CN106834563B - A method of few salt pickling, tanning leather - Google Patents
A method of few salt pickling, tanning leather Download PDFInfo
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- CN106834563B CN106834563B CN201710049179.3A CN201710049179A CN106834563B CN 106834563 B CN106834563 B CN 106834563B CN 201710049179 A CN201710049179 A CN 201710049179A CN 106834563 B CN106834563 B CN 106834563B
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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
- C14C1/08—Deliming; Bating; Pickling; Degreasing
-
- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C3/00—Tanning; Compositions for tanning
- C14C3/02—Chemical tanning
- C14C3/04—Mineral tanning
-
- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C3/00—Tanning; Compositions for tanning
- C14C3/02—Chemical tanning
- C14C3/28—Multi-step processes
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
Abstract
The invention discloses a kind of methods of few salt pickling, tanning leather, including softening raw material, restores fresh hide state etc., and addition deliming agent, degreasing agent, macerating enzyme etc. and rotate repeatedly, by techniques such as artificial detection pH, temperature and Baume degrees, finally controls temperature and go out drum.The present invention is by modified technique, and using the technique tan leather of few salt pickling, physical mechanical property is excellent, significantly reduces the concentration of the CL concentration and SO42 in waste water, greatly reduces pollution of the neutral salt to environment.
Description
Technical field
The present invention relates to a kind of production method of leather more particularly to a kind of methods of few salt pickling, tanning leather.
Background technology
In recent years, the neutral salt pollution in leather making process increasingly causes the attention of process hides.Since neutral salt will not be rapid
And significantly people’s lives are impacted, it tends to ignored.However, the accumulation of neutral salt and its intractable feature
The gradual salinization of water and soil, biological electrolyte dysequilibrium, the living environment for eventually leading to people is set to wreck.
The neutral salt discharged in leather making process is mainly derived from two processes, first, preserving rawhide using salted method
Salt, accounts for the 40%~50% of total release, and another process is the salt inhibited during pickling used in acid plumping, accounts for neutral salt and always discharges
The 30%~40% of amount.
Process for producing leather flow is at present：Immersion → liming → without ammonia deliming → pickling → organic tanning agent pre-tanning → wet in vain
Skin shaving → combination tannage → filling → dyeing → stuffing → water squeezing toggling → buffing → falls soft → covering with paint → finished product.Both at home and abroad
The salt-free pickling technology of concern, it is main to be operated using the inorganic acid completion pickling that pelt be inhibited to expand, to reduce neutrality
Salt pollutes.
Current production technology also needs to be further improved, and reduces environmental pollution and improves the performance of leather.
Invention content
The purpose of the present invention is to provide a kind of method of novel tanning finished leather, few salt pickling, tanning of the invention at
Leather tensile strength, tearing strength and elongation at break are superior to the finished leather of traditional pickling, tanning, and physical mechanical property is excellent.
Technical solution is used by the present invention solves the above problems：
A method of few salt pickling, tanning leather, which is characterized in that include the following steps：
（1）Raw material is softened, fresh hide state is restored, removes unwanted ingredient in fur processing, is passed through in complete thick graywall
Split process is by head layer and two layer separations；
（2）Water 120% is added, controlled at 45 DEG C；
（3）Sodium pyrosulfite 0.4% and deliming agent 0.6% is added, rotates 30min, then water is discharged；
（4）Water 150% is continuously added, controlled at 31 ± 1 DEG C, 15min is rotated, then water is discharged；
（5）Water 80% is continuously added, controlled at 31 ± 1 DEG C；
（6）Degreasing agent 0.3% and deliming agent 1.1% is added, rotates 50min；
（7）PH value is detected, control ph is between 8.0 ± 0.2；
（8）The whether saturating heart of hand inspection deliming checks that notch phenolphthalein reagent is colourless；
（9）Macerating enzyme 0.5% is added, rotates 40min, suspends 10min after often rotating 20min；
（10）PH value and temperature are detected, control ph controls 31 ± 1 DEG C of temperature between 8.0 ± 0.2；
（11）Whether hand inspection softens, buttocks bubble whether homogeneous soft, then water is discharged；
（12）Add water 400%, controlled at 18 ± 5 DEG C, flowing water is washed, control time 30-40min, then by water
50% discharge；
（13）PH value is detected, control ph is between 7.5 ± 0.5；
（14）Add water 50%, controlled at 18 ± 5 DEG C, winter, summer was close to lower limiting value close to upper limit value；
（15）Industrial refined salt 3% is added, detection Baume degrees is 6.0 ± 0.5；
（16）Pre- fatting agent 0.4% is added, by pre- fatting agent according to 1 before addition:3 warm water melt, and rotate 20min；
（17）Salt-free pickling pretanning agent 1.5% is added, rotates 30min；
（18）The formic acid 0.4% of purity 85% is added, by formic acid according to 1 before addition:The dilution of 5 cold water melts, and rotates 20min；
（19）The fur sulfuric acid 0.4% of purity 98% is added, by fur sulfuric acid according to 1 before addition:10 cold water dilutionizations
It opens, rotates 20min；
（20）The fur sulfuric acid 0.4% of purity 98% is added, by fur sulfuric acid according to 1 before addition:10 cold water dilutionizations
It opens, rotates 60min, suspend 10min after often rotating 20min；
（21）PH value, temperature and Baume degrees are detected, control ph controls 24 ± 3 DEG C of temperature, control between 2.8-3.2
Baume degrees processed is 6.0 ± 0.5；
（22）Artificial pickling checks that the saturating heart, notch bromocresol green inspection show full yellow；
（23）Chrome-free tanning agent 1.5% is added, rotates 30min；
（24）Chrome-free tanning agent 1.5% is added, rotates 150min；
（25）The sodium formate 0.5% of purity 96% is added, rotates 30min；
（26）Addition carries alkaline agent 0.25%, rotates 180min；
（27）PH value, temperature are detected, control ph controls 37 ± 3 DEG C of temperature between 3.9-4.3；
（28）Water 50% is continuously added, controlled at 35 ± 3 DEG C；
（29）Addition carries alkaline agent 0.05%, and alkaline agent will be carried before addition according to 1:The dilution of 10 warm water melts；
（30）Syntans 4% is added, rotates 150min；
（31）Water 150% is continuously added, controlled at 33 ± 3 DEG C；
（32）Degreasing agent 0.2% is added, rotates 15min；
（33）PH value, temperature are detected, control ph controls 30 ± 3 DEG C of temperature between 4.0-4.4；
（34）30 ± 3 DEG C of temperature of control goes out drum；
Above each percentage is the weight percent that each ingredient accounts for skin.
Preferably, the deliming agent uses deliming without ammonium agent.
Preferably, the degreasing agent uses alkaline defatting agent.
Preferably, the salt-free pickling pretanning agent and the syntans use nonmetallic salt-free pickling pretanning agent.
Preferably, the macerating enzyme uses the complex enzyme formulation with trypsase.
Preferably, the alkaline agent that carries carries alkaline agent using inorganic.
Compared with prior art, the present invention having the following technical effects：
Few salt pickling, tanning of the present invention significantly reduces the concentration of CL- concentration and SO42- in waste water, greatly reduces
Pollution of the neutral salt to environment.
Specific implementation mode
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in the embodiment of the present invention
Technical solution is clearly and completely described, it is clear that described embodiments are some of the embodiments of the present invention, rather than complete
The embodiment in portion.
The method of a kind of few salt pickling, tanning leather of the present invention, which is characterized in that include the following steps：
（1）Raw material is softened, fresh hide state is restored, removes unwanted ingredient in fur processing, is passed through in complete thick graywall
Split process is by head layer and two layer separations；
（2）Water 120% is added, controlled at 45 DEG C；
（3）Sodium pyrosulfite 0.4% and deliming agent 0.6% is added, rotates 30min, then water is discharged；
（4）Water 150% is continuously added, controlled at 31 ± 1 DEG C, 15min is rotated, then water is discharged；
（5）Water 80% is continuously added, controlled at 31 ± 1 DEG C；
（6）Degreasing agent 0.3% and deliming agent 1.1% is added, rotates 50min；
（7）PH value is detected, control ph is between 8.0 ± 0.2；
（8）The whether saturating heart of hand inspection deliming checks that notch phenolphthalein reagent is colourless；
（9）Macerating enzyme 0.5% is added, rotates 40min, suspends 10min after often rotating 20min；
（10）PH value and temperature are detected, control ph controls 31 ± 1 DEG C of temperature between 8.0 ± 0.2；
（11）Whether hand inspection softens, buttocks bubble whether homogeneous soft, then water is discharged；
（12）Add water 400%, controlled at 18 ± 5 DEG C, flowing water is washed, control time 30-40min, then by water
50% discharge；
（13）PH value is detected, control ph is between 7.5 ± 0.5；
（14）Add water 50%, controlled at 18 ± 5 DEG C, winter, summer was close to lower limiting value close to upper limit value；
（15）Industrial refined salt 3% is added, detection Baume degrees is 6.0 ± 0.5；
（16）Pre- fatting agent 0.4% is added, by pre- fatting agent according to 1 before addition:3 warm water melt, and rotate 20min；
（17）Salt-free pickling pretanning agent 1.5% is added, rotates 30min；
（18）The formic acid 0.4% of purity 85% is added, by formic acid according to 1 before addition:The dilution of 5 cold water melts, and rotates 20min,
Formic acid is added, makes to combine between the collagen of scytoblastema, keeps skin more consolidation plentiful, and the effect of chrome tanning agent is to help the shape of pairing key
At, so that collagen is combined, thus, the dosage that chromium rubs agent can be reduced using formic acid, to more environmentally-friendly；
When in the prior art, using inorganic picking acid, scytoblastema water swelling, thus the prior art needs to add 8% ~ 10% salt
Carry out deacidification swelling, after formic acid, scytoblastema water swelling is reduced, so as to reduce the dosage of salt.Sulfone also can be used in formic acid herein
Class acid replaces, and specifically uses sulfone quasi-oligomer.
（19）The fur sulfuric acid 0.4% of purity 98% is added, by fur sulfuric acid according to 1 before addition:10 cold water dilutionizations
It opens, rotates 20min；
（20）The fur sulfuric acid 0.4% of purity 98% is added, by fur sulfuric acid according to 1 before addition:10 cold water dilutionizations
It opens, rotates 60min, suspend 10min after often rotating 20min；
（21）PH value, temperature and Baume degrees are detected, control ph controls 24 ± 3 DEG C of temperature, control between 2.8-3.2
Baume degrees processed is 6.0 ± 0.5；
（22）Artificial pickling checks that the saturating heart, notch bromocresol green inspection show full yellow；
（23）Chrome-free tanning agent 1.5% is added, rotates 30min；
（24）Chrome-free tanning agent 1.5% is added, rotates 150min；
（25）The sodium formate 0.5% of purity 96% is added, rotates 30min；
（26）Addition carries alkaline agent 0.25%, rotates 180min；
（27）PH value, temperature are detected, control ph controls 37 ± 3 DEG C of temperature between 3.9-4.3；
（28）Water 50% is continuously added, controlled at 35 ± 3 DEG C；
（29）Addition carries alkaline agent 0.05%, and alkaline agent will be carried before addition according to 1:The dilution of 10 warm water melts；
（30）Syntans 4% is added, rotates 150min；
（31）Water 150% is continuously added, controlled at 33 ± 3 DEG C；
（32）Degreasing agent 0.2% is added, rotates 15min；
（33）PH value, temperature are detected, control ph controls 30 ± 3 DEG C of temperature between 4.0-4.4；
（34）30 ± 3 DEG C of temperature of control goes out drum；
Above each percentage is the weight percent that each ingredient accounts for skin.
Wherein, deliming agent uses deliming without ammonium agent.Degreasing agent uses alkaline defatting agent.Salt-free pickling pretanning agent and the conjunction
Nonmetallic salt-free pickling pretanning agent is used at tanning agent.Macerating enzyme uses the complex enzyme formulation with trypsase.It carries alkaline agent and uses nothing
Machine carries alkaline agent.
The performance test such as following table of the present invention：
By upper table it is found that the leather property of the technical solution adopted by the present invention generation is superior, meet the requirements.The present invention changes
Into Process for producing leather；Product quality is improved, the absorptivity of other materials can be improved to save chemical materials and reduce leather dirt
Dye；It is suitable for environmental requirement；Increase economic benefit.In leather industry production, this method will increasingly play important work
With.
The chemical composition of pre- fatting agent in the present embodiment be phosphatization grease, containing special emulsifier, thus with
Lower feature：It can accelerate the infiltration of material during pickling, tanning；With good exhaustion rate, it is not easy to extract from leather；
With high resiliency grain and outstanding pliability；With outstanding light resistance, heat-resisting xanthochromia shape.
Macerating enzyme in the present embodiment is specially Da Weizimu CBK ox-hide macerating enzymes, and product characteristic is：Emollescence is deep
Enter, uniformly, stablize, can leniently loose hide fiber, the grain of scytoblastema will not be caused to damage；Can improve finished leather pliability,
The flat fineness of grain, reduction position is poor, increases area yield of leather；The growth trace excellent for eliminating skin, it is with obvious effects to open line；It can
Loose scurf removes depigmentation, keeps pelt relatively white.
Deliming agent in the present embodiment is specially to reach Willie card DLA deliming without ammonium agent, is a kind of organic acid and inorganic acid salt
Mixture, product characteristic is：Not ammonium salt-containing, clean environment firendly；Complex soluble easily in water, therefore energy can be formed with calcium ion
Intracutaneous lime is thoroughly removed, efficient deliming effect is reached, deliming skin grain pale complexion is totally, smooth careful；With stronger
Cushion performance will not cause the bust of pH；With preferable permeability, the graywall deliming being suitble to after non-split and split；It can subtract
Less or eliminate deliming liquid in sulfide discharge and hydrogen sulfide gas generate danger.
Salt-free pickling pretanning agent in the present embodiment is specifically the salt-free auxiliary pickling agents of Da Weilong FSP, is a kind of modified phenol sulphur
Acid is a kind of unexpansive acid, can further decrease the dosage of salt, mitigates salt pollution；And can help chromium absorption, infiltration and
Distribution, improves the quality of leather；The wrinkle for contributing to elimination surface, improves the planarization of grain；For no chrome tanning or wet-white leather,
With the product pickling, be conducive to the infiltration of syntans and vegetable tanning agent；In pickling, the loosening of hair can be reduced.
The alkaline agent that carries in the present embodiment is that BLANCOROL BA-IN carry alkaline agent, to the absorption aspects of chromium, than traditional
It carries alkaline agent and to put forward alkali method more efficient.
Based on the embodiments of the present invention, those of ordinary skill in the art are obtained without creative efforts
The all other embodiment obtained, shall fall within the protection scope of the present invention.Although the present invention is illustrated with regard to preferred embodiment
And description can be with it is understood by those skilled in the art that without departing from scope defined by the claims of the present invention
Variations and modifications are carried out to the present invention.
Claims (6)
1. a kind of method of few salt pickling, tanning leather, which is characterized in that include the following steps：
（1）Raw material is softened, fresh hide state is restored, removes unwanted ingredient in fur processing, passes through split in complete thick graywall
Process is by head layer and two layer separations；
（2）Water 120% is added, controlled at 45 DEG C；
（3）Sodium pyrosulfite 0.4% and deliming agent 0.6% is added, rotates 30min, then water is discharged；
（4）Water 150% is continuously added, controlled at 31 ± 1 DEG C, 15min is rotated, then water is discharged；
（5）Water 80% is continuously added, controlled at 31 ± 1 DEG C；
（6）Degreasing agent 0.3% and deliming agent 1.1% is added, rotates 50min；
（7）PH value is detected, control ph is between 8.0 ± 0.2；
（8）The whether saturating heart of hand inspection deliming checks that notch phenolphthalein reagent is colourless；
（9）Macerating enzyme 0.5% is added, rotates 40min, suspends 10min after often rotating 20min；
（10）PH value and temperature are detected, control ph controls 31 ± 1 DEG C of temperature between 8.0 ± 0.2；
（11）Whether hand inspection softens, buttocks bubble whether homogeneous soft, then water is discharged；
（12）Add water 400%, controlled at 18 ± 5 DEG C, flowing water is washed, control time 30-40min, then by 50% row of water
Go out；
（13）PH value is detected, control ph is between 7.5 ± 0.5；
（14）Add water 50%, controlled at 18 ± 5 DEG C, winter, summer was close to lower limiting value close to upper limit value；
（15）Industrial refined salt 3% is added, detection Baume degrees is 6.0 ± 0.5；
（16）Pre- fatting agent 0.4% is added, by pre- fatting agent according to 1 before addition:3 warm water melt, and rotate 20min；
（17）Salt-free pickling pretanning agent 1.5% is added, rotates 30min；
（18）The formic acid 0.4% of purity 85% is added, by formic acid according to 1 before addition:The dilution of 5 cold water melts, and rotates 20min；
（19）The fur sulfuric acid 0.4% of purity 98% is added, by fur sulfuric acid according to 1 before addition:The dilution of 10 cold water melts, and turns
Dynamic 20min；
（20）The fur sulfuric acid 0.4% of purity 98% is added, by fur sulfuric acid according to 1 before addition:The dilution of 10 cold water melts, and turns
Dynamic 60min, suspends 10min after often rotating 20min；
（21）PH value, temperature and Baume degrees are detected, control ph controls 24 ± 3 DEG C of temperature between 2.8-3.2, controls wave
U.S. degree is 6.0 ± 0.5；
（22）Artificial pickling checks that the saturating heart, notch bromocresol green inspection show full yellow；
（23）Chrome-free tanning agent 1.5% is added, rotates 30min；
（24）Chrome-free tanning agent 1.5% is added, rotates 150min；
（25）The sodium formate 0.5% of purity 96% is added, rotates 30min；
（26）Addition carries alkaline agent 0.25%, rotates 180min；
（27）PH value, temperature are detected, control ph controls 37 ± 3 DEG C of temperature between 3.9-4.3；
（28）Water 50% is continuously added, controlled at 35 ± 3 DEG C；
（29）Addition carries alkaline agent 0.05%, and alkaline agent will be carried before addition according to 1:The dilution of 10 warm water melts；
（30）Syntans 4% is added, rotates 150min；
（31）Water 150% is continuously added, controlled at 33 ± 3 DEG C；
（32）Degreasing agent 0.2% is added, rotates 15min；
（33）PH value, temperature are detected, control ph controls 30 ± 3 DEG C of temperature between 4.0-4.4；
（34）30 ± 3 DEG C of temperature of control goes out drum；
Above each percentage is the weight percent that each ingredient accounts for skin.
2. a kind of method of few salt pickling, tanning leather according to claim 1, which is characterized in that the deliming agent is adopted
With deliming without ammonium agent.
3. a kind of method of few salt pickling, tanning leather according to claim 1, which is characterized in that the degreasing agent is adopted
Use alkaline defatting agent.
4. a kind of method of few salt pickling, tanning leather according to claim 1, which is characterized in that the salt-free pickling
Pretanning agent and the syntans use nonmetallic salt-free pickling pretanning agent.
5. a kind of method of few salt pickling, tanning leather according to claim 1, which is characterized in that the macerating enzyme is adopted
To the complex enzyme formulation of trypsase.
6. a kind of method of few salt pickling, tanning leather according to claim 1, which is characterized in that the alkaline agent that carries is adopted
Alkaline agent is carried with inorganic.
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| CN201710049179.3A CN106834563B (en) | 2017-01-20 | 2017-01-20 | A method of few salt pickling, tanning leather |
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| CN106834563B true CN106834563B (en) | 2018-08-17 |
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| CN108950101A (en) * | 2018-04-10 | 2018-12-07 | 辽宁富新新材料有限公司 | A kind of automobile skin alkali sulfide free deliming processing method |
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| US20060288494A1 (en) * | 2005-06-24 | 2006-12-28 | Wolverine World Wide, Inc. | Process for producing leather |
| CN102690902B (en) * | 2011-03-21 | 2014-08-20 | 赣州华坚国际鞋城有限公司 | Leather tanning technology |
| ITTV20150055A1 (en) * | 2015-04-21 | 2016-10-21 | Osmo S R L | SKIN TANNING PROCESS |
| CN105132596B (en) * | 2015-07-30 | 2017-05-24 | 兴业皮革科技股份有限公司 | Production technology of cow skin nappa leather |
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