CN113881818A - Tanning method using multi-metal matched tanning agent without pickling - Google Patents
Tanning method using multi-metal matched tanning agent without pickling Download PDFInfo
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- CN113881818A CN113881818A CN202111271757.0A CN202111271757A CN113881818A CN 113881818 A CN113881818 A CN 113881818A CN 202111271757 A CN202111271757 A CN 202111271757A CN 113881818 A CN113881818 A CN 113881818A
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- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14B—MECHANICAL TREATMENT OR PROCESSING OF SKINS, HIDES OR LEATHER IN GENERAL; PELT-SHEARING MACHINES; INTESTINE-SPLITTING MACHINES
- C14B1/00—Manufacture of leather; Machines or devices therefor
- C14B1/40—Softening or making skins or leather supple, e.g. by staking, boarding, or crippling machines, by dry mills
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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
- C14C1/08—Deliming; Bating; Pickling; Degreasing
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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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- 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
- C14C3/28—Multi-step processes
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- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
Abstract
The invention discloses a tanning method using a multi-metal complex tanning agent and without pickling, which is implemented according to the following steps: preparing and weighing softened pelts, determining the proportion of reagents required in the subsequent process through weight, then carrying out pretreatment and tanning: adding 3-15 parts of a multi-metal complex tanning agent DMT-II and 0.5-1% of electrolyte-resistant oil into the raw materials treated in the previous step, rotating for 300-350 min, standing overnight, and then extracting alkali: adding 0.5-3.0 parts of chrome tanning agent into the raw materials treated in the previous step, then adding 1 part of sodium formate solution and 2-3 parts of baking soda solution, rotating and extracting alkali; and finally, liquid supplementing, temperature rising and water washing: and adding 125-165 parts of water into the rotary drum, rotating, discharging liquid and discharging the liquid out of the drum. The invention not only slows down the pollution of heavy metal chromium to the environment, but also reduces the production cost.
Description
Technical Field
The invention belongs to the technical field of leather-making chemistry and engineering, and particularly relates to a tanning method using a multi-metal complex tanning agent and without pickling.
Background
With the increase of national economic level, the beautiful ecological environment of people is required to grow continuously. Therefore, the legal system for environmental protection in China is more and more perfect, and the pollution problem in the tanning industry becomes a great challenge for sustainable development. In recent years, the leather-making industry in China is rapidly developed, and China has become a big global leather-making country and also one of the most active and most potential markets for leather trade in the world. Since the invention of chrome tanning, chrome tanning agents have become the main tanning agent for leather tanning due to the good performance of chrome tanning, and almost no alternatives exist. With the development of the times, chrome tanning is facing a serious challenge.
Meanwhile, in order to adjust the PH of the pelt to be suitable for the tanning operation, we need to treat the pelt with a solution of acid and salt. After the leather fiber is developed, the tanning agent is convenient to penetrate, so that the prepared leather can be soft and delicate. In acid solution, the pelts can swell, the physical and mechanical properties of the leather made of the acid swollen pelts can be greatly reduced, the use of salt can cause the pelts to be dehydrated, so that the leather is flat and not full, and meanwhile, the pickling can also bring the pollution of chloride ions.
Therefore, how to simultaneously realize the tanning process of pickling-free and chrome-less tanning is a key technical problem to be faced by the leather manufacturing process at present. The patent discloses a tanning method based on a multi-metal compound tanning agent and without pickling, which has important significance for relieving the shortage problem of chromium raw materials and exploring a green leather tanning technology.
Disclosure of Invention
The invention aims to provide a tanning method which utilizes a multi-metal complex tanning agent and is not pickled, thereby not only slowing down the pollution of heavy metal chromium to the environment, but also reducing the production cost.
The technical scheme adopted by the invention is that a tanning method using multi-metal matched tanning agent without pickling is implemented according to the following steps:
step 1, preparing and weighing softened pelts, and determining the proportion of reagents required in the subsequent process through weight;
step 2, pretreatment: placing the weighed pelts into a rotary drum, wherein the weight of the pelts is 100 parts, adding 50-150 parts of water into the rotary drum, and adding a pretreatment agent DMT-I and a tanning agent;
step 3, tanning: adding 3-15 parts of a polymetallic complex tanning agent DMT-II and 0.5-1% of electrolyte-resistant oil into the raw material treated in the step (2), rotating for 300-350 min, and standing overnight;
step 4, alkali extraction: adding 0.5-3.0 parts of chrome tanning agent into the raw materials treated in the step 3, then adding 1 part of sodium formate solution and 2-3 parts of sodium bicarbonate solution, rotating, and extracting alkali;
step 5, liquid supplementing and temperature rising: adding 100-120 parts of warm water into the raw materials treated in the step (4), heating, rotating, and standing overnight;
step 6, washing with water: and adding 125-165 parts of water into the rotary drum, rotating, discharging liquid and discharging the liquid out of the drum.
The present invention is also characterized in that,
in the step 2, the pretreating agent DMT-I complex tanning agent is DMT-I zirconium-aluminum-titanium complex tanning agent, wherein the mass ratio of the DMT-I zirconium-aluminum-titanium complex tanning agent to water is 1: and 5, rotating the rotary drum for 20-30 minutes at the temperature of 23-25 ℃ in the drum, wherein the rotating speed is 8-10 r/min.
In the step 3, the multi-metal complex tanning agent DMT-II is a DMT-I zirconium-aluminum-titanium complex tanning agent, wherein the mass ratio of the DMT-I zirconium-aluminum-titanium complex tanning agent to water is 1: 5.
in the step 4, the molar ratio of sodium formate to water in the sodium formate solution is 1: 7-13, and NaHCO is added into the sodium bicarbonate solution3: the molar ratio of water is 1: 17-23.
The rotation time in the step 4 is 50-130 min.
And 4, extracting alkali in the step 4 to ensure that the pH value of the solution is 3.9-4.5.
And (5) adding warm water at the temperature of 50-60 ℃, raising the temperature of the bath liquid in the rotary drum to 42-46 ℃, and rotating for 180-240 min.
The temperature of the water supplemented in the step 6 is 22-26 ℃, and the rotation time is 5-10 min.
The tanning process has the beneficial effects that the tanning process utilizes a multi-metal complex tanning agent and is pickling-free, and is based on the zirconium-aluminum-titanium complex tanning agent under the pickling-free condition, the tanning process is used for tanning pig leather, horse leather and cattle leather by combining the tanning process, the process can ensure effective tanning of the leather after the pickling process is omitted, and the prepared leather has excellent physical property and quality. The whole process flow is simpler and more environment-friendly after the pickling process is omitted, the operation is more convenient, the process cost is saved, and the process has stronger practicability; the invention can also save chrome tanning agent, and reduce the pollution of heavy metal chromium to the environment in the tanning process; the invention does not need special mechanical equipment and has good industrial prospect.
Detailed Description
The present invention will be described in detail with reference to the following embodiments.
The invention relates to a tanning method using a multi-metal complex tanning agent without pickling, which is implemented according to the following steps:
step 1, preparing and weighing softened pelts, and determining the proportion of reagents required in the subsequent process through weight;
step 2, pretreatment: placing the weighed pelts into a rotary drum, wherein the weight of the pelts is 100 parts, adding 50-150 parts of water into the rotary drum, and adding a pretreatment agent DMT-I and a tanning agent;
in the step 2, the pretreating agent DMT-I complex tanning agent is DMT-I zirconium-aluminum-titanium complex tanning agent, wherein the mass ratio of the DMT-I zirconium-aluminum-titanium complex tanning agent to water is 1: and 5, rotating the rotary drum for 20-30 minutes at the temperature of 23-25 ℃ in the drum, wherein the rotating speed is 8-10 r/min.
Step 3, tanning: adding 3-15 parts of a polymetallic complex tanning agent DMT-II and 0.5-1% of electrolyte-resistant oil into the raw material treated in the step (2), rotating for 300-350 min, and standing overnight;
in the step 3, the multi-metal complex tanning agent DMT-II is a DMT-I zirconium-aluminum-titanium complex tanning agent, wherein the mass ratio of the DMT-I zirconium-aluminum-titanium complex tanning agent to water is 1: 5.
step 4, alkali extraction: adding 0.5-3.0 parts of chrome tanning agent into the raw materials treated in the step 3, then adding 1 part of sodium formate solution and 2-3 parts of sodium bicarbonate solution, rotating, and extracting alkali;
in the step 4, the molar ratio of sodium formate to water in the sodium formate solution is 1: 7-13, and NaHCO is added in the sodium bicarbonate solution3: the molar ratio of water is 1: 17-23.
The rotation time in the step 4 is 50-130 min.
And 4, extracting alkali in the step 4 to ensure that the pH value of the solution is 3.9-4.5.
Step 5, liquid supplementing and temperature rising: adding 100-120 parts of warm water into the raw materials treated in the step (4), heating, rotating, and standing overnight;
and (5) adding warm water at the temperature of 50-60 ℃, raising the temperature of the bath liquid in the rotary drum to 42-46 ℃, and rotating for 180-240 min.
Step 6, washing with water: and adding 125-165 parts of water into the rotary drum, rotating, discharging liquid and discharging the liquid out of the drum.
The temperature of the water supplemented in the step 6 is 22-26 ℃, and the rotation time is 5-10 min.
The invention adopts the process of less chromium and more metals matching with the tanning agent and no pickling for tanning, can lead the shrinkage temperature of crust leather to reach more than 90 ℃, and improves various physical and mechanical properties. And the non-pickling process can save resources, reduce the pollution of chloride ions and reduce the chloride ions in the waste liquid to be below 300 mg/L. In addition, the invention saves at least 50 percent of chrome tanning agent, so that Cr in tanning waste liquid is reduced2O3The content of (B) is less than 50 mg/L. Therefore, the invention not only saves resources, but also can reduce cost, and is a process with good industrialization prospect all the time.
Example 1
The invention relates to a tanning method using a multi-metal complex tanning agent without pickling, which is implemented according to the following steps:
step 1, preparing and weighing softened pelts, and determining the proportion of reagents required in the subsequent process through weight;
step 2, pretreatment: placing the weighed pelts into a rotary drum, wherein the weight of the pelts is 100 parts, adding 50 parts of water into the rotary drum, and adding a pretreating agent DMT-I and a complex tanning agent;
in the step 2, the pretreating agent DMT-I complex tanning agent is DMT-I zirconium-aluminum-titanium complex tanning agent, wherein the mass ratio of the DMT-I zirconium-aluminum-titanium complex tanning agent to water is 1: 5, the temperature in the drum is 23 ℃, the rotating drum rotates for 20 minutes, and the rotating speed is 8 r/min.
Step 3, tanning: adding 3 parts of polymetallic complex tanning agent DMT-II and 0.5% electrolyte-resistant oil into the raw materials treated in the step 2, rotating for 300min, and standing overnight;
in the step 3, the multi-metal complex tanning agent DMT-II is a DMT-I zirconium-aluminum-titanium complex tanning agent, wherein the mass ratio of the DMT-I zirconium-aluminum-titanium complex tanning agent to water is 1: 5.
step 4, alkali extraction: adding 0.5 part of chrome tanning agent into the raw materials treated in the step 3, then adding 1 part of sodium formate solution and 2 parts of sodium bicarbonate solution, rotating and extracting alkali;
in the step 4, the molar ratio of sodium formate to water in the sodium formate solution is 1:7, and NaHCO is added in the sodium bicarbonate solution3: the molar ratio of water was 1: 23.
The rotation time in step 4 is 50 min.
After the alkali is extracted in the step 4, the pH value of the solution is 3.9.
Step 5, liquid supplementing and temperature rising: adding 100 parts of warm water into the raw materials treated in the step (4), heating, rotating and standing overnight;
in step 5, adding warm water at 50 deg.C, heating the bath liquid in the rotary drum to 42 deg.C, and rotating for 180 min.
Step 6, washing with water: adding 125 parts of water into the rotary drum, rotating, draining and discharging.
The temperature of the water supplemented in the step 6 is 22 ℃, and the rotation time is 5 min.
Example 2
The invention relates to a tanning method using a multi-metal complex tanning agent without pickling, which is implemented according to the following steps:
step 1, preparing and weighing softened pelts, and determining the proportion of reagents required in the subsequent process through weight;
step 2, pretreatment: placing the weighed pelts into a rotary drum, wherein the weight of the pelts is 100 parts, adding 150 parts of water into the rotary drum, and adding a pretreating agent DMT-I and a complex tanning agent;
in the step 2, the pretreating agent DMT-I complex tanning agent is DMT-I zirconium-aluminum-titanium complex tanning agent, wherein the mass ratio of the DMT-I zirconium-aluminum-titanium complex tanning agent to water is 1: 5, the temperature in the drum is 25 ℃, the rotating drum rotates for 30 minutes, and the rotating speed is 10 r/min.
Step 3, tanning: adding 3-15 parts of a polymetallic complex tanning agent DMT-II and 1% of electrolyte-resistant oil into the raw materials treated in the step 2, rotating for 350min, and standing overnight;
in the step 3, the multi-metal complex tanning agent DMT-II is a DMT-I zirconium-aluminum-titanium complex tanning agent, wherein the mass ratio of the DMT-I zirconium-aluminum-titanium complex tanning agent to water is 1: 5.
step 4, alkali extraction: adding 3.0 parts of chrome tanning agent into the raw materials treated in the step 3, then adding 1 part of sodium formate solution and 3 parts of sodium bicarbonate solution, rotating and extracting alkali;
in the step 4, the molar ratio of sodium formate to water in the sodium formate solution is 1:13, and NaHCO is added in the sodium bicarbonate solution3: the molar ratio of water was 1: 17.
The rotation time in step 4 is 130 min.
After the alkali is extracted in the step 4, the pH value of the solution is 4.5.
Step 5, liquid supplementing and temperature rising: adding 120 parts of warm water into the raw materials treated in the step (4), heating, rotating and standing overnight;
in step 5, adding warm water at 60 deg.C to raise the temperature of bath liquid in the rotary drum to 46 deg.C, and rotating for 240 min.
Step 6, washing with water: adding 165 parts of water into the rotary drum, rotating, discharging liquid and discharging the liquid out of the drum.
The temperature of the water supplemented in the step 6 is 26 ℃, and the rotation time is 10 min.
Example 3
The invention relates to a tanning method using a multi-metal complex tanning agent without pickling, which is implemented according to the following steps:
step 1, preparing and weighing softened pelts, and determining the proportion of reagents required in the subsequent process through weight;
step 2, pretreatment: placing the weighed pelts into a rotary drum, wherein the weight of the pelts is 100 parts, adding 100 parts of water into the rotary drum, and adding a pretreating agent DMT-I and a complex tanning agent;
in the step 2, the pretreating agent DMT-I complex tanning agent is DMT-I zirconium-aluminum-titanium complex tanning agent, wherein the mass ratio of the DMT-I zirconium-aluminum-titanium complex tanning agent to water is 1: and 5, the temperature in the drum is 24 ℃, the rotating drum rotates for 25 minutes, and the rotating speed is 9 r/min.
Step 3, tanning: adding 9 parts of polymetallic complex tanning agent DMT-II and 0.8% electrolyte-resistant oil into the raw materials treated in the step 2, rotating for 320min, and standing overnight;
in the step 3, the multi-metal complex tanning agent DMT-II is a DMT-I zirconium-aluminum-titanium complex tanning agent, wherein the mass ratio of the DMT-I zirconium-aluminum-titanium complex tanning agent to water is 1: 5.
step 4, alkali extraction: adding 2.0 parts of chrome tanning agent into the raw materials treated in the step 3, then adding 1 part of sodium formate solution and 2.5 parts of baking soda solution, rotating and extracting alkali;
in the step 4, the molar ratio of sodium formate to water in the sodium formate solution is 1:10, and NaHCO is added in the sodium bicarbonate solution3: the molar ratio of water was 1: 20.
And in the step 4, the rotating time is 50-13100 min.
After the alkali is extracted in the step 4, the pH value of the solution is 4.1.
Step 5, liquid supplementing and temperature rising: adding 110 parts of warm water into the raw materials treated in the step 4, heating, rotating and standing overnight;
in step 5, adding warm water at 55 deg.C to raise the temperature of bath liquid in the rotary drum to 44 deg.C, and rotating for 200 min.
Step 6, washing with water: adding 130 parts of water into the rotary drum, rotating, draining and discharging.
The temperature of the water supplemented in the step 6 is 24 ℃, and the rotation time is 8 min.
Claims (8)
1. A tanning method using multi-metal matched tanning agent without pickling is characterized by comprising the following steps:
step 1, preparing and weighing softened pelts, and determining the proportion of reagents required in the subsequent process through weight;
step 2, pretreatment: placing the weighed pelts into a rotary drum, wherein the weight of the pelts is 100 parts, adding 50-150 parts of water into the rotary drum, and adding a pretreatment agent DMT-I and a tanning agent;
step 3, tanning: adding 3-15 parts of a polymetallic complex tanning agent DMT-II and 0.5-1% of electrolyte-resistant oil into the raw material treated in the step (2), rotating for 300-350 min, and standing overnight;
step 4, alkali extraction: adding 0.5-3.0 parts of chrome tanning agent into the raw materials treated in the step 3, then adding 1 part of sodium formate solution and 2-3 parts of sodium bicarbonate solution, rotating, and extracting alkali;
step 5, liquid supplementing and temperature rising: adding 100-120 parts of warm water into the raw materials treated in the step (4), heating, rotating, and standing overnight;
step 6, washing with water: and adding 125-165 parts of water into the rotary drum, rotating, discharging liquid and discharging the liquid out of the drum.
2. The method of claim 1, wherein the pretreatment agent DMT-I complex tanning agent in the step 2 is a DMT-I zirconium-aluminum-titanium complex tanning agent, wherein the mass ratio of the DMT-I zirconium-aluminum-titanium complex tanning agent to water is 1: and 5, rotating the rotary drum for 20-30 minutes at the temperature of 23-25 ℃ in the drum, wherein the rotating speed is 8-10 r/min.
3. The method of claim 1, wherein the multi-metal complex tanning agent DMT-II in the step 3 is DMT-I zirconium-aluminum-titanium complex tanning agent, wherein the mass ratio of DMT-I zirconium-aluminum-titanium complex tanning agent to water is 1: 5.
4. the tanning method using multi-metal complex tanning agent without pickling as claimed in claim 3, wherein the molar ratio of sodium formate to water in sodium formate solution in step 4 is 1: 7-13, and NaHCO is added in sodium bicarbonate solution3: the molar ratio of water is 1: 17-23.
5. The tanning method using multi-metal complex tanning agent without pickling as claimed in claim 4, wherein the rotation time in the step 4 is 50-130 min.
6. The method of claim 5, wherein the pH of the solution is 3.9 to 4.5 after the alkali extraction in the step 4.
7. The method for tanning with a polymetallic complex tanning agent without pickling as claimed in claim 6, wherein the temperature of the warm water added in the step 5 is 50-60 ℃, so that the temperature of the bath solution in the rotary drum is raised to 42-46 ℃, and the rotary drum is rotated for 180-240 min.
8. The tanning method using multi-metal complex tanning agent and free from pickling as claimed in claim 7, wherein the temperature of the supplemented water in the step 6 is 22-26 ℃, and the rotation time is 5-10 min.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0270767A1 (en) * | 1986-10-08 | 1988-06-15 | Hoechst Aktiengesellschaft | Tanning process saving chrome |
| CN102787181A (en) * | 2012-08-01 | 2012-11-21 | 四川大学 | Zirconium-aluminum-titanium complex tanning agent based less-chrome tanning method |
| CN102978298A (en) * | 2012-11-27 | 2013-03-20 | 四川大学 | Totally enclosed less-chrome tanning circulation technique based on zirconium-aluminum-titanium cooperation tanning agent |
| CN103773908A (en) * | 2014-01-21 | 2014-05-07 | 中国皮革和制鞋工业研究院 | Method for tanning leather without pickling |
| CN105803133A (en) * | 2016-03-29 | 2016-07-27 | 兴业皮革科技股份有限公司 | Production technology for preparing yellow wet leather on basis of iron-zirconium-aluminum complex tanning agent |
| CN107201414A (en) * | 2017-06-05 | 2017-09-26 | 兴业皮革科技股份有限公司 | A kind of not pickling chrome-free tanning technique based on many metal combination tanning agents |
-
2021
- 2021-10-29 CN CN202111271757.0A patent/CN113881818A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0270767A1 (en) * | 1986-10-08 | 1988-06-15 | Hoechst Aktiengesellschaft | Tanning process saving chrome |
| CN102787181A (en) * | 2012-08-01 | 2012-11-21 | 四川大学 | Zirconium-aluminum-titanium complex tanning agent based less-chrome tanning method |
| CN102978298A (en) * | 2012-11-27 | 2013-03-20 | 四川大学 | Totally enclosed less-chrome tanning circulation technique based on zirconium-aluminum-titanium cooperation tanning agent |
| CN103773908A (en) * | 2014-01-21 | 2014-05-07 | 中国皮革和制鞋工业研究院 | Method for tanning leather without pickling |
| CN105803133A (en) * | 2016-03-29 | 2016-07-27 | 兴业皮革科技股份有限公司 | Production technology for preparing yellow wet leather on basis of iron-zirconium-aluminum complex tanning agent |
| CN107201414A (en) * | 2017-06-05 | 2017-09-26 | 兴业皮革科技股份有限公司 | A kind of not pickling chrome-free tanning technique based on many metal combination tanning agents |
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