CN110628968B - Processing technology of chrome-free tanning of sheep leather, sheep white wet leather and sheep leather - Google Patents
Processing technology of chrome-free tanning of sheep leather, sheep white wet leather and sheep leather Download PDFInfo
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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
- C14C1/04—Soaking
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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
- C14C1/06—Facilitating unhairing, e.g. by painting, by liming
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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
- C14C15/00—Apparatus for chemical treatment or washing of hides, skins, or leather
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- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C3/00—Tanning; Compositions for tanning
- C14C3/02—Chemical tanning
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- 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
- C14C5/00—Degreasing leather
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Abstract
The invention relates to a processing technology of chrome-free tanning of sheep leather, which sequentially comprises the following processing steps: soaking, alkali leaching and hair removal, liming, deliming and softening, degreasing, pickling and tanning, retanning and dyeing, finishing and finishing; in the step of pickling and tanning, chrome-free tanning agent TWLZ is adopted to carry out chrome-free tanning on the degreased leather material to obtain white wet leather, and the white wet leather is subjected to retanning dyeing, finishing and finishing processing to obtain sheep leather; the chrome-free tanning process is successfully applied to the sheep skin to prepare the white wet leather and the sheep leather, and the tanning process does not generate chromium-containing wastewater and chromium leather scraps, so that the method is green and environment-friendly; the prepared white wet leather has the maximum shrinkage temperature of 95 ℃ and good performance; the whiteness is good, the color is not changed within one year, the storage resistance is good, and the yellowing resistance is 4 grades; the finished product of the sheep leather has good air permeability, and the shrinkage temperature reaches more than 90 ℃.
Description
Technical Field
The invention relates to the technical field of processing of sheep leather, in particular to a processing technology of chrome-free tanning of the sheep leather, a sheep white wet leather and the sheep leather.
Background
The leather is animal leather which is obtained by physical and chemical processing such as unhairing, tanning and the like and is denatured and not easy to rot, and the surface of the leather is provided with a special grain layer which has natural grains and luster and comfortable hand feeling. The leather processing technology mainly comprises two working procedures: water fields and dry fields. The water field mainly comprises soaking, unhairing, deliming, alcoholysis, pickling, chrome tanning, dyeing, fatting and skin stretching, and the semi-finished skin after skin stretching can be directly used for producing suede and fur-hammer skins; the dry field mainly comprises the steps of rewetting, milling or softening, buffing, surface coating and embossing, and finally the finished leather is obtained.
In leather processing, tanning operations have a large impact on the properties of the leather. Chrome tanning is a method which is widely applied in the world at present and has excellent tanning effect, and leather tanned by the method has the advantages of humidity resistance, heat resistance, good stability, soft and plump finished leather, good formability and the like. For more than one hundred years, chrome tanning has been the dominant method for its superior tanning performance. On one hand, however, the storage capacity of chromium in the world is limited, chromium resources in China are not abundant, and the situation that a large amount of chromium is exhausted due to use is a reality which is difficult to avoid; on the other hand, the chrome tanning has great pollution to the environment, and a great amount of chromium-containing wastewater and chrome leather scraps are generated in the chrome tanning process, so that the environment protection is not facilitated. In addition, the leather obtained by chrome tanning contains chromium, has greater skin irritation after contacting human skin and belongs to a sensitizer; moreover, the leather is not easy to biodegrade, and the environment is polluted after being discarded.
In order to overcome the above-mentioned drawbacks of chrome tanning, a process has been developed in the prior art that replaces chrome tanning with chrome-free tanning. The invention patent with the publication number of CN 101225450B discloses a non-chrome tanning production process of goat glove leather, which comprises the following steps: softening → pickling → organic phosphine tanning → oxidation → setting aside → squeezing water stretching → shaving → washing → degreasing, rinsing → washing → retanning and fat adding → washing, then proceeding with conventional chrome tanning follow-up process; the advantages of the chrome-free tanning are that: the pollution of heavy metal chromium to the environment can be overcome, and the cost of sewage treatment of enterprises is reduced; the shrinkage temperature (Ts) of the leather produced reaches above 88 ℃.
However, the leather material for leather processing mainly includes goat skin, sheep skin, cow skin, pig skin, horse skin, etc., and different leather materials have different properties and different processing details in the processing process. For example, the pores of cow leather are fine, the pores of cow can hardly be seen, and the hair of cow leather is short, so that the hair removal treatment is easy; goat skin has large pores and hair is longer than cow skin; the pores of the sheep skin are like shark and are finer than those of the goat skin, and the hair is longer than that of the goat; the sheep skin has soft and exquisite handfeel and peculiar surface grains, and is easy to be accepted and favored by consumers.
Therefore, how to successfully apply the chrome-free tanning process to the processing of the sheep skin, overcome the pollution of heavy metal chromium to the environment and ensure the shrinkage temperature of the leather is a problem to be solved urgently by technical personnel in the field.
Disclosure of Invention
The first purpose of the invention is to provide a processing technology of chrome-free tanning of sheep leather, which successfully applies the chrome-free tanning technology to the sheep leather to prepare the sheep leather, does not generate chrome-containing wastewater and chrome leather scraps in the tanning process, and is green and environment-friendly; the shrinkage temperature of the prepared sheep white wet leather is more than 92 ℃, the shrinkage temperature of the finished sheep leather is more than 90 ℃, and the performance is good.
The first purpose of the invention is realized by the following technical scheme:
a processing technology for chrome-free tanning of sheep leather sequentially comprises the following processing steps:
soaking, alkali leaching and hair removal, liming, deliming and softening, degreasing, pickling and tanning, retanning and dyeing, finishing and finishing; in the step of pickling and tanning, chrome-free tanning agent TWLZ is adopted to carry out chrome-free tanning on the degreased leather material to obtain white wet leather, and the white wet leather is subjected to retanning dyeing, finishing and finishing processing to obtain the sheep leather.
By adopting the technical scheme, the chrome-free tanning agent TWLZ has the following advantages: the polysaccharide is prepared by utilizing natural polysaccharide, has rich raw material sources, is a renewable substance and has easily obtained resources; the tanning agent is easy to biodegrade and is an environment-friendly chrome-free tanning agent; because no chromium exists, chromium-containing waste water, chromium leather scraps and chromium-containing sludge are not generated in the tanning process, and the tanning process is green and environment-friendly; the processed leather has zero chromium content, no irritation to human skin, safety and reliability; the shrinkage temperature of the processed sheep white wet skin is up to more than 92 ℃, so that the subsequent dyeing and finishing processing is facilitated; the shrinkage temperature of the finished product of the sheep leather obtained after the white wet leather is processed is above 90 ℃, and the performance is good; the finished leather has excellent air permeability, so that the finished leather can be called breathable leather; the product has sweat absorption and can be absorbed after being rubbed and oiled; the terminal can not cause secondary pollution to the environment after being discarded, and is biodegradable.
Preferably, the pickling tanning step is specifically as follows: adding water into the degreased leather material, and controlling the pickling solution ratio to be 110% of 100-; adding industrial salt 5-10% of the total weight of fur, and turning for 3-10 min; adding DODP 0.1-0.5% of the total weight of fur and surfactant 0.1-0.5% of the total weight of fur, and rotating for 25-35 min; adding F5195 0.3-0.8% of the total weight of fur, and rotating for 15-25 min; adding 85% formic acid 0.08-0.13% of the total weight of fur, and rotating for 15-25 min; adjusting pH to 2.6-2.7, adding 5-10 wt% of chrome-free tanning agent TWLZ, and turning for 2.5-3.5 hr; adding alkali extracting agent 1.1-1.2% of the total weight of fur, and rotating for 4-6 h; adjusting the liquid temperature to 38-43 deg.C, rotating for 2.5-3.5h, controlling pH to 4.0, and standing for 8-15 h; rotating for 50-70min, controlling pH to 4-5, washing, taking out, setting up, and standing to finish tanning steps.
By adopting the technical scheme, DODP (dioctyl phthalate), dioctyl terephthalate and long-chain alkoxy alcohol non-ionic degreasing agent are adopted. F5195, acid-resistant and chromium-resistant fatliquor. In the pickling tanning process, the three auxiliaries can ensure that the TWLZ serving as the chromium-free complex tanning agent can deeply permeate into the whole leather, and the TWLZ can be distributed in the whole leather more uniformly.
The second purpose of the invention is to provide a processing technology of chrome-free tanning of sheep leather, which is different from the technical scheme of the first purpose in that chrome-free tanning agent TWS is adopted to carry out chrome-free tanning on the degreased leather in the step of pickling and tanning, and the step of pickling and tanning specifically comprises the following steps: adding water into the degreased fur material, controlling the ratio of pickling solution to be 55-65%, adding industrial salt accounting for 5-10% of the total weight of fur, and rotating for 12-17 min; adding 85% formic acid 1% of the total weight of fur, and rotating for 40-50 min; 90 percent of sulfuric acid with the total weight of 0.6 percent of fur, and is converted into 170-190 min; adding 3-8% of chrome-free tanning agent TWS (TWS) by the total weight of the fur, and transferring for 220-260 min; adding sodium bicarbonate 0.3-0.5% of the total weight of fur, and transferring for 15-25 min; adding sodium bicarbonate 0.3-0.9% of the total weight of fur, and rotating for 40 min; adding soda ash 0.1-0.3% of the total weight of the fur, and rotating for 35-45 min; controlling the pH value to be 7-8, and standing for 8-15 h; rotating for 30min to control water; the ratio of the fixing liquid to the fixing liquid is 100 percent, 85 percent formic acid accounting for 0.5 to 0.8 percent of the total weight of the fur is added, TWB accounting for 1 to 3 percent of the total weight of the fur is added, the mixture is rotated for 15 to 25min, the mildew preventive accounting for 0.1 to 0.3 percent of the total weight of the fur is added, the mixture is rotated for 80 to 100min, the pH value is adjusted to be 5.0, and the obtained product is discharged out of a drum.
By adopting the technical scheme, the chrome-free tanning agent TWS has the following advantages: low toxicity and no irritation; the white wet leather has biodegradability, and the white wet leather processed by the white wet leather has the highest 96 ℃ resistance, so that the temperature resistance of the white wet leather is improved; the white wet skin is not easy to mildew during storage and has good storage stability; the finished leather processed from the wet white leather has the highest resistance of 93 ℃. TWB, phenolic syntan.
The soaking step in the technical solutions of the first and second objects of the present invention comprises the following steps:
pre-soaking: adding water at 20-25 deg.C in an amount of 200-300 wt% of the fur, adding anionic surfactant, bactericide and inorganic alkali, rotating for 5-7h, taking out, and removing meat;
main soaking: adding water at 20-25 deg.C in an amount of 200-300 wt% of fur, adding anionic surfactant, bactericide and inorganic alkali, rotating for 22-30h, taking out, and controlling water for 3-5 h.
By adopting the technical scheme, meat is removed after pre-soaking, residual meat membrane on fur is removed, and wrinkles are stretched, so that uniform permeation of various chemical materials in a later working section is facilitated, and soaking can be accelerated; the temperature and time of main soaking are controlled, and soaking is only needed, so that the problems of fur vertical lines and fur lengthening caused by excessive soaking are easily caused, the elongation of finished leather is increased, and the setting property is poor; the anionic surfactant is added in the soaking process, so that the soaking can be accelerated and the grease can be emulsified.
The liming steps in the technical scheme of the first object and the second object of the invention are as follows: adding water with 15-25 ℃ accounting for 190-210 percent of the total weight of the fur, adding liming auxiliary agent accounting for 0.8-1.3 percent of the total weight of the fur, sodium sulfide accounting for 0.5-0.8 percent of the total weight of the fur, anionic dispersing wetting agent accounting for 0.3-0.5 percent of the total weight of the fur and calcium hydroxide accounting for 0.8-1.3 percent of the total weight of the fur, and rotating for 25-30h to finish the liming operation.
By adopting the technical scheme, liming operation is carried out after alkali is sprayed and dehairing, which is beneficial to removing epidermis and scale; the liming time needs to be reasonably controlled, otherwise, excessive dispersion of local leather fibers is easily caused, and the extensibility and the tearing strength of finished leather are influenced.
The deashing softening step in the technical scheme of the first object and the second object of the invention is specifically as follows: controlling the ratio of deashing solution to 100%, adding 0.3-0.7% of degreasing agent, 0.3-0.7% of lipase and 1.3-2.1% of deashing agent at 25-35 deg.C, and rotating for 85-95 min; adjusting pH to 8-9, draining, changing water, controlling softening liquid ratio to 150%, adding alkaline softening enzyme 0.2-0.4% of total weight of fur and sawdust 0.08-0.13% of total weight of fur at 33-38 deg.C, rotating for 40-60min, draining, washing with water once, and completing deliming and softening operation.
By adopting the technical scheme, ash alkali on the surface of the fur is removed, the grain surface of the leather is softened, and the wrinkle of the neck part is unfolded and opened conveniently; converting the alkali into soluble salt, removing the physically precipitated and chemically bound ash alkali and capillary ash alkali. Through deliming and softening operations, the finished leather strength of the fur can be improved, and the setting performance of the leather is improved.
The technical scheme of the first object and the second object of the invention comprises the following operation steps: degreasing, softening, filling and dyeing.
By adopting the technical scheme, the uniformity, softness and fullness of the sheep leather are improved and the mechanical strength of the leather is improved by retanning and dyeing.
The retanning dyeing in the technical scheme of the first object and the second object can be further processed by the following operation steps: degreasing, filling and dyeing.
The third purpose of the invention is to provide the sheep white wet skin processed by the processing technology of the chrome-free tanning of the sheep leather of the first purpose or the second purpose, wherein the shrinkage temperature of the sheep white wet skin is not less than 92 ℃.
By adopting the technical scheme, the white wet leather is successfully processed by two chromium-free tanning agents, the shrinkage temperature of the white wet leather reaches more than 92 ℃, and the white wet leather has good storage stability.
A fourth object of the present invention is to provide a process for chrome-free tanning of sheep leather having a shrinkage temperature of not less than 90 c using the first or second object.
In conclusion, the invention has the following beneficial effects:
(1) the two chrome-free tanning agents have biodegradability, belong to environment-friendly tanning agents, have no irritation to human bodies, and are high in safety and more environment-friendly compared with organic chrome tanning agents;
(2) the tanning process does not generate chromium-containing wastewater, chromium-containing leather scraps and chromium-containing sludge, and the TOC content in the wastewater can be reduced by 45 percent at most compared with the traditional process, so that the tanning process is more environment-friendly;
(3) the white wet leather processed by the process has the highest shrinkage temperature of 95 ℃, and the absorptivity of dyeing and finishing materials reaches more than 95%; the storage performance is good, no yellowing, no mildew, no odor and the like are generated after the storage for two years, and the yellowing resistance reaches more than grade 4; the finished product of the sheep leather obtained by processing is ecological and environment-friendly and has excellent air permeability.
Detailed Description
The present invention will be further described with reference to the following specific examples.
The surfactant in the pickling tanning is selected from A108 of New Material GmbH of Szechwan river in Sichuan; f5195 is selected from Sichuan Tingjiang New materials GmbH; the chrome-free tanning agent TWLZ is selected from Sichuan Tingjiang New materials GmbH; the alkali extracting agent is MGO automatic alkali extracting agent of Craine; the chrome-free tanning agent TWS is selected from Sichuan Tingjiang New materials GmbH; the phenolic syntan TWB is selected from Sichuan Tingjiang New materials GmbH; the mildew inhibitor is 30L of Bakmann chemical industry (Shanghai) Co; the anionic surfactant is selected from WT-H of Sichuan Desair chemical industry Co., Ltd; the bactericide is selected from 1078 of Bakman chemical industry (Shanghai) Co., Ltd; the anionic dispersing wetting agent in the liming operation is selected from the group consisting of Boron A of Driffl; the liming auxiliary agent is selected from an amine compound liming auxiliary agent LM-5 of Sichuan Desaier chemical industry and industry Co., Ltd; the degreasing agent is selected from Sichuan Dawei science and technology company Limited; the lipase is selected from FD of Umbelliferae, or Umbelliferae; the deliming agent is selected from ammonium-free deliming agent TM of organic acid salts of Desel corporation in Sichuan and ASB of TFL corporation; the alkaline softening enzyme is selected from pancreatin U2 of Dessel chemical industry Co., Ltd, Sichuan; the sawdust is poplar and willow; the anionic dispersing wetting agent is selected from DG309 from West chemical trade, Guangzhou; the interstitial remover is selected from a compound of various surfactants containing special alkoxy compounds of New materials GmbH of Sichuan, and the interstitial remover TJ-A179.
In the invention, except for special description, the addition amount of each auxiliary agent is based on the total weight of the raw leather; for example, 200% of water at 20 ℃ refers to 200% of water at 20 ℃ based on the total weight of the hide.
Example 1
A processing technology for chrome-free tanning of sheep leather comprises the following processing steps:
1. throwing salt on the raw material skin: putting the raw material skin into a rotating cage for rotating, and rotating out the salt in the raw material skin;
2. soaking in water
2.1, pre-soaking: selecting six sheets of raw material skins after salt falling, wherein the total weight is 21kg, and putting the six sheets of raw material skins into a rotary drum; adding 200% of water with the temperature of 20 ℃ into the rotary drum, adding 0.4% of anionic surfactant, 0.1% of bactericide and 0.4% of soda ash, rotating for 5 hours, discharging from the drum, and removing flesh from the fur;
2.2, main soaking: putting the fleshed fur into an empty rotary drum, adding 200% of water with the temperature of 20 ℃, adding 0.5% of anionic surfactant, 0.2% of bactericide and 0.6% of inorganic alkali, rotating for 22 hours, taking out the rotary drum and setting up a horse, and controlling the water for 3 hours;
3. alkali leaching and dehairing: preparing 180g/L and 30g/L alkali liquor by adding water into sodium sulfide, respectively adding calcium hydroxide, respectively thickening the concentrations of the two alkali liquor to 33 Baume and 20 Baume, and adding 10g/L liming auxiliary LM-5 into the high-concentration alkali liquor; spraying high-concentration alkali liquor to the middle back position of the fur with an alkali spraying machine at a speed of 14m/min, spraying low-concentration alkali liquor to the side ribs and ribs position of the fur, standing for 1.5h after spraying is finished, and performing mechanical dehairing with a dehairing machine to obtain dehaired fur;
4. liming: adding the dehaired skins into an empty rotary drum, adding 190% of water at 15 ℃, adding 0.8% of liming auxiliary agent LM-5, 0.5% of sodium sulfide, 0.3% of anionic dispersing wetting agent and 0.8% of calcium hydroxide, rotating for 25h, taking out of the drum, removing meat, and finishing liming operation;
5. deliming and softening: controlling the ratio of deashing liquid to be 100%, adding 0.3% of degreasing agent, 0.3% of lipase, 0.5% of deashing agent TM and 0.8% of deashing agent ASB at 25 ℃, and transferring for 85min in a rotary drum; wherein, the deliming agent TM and the deliming agent ASB are added equally in two times, and the time intervals of the two times are the same; adjusting the pH value to 8, and draining; changing clear water into the drum, controlling the ratio of softening liquid to be 150%, adding 0.2% of alkaline softening enzyme and 0.08% of sawdust at 33 ℃, rotating for 40min, draining water, washing once, discharging the cleaning water, and finishing the deliming and softening operation;
6. degreasing: adding water into the deashed and softened rotary drum, controlling the liquid ratio to be 30%, adding 4% of anionic dispersion wetting agent DG309 and 0.5% of anionic dispersion wetting agent Polon A at 39 ℃, and treating for 3 h; washing twice with 35 ℃ water, washing twice with 25 ℃ water, discharging the washing water, and finishing the degreasing operation;
7. pickling and tanning: adding water into the degreased leather, and controlling the pickling solution ratio to be 100%; adding 5% of 8 Baume industrial salt, and turning for 3 min; adding DODP 0.1% and surfactant 0.1%, and rotating for 25 min; adding 0.3% of F5195, and rotating for 15 min; adding 0.08% of formic acid with the mass concentration of 85%, and turning for 15 min; adjusting pH to 2.6, adding 5% chrome-free tanning agent TWLZ, and rotating for 2.5 h; adding 1.1% of an alkali extracting agent, and rotating for 4 hours; supplementing hot water until the liquid temperature is 38 ℃, rotating for 2.5h, controlling the pH value to be 4.0, and standing overnight for 8 h; rotating for 50min the next day, controlling the pH to be 4, washing, taking out the leather drum, setting up, standing, finishing the tanning step and obtaining white wet leather;
8. the retanning dyeing is divided into two different processes of clothing leather and vamp leather, and the retanning dyeing operation of the clothing leather is as follows:
8.1, degreasing: controlling the liquid ratio with water at 43 ℃ to be 200%, adding 2% of degreasing agent, 1% of DODP and 1% of interstitial substance remover, rotating for 60min, adjusting the pH value to be 4.2, and washing with water at 25 ℃;
8.2, softening: controlling the liquid ratio with 43 deg.C water to 200%, adding 4% acid softening enzyme A489, and rotating for 3 hr; adding 1% of 95% sodium formate and 1% of ammonium bicarbonate with nitrogen content more than or equal to 17.2%, rotating for 120min, standing for 10h, and standing overnight; rotating for 30min the next day, adjusting pH to 5.4, and washing with water at 25 deg.C;
8.3, filling: controlling the liquid ratio with 40 deg.C water to 150%, adding 3% fatty aldehyde PF, 1.5% synthetic oil containing long-chain natural fat HLW, 1.5% synthetic fatting agent F5193, and rotating for 40 min; adding 0.8% of 85% formic acid, and rotating for 20 min; adjusting pH to 3.9, adding 4% retanning agent MB-1, and transferring for 40 min; adjusting pH to 4.8, adding 2.5% water-borne acrylic polymer AR, 2% acrylic resin AA, and 1% GMF (p-benzoquinone dioxime), and transferring for 40 min; adjusting pH to 5.2, adding 3% melamine resin type synthetic retanning agent RTD, 2% AG dicyandiamide resin and 2% tannin extract R231, and rotating for 40 min; adding 4% tannin R772, and rotating for 60 min; heating to 50 deg.C in the drum, adding 3% water repellent A9981, 2% dispersing fatting agent F5193, and 3% synthetic oil softener and emulsifier compound 94S, and rotating for 60 min; adding 1% of synthetic oil HLW containing long-chain natural fat, 3% of synthetic oil 51, 2% of protein filler R950, dye and 2% of melamine resin type synthetic retanning agent RTD, and turning for 30 min; adding 2.5% of 85% formic acid, transferring for 15min, adding 2.5% of 85% formic acid, transferring for 15 min; adjusting pH to 3.5, controlling water-liquid ratio with 50 deg.C water to 200%, adding 0.3% sulfited neat dock root oil CPB and 0.5% cationic fatting agent U, transferring for 10min, adding 0.5% deironing agent SLD, transferring for 10min, adjusting pH to 3.5, and washing with water to obtain a drum;
9. and (4) performing surface finishing and coating on the leather after the retanning dyeing to obtain the finished product of the sheep leather.
Example 2
A processing technology for chrome-free tanning of sheep leather comprises the following processing steps:
1. throwing salt on the raw material skin: putting the raw material skin into a rotating cage for rotating, and rotating out the salt in the raw material skin;
2. soaking in water
2.1, pre-soaking: selecting six sheets of raw material skins after salt falling, wherein the total weight is 21kg, and putting the six sheets of raw material skins into a rotary drum; adding 200% of water with the temperature of 23 ℃ into the rotary drum, adding 0.4% of anionic surfactant, 0.1% of bactericide and 0.4% of soda ash, rotating for 6 hours, discharging from the drum, and removing flesh from the fur;
2.2, main soaking: putting the fleshed fur into an empty rotary drum, adding 200% of water with the temperature of 22 ℃, adding 0.5% of anionic surfactant, 0.2% of bactericide and 0.6% of inorganic alkali, rotating for 26 hours, taking out the rotary drum and setting up a horse, and controlling the water for 4 hours;
3. alkali leaching and dehairing: preparing 180g/L and 30g/L alkali liquor by adding water into sodium sulfide, respectively adding calcium hydroxide, respectively thickening the concentrations of the two alkali liquor to 33 Baume and 20 Baume, and adding 10g/L liming auxiliary LM-5 into the high-concentration alkali liquor; spraying high-concentration alkali liquor to the middle back position of the fur with an alkali spraying machine at a speed of 14m/min, spraying low-concentration alkali liquor to the side ribs and ribs position of the fur, standing for 1.5h after spraying is finished, and performing mechanical dehairing with a dehairing machine to obtain dehaired fur;
4. liming: adding the dehaired skins into an empty rotary drum, adding 190% of water at 20 ℃, adding 0.8% of liming auxiliary agent LM-5, 0.5% of sodium sulfide, 0.3% of anionic dispersing wetting agent and 0.8% of calcium hydroxide, rotating for 28 hours, taking out of the drum, removing meat, and finishing liming operation;
5. deliming and softening: controlling the ratio of deashing liquid to be 100%, adding 0.3% of degreasing agent, 0.3% of lipase, 0.5% of deashing agent TM and 0.8% of deashing agent ASB at 31 ℃, and transferring for 91min in a rotary drum; wherein, the deliming agent TM and the deliming agent ASB are added equally in two times, and the time intervals of the two times are the same; adjusting the pH value to 8.2, and draining; changing clear water into the drum, controlling the ratio of softening liquid to be 150%, adding 0.2% of alkaline softening enzyme and 0.08% of sawdust at 36 ℃, rotating for 50min, draining water, washing once, discharging cleaning water, and finishing deliming and softening operations;
6. degreasing: adding water into the deashed and softened rotary drum, controlling the liquid ratio to be 30%, adding 4% of anionic dispersing wetting agent DG309 and 0.5% of anionic dispersing wetting agent Polon A at 39.6 ℃, and treating for 3 h; washing with 35 deg.C water twice, washing with 23 deg.C water twice, discharging the washing water, and finishing the degreasing operation;
7. pickling and tanning: adding water into the degreased leather, and controlling the pickling solution ratio to be 100%; adding 5% of 8 Baume industrial salt, and turning for 6 min; adding DODP 0.1% and surfactant 0.1%, and rotating for 30 min; adding 0.3% of F5195, and rotating for 20 min; adding 0.08% of formic acid with the mass concentration of 85%, and rotating for 20 min; adjusting pH to 2.7, adding 5% chrome-free tanning agent TWLZ, and turning for 3 h; adding 1.2% of an alkali extracting agent, and turning for 5 hours; supplementing hot water until the liquid temperature is 41 ℃, rotating for 3h, controlling the pH value to be 4.0, and standing overnight for 12 h; rotating for 60min the next day, controlling the pH to be 4.5, washing, taking out, setting up and standing to finish the tanning step to obtain white wet leather;
8. the retanning dyeing is divided into two different processes of clothing leather and vamp leather, and the retanning dyeing operation of the clothing leather is as follows:
8.1, degreasing: controlling the liquid ratio with water at 43 ℃ to be 200%, adding 2% of degreasing agent, 1% of DODP and 1% of interstitial substance remover, rotating for 60min, adjusting the pH value to be 4.2, and washing with water at 25 ℃;
8.2, softening: controlling the liquid ratio with 43 deg.C water to 200%, adding 4% softening enzyme A489, and rotating for 3 hr; adding 1% of 95% sodium formate and 1% of ammonium bicarbonate with nitrogen content more than or equal to 17.2%, rotating for 120min, standing for 10h, and standing overnight; rotating for 30min the next day, adjusting pH to 5.4, and washing with water at 25 deg.C;
8.3, filling: controlling the liquid ratio with 40 deg.C water to 150%, adding 3% fatty aldehyde PF, 1.5% synthetic oil containing long-chain natural fat HLW, 1.5% synthetic fatting agent F5193, and rotating for 40 min; adding 0.8% of 85% formic acid, and rotating for 20 min; adjusting pH to 3.9, adding 4% retanning agent MB-1, and transferring for 40 min; adjusting pH to 4.8, adding 2.5% water-borne acrylic polymer AR, 2% acrylic resin AA, and 1% GMF (p-benzoquinone dioxime), and transferring for 40 min; adjusting pH to 5.2, adding 3% melamine resin type synthetic retanning agent RTD, 2% AG dicyandiamide resin and 2% tannin extract R231, and rotating for 40 min; adding 4% tannin R772, and rotating for 60 min; heating to 50 deg.C in the drum, adding 3% water repellent A9981, 2% dispersing fatting agent F5193, and 3% synthetic oil softener and emulsifier compound 94S, and rotating for 60 min; adding 1% of synthetic oil HLW containing long-chain natural fat, 3% of synthetic oil 51, 2% of protein filler R950, dye and 2% of melamine resin type synthetic retanning agent RTD, and turning for 30 min; adding 2.5% of 85% formic acid, transferring for 15min, adding 2.5% of 85% formic acid, transferring for 15 min; adjusting pH to 3.5, controlling water-liquid ratio with 50 deg.C water to 200%, adding 0.3% sulfited neat dock root oil CPB and 0.5% cationic fatting agent U, transferring for 10min, adding 0.5% deironing agent SLD, transferring for 10min, adjusting pH to 3.5, and washing with water to obtain a drum;
9. and (4) performing surface finishing and coating on the leather after the retanning dyeing to obtain the finished product of the sheep leather.
Example 3
A processing technology for chrome-free tanning of sheep leather comprises the following processing steps:
1. throwing salt on the raw material skin: putting the raw material skin into a rotating cage for rotating, and rotating out the salt in the raw material skin;
2. soaking in water
2.1, pre-soaking: selecting six sheets of raw material skins after salt falling, wherein the total weight is 21kg, and putting the six sheets of raw material skins into a rotary drum; adding 200% of water with the temperature of 25 ℃ into the rotary drum, adding 0.4% of anionic surfactant, 0.1% of bactericide and 0.4% of soda ash, rotating for 7 hours, discharging from the drum, and removing flesh from the fur;
2.2, main soaking: putting the fleshed fur into an empty rotary drum, adding 200% of water with the temperature of 25 ℃, adding 0.5% of anionic surfactant, 0.2% of bactericide and 0.6% of inorganic alkali, rotating for 30h, taking out of the drum, and controlling the water for 5 h;
3. alkali leaching and dehairing: preparing 180g/L and 30g/L alkali liquor by adding water into sodium sulfide, respectively adding calcium hydroxide, respectively thickening the concentrations of the two alkali liquor to 33 Baume and 20 Baume, and adding 10g/L liming auxiliary LM-5 into the high-concentration alkali liquor; spraying high-concentration alkali liquor to the middle back position of the fur with an alkali spraying machine at a speed of 14m/min, spraying low-concentration alkali liquor to the side ribs and ribs position of the fur, standing for 1.5h after spraying is finished, and performing mechanical dehairing with a dehairing machine to obtain dehaired fur;
4. liming: adding the dehaired skins into an empty rotary drum, adding 190% of water at 25 ℃, adding 0.8% of liming auxiliary agent LM-5, 0.5% of sodium sulfide, 0.3% of anionic dispersing wetting agent and 0.8% of calcium hydroxide, rotating for 30 hours, taking out of the drum, removing meat, and finishing liming operation;
5. deliming and softening: controlling the ratio of deashing liquid to be 100%, adding 0.3% of degreasing agent, 0.3% of lipase, 0.5% of deashing agent TM and 0.8% of deashing agent ASB at 35 ℃, and transferring for 95min in a rotary drum; wherein, the deliming agent TM and the deliming agent ASB are added equally in two times, and the time intervals of the two times are the same; adjusting the pH value to 9, and draining; changing clear water into the drum, controlling the ratio of softening liquid to be 150%, adding 0.2% of alkaline softening enzyme and 0.08% of sawdust at 38 ℃, rotating for 60min, draining water, washing once, discharging cleaning water, and finishing deliming and softening operations;
6. degreasing: adding water into the deashed and softened rotary drum, controlling the liquid ratio to be 30%, adding 4% of anionic dispersion wetting agent DG309 and 0.5% of anionic dispersion wetting agent Polon A at 40 ℃, and treating for 3 h; washing with 35 deg.C water twice, washing with 23 deg.C water twice, discharging the washing water, and finishing the degreasing operation;
7. pickling and tanning: adding water into the degreased leather, and controlling the pickling solution ratio to be 100%; adding 5% of 8 Baume industrial salt, and rotating for 10 min; adding DODP 0.1% and surfactant 0.1%, and rotating for 35 min; adding 0.3% of F5195, and rotating for 25 min; adding 0.08% of formic acid with the mass concentration of 85%, and turning for 25 min; adjusting pH to 2.7, adding 5% chrome-free tanning agent TWLZ, and rotating for 3.5 h; adding 1.1% of an alkali extracting agent, and turning for 6 hours; supplementing hot water until the liquid temperature is 43 ℃, rotating for 3.5h, controlling the pH value to be 4.0, and standing overnight for 15 h; turning for 70min the next day, controlling pH to 5, washing, taking out, standing, and finishing tanning to obtain white wet leather;
8. the retanning dyeing is divided into two different processes of clothing leather and vamp leather, and the retanning dyeing operation of the clothing leather is as follows:
8.1, degreasing: controlling the liquid ratio with water at 43 ℃ to be 200%, adding 2% of degreasing agent, 1% of DODP and 1% of interstitial substance remover, rotating for 60min, adjusting the pH value to be 4.2, and washing with water at 25 ℃;
8.2, softening: controlling the liquid ratio with 43 deg.C water to 200%, adding 4% softening enzyme A489, and rotating for 3 hr; adding 1% of 95% sodium formate and 1% of ammonium bicarbonate with nitrogen content more than or equal to 17.2%, rotating for 120min, standing for 10h, and standing overnight; rotating for 30min the next day, adjusting pH to 5.4, and washing with water at 25 deg.C;
8.3, filling: controlling the liquid ratio with 40 deg.C water to 150%, adding 3% fatty aldehyde PF, 1.5% synthetic oil containing long-chain natural fat HLW, 1.5% synthetic fatting agent F5193, and rotating for 40 min; adding 0.8% of 85% formic acid, and rotating for 20 min; adjusting pH to 3.9, adding 4% retanning agent MB-1, and transferring for 40 min; adjusting pH to 4.8, adding 2.5% water-borne acrylic polymer AR, 2% acrylic resin AA, and 1% GMF (p-benzoquinone dioxime), and transferring for 40 min; adjusting pH to 5.2, adding 3% melamine resin type synthetic retanning agent RTD, 2% AG dicyandiamide resin and 2% tannin extract R231, and rotating for 40 min; adding 4% tannin R772, and rotating for 60 min; heating to 50 deg.C in the drum, adding 3% water repellent A9981, 2% dispersing fatting agent F5193, and 3% synthetic oil softener and emulsifier compound 94S, and rotating for 60 min; adding 1% of synthetic oil HLW containing long-chain natural fat, 3% of synthetic oil 51, 2% of protein filler R950, dye and 2% of melamine resin type synthetic retanning agent RTD, and turning for 30 min; adding 2.5% of 85% formic acid, transferring for 15min, adding 2.5% of 85% formic acid, transferring for 15 min; adjusting pH to 3.5, controlling water-liquid ratio with 50 deg.C water to 200%, adding 0.3% sulfited neat dock root oil CPB and 0.5% cationic fatting agent U, transferring for 10min, adding 0.5% deironing agent SLD, transferring for 10min, adjusting pH to 3.5, and washing with water to obtain a drum;
9. and (4) performing surface finishing and coating on the leather after the retanning dyeing to obtain the finished product of the sheep leather.
Example 4
A processing technology for chrome-free tanning of sheep leather comprises the following processing steps:
1. throwing salt on the raw material skin: putting the raw material skin into a rotating cage for rotating, and rotating out the salt in the raw material skin;
2. soaking in water
2.1, pre-soaking: selecting six sheets of raw material skins after salt falling, wherein the total weight is 21kg, and putting the six sheets of raw material skins into a rotary drum; adding 255% of water with the temperature of 25 ℃ into the rotary drum, adding 0.4% of anionic surfactant, 0.1% of bactericide and 0.4% of soda ash, rotating for 6 hours, discharging from the drum, and removing flesh from the fur;
2.2, main soaking: putting the fleshed fur into an empty rotary drum, adding 255% of water with the temperature of 25 ℃, adding 0.5% of anionic surfactant, 0.2% of bactericide and 0.6% of inorganic alkali, rotating for 27 hours, taking out of the drum and setting up a horse, and controlling the water for 5 hours;
3. alkali leaching and dehairing: preparing 180g/L and 30g/L alkali liquor by adding water into sodium sulfide, respectively adding calcium hydroxide, respectively thickening the concentrations of the two alkali liquor to 33 Baume and 20 Baume, and adding 10g/L liming auxiliary LM-5 into the high-concentration alkali liquor; spraying high-concentration alkali liquor to the middle back position of the fur with an alkali spraying machine at a speed of 14m/min, spraying low-concentration alkali liquor to the side ribs and ribs position of the fur, standing for 1.5h after spraying is finished, and performing mechanical dehairing with a dehairing machine to obtain dehaired fur;
4. liming: adding the dehaired skins into an empty rotary drum, adding 200% of water at 22 ℃, adding 1.0% of liming auxiliary agent LM-5, 0.65% of sodium sulfide, 0.4% of anionic dispersing wetting agent and 1.0% of calcium hydroxide, rotating for 30 hours, taking out of the drum, removing meat, and finishing liming operation;
5. deliming and softening: controlling the ratio of deashing liquid to be 100%, adding 0.5% of degreasing agent, 0.5% of degreasing enzyme, 0.6% of deashing agent TM and 1.0% of deashing agent ASB at 32 ℃, and transferring for 90min in a rotary drum; wherein, the deliming agent TM and the deliming agent ASB are added equally in two times, and the time intervals of the two times are the same; adjusting the pH value to 9, and draining; changing clear water into the drum, controlling the ratio of softening liquid to be 150%, adding 0.3% of alkaline softening enzyme and 0.1% of sawdust at 36 ℃, rotating for 50min, draining water, washing once, discharging cleaning water, and finishing deliming and softening operations;
6. degreasing: adding water into the deashed and softened rotary drum, controlling the liquid ratio to be 30%, adding 4% of anionic dispersion wetting agent DG309 and 0.5% of anionic dispersion wetting agent Polon A at 40 ℃, and treating for 3 h; washing with 35 deg.C water twice, washing with 23 deg.C water twice, discharging the washing water, and finishing the degreasing operation;
7. pickling and tanning: adding water into the degreased leather, and controlling the pickling solution ratio to be 106%; adding 8% of 8 Baume industrial salt, and turning for 8 min; adding DODP 0.3% and surfactant 0.3%, and rotating for 31 min; adding 0.6% of F5195, and rotating for 22 min; adding 0.1% formic acid with mass concentration of 85%, and rotating for 20 min; adjusting pH to 2.5, adding 8% chrome-free tanning agent TWLZ, and turning for 3 h; adding 1.1% of an alkali extracting agent, and turning for 5 hours; supplementing hot water until the liquid temperature is 41 ℃, rotating for 3h, controlling the pH value to be 4.0, and standing overnight for 12 h; turning for 62min the next day, controlling the pH to be 5, washing, taking out the drum, setting up, standing, finishing the tanning step, and obtaining white wet leather;
8. the retanning dyeing is divided into two different processes of clothing leather and vamp leather, and the retanning dyeing operation of the clothing leather is as follows:
8.1, degreasing: controlling the liquid ratio with water at 43 ℃ to be 200%, adding 2% of degreasing agent, 1% of DODP and 1% of interstitial substance remover, rotating for 60min, adjusting the pH value to be 4.2, and washing with water at 25 ℃;
8.2, softening: controlling the liquid ratio with 43 deg.C water to 200%, adding 4% softening enzyme A489, and rotating for 3 hr; adding 1% of 95% sodium formate and 1% of ammonium bicarbonate with nitrogen content more than or equal to 17.2%, rotating for 120min, standing for 10h, and standing overnight; rotating for 30min the next day, adjusting pH to 5.4, and washing with water at 25 deg.C;
8.3, filling: controlling the liquid ratio with 40 deg.C water to 150%, adding 3% fatty aldehyde PF, 1.5% synthetic oil containing long-chain natural fat HLW, 1.5% synthetic fatting agent F5193, and rotating for 40 min; adding 0.8% of 85% formic acid, and rotating for 20 min; adjusting pH to 3.9, adding 4% retanning agent MB-1, and transferring for 40 min; adjusting pH to 4.8, adding 2.5% water-borne acrylic polymer AR, 2% acrylic resin AA, and 1% GMF (p-benzoquinone dioxime), and transferring for 40 min; adjusting pH to 5.2, adding 3% melamine resin type synthetic retanning agent RTD, 2% AG dicyandiamide resin and 2% tannin extract R231, and rotating for 40 min; adding 4% tannin R772, and rotating for 60 min; heating to 50 deg.C in the drum, adding 3% water repellent A9981, 2% dispersing fatting agent F5193, and 3% synthetic oil softener and emulsifier compound 94S, and rotating for 60 min; adding 1% of synthetic oil HLW containing long-chain natural fat, 3% of synthetic oil 51, 2% of protein filler R950, dye and 2% of melamine resin type synthetic retanning agent RTD, and turning for 30 min; adding 2.5% of 85% formic acid, transferring for 15min, adding 2.5% of 85% formic acid, transferring for 15 min; adjusting pH to 3.5, controlling water-liquid ratio with 50 deg.C water to 200%, adding 0.3% sulfited neat dock root oil CPB and 0.5% cationic fatting agent U, transferring for 10min, adding 0.5% deironing agent SLD, transferring for 10min, adjusting pH to 3.5, and washing with water to obtain a drum;
9. and (4) performing surface finishing and coating on the leather after the retanning dyeing to obtain the finished product of the sheep leather.
Example 5
A processing technology for chrome-free tanning of sheep leather comprises the following processing steps:
1. throwing salt on the raw material skin: putting the raw material skin into a rotating cage for rotating, and rotating out the salt in the raw material skin;
2. soaking in water
2.1, pre-soaking: selecting six sheets of raw material skins after salt falling, wherein the total weight is 21kg, and putting the six sheets of raw material skins into a rotary drum; adding 300% of water with the temperature of 25 ℃ into the rotary drum, adding 0.4% of anionic surfactant, 0.1% of bactericide and 0.4% of soda ash, rotating for 6 hours, discharging from the drum, and removing flesh from the fur;
2.2, main soaking: putting the fleshed fur into an empty rotary drum, adding 300% of water with the temperature of 25 ℃, adding 0.5% of anionic surfactant, 0.2% of bactericide and 0.6% of inorganic alkali, rotating for 27h, taking out of the drum, and controlling the water for 5 h;
3. alkali leaching and dehairing: preparing 180g/L and 30g/L alkali liquor by adding water into sodium sulfide, respectively adding calcium hydroxide, respectively thickening the concentrations of the two alkali liquor to 33 Baume and 20 Baume, and adding 10g/L liming auxiliary LM-5 into the high-concentration alkali liquor; spraying high-concentration alkali liquor to the middle back position of the fur with an alkali spraying machine at a speed of 14m/min, spraying low-concentration alkali liquor to the side ribs and ribs position of the fur, standing for 1.5h after spraying is finished, and performing mechanical dehairing with a dehairing machine to obtain dehaired fur;
4. liming: adding the dehaired skins into an empty rotary drum, adding 210% of water at 22 ℃, adding 1.3% of liming auxiliary agent LM-5, 0.8% of sodium sulfide, 0.5% of anionic dispersing wetting agent and 1.3% of calcium hydroxide, rotating for 30h, taking out of the drum, removing meat, and finishing liming operation;
5. deliming and softening: controlling the ratio of deashing liquid to be 100%, adding 0.7% of degreasing agent, 0.7% of degreasing enzyme, 0.8% of deashing agent TM and 1.3% of deashing agent ASB at 32 ℃, and transferring for 90min in a rotary drum; wherein, the deliming agent TM and the deliming agent ASB are added equally in two times, and the time intervals of the two times are the same; adjusting the pH value to 9, and draining; changing clear water into the drum, controlling the ratio of softening liquid to be 150%, adding 0.4% of alkaline softening enzyme and 0.13% of sawdust at 36 ℃, rotating for 50min, draining water, washing once, discharging cleaning water, and finishing deliming and softening operations;
6. degreasing: adding water into the deashed and softened rotary drum, controlling the liquid ratio to be 30%, adding 4% of anionic dispersion wetting agent DG309 and 0.5% of anionic dispersion wetting agent Polon A at 40 ℃, and treating for 3 h; washing with 35 deg.C water twice, washing with 23 deg.C water twice, discharging the washing water, and finishing the degreasing operation;
7. pickling and tanning: adding water into the degreased leather, and controlling the pickling solution ratio to be 110%; adding 10% of 8 Baume industrial salt, and turning for 8 min; adding DODP 0.5% and surfactant 0.5%, and rotating for 31 min; adding 0.8% of F5195, and rotating for 22 min; adding 0.13% formic acid with mass concentration of 85%, and rotating for 20 min; adjusting pH to 2.5, adding 10% chrome-free tanning agent TWLZ, and turning for 3 h; adding 1.1% of an alkali extracting agent, and turning for 5 hours; supplementing hot water until the liquid temperature is 41 ℃, rotating for 3h, controlling the pH value to be 4.0, and standing overnight for 12 h; turning for 62min the next day, controlling the pH to be 5, washing, taking out the drum, setting up, standing, finishing the tanning step, and obtaining white wet leather;
8. the retanning dyeing is divided into two different processes of clothing leather and vamp leather, and the retanning dyeing operation of the clothing leather is as follows:
8.1, degreasing: controlling the liquid ratio with water at 43 ℃ to be 200%, adding 2% of degreasing agent, 1% of DODP and 1% of interstitial substance remover, rotating for 60min, adjusting the pH value to be 4.2, and washing with water at 25 ℃;
8.2, softening: controlling the liquid ratio with 43 deg.C water to 200%, adding 4% softening enzyme A489, and rotating for 3 hr; adding 1% of 95% sodium formate and 1% of ammonium bicarbonate with nitrogen content more than or equal to 17.2%, rotating for 120min, standing for 10h, and standing overnight; rotating for 30min the next day, adjusting pH to 5.4, and washing with water at 25 deg.C;
8.3, filling: controlling the liquid ratio with 40 deg.C water to 150%, adding 3% fatty aldehyde PF, 1.5% synthetic oil containing long-chain natural fat HLW, 1.5% synthetic fatting agent F5193, and rotating for 40 min; adding 0.8% of 85% formic acid, and rotating for 20 min; adjusting pH to 3.9, adding 4% retanning agent MB-1, and transferring for 40 min; adjusting pH to 4.8, adding 2.5% water-borne acrylic polymer AR, 2% acrylic resin AA, and 1% GMF (p-benzoquinone dioxime), and transferring for 40 min; adjusting pH to 5.2, adding 3% melamine resin type synthetic retanning agent RTD, 2% AG dicyandiamide resin and 2% tannin extract R231, and rotating for 40 min; adding 4% tannin R772, and rotating for 60 min; heating to 50 deg.C in the drum, adding 3% water repellent A9981, 2% dispersing fatting agent F5193, and 3% synthetic oil softener and emulsifier compound 94S, and rotating for 60 min; adding 1% of synthetic oil HLW containing long-chain natural fat, 3% of synthetic oil 51, 2% of protein filler R950, dye and 2% of melamine resin type synthetic retanning agent RTD, and turning for 30 min; adding 2.5% of 85% formic acid, transferring for 15min, adding 2.5% of 85% formic acid, transferring for 15 min; adjusting pH to 3.5, controlling water-liquid ratio with 50 deg.C water to 200%, adding 0.3% sulfited neat dock root oil CPB and 0.5% cationic fatting agent U, transferring for 10min, adding 0.5% deironing agent SLD, transferring for 10min, adjusting pH to 3.5, and washing with water to obtain a drum;
9. and (4) performing surface finishing and coating on the leather after the retanning dyeing to obtain the finished product of the sheep leather.
Example 6
Example 6 differs from example 4 in that:
7. the pickling tanning operation is different, and specifically comprises the following steps: adding water into the degreased leather, controlling the pickling solution ratio to be 55%, adding 5% of 8 Baume industrial salt, and turning for 12 min; adding 1% of 85% formic acid, and rotating for 40 min; adding 0.6% 90% sulfuric acid, and rotating for 170 min; adding 3% of chrome-free tanning agent TWS, and turning for 220 min; adding 0.3% sodium bicarbonate, and transferring for 15 min; adding 0.3% sodium bicarbonate, and rotating for 40 min; adding 0.1% sodium carbonate, and rotating for 35 min; controlling the pH value to be 7, standing overnight for 8 h; controlling water for 30min the next day; fixing the ratio of the liquid to be 100%, adding 0.5% of 85% formic acid and 1% of TWB, turning for 15min, adding 0.1% of mildew preventive, turning for 80min, adjusting the pH value to 5.0, and discharging to finish the tanning step to obtain the white wet leather.
Example 7
Example 7 differs from example 4 in that:
7. the pickling tanning operation is different, and specifically comprises the following steps: adding water into the degreased leather, controlling the pickling solution ratio to be 60%, adding 7% of industrial salt, and turning for 15 min; adding 1% of 85% formic acid, and rotating for 45 min; adding 0.6% 90% sulfuric acid, and rotating for 180 min; adding 5% of chrome-free tanning agent TWS, and turning for 245 min; adding 0.4% sodium bicarbonate, and rotating for 20 min; adding 0.7% sodium bicarbonate, and rotating for 40 min; adding 0.2% sodium carbonate, and rotating for 40 min; controlling the pH value to be 7.4, and standing overnight for 11 h; controlling water for 30min the next day; fixing the ratio of the liquid to be 100%, adding 85% formic acid accounting for 0.6% of the total weight of the fur, adding 2% TWB, turning for 20min, adding 0.2% of a mildew preventive, turning for 90min, adjusting the pH value to 5.0, and discharging to finish the tanning step to obtain the white wet leather.
Example 8
Example 8 differs from example 4 in that:
7. the pickling tanning operation is different, and specifically comprises the following steps: adding water into the degreased leather, controlling the pickling solution ratio to be 65%, adding 10% of industrial salt, and turning for 17 min; adding 1% of 85% formic acid, and rotating for 50 min; adding 0.6% 90% sulfuric acid, and rotating for 190 min; adding 8% of chrome-free tanning agent TWS, and turning for 260 min; adding 0.5% sodium bicarbonate, and rotating for 25 min; adding 0.9% sodium bicarbonate, and rotating for 40 min; adding 0.3% of soda ash, and rotating for 45 min; controlling the pH value to be 8, standing overnight for 15 h; controlling water for 30min the next day; fixing the ratio of the liquid to the liquid of 100%, adding 0.8% of 85% formic acid and 3% of TWB, turning for 25min, adding 0.3% of mildew preventive, turning for 100min, adjusting the pH value to 5.0, and discharging to obtain the white wet leather.
Example 9
Example 9 differs from example 4 in that:
8. the process of the upper leather is adopted in the retanning dyeing, and the operation is as follows:
8.1, degreasing: washing with water at 23 deg.C once after 60min by using water control solution at 43 deg.C in a ratio of 200%, degreasing agent DODP 2% and interstitial substance removing agent 0.5%;
8.2, filling: controlling the liquid ratio with 35 deg.C water to 100%, adding 1% tannin essence PAK-N-C, transferring to 30min, pH4.4, adding 3% polymer retanning agent TGR, transferring to 30min, pH5.2; adding 2% of fatty aldehyde PF and 0.5% of dispersing fatting agent F5195, and rotating for 30 min; adding 3% amphoteric concentrated melamine resin MAU, 2% white tannin R772 and 1% GMF, and rotating for 60 min; adding 4% of environment-friendly amino resin R479 and 3% of dicyandiamide resin AG, and rotating for 40 min; adding 4% of wattle bark tannin extract FS, 1% of GMF, 3% of synthetic tanning agent TWT7898, 0.5% of ABN (azo (di) isobutyronitrile), 3% of acrylic polymer retanning agent R83, and turning for 30 min; adding 4% quebracho tannin extract ATO, 4% wattle bark tannin extract FS, 2% dicyandiamide resin AG and 1% GMF, and rotating for 60 min; heating to 50 deg.C, adding 3% protein R950 and 3% environmental friendly retanning agent TWT7898, and rotating for 20 min; adding 2% of a waterproofing agent A9981, and rotating for 60 min; adding 2% of natural phospholipid and synthetic softener BA, 2% of sulfonated fatting agent 51, 1.5% of sulfated neat's foot oil F113, dye, 0.3% of leather dyeing auxiliary agent TameNOL and 3% of acrylic resin polymer solution TP340, and rotating for 30 min; adding 1.2% 85% formic acid, rotating for 20min, and adjusting pH to 4.2; adding 2% of medium-small molecular acrylic polymer TWT5218, and rotating for 20 min; adding 1.8% of 85% formic acid within 15min, adjusting pH to 3.5, and controlling water; adding 0.3CPB 1% cationic fatting agent U into water at 50 deg.C at a ratio of 200%, transferring for 10min, adding iron removing agent LSD, transferring for 10min, and washing with water to obtain the final product.
Example 10
Example 10 differs from example 7 in that:
8. the process of the upper leather is adopted in the retanning dyeing, and the operation is as follows:
8.1, degreasing: washing with water at 23 deg.C once after 60min by using water control solution at 43 deg.C in a ratio of 200%, degreasing agent DODP 2% and interstitial substance removing agent 0.5%;
8.2, filling: controlling the liquid ratio with 35 deg.C water to 100%, adding 1% tannin essence PAK-N-C, transferring to 30min, pH4.4, adding 3% polymer retanning agent TGR, transferring to 30min, pH5.2; adding 2% of fatty aldehyde PF and 0.5% of dispersing fatting agent F5195, and rotating for 30 min; adding 3% amphoteric concentrated melamine resin MAU, 2% white tannin R772 and 1% GMF, and rotating for 60 min; adding 4% of environment-friendly amino resin R479 and 3% of dicyandiamide resin AG, and rotating for 40 min; adding 4% of wattle bark tannin extract FS, 1% of GMF, 3% of synthetic tanning agent TWT7898, 0.5% of ABN (azo (di) isobutyronitrile), 3% of acrylic polymer retanning agent R83, and turning for 30 min; adding 4% quebracho tannin extract ATO, 4% wattle bark tannin extract FS, 2% dicyandiamide resin AG and 1% GMF, and rotating for 60 min; heating to 50 deg.C, adding 3% protein R950 and 3% environmental friendly retanning agent TWT7898, and rotating for 20 min; adding 2% of a waterproofing agent A9981, and rotating for 60 min; adding 2% of natural phospholipid and synthetic softener BA, 2% of sulfonated fatting agent 51, 1.5% of sulfated neat's foot oil F113, dye, 0.3% of leather dyeing auxiliary agent TameNOL and 3% of acrylic resin polymer solution TP340, and rotating for 30 min; adding 1.2% 85% formic acid, rotating for 20min, and adjusting pH to 4.2; adding 2% of medium-small molecular acrylic polymer TWT5218, and rotating for 20 min; adding 1.8% of 85% formic acid within 15min, adjusting pH to 3.5, and controlling water; adding 0.3CPB 1% cationic fatting agent U into water at 50 deg.C at a ratio of 200%, transferring for 10min, adding iron removing agent LSD, transferring for 10min, and washing with water to obtain the final product.
Comparative example 1
The split leather processed by the embodiment in the invention patent application with the application publication number of CN 105567886A.
Performance testing
The white wet hides, leather, and split hides of the examples of the invention and comparative example 1 were each tested as follows:
content of formaldehyde: the detection standard and method of GB/T19941 are adopted;
hexavalent chromium content: adopting a GB/T22807 detection standard and method;
tensile strength: adopting QB/T2710 detection standard and method;
tear strength: adopting the detection standard and method of GBT 17928-1999;
shrinkage temperature: adopting QB/T2713 detection standard and method;
yellowing resistance: adopting the detection standard and method of ASTM-D1148-95;
air permeability: the determination method of GB/T4689.22-1996 is adopted;
the results of testing the properties of the white wet skins of examples 1-8 and the sheeted skins of comparative example 1 are shown in Table 1, and the results of testing the finished sheep leather of examples 1-10 are shown in Table 2.
TABLE 1 results of testing the properties of the white wet skins of examples 1-8 and the sheeted skins of comparative example 1
The detection results in the table 1 show that the white wet leather processed by the processing technology has good whiteness, no color change within one year, good storage resistance and yellowing resistance of grade 4; the maximum shrinkage temperature reaches 95 ℃, the softness is 8.2mm, the maximum tensile strength reaches 15.7N/mm, and the maximum tear strength reaches 61.0N/mm; the low free formaldehyde, ecological environmental protection, can be pasted on the body without stimulation, and can be discarded and biodegraded.
Table 2 results of performance test of the finished sheep leather of examples 1-10
The detection results in table 2 show that the finished product of the sheep leather processed by the process of the invention has the shrinkage temperature of over 90 ℃, extremely low free formaldehyde, ecological and environment-friendly property, can be worn by people and has no stimulation. The detection result of the air permeability shows that the leather has excellent air permeability and can be called as breathable leather; the finished leather has oil absorption performance and can be naturally absorbed after being rubbed and oiled.
The wastewater generated after pickling and tanning in the processing technologies of the embodiment 2, the embodiment 4 and the embodiment 7 is selected by adopting a GB 13193-91 method, and is detected according to standard requirements, and the TOC content in the wastewater is respectively 3300mg/L, 3350mg/L and 3400 mg/L. The TOC content in the wastewater generated after the traditional chrome tanning process is 5500-6000mg/L, so that the chrome-free tanning process does not generate chrome-containing wastewater, chrome-containing leather scraps and chrome-containing sludge in the tanning process, and the TOC content in the wastewater can be reduced by 45 percent at most compared with that in the traditional process, so that the process is more environment-friendly.
The above-mentioned embodiments are merely illustrative and not restrictive, and those skilled in the art can modify the embodiments without inventive contribution as required after reading this specification, but only fall within the scope of the claims of the present invention.
Claims (5)
1. The processing technology for chrome-free tanning of the sheep leather is characterized by sequentially comprising the following processing steps:
soaking, alkali leaching and hair removal, liming, deliming and softening, degreasing, pickling and tanning, retanning and dyeing, finishing and finishing; in the step of pickling and tanning, performing chrome-free tanning on the degreased leather material by adopting a chrome-free tanning agent TWLZ to obtain white wet leather, performing retanning dyeing on the white wet leather, and finishing to obtain sheep leather;
the liming step specifically comprises the following steps: adding water with 15-25 ℃ accounting for 190-210 percent of the total weight of the fur, adding liming auxiliary agent accounting for 0.8-1.3 percent of the total weight of the fur, sodium sulfide accounting for 0.5-0.8 percent of the total weight of the fur, anionic dispersing wetting agent accounting for 0.3-0.5 percent of the total weight of the fur and calcium hydroxide accounting for 0.8-1.3 percent of the total weight of the fur, and rotating for 25-30 hours to finish the liming operation;
the deashing softening step specifically comprises the following steps: controlling the ratio of deashing solution to 100%, adding 0.3-0.7% of degreasing agent, 0.3-0.7% of lipase and 1.3-2.1% of deashing agent at 25-35 deg.C, and rotating for 85-95 min; adjusting pH to 8-9, draining, changing water, controlling softening liquid ratio to 150%, adding alkaline softening enzyme 0.2-0.4% and sawdust 0.08-0.13% of total weight of fur at 33-38 deg.C, rotating for 40-60min, draining, washing with water once, and completing deliming and softening operation;
the pickling tanning step specifically comprises the following steps: adding water into the degreased leather material, and controlling the pickling solution ratio to be 110% of 100-; adding industrial salt 5-10% of the total weight of fur, and turning for 3-10 min; adding DODP 0.1-0.5% of the total weight of fur and surfactant 0.1-0.5% of the total weight of fur, and rotating for 25-35 min; adding F5195 0.3-0.8% of the total weight of fur, and rotating for 15-25 min; adding 85% formic acid 0.08-0.13% of the total weight of fur, and rotating for 15-25 min; adjusting pH to 2.6-2.7, adding 5-10 wt% of chrome-free tanning agent TWLZ, and turning for 2.5-3.5 hr; adding alkali extracting agent 1.1-1.2% of the total weight of fur, and rotating for 4-6 h; adjusting the liquid temperature to 38-43 deg.C, rotating for 2.5-3.5h, controlling pH to 4.0, and standing for 8-15 h; rotating for 50-70min, controlling pH to 4-5, washing, taking out, setting up, and standing to finish tanning steps.
2. The chrome-free tanning process of sheep leather as claimed in claim 1, wherein said soaking step comprises the following operative steps:
pre-soaking: adding water at 20-25 deg.C in an amount of 200-300 wt% of the fur, adding anionic surfactant, bactericide and inorganic alkali, rotating for 5-7h, taking out, and removing meat;
main soaking: adding water at 20-25 deg.C in an amount of 200-300 wt% of fur, adding anionic surfactant, bactericide and inorganic alkali, rotating for 22-30h, taking out, and controlling water for 3-5 h.
3. Process for chrome-free tanning of sheep leather according to claim 1, characterized in that said retanning dyeing comprises the following operative steps: degreasing, filling and dyeing.
4. A wet white sheep skin processed by the chrome-free sheep leather tanning process of claim 1, wherein the wet white sheep skin is characterized in that: the shrinkage temperature of the sheep white wet skin is not less than 92 ℃.
5. A sheepskin processed using the chrome-free tanned process of claim 1, wherein: the shrinkage temperature of the sheep leather is not less than 90 ℃.
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| CN113718066B (en) * | 2020-12-25 | 2022-08-19 | 宁夏金海皮业有限责任公司 | Production process for producing horse gear leather |
| CN114410854A (en) * | 2022-02-24 | 2022-04-29 | 四川大学 | High-temperature-dyeable ecological fur chrome-free combined main tanning process |
| CN114410853B (en) * | 2022-02-24 | 2022-09-23 | 四川大学 | Ecological fur non-chromium tanning process |
| CN114410855B (en) * | 2022-02-24 | 2022-10-11 | 四川大学 | Chromium-free tanning process for ecological leather |
| CN114672598B (en) * | 2022-04-02 | 2024-01-19 | 隆丰革乐美时尚有限公司 | Chrome-free tanned sheepskin clothing leather and chrome-free tannage method thereof |
| CN116397056B (en) * | 2023-05-09 | 2024-02-20 | 辛集市凌爵皮革有限责任公司 | Processing technology and application of washable waterproof sheep leather |
| CN116497163B (en) * | 2023-05-23 | 2024-02-20 | 辛集市凌爵皮革有限责任公司 | Antibacterial environment-friendly chrome-free tanning leather and processing technology thereof |
| CN116769979A (en) * | 2023-08-03 | 2023-09-19 | 江西隆华材料科技股份有限公司 | Preparation method of sheep leather |
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