CN101760569B - Leather making bio-pretreatment method - Google Patents
Leather making bio-pretreatment method Download PDFInfo
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- CN101760569B CN101760569B CN 200810187534 CN200810187534A CN101760569B CN 101760569 B CN101760569 B CN 101760569B CN 200810187534 CN200810187534 CN 200810187534 CN 200810187534 A CN200810187534 A CN 200810187534A CN 101760569 B CN101760569 B CN 101760569B
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Abstract
The invention discloses a leather making bio-pretreatment method. By using a biotechnology to replace or partly replace a chemical method and utilizing compound enzyme preparations including lipase and protease, the method strengthens processes of soaking and degreasing, accelerates dispersion of collagen fibers, optimizes the enzyme bating process, shortens the treatment time and reduces the consumption of water and the use of a chemical additive. Compared with the traditional leather-making technology, the leather making bio-pretreatment method can accelerate the soaking process and the fiber dispersion process, shorten the process time by 6-12h, realize water saving by about 30 percent and COD (Chemical Oxygen Demand) emission reduction by 20-40 percent, lower the dosage of protosulphide by 40-50 percent and the like. In the invention, on the basis of lowering the consumption of the protosulphide by using a hair-saving method, an environmental friendly auxiliary liming agent which is prepared by utilizing the biotechnology and a physicochemistry principle can completely consume residual sulfide in waste liquid to enable unhairing waste liquid and limed pelts not to contain the sulfide and completely eliminate pollution of the sulfide; therefore, the invention has the advantages of simple operation and low cost without influencing the product quality. In addition, in the whole pretreatment process, the biological enzyme preparation is considered to be utilized to efficiently and harmlessly remove components on animal skin unrelated to leather making.
Description
Technical field
The present invention relates to a kind of process hides treatment technology.Specifically, relate to a kind of leather making bio pretreatment technology.
Background technology
Tanning industry is a heavy polluted industry.In the process hides chemical process, remove on the one hand the useless Proteins (hair, fat, interfibrillar substance etc.) on animal skin, produce a large amount of COD, BOD
5Used on the other hand poisonous and hazardous chemical substance, a large amount of chemical materialss is not fully absorbed and utilizes in making the course of processing, enters in waste water, brings new pollution.The problem of this two aspect is as can not effectively being solved, and problem of environmental pollution especially will become the important factor of serious restriction China leather industry Sustainable development, faces closure even in the near future, atrophy.Therefore, at the leather-making technology that strives for improvement, in the time of exploitation high-efficiency low-toxicity Leather Chemicals, use the traditional process hides industry of new and high technology transformation, become one of the important measures of China's tanning industry Sustainable development and urgent task.
In process hides pre-treatment workshop section, not only water loss is large, and discharges a large amount of organic pollutants and part hazardous and noxious substances, to the ecotope harm.According to statistics, the pollution in leather industry thing approximately 80% derives from the process hides preparatory stage, and 1000 tons of wet salted hides of every processing need to consume 50m
3Water (domestic enterprise's water loss is 60-90m
3) and the about all kinds of chemical materialss of 570kg, only can obtain the useful finished product leather of 200kg, will produce 500-600kg solid waste and 50m
3Waste water, this 50m
3Waste water in contain 5-6kg chromium, approximately 10kg sulfide, 230-250kgCOD and about 100kgBOD
5, wherein approximately 80% COD and BOD
5Derive from again process hides depilation operation.
The preparation workshop section of conventional leather-making technology comprises: the operations such as immersion, depilation, liming, deliming, softening and pickling.The Main Function of preparation workshop section is summarized simply 2 points: 1. remove in animal skin and the composition that has nothing to do with process hides on skin, as hair, epidermis, grease etc.; 2. loose collegen filament.Therefore, preparing workshop section is the basis of process hides, most important to the quality and performance of finished leather.Workshop section mainly adopts the chemical such as acid, alkali, salt and tensio-active agent that rawhide is processed due to traditional preparation, and the primary pollution source that a large amount of protein degradation thing, suspended substance and solid residue that raw hide produces have consisted of the process hides process is processed in the material such as lime used, sodium sulphite, sodium-chlor and their.Prepare workshop section and pollute the most serious workshop section, its total amount of pollutant accounts for 80% of whole process hides process.Therefore, how avoiding preparing the environmental pollution that workshop section brings, is that tanning chemistry man and engineering technical personnel make great efforts one of direction of studying always.
Summary of the invention
For the deficiencies in the prior art part, the objective of the invention is on existing achievement in research basis aspect the leather making bio pretreatment technology, further carry out the integrated of Bio-Pretreatment technology, with biotechnology substitute/part instead of chemical method strengthens the processing to operation before process hides, effectively remove the structural constituent that has nothing to do with process hides in rawhide, and the dispersion that promotes collegen filament, reduce the discharging of pollution in leather industry thing, improve finished product keratin amount.
For achieving the above object, technical solution of the present invention is:
Leather making bio-pretreatment method, its each operation concrete operation step and material therefor are as follows: material therefor is by mass parts,
(1) pre-immersion: carry out in rotary drum, get 100 parts of salt marsh cattle hides, add clear water 100-200 part, soaking enzyme 0.05-0.2 part, Soaking 0.02-0.5 part, sterilant 0-0.3 part, under temperature 15-25 ℃, implement immersion 4-6 hour, therebetween the rotary drum intermittent rotary, every rotation 30 minutes stopped 30 minutes;
(2) main immersion: carry out in rotary drum, get 100 parts of cattle hides after above-mentioned fleshing, add 100 parts, water, add soaking enzyme preparation 0.05-0.4 part, Soaking 0.1-0.5 part, sterilant 0.02-0.4 part, rotate after 4 hours continuously, add soda ash 0.1-0.5 part, then the rotary drum intermittent rotary is more than 10 hours, described intermittent rotary adopts and turns 10 minutes, stops 50 minutes;
(3) liming: carry out in rotary drum, get the pelt after above-mentioned immersion degreasing, in 100 parts of the tare weights after immersion, add entry 50-200 part, auxiliary liming agent 0.1-0.8 part, liming enzyme 0.1-0.5 part, caustic soda 0-0.3 part, rotate filter hair after 60 minutes, add Sodium sulfhydrate 0.4-1.2 part, lime 1-4 part is after rotary drum rotates 45 minutes continuously again, by every rotation 5 minutes, stop 55 minutes intermittent rotary 12-18 hour;
(4) deashing and softening: carry out in rotary drum, get 100 parts of liming pelts after above-mentioned abundant washing, add entry 40-100 part, add sodium bisulfite 0-1.0 part, divide again and add deliming without ammonium agent 1-2.5 part for 3 times, added the interval 20 minutes at every turn, rotated 120 minutes in temperature 30-36 ℃ of lower rotary drum, moisturizing is 50 parts again, macerating enzyme 0.1-1.5 part, rotated 60 minutes continuously in temperature 32-37 ℃ of lower rotary drum, then at skin base body lotion pH=7.5-8.0, water temperature 30-35 ℃ and the water yield reach the Water Under of 100-200 part and wash, rotary drum rotated 30 minutes, at last when the water yield reaches 100-200 part, wash once again under normal temperature, rotary drum rotated 30 minutes.
The usefulness of technique scheme is:
1. utilize biotechnology instead of chemical method, reduce the use of harmful chemical;
2. adopt few sulphur enzyme to protect hair depilation technology, avoid the fleece chemical reducing agent to degrade, significantly reduce COD and BOD loading in depilation waste liquor, and reclaim hair and do the protein resource utilization;
3. realize proteolytic enzyme to the dispersion of collegen filament, reduce the use of lime, reduce suspension content in waste water.
Description of drawings
Fig. 1 is leather making bio pretreatment technology process flow diagram of the present invention.
Embodiment
The present invention now is described in conjunction with the accompanying drawings and embodiments.
Gordian technique of the present invention is that the biotechnology take the biological enzyme agent as the basis substitutes the traditional chemical method rawhide is processed, with remove on rawhide with process hides irrelevant protein ingredient.
The processing object of preparing each operation in workshop section is mainly range protein (as the albumin in Keratin sulfate, collagen protein, reticulin, elastin and interfibrillar substance, sphaeroprotein, protein-polysaccharide etc.) and fat etc.Because enzyme has high efficiency and specificity, therefore can be according to the needs of its effective object in each operation of preparing workshop section, the targeted various zymins of choice for use, situation at less consumption is issued to desirable effect, reduce the use of objectionable impurities, shorten the treatment time, improve or improve the quality of finished leather.Replace preparing the acid of being used, alkali, salt in workshop section with efficient, single-minded zymin.Prepare workshop section in process hides and utilize advanced biotechnology to substitute traditional chemical method, implementing the leather making bio pre-treatment is the effective way that solves pollution in leather industry.
Zymin wet processing workshop section before the application of process hides process is mainly reflected in process hides and tans.On the one hand, utilize enzyme to substitute the traditional chemical method and remove the noncollagen protein composition, reduce the use of harmful chemical, reduce the discharging of pollutent; On the other hand, by means of the effect of enzyme, promote the dispersion of collegen filament, to improve the quality of finished leather.
Enzyme has more effective performance in the immersion process: scurf 1. loosens; 2. shorten soaking time; 3. reduce the grain wrinkle; 4. increase the homogeneity of immersion.Particularly lipase adds and more helps to remove grease between hide fiber in when immersion, hair root is obtained loose, for the enforcement of follow-up depilation creates favorable conditions.
As shown in Figure 1, preparation each operation concrete operation step of workshop section and the material therefor of leather-making technology of the present invention are as follows: material therefor is by mass parts,
(1) pre-immersion: carry out in rotary drum, get 100 parts of salt marsh cattle hides, add 100 parts, clear water, 0.2 part of soaking enzyme BORRON DL or LANAZIM KB, Soaking (comprises CISMOLLAN BH-C, PELLVITMN-A, SOAKING SK-6, SOAKS 1S, ANTIWRINKLE AW etc.) 0.2 part, sterilant (comprises BUSAN242, ARACIT KL-A, BACTERCIDE 2B, ANTIMOULD AGENT 30E, BUSAN 1236 etc.) 0.1 part, implement immersion 4 hours in temperature under less than 25 ℃ in rotary drum, the rotary drum intermittent rotary, be every rotation 30 minutes, stopped 30 minutes.Then the washing, fleshing.
(2) main immersion: carry out in rotary drum, get 100 parts of cattle hides after above-mentioned fleshing, add 100 parts, water, add 0.2 part of soaking enzyme preparation BORRON DL or LANAZIM KB, Soaking (comprises CISMOLLAN BH-C, PELLVIT MN-A, SOAKING SK-6, SOAKS 1S, ANTIWRINKLE AW etc.) 0.3 part, sterilant (comprises BUSAN 242, ARACIT KL-A, BACTERCIDE 2B, ANTIMOULD AGENT 30E, BUSAN1236 etc.) 0.1 part, rotate continuously after 4 hours, add again 0.5 part of soda ash, then the rotary drum intermittent rotary is more than 10 hours, described intermittent rotary adopts and turns 10 minutes, stopped 50 minutes.The soft degree of final skin base reaches and meets the requirements, and the bath temperature scope is that 15-25 ℃, degree Beaume are 6-10 and pH value=9.0-11.0.
(3) liming: carry out in rotary drum, get 100 parts of pelts (in the tare weight after immersion) after above-mentioned immersion degreasing, add 80 parts of entry, 0.5 part of auxiliary liming agent, 0.15 part of liming enzyme NL or AB, 0.2 part, caustic soda rotates after 60 minutes filter mao.Add again 1 part of Sodium sulfhydrate, 2 parts, lime, after rotary drum rotated 45 minutes continuously, rotary drum was followed intermittent rotary 12 hours, namely by every rotation 5 minutes, stopped 55 minutes.Pelt should appropriateness expand, and the skin base is flexible, and thickness obviously increases, but unlikely overplumping; Hair root removes fully, i.e. noresidue hair root in the skin base, and surface is clear; Degree Beaume is 6-10.
(4) deashing and softening: carry out in rotary drum, get 100 parts of liming pelts after above-mentioned abundant washing, add 40 parts of entry, 0.5 part of sodium bisulfite, then divide and add totally 1.5 parts of deliming without ammonium agent DERMASCAL F for 3 times, added the interval 20 minutes at every turn.Rotated 120 minutes in 30 ℃ of lower rotary drums of temperature, substantially colourless with the phenolphthalein indicator inspection to the buttocks otch.Add 50 parts, water, macerating enzyme BORRON DN or OROPON OO, or OROPONW, or 0.1 part of macerating enzyme NG or its combination rotated 60 minutes under the temperature condition of 35 ℃ continuously again.Then 30 ℃ of skin base body lotion pH=7.5-8.0, water temperatures, the Water Under that the water yield is 100 parts is washed, and rotary drum rotated 30 minutes, washes once under 100 parts of the water yields, normal temperature at last again, and rotary drum rotated 30 minutes.
The present invention has abandoned existing production technology and mainly has been based on useless composition and loosen collagen fibre in chemical process removal skin, as ash alkali unhairing, lime loosen collagen fibre, ammonium salt deliming technology etc.Utilize the compound enzymic preparations such as lipase, proteolytic enzyme, strengthen immersion, skimming processes, and accelerate the dispersion of collegen filament, and optimize the enzyme bating process, shorten the treatment time, reduce the consumption of water and the use of chemical assistant.After Bio-Pretreatment, compare with traditional leather-making technology, can accelerate immersion and loosen collagen fibre process, shortens process time 6-12 hour, realize to economize on water approximately 30%, COD reduces discharging 20-40%, reduction sulfide consumption 40-50% etc.The present invention utilizes biotechnology and materialization principle development environment-friendly type auxiliary liming agent, reduce on sulfide consumption basis use protecting the hair epilation, remaining sulfide in energy completely consumed waste liquid, make in depilation waste liquor and graywall not sulfur compound, thoroughly eliminate the pollution of sulfide, thereby simple to operate, with low cost, and do not affect quality product.And all consider to utilize on efficient, the innoxious removal animal skin of reaching of biological enzyme formulation the composition irrelevant with process hides in whole pretreatment procedure.
The energy-saving and emission-reduction of after the invention process, workshop section is prepared in process hides will bring about tangible results, and its key technical indexes is as follows:
-sulfide reduces discharging 55%;
-COD reduces discharging more than 60%;
-BOD
5Reduce discharging more than 45%;
-suspended substance (SS) and insoluble total solid amount reduce 30%-40%;
-sewage total amount reduces discharging 25-30%;
The water saving of-technological process is more than 25%;
Economic benefit and social benefit are very huge.
Claims (1)
1. leather making bio-pretreatment method is characterized in that each operation concrete operation step and material therefor are as follows: material therefor is by mass parts,
(1) pre-immersion: carry out in rotary drum, get 100 parts of salt marsh cattle hides, add clear water 100-200 part, soaking enzyme 0.05-0.2 part, Soaking 0.02-0.5 part, sterilant 0-0.3 part, under temperature 15-25 ℃, implement immersion 4-6 hour, therebetween the rotary drum intermittent rotary, every rotation 30 minutes stopped 30 minutes;
(2) main immersion: carry out in rotary drum, get 100 parts of skin bases after above-mentioned fleshing, add 100 parts, water, add soaking enzyme preparation 0.05-0.4 part, Soaking 0.1-0.5 part, sterilant 0.02-0.4 part, rotate after 4 hours continuously, add soda ash 0.1-0.5 part, then the rotary drum intermittent rotary is more than 10 hours, described intermittent rotary adopts and turns 10 minutes, stops 50 minutes;
(3) liming: carry out in rotary drum, get the pelt after above-mentioned immersion degreasing, in 100 parts of the tare weights after immersion, add entry 50-200 part, auxiliary liming agent 0.1-0.8 part, liming enzyme 0.1-0.5 part, caustic soda 0-0.3 part, rotate filter hair after 60 minutes, add Sodium sulfhydrate 0.4-1.2 part, lime 1-4 part is after rotary drum rotates 45 minutes continuously again, by every rotation 5 minutes, stop 55 minutes intermittent rotary 12-18 hour;
(4) deashing and softening: carry out in rotary drum, get 100 parts of liming pelts after above-mentioned abundant washing, add entry 40-100 part, add sodium bisulfite 0-1.0 part, divide again and add deliming without ammonium agent 1-2.5 part for 3 times, added the interval 20 minutes at every turn, rotated 120 minutes in temperature 30-36 ℃ of lower rotary drum, moisturizing is 50 parts again, macerating enzyme 0.1-1.5 part, rotated 60 minutes continuously in temperature 32-37 ℃ of lower rotary drum, then at skin base body lotion pH=7.5-8.0, water temperature 30-35 ℃ and the water yield reach the Water Under of 100-200 part and wash, rotary drum rotated 30 minutes, at last when the water yield reaches 100-200 part, wash once again under normal temperature, rotary drum rotated 30 minutes.
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Families Citing this family (13)
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| TW201309864A (en) * | 2011-08-22 | 2013-03-01 | Jollity Entpr Co Ltd | Depilation method of animal skin |
| CN102952907B (en) * | 2011-08-26 | 2015-05-13 | 约泰实业股份有限公司 | Method for depilating animal skin |
| CN102517408B (en) * | 2011-11-17 | 2013-06-19 | 烟台大学 | Sheepskin tanning process capable of replacing enzyme softening with excessive deliming |
| CN103725810B (en) * | 2012-10-15 | 2017-02-08 | 焦作隆丰皮草企业有限公司 | Method for tanning sheep shorn-pile |
| CN103627825A (en) * | 2013-11-20 | 2014-03-12 | 邱占伟 | Method for carrying out softening treatment on leather |
| CN105053144B (en) * | 2015-07-24 | 2017-12-01 | 淄博黄河龙生物工程有限公司 | Brined hide technique |
| 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 |
| CN105624339B (en) * | 2015-12-23 | 2018-05-18 | 天津科技大学 | A kind of method for shortening process hides soaking time |
| CN105734182B (en) * | 2016-01-29 | 2017-10-24 | 佛山市聚成生化技术研发有限公司 | A kind of handling process before pigskin tanning and the pigskin before resulting tanning |
| CN106350619B (en) * | 2016-09-29 | 2019-04-09 | 天津科技大学 | The method of few chromium combination tanning after a kind of immersion of complex enzyme formulation |
| CN107779526B (en) * | 2017-10-28 | 2020-06-23 | 海宁森德皮革有限公司 | Production method of seat leather special for high-speed train |
| CN109609484B (en) * | 2018-12-06 | 2022-06-10 | 河北省微生物研究所有限公司 | Preparation method of composite depilatory enzyme preparation and application of composite depilatory enzyme preparation in depilation of imported oxhide containing feather |
| CN110042178A (en) * | 2019-01-13 | 2019-07-23 | 福建省全杰生物科技有限公司 | A kind of process hides processing water saving art |
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