CN112941248A

CN112941248A - Sheep fur leather and processing technology of chrome-free tanning thereof

Info

Publication number: CN112941248A
Application number: CN202110139197.7A
Authority: CN
Inventors: 董贺翔; 缪新全; 罗恒祎
Original assignee: Xinji Meihua Leather Industry Co ltd
Current assignee: Xinji Meihua Leather Industry Co ltd
Priority date: 2021-02-01
Filing date: 2021-02-01
Publication date: 2021-06-11
Anticipated expiration: 2041-02-01
Also published as: CN112941248B

Abstract

The application relates to the technical field of sheep fur leather processing, in particular to a processing technology of sheep fur leather and chrome-free tanning thereof, which sequentially comprises the following processing steps: soaking raw fur in water, soaking again in water, degreasing, pickling, TWS chrome-free tanning, oxidizing, washing with water, filling and retanning, drying and finishing to obtain a semi-finished fur and leather product; carrying out backwater degreasing, primary water washing, filling retanning before dyeing, secondary water washing, plate dyeing, tertiary water washing, drying finishing and coating on the semi-finished fur and leather to obtain a finished sheep fur and leather product; the method comprises the following steps of (1) recovering a tanning solution in the TWS chromium-free tanning to obtain a circulating tanning solution, and using the circulating tanning solution in the next batch of TWS chromium-free tanning; the process achieves the effects of energy conservation and emission reduction; the TWS is adopted for chrome-free tanning, so that the shrinkage temperature of the fur leather can meet the required requirements, the environmental pollution problem and the safety problem of the chrome tanning process are solved, and the processed fur leather has high shrinkage temperature and excellent mechanical property.

Description

Sheep fur leather and processing technology of chrome-free tanning thereof

Technical Field

The application relates to the technical field of sheep fur leather processing, in particular to sheep fur leather and a processing technology of chrome-free tanning thereof.

Background

The fur and leather products are the modern and elegant names, and are called soft gold. For example, products such as cotton leather hats, cotton fur clothing, snow boots and the like belong to fur and leather products. Different from common leather, fur leather is a fur-integrated product obtained by carrying out a series of processing operations such as soaking, re-soaking, degreasing, pickling, main tanning, re-tanning, drying and finishing on fur-integrated animal skins; the common leather is a product obtained by processing the single-layer leather plate after unhairing. However, tanning operations are critical whether for fur or general leather. After tanning, the original loose leather becomes stiff, smooth and plump leather, and leather products with good shrinkage temperature can be obtained.

The traditional leather tanning method is mainly a chrome tanning method, and leather obtained by chrome tanning has high shrinkage temperature, soft and plump finished leather, good stability and washing resistance. The main tanning method for the industrial production of furs is also chrome tanning, but is different from common leather in that rust and fur are caused by technical or liquid ratio in fur processing, so that the water consumption in the chrome tanning process is very large and is almost 10 to 20 times of that in the chrome tanning process of the common leather, and the use and waste of water resources are prominent. In addition, the utilization rate of chromium in the chrome tanning is only 65-75%, and a large amount of unabsorbed chromium is directly discharged along with tanning liquid, thereby causing serious chromium resource waste and environmental pollution; simultaneously, in the dyeing and finishing process in later stage, combine not firm chromium and unabsorbed dyeing and finishing material to get into the waste water together, and the existence of dyeing and finishing material can make the processing degree of difficulty of chromium-containing waste water further increase.

In order to solve the problems in the fur and leather chrome tanning processing, the related technology discloses a chrome-free tanning production process of beach sheep fur, which comprises the following specific process steps: soaking, fleshing, degreasing, softening, TWT tanning, alkali extracting after tanning, wet grinding, washing, air drying, rewetting, retanning, alkali extracting after retanning, fatliquoring, air drying, peeling, dry grinding and brushing ash to obtain a finished product; wherein, the liquid ratio in the soaking step is 20-30; the liquid ratio in the degreasing step is 20-40; the tanning step is as follows: the tanning liquor comprises the following components: 0.1-1.5g/L of chelating dispersant DT-A101 (Germany chemical), 5-15g/L of chrome-free tanning agent TWT (Germany chemical), 0.1-1.5g/L of brightener Blankit IN (basf), 0.1-1.5g/L of degreasing agent DT-A121 (Germany chemical), and the balance of water; the amount of the tanning liquid is added according to the mass ratio of water to fur in the tanning liquid of 20-40, the tanning time is 1-4h at the temperature of 35-45 ℃, and the tanning liquid is stood for 12-24h overnight; the liquid ratio in the rewetting step is 20-40; the liquid ratio in the retanning step is 20-40. According to the related technology, the chrome-free tanning agent TWT is used as a main tanning agent to tan the Tan sheep fur, so that the problems of chromium pollution and chromium-containing wastewater pollution after chromium tanning are fundamentally solved, and chrome-free clean production is realized; the shrinkage temperature of the fur after the chrome-free tanning is higher than 80 ℃, and the physical and mechanical properties of the fur completely reach the fur obtained by the common chrome tanning method.

However, the above-described related art has the following problems: firstly, the mass ratio of water to fur in the tanning liquid is 20-40, the water consumption is high, and the tanning liquid is not recycled, so that the water resource waste is caused; secondly, the water consumption in the steps of soaking, degreasing, retanning, rewetting and the like is huge, and the production cost is high.

Disclosure of Invention

Aiming at the defects in the prior art, one of the purposes of the application is to provide a chrome-free tanning processing technology for sheep fur leather, a chrome-free tanning agent is adopted for main tanning, and a tanning solution after the main tanning is recycled, so that the effects of energy conservation and emission reduction are achieved.

The second purpose of the application is to provide the sheep fur and leather processed by the chrome-free tanning processing technology of the first purpose, the shrinkage temperature can reach more than 94 ℃, the formaldehyde content is less than 60mg/kg, and the tensile strength and the tearing strength both meet the standard requirements.

The above object of the present application is achieved by the following technical solutions:

a chrome-free tanning processing technology for sheep fur leather sequentially comprises the following processing steps:

soaking raw fur in water, soaking again in water, degreasing, pickling, TWS chrome-free tanning, oxidizing, washing with water, filling and retanning, drying and finishing to obtain a semi-finished fur and leather product;

carrying out backwater degreasing, primary water washing, filling retanning before dyeing, secondary water washing, plate dyeing, tertiary water washing, drying finishing and coating on the semi-finished fur and leather to obtain a finished sheep fur and leather product; and recovering the tanning liquid in the TWS chromium-free tanning to obtain a circulating tanning liquid, and using the circulating tanning liquid in the next batch of TWS chromium-free tanning.

By adopting the technical scheme, the chrome-free tanning agent TWS has the advantages of low toxicity, no stimulation, biodegradability and the like. According to the application, the TWS is adopted for chrome-free tanning, and due to the moderate masking capability and the excellent tanning performance, chemical materials can be uniformly permeated into fur, so that the fur can reach the shrinkage temperature required by processing, and the environmental pollution problem and the safety problem of a chrome tanning process are solved; meanwhile, the TWS chrome-free tanning liquid is recycled, and the circulating tanning liquid is used for the chrome-free tanning processing of the fur and leather of the next batch, so that the water resource is saved, the wastewater discharge is reduced, and the effects of energy conservation and emission reduction are achieved.

Preferably, the method comprises the following steps: the TWS chrome-free tanning specifically comprises the following steps: adding the pickled fur into the mixture according to the liquor ratio of 1: 17, adding 5.5-6.0 Baume industrial salt and 13-17g/L of chrome-free tanning agent TWS into water, adjusting the pH to 4.5-5.0, rotating for 170-70 min, stopping for 25-35min, rotating for 50-70min, stopping for 230-250 min; adding soda to adjust the pH value to 7.0-8.0, rotating for 110-.

Preferably, the method comprises the following steps: when the circulating tanning liquid is used for the next batch of TWS chromium-free tanning, the added amount of TWS is 45-50wt% of the initial amount of TWS, and the added amount of water is 2.0-2.5 wt% of the initial amount of water.

By adopting the technical scheme, for example, 17 liters of water is needed to be added into a single leather for tanning when chrome-free tanning is carried out for the first day, after the tanning liquid is recovered, only 0.34 liter of water needs to be additionally added into the single leather for the next day, and only half of the first day needs to be added into the TWS, so that the water resource and the usage amount of the chrome-free tanning agent are saved, the wastewater discharge amount is reduced, and the processing cost is saved.

Preferably, the method comprises the following steps: the soaking operation specifically comprises the following steps: adding raw fur into the mixture according to the liquor ratio of 1: adding 0.4-0.6g/L of soaking agent, 0.1-0.3g/L of bactericide and 2.0-3.0g/L of surfactant into water of 19, rotating for 15-25min, stopping for 12-14h, peeling, and shearing hair with a scraper; the operation of re-soaking is as follows: adding the fur after the soaking step into a solution with the ratio of 1: 14, adding 0.4-0.6g/L of soda ash, 0.4-0.6g/L of lipase removal enzyme, 0.2-0.4g/L of water soaking agent and 0.7-1.2g/L of surfactant into water at the water temperature of 30 ℃, rotating for 25-35min, standing overnight, and removing meat the next day.

By adopting the technical scheme, the scraper plate removes residual meat membrane on the fur after soaking, and extends the fold, thereby not only facilitating the uniform permeation of subsequent chemical materials, but also accelerating the soaking; the surfactant is added, so that the soaking can be accelerated, and the grease can be emulsified; the addition amount of water is controlled, and the leather is soaked, so that the problems of fur erection and fur formation are easily caused when the leather is soaked excessively, and the finished leather setting property is poor.

Preferably, the method comprises the following steps: the degreasing operation specifically comprises the following steps: the liquid ratio is 1: 13, rotating the mixture for 110-; the pickling operation specifically comprises the following steps: the liquid ratio is 1: 17, adding 6.0-7.0 Baume industrial salt and 85% formic acid at the water temperature of 30 ℃, rotating for 55-65min, and standing for 12 h; 90% sulfuric acid was added to adjust the pH to 3.0.

By adopting the technical scheme, the degreasing and pickling are beneficial to the proper separation of the leather fibers, and the grain surface of the finished leather is flat and fine; the industrial salt is proper, and excessive industrial salt can dehydrate the fur and is not beneficial to pickling; after degreasing and pickling operations, the chrome-free tanning agent is beneficial to uniform penetration to the skin core.

Preferably, the method comprises the following steps: the filling retanning operation specifically comprises the following steps: the liquid ratio is 1:10, adding fat liquor at the temperature of 38 ℃ and 1.3-1.7g/L, and rotating for 25-35 min; adding 35-45g/L of phenolic synthetic tanning agent, and rotating for 110-; adding fatting agent 1.4-1.6g/L, rotating for 110-; adding 85% formic acid to adjust pH to 3.8, rotating for 2h, stopping for 2h, draining, taking out, and standing overnight.

By adopting the technical scheme, the sheep fur is different from other leather materials, the tearing strength of the sheep fur is relatively low, and most of retanning filling materials can reduce the tearing strength of a fur finished product, so that the sheep fur filling materials are improperly selected, and the leather strength can not meet the requirement. By adopting the filling material in the application, the tearing strength of the fur finished product can not be reduced, but can be properly improved, so that the finished product can be suitable for shoe upper leather.

Preferably, the method comprises the following steps: the operation of dyeing the wool is specifically as follows: the liquid ratio is 1:20, the water temperature is 68 ℃, a leveling agent is added for 0.4-0.6g/L, anhydrous sodium sulphate is added for 8-12g/L, sodium formate is added for 0.2-0.4g/L, the rotation is carried out for 8-13min, an acid dye and 85% formic acid are added for 0.4-0.6g/L, the rotation is carried out for 15-25min, and water is drained and the skin is discharged; the operation of the dyeing plate is specifically as follows: adding 3-5g/L of neutralized tannin and 0.8-1.3g/L of sodium formate at a liquid ratio of 1:10, and rotating for 25-35 min; adding dispersant 1.5-2.5g/L and hair detergent 0.8-1.3g/L, and rotating for 8-13 min; adding animal protein 2-4g/L, and rotating for 25-35 min; adding dye, and rotating for 25-35 min; adding fat-liquoring agent 1.0-3.0g/L and oil dispersant 0.4-0.6g/L, and rotating for 25-35 min; adding 85% formic acid to adjust pH to 3.5, draining water and peeling.

Preferably, the method comprises the following steps: the liquid ratio of the semi-finished product backwater degreasing to the first washing and the second washing is 1: 10; the washing liquid in the hide degreasing step is recycled and then used in the main soaking water; and recovering the washing liquid in the oxidation washing step and then using the washing liquid in the oxidation washing step in the oxidation.

By adopting the technical scheme, due to the adoption of the TWS chrome-free tanning agent, the appropriate masking capability and excellent tanning performance of the TWS chrome-free tanning agent enable the chemical materials to uniformly permeate into fur, bright and light color can be dyed, water consumption of return water degreasing, primary water washing and secondary water washing after main tanning can be relatively reduced, water resources are saved, and processing cost is reduced; in the steps of degreasing and washing after oxidation, the washing liquid is recycled and then repeatedly applied to the corresponding preorders, so that the performance of the finished fur and leather product is not influenced, and water resources can be further saved.

Preferably, the method comprises the following steps: the dyeing plate adopts a spraying or roller coating process, and after the dyeing plate is dyed, the finished product sheep fur and leather is obtained through finishing and coating.

By adopting the technical scheme, on the basis of adopting the TWS chrome-free tanning agent, the light-color bright dyeing effect can be obtained by using an anhydrous dyeing process, and compared with a dip dyeing process in a dye solution, the water resource is greatly saved, and the wastewater discharge is reduced; and the finished product can be obtained by direct drying, finishing and coating without repeated water washing operation after the waterless dyeing, so that the water resource is further saved, and the wastewater discharge is reduced.

The second application object of the present application is achieved by the following technical scheme:

a sheep fur leather produced by a process according to any one of claims 1 to 9 which is chrome-free.

In summary, the present application includes at least one of the following beneficial technical effects:

(1) the chrome-free tanning agent TWS is adopted for carrying out chrome-free tanning, and tanning liquor after main tanning is recycled, so that about 3.2 ten thousand tons of water can be saved every year, the wastewater discharge amount of about 3.2 ten thousand tons is reduced, and the effects of energy conservation and emission reduction are achieved;

(2) the shrinkage temperature of the sheep fur and leather processed by the chrome-free tanning process can reach over 94 ℃ and can reach 100 ℃ at most; the dry friction faded rough surface and the leather surface reach 4 grades, the wet friction faded rough surface reaches 3.5 grades, the leather surface reaches 4 grades, and the color fastness performance is excellent; the tensile strength and the tearing strength both meet the standard requirements;

(3) on the basis of TWS (two-way dye system) chrome-free tanning, a leather plate is dyed by adopting an anhydrous dyeing process, about 11.9 ten thousand tons of water can be saved every year, about 11.9 ten thousand tons of wastewater discharge is reduced, the dry friction color fastness of the processed sheep fur leather can reach three levels to the maximum, and the wet friction color fastness can reach three levels to the maximum;

(4) in the process, the water washing liquid after degreasing is applied to repeated soaking, the circulating tanning liquid is utilized in chrome-free tanning, and the water washing liquid in the water washing step is applied to oxidation and is subjected to waterless dyeing when a board is dyed simultaneously, so that the water consumption of about 17.6 ten thousand tons can be saved every year, the processing cost is greatly saved, and the wastewater discharge of about 17.6 ten thousand tons can be reduced.

Detailed Description

The present application will be described in further detail with reference to specific examples.

The variety and source of each chemical material in the wet white leather processing procedure are as follows: the soaking agent in the soaking operation is selected from Spanish Cromo corporation, model AS-21; the germicide is selected from Dow corporation, model 830; the surfactant is selected from Keka corporation, model MH 2. The lipase in the secondary soaking operation is selected from Darwey corporation, model HKM; the soaking agent is selected from Spanish Cromo corporation, model AS-21; the surfactant is selected from Keka corporation, model MH 2. The degreasing enzyme in the degreasing operation is selected from the group consisting of Darwey corporation, model HKM; the degreasing agent is selected from Sichuan Tenjiang New materials GmbH, model A02. The TWS in the TWS chrome-free tanning is selected from Sichuan Tenjiang New materials GmbH. The water purifying agent in the oxidation operation is sodium hexametaphosphate; the degreasing agent is selected from degreasing agent O-1 of Xinjingrun. In the washing operation after oxidation, the mildewcide is selected from the group of Dow corporation, model 890. The fatliquor in the filling retanning is selected from Kekei, model HG; the phenolic syntan RL is selected from TFL, DLE is selected from Pasf, and BTL is selected from Desel.

In the application, the types and sources of various chemicals in the processing procedure of preparing the sheep fur leather from the wet white leather are as follows: the nonionic rewetting agent in backwater degreasing is selected from CC of Kekai corporation. The neutralized tannin in the filling retanning before dyeing is selected from Dreher, model NG; the micromolecular acrylic acid retanning agent is selected from Deshel, model RST; the melamine retanning agent is selected from basf, model DLF; the animal protein filler is selected from mesoderm, model BO 4; fatliquor SC-4 is selected from cromolol; the fatting agent is selected from Kekei, model HG; the aluminium tanning agent ALF is selected from dessel. A leveling agent AL is selected as a leveling agent in the dyed hair; the acid dyes red E and blue E are selected from Basff. The neutralized tannin in the dye plate is selected from baskatom, type NA; the dispersant Tam M is selected from Pasteur; the hair detergent is selected from Basff, model LPK-E; the animal protein is selected from mesoderm, model B04; the dye is selected from basf; the fatting agent is selected from Kekei, model HG; the grease dispersant is selected from SAF of TFL. The hair detergent in the third water washing is selected from Basff, model LPK-E; the aldehyde removing agent is selected from Tingjiang, model A980. In the waterless dyeing, the sources of the reagents of the spraying process and the roller coating process are as follows: the gloss oil is selected from Pickle; the size resin is selected from Dawei, model 5050/1109/1210/2581 and the like; the dye paste is mainly selected from Dawei, red/yellow/blue/black; the foaming agent is selected from Aspalathus, model WPU-2309; the aqueous binder is selected from the group consisting of doctor da, model number WPU-5150.

In the application, except for special description, the liquid ratio is based on 1 piece of skin, for example, the liquid ratio of 1:20 means that 20L of water is added into 1 piece of skin; the default water temperature, with the exception of the indicated water temperature, is ambient temperature water without heat treatment, typically 23-26 ℃.

The processing technology of the application can obtain bright light-color fur and leather, and the light-pink upper leather is taken as an example for explanation.

Example 1

1. processing of semi-finished fur and leather products

1.1, soaking: putting raw sheep fur into a rotary drum, wherein the liquid ratio is 1: 19, adding 0.4g/L of soaking agent, 0.2g/L of bactericide and 2.0g/L of surfactant, rotating for 15min, stopping for 12h overnight, peeling the skin the next day, and shearing the hair by a scraper;

1.2, soaking again: in a rotary drum, adding the soaked sheared fur into the mixture with the liquid ratio of 1: 13, adding 0.4g/L of soda ash, 0.4g/L of lipase removal enzyme, 0.2g/L of water soaking agent and 0.7g/L of surfactant into water at the water temperature of 30 ℃, rotating for 25min, standing overnight, and removing meat the next day;

1.3, degreasing: in the rotary drum, the liquid ratio is 1: 13, water temperature of 40 ℃, 0.3g/L of soda ash, 0.4g/L of lipase and 4g/L of degreasing agent, rotating for 110min, peeling and washing with water, wherein the ratio of the washing liquid to the washing liquid is 1: 13;

1.4, pickling: in the groove, the liquid ratio is 1: 15, adding 6.0 Baume industrial salt and 3 g/L85% formic acid at the water temperature of 30 ℃, rotating for 55min, and standing for 12 h; adding 90% sulfuric acid 2.0g/L, adjusting pH to 3.0, and standing for 6 h; draining water and peeling;

1.5, TWS chrome-free tanning: adding the pickled fur into a paddle vat, and controlling the liquor ratio to be 1: 17, adding 5.5 Baume industrial salt and 13g/L of chrome-free tanning agent TWS, adding 0.5g/L of soda ash to adjust the pH value to 4.5, rotating for 170min, stopping for 25min, rotating for 50min, and stopping for 230 min; adding soda at a speed of 0.5g/L every time and 30min between two times to adjust the pH value to 7.0, rotating for 110min, heating to 37 ℃, standing for 110min, and finishing TWS chromium-free tanning; discharging the tanning liquid from the paddle tank to a recovery tank for recycling as the tanning liquid for the next batch of TWS chrome-free tanning, and taking out the fur;

1.6, oxidation: the liquid ratio is 1: 17, adding 0.5g/L of soda ash, 0.5g/L of water purifying agent, 4.0g/L of 28 wt% of hydrogen peroxide and 3.0g/L of degreasing agent at the water temperature of 45 ℃, rotating for 90min, and draining; the purpose of oxidation is mainly used for protecting the hair color and removing formaldehyde;

1.7, washing: the liquid ratio is 1: 17, adding 0.1g/L of mildew preventive at the temperature of 35 ℃, rotating for 30min, draining water, discharging the leather, and standing for 24h for buffing; wherein, the water in the water washing step is recycled and used as the oxidation water in the step 6, thereby saving water and reducing emission;

1.8, filling and retanning: in the rotary drum, the liquid ratio is 1:10, adding a fatting agent of 1.3g/L at the water temperature of 38 ℃, and rotating for 25 min; adding 35g/L of phenolic synthetic tanning agent, and rotating for 110 min; adding fatting agent 1.4g/L, rotating for 110min, stopping for 60min, and rotating for 60 min; adding 85% formic acid 0.5g/L once every 30 minutes, adjusting pH to 3.8, turning for 2h, stopping for 2h, draining, taking out, standing overnight, and dehydrating the next day;

1.9, drying and finishing: drying on a toggling plate at 60 ℃, drying for 4h, standing for 24h with moist water, edge cleaning, horizontal softening, shearing, ironing, dry cleaning, one (twice) moist water at intervals of 4h, buffing and dedusting to obtain a semi-finished fur and leather product;

2. processing the semi-finished fur and leather to obtain the finished sheep fur and leather

2.1, backwater degreasing: in the rotary drum, the liquid ratio is 1: 15, adding a non-ionic rewetting agent of 0.5g/L at the temperature of 40 ℃, and rotating for 120 min;

2.2, first water washing: the liquid ratio is 1: rotating at 35 deg.C for 15min at 10 deg.C, and peeling;

2.3, filling and retanning before dyeing: in the rotary drum, the liquid ratio is 1:10, at the temperature of 35 ℃, adding 2.0g/L of neutralized tannin, and rotating for 30 min; adding micromolecular acrylic acid retanning agent 2.5g/L, and rotating for 30 min; adding 1.5g/L of melamine retanning agent, and rotating for 30 min; adding animal protein filler 5.0g/L, and rotating for 30 min; adding fatting agent SC-41.0 g/L and fatting agent 1.0g/L, and rotating for 60 min; adding 85% formic acid for three times at the speed of 0.5g/L every time and adding once every 30min, and adjusting the pH to 3.3; adding aluminum tanning agent 3.0g/L, and rotating for 120 min; adding sodium acetate at a speed of 0.5g/L every time and 30min interval every two times, adding the sodium acetate by 4 times, adjusting the pH to 3.8, rotating for 120min, stopping the machine, draining water and peeling to obtain white chromium-free wet leather;

2.4, dyeing wool: in the rotary drum, the liquid ratio is 1: 17, at the temperature of 60 ℃, adding a leveling agent of 0.4g/L, anhydrous sodium sulphate of 8g/L and sodium formate of 0.2g/L, and rotating for 8 min; adding 0.02g/L of acid dye red 18B, 0.0066g/L of BASF yellow E and 0.4g/L of 85% formic acid, rotating for 15min, adjusting pH to 3.5, and draining water to remove peel;

2.5, second water washing: the liquid ratio is 1:10, rotating for 15 min;

2.6, dyeing plate: in the rotary drum, the liquid ratio is 1:10, adding 3.0g/L of neutralized tannin and 0.8g/L of sodium formate, and rotating for 25 min; adding dispersant Tamu M1.5g/L and wool detergent 0.8g/L, and rotating for 8 min; adding animal protein 2g/L, and rotating for 25 min; 0.1g/L of Gabasf LF, 0.036g/L of orange HF-010.075 g/L and Delry (TFL) red H of British company, and rotating for 25 min; adding fat-liquoring agent 1.0g/L, grease dispersing agent TFL0.2g/L and grease dispersing agent SAF0.2g/L, rotating for 30min, adding 85% formic acid at a speed of 0.5g/L each time and 10min interval between two times, adjusting pH to 3.5, and draining water to remove skin;

2.7, third water washing: the liquid ratio is 1: 18, adding 1.0g/L of 85% formic acid, 0.5g/L of a wool detergent BASF and 0.5g/L of a wool detergent LPK-E0.5g/L, and rotating for 10 min; the liquid ratio is 1: 18, adding 1.0g/L oxalic acid and 2.0g/L aldehyde removing agent, rotating for 30min, draining water and peeling;

2.8, drying, finishing and coating: and (3) dewatering fur, extruding, drying by a toggling plate, finishing, wetting, softening, shearing and scalding fur, coating and edge cleaning to obtain a finished product of sheep fur and leather.

Example 2

1. processing of semi-finished fur and leather products

1.2, soaking again: in a rotary drum, adding the soaked sheared fur into the mixture with the liquid ratio of 1: 13 adding soda 0.5g/L, lipase 0.5g/L, soaking agent 0.3g/L and surfactant 1.0g/L into water at 30 deg.C, rotating for 25min, standing overnight, and removing meat the next day;

1.3, degreasing: in the rotary drum, the liquid ratio is 1: 13, rotating the water at 40 ℃, 0.4g/L of soda ash, 0.5g/L of lipase and 5g/L of degreasing agent for 110min, and peeling and washing the skin;

1.4, pickling: in the groove, the liquid ratio is 1: 15, adding 7.0 Baume industrial salt and 85% formic acid at the temperature of 30 ℃, rotating for 55min, and standing for 12 h; adding 90% sulfuric acid 2.0g/L, adjusting pH to 3.0, and standing for 6 h; draining water and peeling;

1.5, TWS chrome-free tanning: adding the pickled fur into a paddle vat, and controlling the liquor ratio to be 1: 17, adding 6.0 Baume industrial salt and 15g/L of chrome-free tanning agent TWS, adding 0.5g/L of soda ash to adjust the pH value to 5, rotating for 170min, stopping for 25min, rotating for 50min, and stopping for 230 min; adding soda at a speed of 0.5g/L every time and 30min between two times to adjust the pH value to 8.0, rotating for 110min, heating to 38 ℃, standing for 110min, and finishing TWS chromium-free tanning; discharging the tanning liquid from the paddle tank to a recovery tank for recycling as the tanning liquid in the next day TWS chromium-free tanning, and taking out the fur;

1.6, oxidation: the same as example 1;

1.7, washing: the same as example 1;

1.8, filling and retanning: in the rotary drum, the liquid ratio is 1:10, adding a fatting agent at 1.5g/L at the water temperature of 38 ℃, and rotating for 25 min; adding 40g/L of phenolic synthetic tanning agent, and rotating for 110 min; adding fatting agent 1.5g/L, rotating for 110min, stopping for 60min, and rotating for 60 min; adding 85% formic acid 0.5g/L once every 30 minutes, adjusting pH to 3.8, turning for 2h, stopping for 2h, draining, taking out, standing overnight, and dehydrating the next day;

1.9, drying and finishing: the same as example 1;

2.1, backwater degreasing: the same as example 1;

2.2, first water washing: the same as example 1;

2.3, filling and retanning before dyeing: the same as example 1;

2.4, dyeing wool: in the rotary drum, the liquid ratio is 1: 17, at the temperature of 60 ℃, adding a leveling agent of 0.5g/L, anhydrous sodium sulphate of 10g/L and sodium formate of 0.3g/L, and rotating for 8 min; adding 0.02g/L acid dye red 18B, 0.0066g/LBASF yellow E and 0.5 g/L85% formic acid of Yongtai company, rotating for 15min, adjusting pH to 3.5, draining water and peeling;

2.5, second water washing: the same as example 1;

2.6, dyeing plate: in the rotary drum, the liquid ratio is 1:10, adding 4.0g/L of neutralized tannin and 1.0g/L of sodium formate, and rotating for 25 min; adding 2.0g/L of dispersant Tamu M and 1.0g/L of wool detergent, and rotating for 8 min; adding animal protein 3g/L, and rotating for 25 min; 0.1g/L of Gabasf LF, 0.036g/L of orange HF-010.075 g/L and Delry (TFL) red H of British company, and rotating for 25 min; adding fat-liquoring agent 2.0g/L, fat-liquoring agent TFL0.2g/L and fat-liquoring agent SAF0.2g/L, rotating for 25min, adding 85% formic acid at a speed of 0.5g/L each time and 10min interval between two times, adjusting pH to 3.5, draining water and peeling;

2.7, third water washing: the same as example 1;

Example 3

1. processing of semi-finished fur and leather products

1.1, soaking: putting raw sheep fur into a rotary drum, wherein the liquid ratio is 1: 17, adding 0.4g/L of soaking agent, 0.2g/L of bactericide and 2.0g/L of surfactant, rotating for 15min, stopping for 12h overnight, peeling the skin the next day, and shearing the hair by a scraper;

1.2, soaking again: in a rotary drum, adding the soaked sheared fur into the mixture with the liquid ratio of 1: 13, adding 0.6g/L of sodium carbonate, 0.6g/L of lipase removal enzyme, 0.4g/L of water soaking agent and 1.2g/L of surfactant into water at the water temperature of 30 ℃, rotating for 25min, standing overnight, and removing meat the next day;

1.3, degreasing: in the rotary drum, the liquid ratio is 1: 13, rotating the water at 40 ℃, 0.5g/L of soda ash, 0.6g/L of lipase and 6g/L of degreasing agent for 110min, and peeling and washing the skin;

1.4, pickling: in the groove, the liquid ratio is 1: 15, adding 7.0 Baume industrial salt and 85% formic acid at a concentration of 5g/L at a water temperature of 30 ℃, rotating for 55min, and standing for 12 h; adding 90% sulfuric acid 2.0g/L, adjusting pH to 3.0, and standing for 6 h; draining water and peeling;

1.5, TWS chrome-free tanning: adding the pickled fur into a paddle vat, and controlling the liquor ratio to be 1: 17, adding 6.0 Baume industrial salt and 17g/L of chrome-free tanning agent TWS, adding 0.5g/L of soda ash to adjust the pH value to 5, rotating for 170min, stopping for 25min, rotating for 50min, and stopping for 230 min; adding soda at a speed of 0.5g/L every time and 30min between two times to adjust the pH value to 8.0, rotating for 110min, heating to 38 ℃, standing for 115min, and finishing TWS chromium-free tanning; discharging the tanning liquid from the paddle tank to a recovery tank for recycling as the tanning liquid in the next day TWS chromium-free tanning, and taking out the fur;

1.6, oxidation: the same as example 1;

1.7, washing: the same as example 1;

1.8, filling and retanning: in the rotary drum, the liquid ratio is 1:10, adding a fatting agent of 1.6g/L at the water temperature of 38 ℃, and rotating for 25 min; adding 45g/L of phenolic synthetic tanning agent, and rotating for 110 min; adding fatting agent 1.6g/L, rotating for 110min, stopping for 60min, and rotating for 60 min; adding 85% formic acid 0.5g/L once every 30 minutes, adjusting pH to 3.8, turning for 2h, stopping for 2h, draining, taking out, standing overnight, and dehydrating the next day;

1.9, drying and finishing: the same as example 1;

2.1, backwater degreasing: the same as example 1;

2.2, first water washing: the same as example 1;

2.3, filling and retanning before dyeing: the same as example 1;

2.4, dyeing wool: in the rotary drum, the liquid ratio is 1: 17, at the temperature of 60 ℃, adding a leveling agent of 0.6g/L, anhydrous sodium sulphate of 12g/L and sodium formate of 0.4g/L, and rotating for 8 min; adding 0.02g/L of acid dye red 18B, 0.0066g/L of BASF yellow E and 0.6g/L of 85% formic acid, rotating for 15min, adjusting pH to 3.5, and draining water to remove peel;

2.5, second water washing: the same as example 1;

2.6, dyeing plate: in the rotary drum, the liquid ratio is 1:10, adding 5.0g/L of neutral tannin and 1.3g/L of sodium formate, and rotating for 25 min; adding 2.5g/L dispersant Tamu M and 1.3g/L wool detergent, and rotating for 8 min; adding animal protein 4g/L, and rotating for 25 min; 0.1g/L of Gabasf LF, 0.036g/L of orange HF-010.075 g/L and Delry (TFL) red H of British company, and rotating for 25 min; adding fatting agent 3.0g/L, grease dispersing agent TFL0.2g/L, grease dispersing agent SAF0.2g/L, rotating for 25min, adding 85% formic acid at a speed of 0.5g/L each time and 10min interval, adjusting pH to 3.5, draining water and peeling;

2.7, third water washing: the same as example 1;

Example 4

1. processing of semi-finished fur and leather products

1.1, soaking: putting raw sheep fur into a rotary drum, wherein the liquid ratio is 1: 19, adding 0.5g/L of soaking agent, 0.1g/L of bactericide and 2.5g/L of surfactant, rotating for 20min, stopping for 13h overnight, peeling the skin the next day, and shearing the hair by a scraper;

1.2, soaking again: in a rotary drum, adding the soaked sheared fur into the mixture with the liquid ratio of 1: 13, adding 0.5g/L of sodium carbonate, 0.5g/L of lipase removal enzyme, 0.3g/L of water soaking agent and 1.0g/L of surfactant into water with the water temperature of 30 ℃, rotating for 30min, standing overnight, and removing meat the next day;

1.3, degreasing: in the rotary drum, the liquid ratio is 1: 13, rotating the water at 40 ℃, 0.4g/L of soda ash, 0.5g/L of lipase and 5g/L of degreasing agent for 120min, and peeling and washing the skin;

1.4, pickling: in the groove, the liquid ratio is 1: 15, adding 7.0 Baume industrial salt and 85% formic acid at the temperature of 30 ℃, rotating for 60min, and standing for 12 h; adding 90% sulfuric acid 2.0g/L, adjusting pH to 3.0, and standing for 6 h; draining water and peeling;

1.5, TWS chrome-free tanning: adding the pickled fur into a paddle vat, and controlling the liquor ratio to be 1: 17, adding 6.0 Baume industrial salt and 15g/L of chrome-free tanning agent TWS, adding 0.5g/L of soda ash to adjust the pH value to 5, rotating for 180min, stopping for 30min, rotating for 60min, and stopping for 240 min; adding soda at a speed of 0.5g/L every time and 30min between two times to adjust the pH value to 8.0, rotating for 120min, heating to 38 ℃, standing for 120min, and finishing the TWS chromium-free tanning; discharging the tanning liquid from the paddle tank to a recovery tank for recycling as the tanning liquid in the next day TWS chromium-free tanning, and taking out the fur;

1.6, oxidation: the same as example 1;

1.7, washing: the same as example 1;

1.8, filling and retanning: in the rotary drum, the liquid ratio is 1:10, adding a fatting agent of 1.5g/L at the water temperature of 38 ℃, and rotating for 30 min; adding 40g/L of phenolic synthetic tanning agent, and rotating for 120 min; adding fat liquor 1.5g/L, rotating for 120min, stopping for 60min, and rotating for 60 min; adding 85% formic acid 0.5g/L once every 30 minutes, adjusting pH to 3.8, turning for 2h, stopping for 2h, draining, taking out, standing overnight, and dehydrating the next day;

1.9, drying and finishing: the same as example 1;

2.1, backwater degreasing: the same as example 1;

2.2, first water washing: the same as example 1;

2.3, filling and retanning before dyeing: the same as example 1;

2.4, dyeing wool: in the rotary drum, the liquid ratio is 1: 17, at the temperature of 60 ℃, adding a leveling agent of 0.5g/L, anhydrous sodium sulphate of 10g/L and sodium formate of 0.3g/L, and rotating for 10 min; adding 0.02g/L of acid dye red 18B, 0.0066g/L of BASF yellow E and 0.5g/L of 85% formic acid, rotating for 20min, adjusting pH to 3.5, and draining water to remove peel;

2.5, second water washing: the same as example 1;

2.6, dyeing plate: in the rotary drum, the liquid ratio is 1:10, adding 4.0g/L of neutralized tannin and 1.0g/L of sodium formate, and rotating for 30 min; adding 2.0g/L of dispersant Tamu M and 1.0g/L of wool detergent, and rotating for 10 min; adding animal protein 3g/L, and rotating for 30 min; 0.1g/L of Gabasf LF, 0.036g/L of orange HF-010.075 g/L and Delry (TFL) red H of British company, and rotating for 30 min; adding fat-liquoring agent 2.0g/L, grease dispersing agent TFL 0.25g/L and grease dispersing agent SAF0.25g/L, rotating for 30min, adding 85% formic acid at a speed of 0.5g/L each time and 10min interval between two times, adjusting pH to 3.5, and draining water to remove skin;

2.7, third water washing: the same as example 1;

Example 5

1. processing of semi-finished fur and leather products

1.1, soaking: putting raw sheep fur into a rotary drum, wherein the liquid ratio is 1: 19, adding 0.6g/L of soaking agent, 0.3g/L of bactericide and 3.0g/L of surfactant, rotating for 25min, stopping for 14h overnight, peeling the skin the next day, and shearing the hair by a scraper;

1.2, soaking again: in a rotary drum, adding the soaked sheared fur into the mixture with the liquid ratio of 1: 13 adding soda 0.5g/L, lipase 0.5g/L, soaking agent 0.3g/L and surfactant 1.0g/L into water at 30 deg.C, rotating for 35min, standing overnight, and removing meat the next day;

1.3, degreasing: in the rotary drum, the liquid ratio is 1: 13, rotating the water at 40 ℃, 0.4g/L of soda ash, 0.5g/L of lipase and 5g/L of degreasing agent for 130min, and peeling and washing the skin;

1.4, pickling: in the groove, the liquid ratio is 1: 15, adding 7.0 Baume industrial salt and 85% formic acid at the temperature of 30 ℃, rotating for 65min, and standing for 12 h; adding 90% sulfuric acid 2.0g/L, adjusting pH to 3.0, and standing for 6 h; draining water and peeling;

1.5, TWS chrome-free tanning: adding the pickled fur into a paddle vat, and controlling the liquor ratio to be 1: 17, adding 6.0 Baume industrial salt and 15g/L of chrome-free tanning agent TWS, adding 0.5g/L of soda ash to adjust the pH value to 5, rotating for 185min, stopping for 35min, rotating for 70min, and stopping for 250 min; adding soda at a speed of 0.5g/L every time and 30min between two times to adjust the pH value to 8.0, rotating for 130min, heating to 38 ℃, standing for 125min, and finishing the TWS chromium-free tanning; discharging the tanning liquid from the paddle tank to a recovery tank for recycling as the tanning liquid in the next day TWS chromium-free tanning, and taking out the fur;

1.6, oxidation: the same as example 1;

1.7, washing: the same as example 1;

1.8, filling and retanning: in the rotary drum, the liquid ratio is 1:10, adding a fatting agent of 1.5g/L at the water temperature of 38 ℃, and rotating for 35 min; adding 40g/L of phenolic synthetic tanning agent, and rotating for 130 min; adding fat liquor 1.5g/L, rotating for 130min, stopping for 60min, and rotating for 60 min; adding 85% formic acid 0.5g/L once every 30 minutes, adjusting pH to 3.8, turning for 2h, stopping for 2h, draining, taking out, standing overnight, and dehydrating the next day;

1.9, drying and finishing: the same as example 1;

2.1, backwater degreasing: the same as example 1;

2.2, first water washing: the same as example 1;

2.3, filling and retanning before dyeing: the same as example 1;

2.4, dyeing wool: in the rotary drum, the liquid ratio is 1: 17, at the temperature of 60 ℃, adding a leveling agent of 0.5g/L, anhydrous sodium sulphate of 10g/L and sodium formate of 0.3g/L, and rotating for 13 min; adding 0.02g/L of acid dye red 18B, 0.0066g/L of BASF yellow E and 0.5g/L of 85% formic acid, rotating for 25min, adjusting pH to 3.5, and draining water to remove peel;

2.5, second water washing: the same as example 1;

2.6, dyeing plate: in the rotary drum, the liquid ratio is 1:10, adding 4.0g/L of neutralized tannin and 1.0g/L of sodium formate, and rotating for 35 min; adding 2.0g/L of dispersant Tamu M and 1.0g/L of wool detergent, and rotating for 13 min; adding animal protein 3g/L, and rotating for 35 min; 0.1g/L of Gabasf LF, 0.036g/L of orange HF-010.075 g/L and Delry (TFL) red H of British company, and rotating for 35 min; adding fat liquor 2.0g/L, grease dispersing agent TFL0.3 g/L and grease dispersing agent SAF0.3g/L, rotating for 35min, adding 85% formic acid at a speed of 0.5g/L each time and 10min interval for two times, adjusting pH to 3.5, and draining water and peeling;

2.7, third water washing: the same as example 1;

Example 6

A chrome-free tanning processing technology for sheep fur leather comprises the following operations of TWS chrome-free tanning:

adding the pickled fur into a paddle vat, and controlling the liquor ratio to be 1: 17, adopting recycled tanning liquid recovered after TWS chrome-free tanning of the sheep fur leather on the previous day or the previous batch, supplementing 0.34L of water for 1 piece of leather, and additionally supplementing clear water; adding industrial salt with Baume degree of 6.0, chrome-free tanning agent TWS 7.5g/L, adding soda ash 0.5g/L to adjust pH to 5, rotating for 180min, stopping for 30min, rotating for 60min, and stopping for 240 min; adding soda at a speed of 0.5g/L every time and 30min between two times to adjust the pH value to 8.0, rotating for 120min, heating to 38 ℃, standing for 120min, and finishing the TWS chromium-free tanning; discharging the tanning liquid from the paddle tank to a recovery tank for recycling as the tanning liquid for the next batch of TWS chrome-free tanning, and taking out the fur; the rest of the operation was the same as in example 4.

It should be noted that the circulating tanning solution in the application needs to be replaced once after being used repeatedly for 100 days, so as to ensure that the fur and leather meeting the performance requirements can be processed.

Example 7

adding the pickled fur into a paddle vat, and controlling the liquor ratio to be 1: 17, recycling tanning liquid recovered after TWS chrome-free tanning of the sheep fur leather on the previous day or the previous batch is adopted as the tanning liquid, and adding 0.425L of water into 1 piece of leather and additionally adding clean water; adding industrial salt with Baume degree of 6.0, chrome-free tanning agent TWS 7.5g/L, adding soda ash 0.5g/L to adjust pH to 5, rotating for 180min, stopping for 30min, rotating for 60min, and stopping for 240 min; adding soda at a speed of 0.5g/L every time and 30min between two times to adjust the pH value to 8.0, rotating for 120min, heating to 38 ℃, standing for 120min, and finishing the TWS chromium-free tanning; discharging the tanning liquid from the paddle tank to a recovery tank for recycling as the tanning liquid for the next batch of TWS chrome-free tanning, and taking out the fur; the rest of the operation was the same as in example 4.

Example 8

adding the pickled fur into a paddle vat, and controlling the liquor ratio to be 1: 17, adding 0.40L of water into 1 piece of skin and additionally adding clean water into the recycled tanning liquid recovered after TWS chrome-free tanning of the sheep fur leather on the previous day or the previous batch; adding industrial salt with Baume degree of 6.0, chrome-free tanning agent TWS 7.5g/L, adding soda ash 0.5g/L to adjust pH to 5, rotating for 180min, stopping for 30min, rotating for 60min, and stopping for 240 min; adding soda at a speed of 0.5g/L every time and 30min between two times to adjust the pH value to 8.0, rotating for 120min, heating to 38 ℃, standing for 120min, and finishing the TWS chromium-free tanning; discharging the tanning liquid from the paddle tank to a recovery tank for recycling as the tanning liquid for the next batch of TWS chrome-free tanning, and taking out the fur; the rest of the operation was the same as in example 4.

Example 9

adding the pickled fur into a paddle vat, and controlling the liquor ratio to be 1: 17, adding 0.40L of water into 1 piece of skin and additionally adding clean water into the recycled tanning liquid recovered after TWS chrome-free tanning of the sheep fur leather on the previous day or the previous batch; adding industrial salt with Baume degree of 6.0, chrome-free tanning agent TWS 6.75g/L, adding soda ash 0.5g/L to adjust pH to 5, rotating for 180min, stopping for 30min, rotating for 60min, and stopping for 240 min; adding soda at a speed of 0.5g/L every time and 30min between two times to adjust the pH value to 8.0, rotating for 120min, heating to 38 ℃, standing for 120min, and finishing the TWS chromium-free tanning; discharging the tanning liquid from the paddle tank to a recovery tank for recycling as the tanning liquid for the next batch of TWS chrome-free tanning, and taking out the fur; the rest of the operation was the same as in example 4.

Example 10

adding the pickled fur into a paddle vat, and controlling the liquor ratio to be 1: 17, adopting recycled tanning liquid recovered after TWS chrome-free tanning of the sheep fur leather on the previous day or the previous batch, supplementing 0.34L of water for 1 piece of leather, and additionally supplementing clear water; adding industrial salt with Baume degree of 6.0, chrome-free tanning agent TWS 7.2g/L, adding soda ash 0.5g/L to adjust pH to 5, rotating for 180min, stopping for 30min, rotating for 60min, and stopping for 240 min; adding soda at a speed of 0.5g/L every time and 30min between two times to adjust the pH value to 8.0, rotating for 120min, heating to 38 ℃, standing for 120min, and finishing the TWS chromium-free tanning; discharging the tanning liquid from the paddle tank to a recovery tank for recycling as the tanning liquid for the next batch of TWS chrome-free tanning, and taking out the fur; the rest of the operation was the same as in example 4.

Example 11

A chrome-free tanning processing technology of sheep fur leather, which is different from the processing technology of the example 10 in the following points:

2.6, adopting a spraying process for dyeing the plate, and the rest of the operation is the same as that of the embodiment 10, wherein the spraying operation is as follows:

2.6.1, hand feeling layer: gloss oil and water were mixed at a ratio of 1.3: 1, uniformly stirring, spraying a layer of release paper with the spraying amount of 60g, and drying for 3min at 100 ℃;

2.6.2, surface sizing layer: sizing resin: water: the dye paste is prepared by mixing the following components in percentage by weight: 3: 1, uniformly stirring, spraying 100g on the hand feeling layer for three times, and drying for 2min at 100 ℃ for each time;

2.6.3, foamed resin layer: stirring and foaming the foaming agent until the volume is increased by 1.5 times, uniformly thinning the foam, mixing with the dye paste according to the ratio of 20: 1, uniformly stirring, spraying the mixture on a surface slurry layer twice, and drying for 2min at 130 ℃;

2.6.4, adhesive layer: mixing the water-based adhesive with water according to the ratio of 5: 1, uniformly stirring, and spraying on the foamed resin layer once; and (3) flatly paving the skin on release paper sprayed with the slurry of each layer, flatly flattening, drying for 6min at 100 ℃, completely drying, taking out, removing the skin, finishing and coating after the whole operation procedure is finished, thus obtaining the sheep fur and leather.

Example 12

2.6, adopting a roller coating process for dyeing the plate, wherein the rest operations are the same as those in the embodiment 10, and the roller coating operation is as follows:

2.6.1, stirring and foaming the foaming resin until the volume is increased to 1.5 times, adjusting the viscosity to 4200Pa · s, and carrying out the following steps of: 5, rolling twice by using a roller and drying for 6min at 110 ℃; wherein, the sizing proportion refers to the rotating speed proportion of the upper roller and the lower roller;

2.6.2, mixing the pulp layer resin raw materials according to the weight ratio of 8: 4, roller coating once, and drying for 6min at 110 ℃;

2.6.3 gloss oil and water were mixed according to a ratio of 2: 1, uniformly stirring, spraying once, and drying for 6min at 110 ℃; completely drying, taking out, finishing the whole operation process, finishing and finishing to obtain the sheep fur and leather.

Example 13

A chrome-free tanning processing technology of sheep fur leather, which is different from the processing technology of the embodiment 11 in that:

the same operations as in example 11 were carried out except that the aqueous washing solution obtained in step 1.3 was recovered and applied to the double immersion in step 1.2 and the aqueous washing solution obtained in step 1.7 was recovered and applied to the oxidation step 1.6.

Comparative example 1

A chrome-free tanning process for tanning low-formaldehyde beach sheep fur by using a chrome-free tanning agent TWT sequentially comprises the following steps:

soaking: soaking the beach sheep fur in a soaking solution for 12-24 hours at the temperature of 30-35 ℃, wherein the soaking solution comprises the following components: 0.5-1.5g/L of Diamoll WEF Powder, 10-25g/L of salt, 0.5-2.5g/L of degreasing agent TPL, 0.1-1.5g/L of water-soaking enzyme Feliderm SE 3Powder, and the balance of water; the dosage of the soaking liquid is 20-30 of the mass ratio of the water in the soaking liquid to the fur; removing meat;

degreasing: moving the degreased liquid for 30-120min at the temperature of 35-40 ℃, wherein the degreased liquid comprises the following components: 0.5-1.5g/L of soda, 0.1-1.5g/L of compound enzyme DESOBE LG, 0.5-1.5g/L of penetrating agent JFC, 2-5g/L of degreasing agent PX, and the balance of water; the dosage of the degreasing fluid is 20-40 of the mass ratio of water to fur in the degreasing fluid;

softening: adding alkaline softening enzyme DESOBATE B2 into the defatted solution to obtain softening solution with softening enzyme concentration of 1.0-2.0g/L and softening time of 5-10 hr;

tanning: the Tan sheep skin is treated by the steps and then is placed IN a groove for tanning, 30L of water is used for each Tan sheep skin during tanning, a chelating dispersant DT-A101 (Germany chemical engineering) is added at 0.9g/L, a chrome-free tanning agent TWT (Germany chemical engineering) is added at 10g/L, a whitening agent Blanket IN (Passion) is added at 0.6g/L, a degreasing agent DT-A121 (Germany chemical engineering) is added at 0.8g/L, the temperature is 39 ℃, the pH is adjusted to 5.0, the Tan sheep skin stands overnight after being scratched for 90min, the color of a cut is checked by using a fuchsin indicator on the next day, and if the Tan sheep skin is purple and uniform IN color, the penetration is proved to be complete;

alkali extraction after tanning: adding baking soda into the standing tanning liquid for alkali extraction. The concentration of the baking soda is 1g/L, 10 times of tanning solution is taken out to dilute the baking soda, the diluted baking soda solution is added into the tanning solution for three times, the interval of each time is 30min, the pH value is adjusted to 6.9, and soda ash is added into the tanning solution for alkali extraction after 90min from the first time of adding the baking soda solution. The concentration of soda is 1.2g/L, the liquid obtained by extracting soda with 10 times of sodium bicarbonate is taken out to dilute the soda, the diluted soda solution is added into the tanning liquid for four times at intervals of 30min each time, the pH value is adjusted to 8.2, 120min is counted from the first time of adding the soda solution, an aldehyde removing agent DT-A9810 (Germany chemical industry) is added, wherein the concentration of the aldehyde removing agent DT-A9810 (Germany chemical industry) is 1.2g/L, 30min is scratched to remove the leather, small blocks cut from the tanned crust leather are measured, the shrinkage temperature is 83 ℃, and the next step is carried out;

and (3) rewetting: carrying out rewetting operation on the dried crust leather of the Tan sheep, adding 1.2g/L of chelating dispersant DT-A101 (Demei chemical engineering), 50g/L of salt, 0.9g/L of water-soaking enzyme Davzam SK (Dawei) and 1.5g/L of water-soaking auxiliary agent DT-FUR2Z06 (Demei chemical engineering) into 30 ℃ of water for each crust leather of the Tan sheep during rewetting, and standing overnight after intermittent scratching for 4 hours;

retanning: the crust leather after being rewetted is placed IN a groove for retanning, the liquid-liquid ratio of retanning is 20, and the crust leather comprises 0.4g/L of chelating dispersant DT-A101 (Germany chemical), 4g/L of chrome-free tanning agent TWT (Germany chemical), 0.3g/L of whitening agent Blankit IN (basf), 1.5g/L of fatting agent Eschka lead GLH (Baume) and 1.2g/L of environment-friendly retanning agent DT-R548 (Germany chemical), the temperature is controlled at 40 ℃, the pH is adjusted to 4.5, and alkali is extracted after retanning for 5 hours;

alkali extraction after retanning: adding baking soda into retanning liquor for alkali extraction, wherein the concentration of the baking soda is 1.2g/L, taking out 10 times of the retanning liquor to dilute the baking soda, adding the diluted baking soda solution into the retanning liquor for five times at intervals of 30min, adjusting the pH value to 5.8, and adding soda into the retanning liquor for alkali extraction after 150min from the first addition of the baking soda solution. The concentration of soda is 1.6g/L, the liquid obtained by extracting soda with 10 times of sodium bicarbonate is taken out to dilute the soda, the diluted soda solution is added into the tanning liquid for four times, the interval of each time is 30min, the pH value is adjusted to 7.8, 120min is counted from the first time of adding the soda solution, an aldehyde removing agent DT-A9810 (Germany chemical industry) is added, wherein the concentration of the aldehyde removing agent DT-A9810 (Germany chemical industry) is 1.2g/L, the scratching is carried out for 30min, and the standing is carried out overnight after the scratching is carried out for 5 h;

fat liquoring: the fat liquor is water solution containing fat liquor Escadan GLH (Baume) 5-50 g/L; the dosage of the fatliquoring solution is added according to the mass ratio of water to fur in the fatliquoring solution of 10-20, and the fatliquoring is carried out at the temperature of 55-65 ℃;

air drying, moisture regaining, peeling, dry grinding and brushing ash to obtain the finished product.

Comparative example 2

Comparative example 2 differs from example 1 in that: the same amount of the chrome-free tanning agent TWS in chrome-free tanning was replaced with the chrome-free tanning agent TWT, and the rest was the same as in example 1.

Comparative example 3

Comparative example 3 differs from example 1 in that: the same amount of the chrome-free tanning agent TWS in chrome-free tanning was replaced with the chrome-free tanning agent TWLZ, and the rest was the same as in example 1.

Comparative example 4

Comparative example 4 differs from example 6 in that: the same amount of the chrome-free tanning agent TWS in chrome-free tanning was replaced with the chrome-free tanning agent TWT, and the rest was the same as in example 6.

Comparative example 5

Comparative example 5 differs from example 6 in that: the same amount of the chrome-free tanning agent TWS in chrome-free tanning was replaced with the chrome-free tanning agent TWLZ, and the rest was the same as in example 6.

Comparative example 6

Comparative example 6 differs from example 11 in that: the same amount of the chrome-free tanning agent TWS in chrome-free tanning was replaced with the chrome-free tanning agent TWT, and the rest was the same as in example 11.

Comparative example 7

Comparative example 7 differs from example 12 in that: the same amount of the chrome-free tanning agent TWS in chrome-free tanning was replaced with the chrome-free tanning agent TWT, and the rest was the same as in example 12.

Performance detection

The performance tests of the sheep furs of examples 1-13 and comparative examples 1-7 were carried out using the following test standards and test methods, respectively, and the test results are detailed in tables 1-3:

formaldehyde content (unit: mg/kg): GB/T19941.2-2019;

shrinkage temperature (unit:. degree. C.): QB/T2713-;

matte friction fading (dry, wet): AATCC 8-2016;

leather surface friction fading (dry, wet): AATCC 8-2016;

tensile strength (unit: kg/1.27 cm): ASTM D2209;

tear Strength (unit: kg): SATRA PM 162.

Table 1 results of performance tests of sheep furs of examples 1 to 7

Table 2 results of performance tests of sheep furs of examples 8 to 13

The detection results in the tables 1 and 2 show that the shrinkage temperature of the sheep fur and leather processed by the method is above 94 ℃ and can reach 100 ℃ at most; the dry friction faded rough surface and the leather surface reach 4 grades, the wet friction faded rough surface reaches 3.5 grades, the leather surface reaches 4 grades, and the color fastness performance is excellent; the tensile strength is more than 15kg/1.27cm in the length direction and more than 14kg/1.27cm in the width direction, and both meet the standard requirements; the tearing strength in the length direction and the width direction is more than 8kg, and both meet the standard requirements.

TABLE 3 Performance test results of sheep fur and leather of comparative examples 1-7

The detection results in table 3 show that the shrinkage temperature and the rubbing color fastness of the sheep fur leather processed by the process are superior to those of the sheep fur leather in the related technology (comparative example 1). According to the detection results of the comparative examples 2-7, in the process, the performance of the final sheep fur is greatly influenced by the non-chromium tanning agent TWS in the non-chromium tanning, and the comprehensive performance of the fur is reduced after the non-chromium tanning agent TWS is replaced by other non-chromium tanning agents.

The water consumption in each processing step of examples 1, 10, 11, 13 and 1 of the present application was counted, each step is expressed as a liquid ratio, and the statistical results are detailed in table 4.

TABLE 4 Water consumption in the working steps of examples 10 to 11, example 13 and comparative example 1

As can be seen from Table 4, compared with comparative example 1, the liquid ratio of the water immersion, degreasing, rewetting and filling retanning is much smaller than that of comparative example 1, and the maximum difference of the liquid ratio can be up to 10 times. In the chrome-free tanning, only 17L of water is needed for each piece of leather at most, 30L of water is needed in a comparative example 1, after the circulating tanning liquid is utilized subsequently, only 0.34L of water is needed for each piece of leather at most, and the water consumption is different from that in the chrome-free tanning in the comparative example 1 by two orders of magnitude; taking the daily yield of 8-slot fur and leather, 700 furs per slot and 340 days of the annual working day after the replacement of the circulating tanning liquid as an example, the annual yield is 8 multiplied by 700 multiplied by 340 to 1904000, so that the water consumption of 1904000 multiplied by (30-0.34) to 56472640L to 5.65 ten thousand tons can be saved in the annual chromium-free tanning, and the water resource is greatly saved.

As can be seen from the comparison between example 1 and example 10, in the process of the present application, after the recycled tanning liquor is used in chrome-free tanning, 17-0.34 to 16.66L of water can be saved for each piece of hide, and the water consumption of 1904000 × 16.66 to 31720640L to 3.2 ten thousand tons can be saved each year, so that the processing cost is greatly saved, and the wastewater discharge of about 3.2 ten thousand tons can be reduced, thereby being more environment-friendly.

As can be seen from the comparison between example 1 and example 11, in the process of the present application, after the cyclic tanning liquid is used in chrome-free tanning and the spraying process is adopted in dyeing the board, water can be saved by (17-0.34) +10+36 ═ 62.66L for each piece of leather, water consumption of 1904000 × 62.66 ≈ 119304640L ≈ 11.9 ten thousand tons can be saved each year, processing cost is greatly saved, and wastewater discharge of 11.9 ten thousand tons can be reduced, which is more environment-friendly.

As can be seen from comparison between example 1 and example 13, in the process of the present application, after the water washing solution after degreasing is applied to the re-immersion water, the water washing solution in the water washing step is applied to the oxidation by using the cyclic tanning solution in the chrome-free tanning, and the spraying process is adopted when the plate is dyed simultaneously, water can be saved by (17-0.34) +10+36+13+17 ═ 92.66L per skin, water consumption of 1904000 × 92.66 ═ 176424640L ≈ 17.6 ten thousand tons can be saved every year, processing cost is greatly saved, wastewater discharge of 17.6 ten thousand tons can be reduced, and effects of energy saving, environmental protection and production cost reduction are achieved.

The embodiments of the present invention are preferred embodiments of the present application, and the scope of the present application is not limited by the embodiments of the present application, so: all equivalent changes made according to the structure, shape and principle of the present application shall be covered by the protection scope of the present application.

Claims

1. A chrome-free tanning processing technology for sheep fur leather is characterized by sequentially comprising the following processing steps:

2. The processing technology of the sheep fur and leather chrome-free tanning according to claim 1, characterized in that the TWS chrome-free tanning specifically comprises: adding the pickled fur into the mixture according to the liquor ratio of 1: 17, adding 5.5-6.0 Baume industrial salt and 13-17g/L of chrome-free tanning agent TWS into water, adjusting the pH to 4.5-5.0, rotating for 170-70 min, stopping for 25-35min, rotating for 50-70min, stopping for 230-250 min; adding soda to adjust the pH value to 7.0-8.0, rotating for 110-.

3. The chrome-free tanning process for sheep fur and leather according to claim 1, characterized in that: when the circulating tanning liquid is used for the next batch of TWS chromium-free tanning, the added amount of TWS is 45-50wt% of the initial amount of TWS, and the added amount of water is 2.0-2.5 wt% of the initial amount of water.

4. The processing technology of the chrome-free tanning of the sheep fur and leather according to claim 1, wherein the operation of soaking specifically comprises: adding raw fur into the mixture according to the liquor ratio of 1: adding 0.4-0.6g/L of soaking agent, 0.1-0.3g/L of bactericide and 2.0-3.0g/L of surfactant into water of 19, rotating for 15-25min, stopping for 12-14h, peeling, and shearing hair with a scraper; the operation of re-soaking is as follows: adding the fur after the soaking step into a solution with the ratio of 1: 14, adding 0.4-0.6g/L of soda ash, 0.4-0.6g/L of lipase removal enzyme, 0.2-0.4g/L of water soaking agent and 0.7-1.2g/L of surfactant into water at the water temperature of 30 ℃, rotating for 25-35min, standing overnight, and removing meat the next day.

5. The chrome-free tanning process for sheep fur and leather according to claim 1, characterized in that: the degreasing operation specifically comprises the following steps: the liquid ratio is 1: 14, water temperature is 40 ℃, 0.3-0.5g/L of sodium carbonate, 0.4-0.6g/L of lipase and 4-6g/L of degreasing agent are rotated for 110-; the pickling operation specifically comprises the following steps: the liquid ratio is 1: 17, adding 6.0-7.0 Baume industrial salt and 85% formic acid at the water temperature of 30 ℃, rotating for 55-65min, and standing for 12 h; adding 90% sulfuric acid, adjusting pH to 3.0, and peeling.

6. The chrome-free tanning process for sheep fur and leather according to claim 1, characterized in that: the filling retanning operation specifically comprises the following steps: the liquid ratio is 1:10, adding a fatting agent of 1.6g/L at the water temperature of 38 ℃, and rotating for 25-35 min; adding 35-45g/L of phenolic synthetic tanning agent, and rotating for 110-; adding fatting agent 1.6g/L, rotating for 110-; adding 85% formic acid to adjust pH to 3.8, rotating for 2h, stopping for 2h, draining, taking out, and standing overnight.

7. The chrome-free tanning process for sheep fur and leather according to claim 1, characterized in that: the operation of dyeing the wool is specifically as follows: the liquid ratio is 1:20, the water temperature is 68 ℃, a leveling agent is added for 0.4-0.6g/L, anhydrous sodium sulphate is added for 8-12g/L, sodium formate is added for 0.2-0.4g/L, the rotation is carried out for 8-13min, an acid dye and 85% formic acid are added for 0.4-0.6g/L, the rotation is carried out for 15-25min, and water is drained and the skin is discharged; the operation of the dyeing plate is specifically as follows: adding 3-5g/L of neutralized tannin and 0.8-1.3g/L of sodium formate at a liquid ratio of 1:10, and rotating for 25-35 min; adding dispersant 1.5-2.5g/L and hair detergent 0.8-1.3g/L, and rotating for 8-13 min; adding animal protein 2-4g/L, and rotating for 25-35 min; adding dye, and rotating for 25-35 min; adding fat-liquoring agent 1.0-3.0g/L and oil dispersant 0.4-0.6g/L, and rotating for 25-35 min; adding 85% formic acid to adjust pH to 3.5, draining water and peeling.

8. The chrome-free tanning process for sheep fur and leather according to claim 1, characterized in that: the liquid ratio of backwater degreasing, primary water washing and secondary water washing is 1: 10; the washing liquid in the degreasing step is recycled and then used in the main soaking water; and recovering the washing liquid in the washing step and then using the washing liquid in the oxidation.

9. The chrome-free tanning process for sheep fur and leather according to claim 1, characterized in that: the dyeing plate adopts a spraying or roller coating process, and after the dyeing plate is dyed, the finished product sheep fur and leather is obtained through finishing and coating.

10. A sheep fur leather is characterized in that: which is processed by the processing technology of the chrome-free tanning of the sheep fur leather according to any one of claims 1 to 9.