrome tannate tanning additive is 116 ℃, and the waste liquid Cr is measured2O3The content was 0.23 g/L.
Embodiment three, a preparation method of a modified tannic acid chrome tanning auxiliary agent comprises the following steps:
1) dissolving 34g tannic acid in 160g deionized water, and neutralizing with anhydrous sodium carbonate at 5 deg.C to pH 7.5;
2) 22g of monochloroacetic acid are dissolved in 35g of deionized water and neutralized to pH 7.5 with anhydrous sodium carbonate at 5 ℃;
3) and (2) adding the two solutions into a 500mL four-neck flask, heating to 50 ℃, dropwise adding a sodium hydroxide aqueous solution (the mass fraction is 30%) with the same mole as chloroacetic acid for 5 times, dropwise adding the aqueous solution once every 30min, heating the system to 60 ℃ after the last dropwise adding is finished, carrying out heat preservation reaction for 3h, and discharging to obtain the modified tannic acid chrome tanning aid, wherein the pH value of the modified tannic acid chrome tanning aid is 7, and the modified tannic acid chrome tanning aid is a reddish brown liquid.
The application method of the modified tannic acid chrome tanning auxiliary agent comprises the following steps:
1) pre-tanning: putting the delimed, softened and washed cow leather into a rotary drum, adding water accounting for 100% of the weight of the cow leather and a modified tannic acid chrome tanning aid accounting for 15%, and rotating for 2 hours at 25 ℃; adjusting the pH to 9.0 within 1h by using baking soda diluted by 10 times of water, and continuing rotating for 2 h;
2) pickling: adding 10 times of water diluted formic acid into the bath liquid in the step 1), adjusting the pH of the bath liquid to 3.0 within 1h, and continuously rotating for 2h at 25 ℃;
3) chrome tanning: adding chromium powder (Cr) 6 wt% of cow leather2O3Content of 25%), 25 ℃ and 2 h; adding baking soda 2.2% of cowhide weight into 10% aqueous solution at intervals of 20min for 6 times, adjusting pH to 4.0, rotating for 1 hr, adding 150% hot water at 40 deg.C, and rotating for 2 hr; stopping the drum, standing overnight, rotating for 0.5h the next day, taking out the drum, and standing.
The shrinkage temperature of the wet blue leather measured by using the modified tannic acid chrome tanning additive of the embodiment is 113 ℃, and the waste liquid Cr2O3The content was 0.60 g/L.

Claims (4)

1. The preparation method of the modified tannic acid chrome tanning auxiliary agent is characterized by comprising the following steps:
1) dissolving 25-34 parts of polyhydroxy phenolic compound in 120-160 parts of first solvent, and neutralizing with alkaline substance X at 0-5 ℃ to ensure that the pH value is 7 +/-0.5;
2) dissolving 11-22 parts of chloroacetic acid in 25-35 parts of second solvent, and neutralizing with an alkaline substance X at 0-5 ℃ to ensure that the pH value is 7 +/-0.5;
3) adding the two solutions into a 500mL four-neck flask at the same time, heating to 50 ℃, dropwise adding an alkaline substance Y aqueous solution with the same mole as chloroacetic acid for 5 times, wherein the mass fraction of the alkaline substance Y aqueous solution is 30%, dropwise adding the alkaline substance Y aqueous solution once every 30min, heating the system to 60 ℃ after the last dropwise adding is finished, carrying out heat preservation reaction, testing the pH, and stopping the reaction until the pH is 7 to obtain the modified tannic acid chrome tanning aid, wherein the parts are parts by mass;
the polyhydroxy phenolic compound is tannic acid;
the chloroacetic acid is monochloroacetic acid;
the first solvent and the second solvent are deionized water;
the alkaline substance X is anhydrous sodium carbonate;
the alkaline substance Y is sodium hydroxide.
2. The application method of the modified chrome tannate tannage assistant according to claim 1, characterized by comprising the following steps:
1) pre-tanning: putting the delimed and softened water washed liminated leather into a rotary drum, adding water accounting for 100 percent of the weight of the liminated leather and a modified tannic acid chromium tanning auxiliary agent accounting for 15 percent of the weight of the liminated leather, and rotating for 1 to 2 hours at the temperature of between 20 and 25 ℃; adjusting the pH value to 8.5-9.0 within 1h by using an alkaline substance Z diluted by 10 times of water, and continuously rotating for 1-2 h;
2) pickling: adding acidic substances diluted by 10 times of water into the bath liquid in the step 1), adjusting the pH value of the bath liquid to 2.5-3.0 within 1h, and continuously rotating for 1-2h at 20-25 ℃;
3) chrome tanning: adding chromium powder accounting for 5-6% of the weight of the ash soaking skin, wherein Cr is contained in the chromium powder2O3The content is 25 percent, and the temperature is changed for 2 hours at 20-25 ℃; adding baking soda 1.8-2.2% of the weight of the ash soaking skin and preparing into 10% aqueous solution, adding at 6 times at intervals of 20min, adjusting pH to 3.8-4.0, rotating for 1h, adding 150% hot water at 40 deg.C, and rotating for 2 h; stopping the drum for overnight, rotating for 0.5h the next day, taking out the drum, and standing by setting up a bridge;
the alkaline substance Z is baking soda or sodium carbonate.
3. The application method of the modified chrome tannate tannage assistant according to claim 2, characterized in that: the ash dipping skin is sheepskin, cowhide or pigskin.
4. The application method of the modified chrome tannate tannage assistant according to claim 2, characterized in that: the acidic substance is formic acid or sulfuric acid.
CN201811613224.4A 2018-12-27 2018-12-27 Preparation and application of modified tannic acid chromium tanning auxiliary Active CN109628662B (en)

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CN117418047A (en) * 2023-10-19 2024-01-19 齐鲁工业大学(山东省科学院) High-absorption chrome tanning auxiliary agent containing dithiocarbamate structure, and preparation method and application thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103509888A (en) * 2013-10-22 2014-01-15 陕西科技大学 Salt-free pickling-free less-chrome combination tanning method for first layer cattle shoe upper leather
CN103525956A (en) * 2013-10-22 2014-01-22 陕西科技大学 Less-chrome tanning technology for tanning sheep skin through nano-composite high absorption chrome tanning assistant
CN104762423A (en) * 2015-03-25 2015-07-08 陕西科技大学 Preparation and application of carboxyl-containing carbamyl sulfonate chrome tanning assistant

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103509888A (en) * 2013-10-22 2014-01-15 陕西科技大学 Salt-free pickling-free less-chrome combination tanning method for first layer cattle shoe upper leather
CN103525956A (en) * 2013-10-22 2014-01-22 陕西科技大学 Less-chrome tanning technology for tanning sheep skin through nano-composite high absorption chrome tanning assistant
CN104762423A (en) * 2015-03-25 2015-07-08 陕西科技大学 Preparation and application of carboxyl-containing carbamyl sulfonate chrome tanning assistant

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