CN101760569A - Leather making bio-pretreatment method - Google Patents
Leather making bio-pretreatment method Download PDFInfo
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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 the useless albumen composition (hair, fat, interfibrillar substance etc.) on the animal skin on the one hand, produce a large amount of COD, BOD
5Used poisonous and hazardous chemical substance on the other hand, a large amount of chemical materialss is not fully absorbed and is utilized in making the course of processing, enters in the 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, in addition face closure 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 chemical industry material, the utilization new and high technology is transformed traditional process hides industry, has 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 big, and discharges a large amount of organic pollutants and part hazardous and noxious substances, and ecotope is caused serious harm.According to statistics, pollution in leather industry thing about 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 all kinds of chemical materialss of about 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, about 10kg sulfide, 230-250kgCOD and about 100kgBOD
5, wherein about 80% COD and BOD
5Derive from process hides depilation operation again.
The preparation workshop section of conventional leather-making technology comprises: operations such as immersion, depilation, liming, deliming, softening and pickling.The main effect of preparation workshop section is summarized simply 2 points: 1. remove in the animal skin and the composition that has nothing to do with process hides on the 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 the performance of finished leather.Because traditional preparation workshop section mainly adopts chemical such as acid, alkali, salt and tensio-active agent that rawhide is handled, the primary pollution source that amounts of protein degradation product, suspended substance and solid residue that raw hide produced have constituted the process hides process is handled in material such as used lime, 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
At 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 biological pretreatment technology, with biotechnology substitute/part instead of chemical method strengthens the processing to operation before the process hides, remove the structural constituent that has nothing to do with process hides in the rawhide effectively, 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 operations step and material therefor are as follows: material therefor is by mass parts,
(1) pre-immersion: in rotary drum, carry out, get 100 parts of salt marsh cattle hides, add clear water 100-200 part, soaking enzyme 0.05-0.2 part, immersion auxiliary agent 0.02-0.5 part, sterilant 0-0.3 part, under temperature 15-25 ℃, implement immersion 4-6 hour, rotary drum intermittently rotates therebetween, moving 30 minutes of revolution stopped 30 minutes;
(2) main immersion: in rotary drum, carry out, get 100 parts of cattle hides behind the above-mentioned fleshing, add 100 parts in water, add soaking enzyme preparation 0.05-0.4 part, immersion auxiliary agent 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 rotary drum intermittently rotated more than 10 hours, rotating described intermittence to adopt changeed 10 minutes, stopped 50 minutes;
(3) liming: carry out in the rotary drum, get 100 parts of pelts (in the tare weight after the immersion) after the above-mentioned immersion degreasing, 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 is rotated filter hair after 60 minutes, adds Sodium sulfhydrate 0.4-1.2 part again, lime 1-4 part, rotary drum rotates after 45 minutes continuously, presses revolution moving 5 minutes, and rotated 12-18 hour intermittence that stopped 55 minutes;
(4) deashing and softening: in rotary drum, carry out, get 100 parts of liming pelts after the above-mentioned abundant washing, add entry 40-100 part, add sodium bisulfite 0-1.0 part, divide 3 no ammoniums of adding to take off agent 1-2.5 part again, the each adding 20 minutes at interval, rotated 120 minutes in temperature 30-36 ℃ of following rotary drum, moisturizing is 50 parts again, macerating enzyme 0.1-1.5 part, rotated 60 minutes continuously in temperature 32-37 ℃ of following rotary drum, then wash under skin base body lotion pH=7.5-8.0, water temperature 30-35 ℃ and the water yield reach the condition of 100-200 part, rotary drum rotated 30 minutes.When the water yield reaches 100-200 part, wash once under the normal temperature at last, rotary drum rotated 30 minutes again.
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, reduce COD and BOD loading in the depilation waste liquor significantly, and reclaim hair and do the protein resource utilization;
3. realize the dispersion of proteolytic enzyme, reduce the use of lime, reduce suspension content in the waste water collegen filament.
Description of drawings
Fig. 1 is a 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 to substitute the traditional chemical method based on the biotechnology of biological enzyme agent rawhide is handled, with remove on the rawhide with process hides irrelevant protein ingredient.
The process object of preparing each operation in the workshop section mainly is range protein (as the albumin in Keratin sulfate, collagen protein, reticulin, elastin and the interfibrillar substance, sphaeroprotein, protein-polysaccharide etc.) and fat etc.Because enzyme has high efficiency and specificity, therefore can be in each operation of preparing workshop section according to the needs of its effective object, select to use various zymins targetedly, situation at less consumption is issued to the ideal effect, reduce the use of objectionable impurities, shorten the treatment time, improve or improve the quality of finished leather.With employed acid, alkali, the salt in efficient, the single-minded zymin replacement preparation workshop section.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 is mainly reflected in the processing workshop section that wets before process hides is tanned in the application of process hides process.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,, promote the dispersion of collegen filament, to improve the quality of finished leather by means of the effect of enzyme.
Enzyme has more effective performance in the immersion process: 1. loose scurf; 2. shorten soaking time; 3. reduce the grain wrinkle; 4. increase the homogeneity of immersion.Particularly lipase adds the grease more help to remove between hide fiber when immersion, and it is loose that hair root is obtained, for the enforcement of follow-up depilation creates favorable conditions.
As shown in Figure 1, each operation concrete operations step of the preparation workshop section of leather-making technology of the present invention and material therefor are as follows: material therefor is by mass parts,
(1) pre-immersion: in rotary drum, carry out, get 100 parts of salt marsh cattle hides, add 100 parts in clear water, 0.2 part of soaking enzyme BORRON DL or LANAZIM KB, the immersion auxiliary agent (comprises CISMOLLAN BH-C, PELLVIT MN-A, SOAKING SK-6, SOAKS 1S, ANTIWRINKLE AW etc.) 0.2 part, sterilant (comprises BUSAN 242, ARACIT KL-A, BACTERCIDE 2B, ANTIMOULD AGENT30E, BUSAN 1236 etc.) 0.1 part, in rotary drum, implement immersion 4 hours in temperature under less than 25 ℃, rotary drum intermittently rotates, and promptly revolution is moving 30 minutes, stops 30 minutes.Then the washing, fleshing.
(2) main immersion: in rotary drum, carry out, get 100 parts of cattle hides behind the above-mentioned fleshing, add 100 parts in water, add 0.2 part of soaking enzyme preparation BORRON DL or LANAZIM KB, the immersion auxiliary agent (comprises CISMOLLANBH-C, PELLVIT MN-A, SOAKING SK-6, SOAKS 1S, ANTIWRINKLE AW etc.) 0.3 part, sterilant (comprises BUSAN 242, ARACIT KL-A, BACTERCIDE 2B, ANTIMOULDAGENT 30E, BUSAN 1236 etc.) 0.1 part, rotate after 4 hours continuously, add 0.5 part of soda ash again, then rotary drum intermittently rotated more than 10 hours, rotating described intermittence to adopt changeed 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 the rotary drum, get 100 parts of pelts (in the tare weight after the immersion) after the 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 in caustic soda rotates after 60 minutes filter mao.Add 1 part of Sodium sulfhydrate again, 2 parts in lime, after rotary drum rotated 45 minutes continuously, rotary drum then intermittently rotated 12 hours, promptly pressed revolution moving 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 the above-mentioned abundant washing, add 40 parts of entry, 0.5 part of sodium bisulfite divides to add no ammoniums for 3 times and take off totally 1.5 parts of agent DERMASCAL F again, adds the interval 20 minutes at every turn.Rotated 120 minutes in 30 ℃ of following rotary drums of temperature, colourless substantially to the buttocks otch with the phenolphthalein indicator inspection.Add 50 parts in water again, macerating enzyme BORRON DN or OROPON00, or OROPON W, or 0.1 part of macerating enzyme NG or its combination rotated 60 minutes down continuously in 35 ℃ temperature condition.Then 30 ℃ of skin base body lotion pH=7.5-8.0, water temperatures, wash under the condition that the water yield is 100 parts, rotary drum rotated 30 minutes.Wash once under 100 parts of the water yields, normal temperature at last, rotary drum rotated 30 minutes again.
The present invention has abandoned existing production technology and mainly has been based on useless composition and loosen collagen fibre in the chemical process removal skin, as ash alkali unhairing, lime loosen collagen fibre, ammonium salt deliming technology etc.Utilize compound enzymic preparations such as lipase, proteolytic enzyme, strengthen immersion, skimming processes, and quicken 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 biological pre-treatment, compare with traditional leather-making technology, can quicken immersion and loosen collagen fibre process, shortens process time 6-12 hour, it is about 30% realize to economize on water, and 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, using guarantor's hair epilation to reduce on the sulfide consumption basis, remaining sulfide in the energy completely consumed waste liquid, make in depilation waste liquor and the graywall not sulfur compound, thoroughly eliminate the pollution of sulfide, thereby simple to operate, with low cost, and do not influence quality product.And in whole pretreatment procedure, all consider to utilize on efficient, the innoxious removal animal skin of reaching of biological enzyme formulation and the irrelevant composition of process hides.
Energy-saving and emission-reduction to process hides preparation workshop section after the invention process 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 operations step and material therefor are as follows: material therefor is by mass parts,
(1) pre-immersion: in rotary drum, carry out, get 100 parts of salt marsh cattle hides, add clear water 100-200 part, soaking enzyme 0.05-0.2 part, immersion auxiliary agent 0.02-0.5 part, sterilant 0-0.3 part, under temperature 15-25 ℃, implement immersion 4-6 hour, rotary drum intermittently rotates therebetween, moving 30 minutes of revolution stopped 30 minutes;
(2) main immersion: in rotary drum, carry out, get 100 parts of skin bases behind the above-mentioned fleshing, add 100 parts in water, add soaking enzyme preparation 0.05-0.4 part, immersion auxiliary agent 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 rotary drum intermittently rotated more than 10 hours, rotating described intermittence to adopt changeed 10 minutes, stopped 50 minutes;
(3) liming: carry out in the rotary drum, get 100 parts of pelts (in the tare weight after the immersion) after the above-mentioned immersion degreasing, 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 is rotated filter hair after 60 minutes, adds Sodium sulfhydrate 0.4-1.2 part again, lime 1-4 part, rotary drum rotates after 45 minutes continuously, presses revolution moving 5 minutes, and rotated 12-18 hour intermittence that stopped 55 minutes;
(4) deashing and softening: in rotary drum, carry out, get 100 parts of liming pelts after the above-mentioned abundant washing, add entry 40-100 part, add sodium bisulfite 0-1.0 part, divide 3 no ammoniums of adding to take off agent 1-2.5 part again, the each adding 20 minutes at interval, rotated 120 minutes in temperature 30-36 ℃ of following rotary drum, moisturizing is 50 parts again, macerating enzyme 0.1-1.5 part, rotated 60 minutes continuously in temperature 32-37 ℃ of following rotary drum, then wash under skin base body lotion pH=7.5-8.0, water temperature 30-35 ℃ and the water yield reach the condition of 100-200 part, rotary drum rotated 30 minutes.When the water yield reaches 100-200 part, wash once under the normal temperature at last, rotary drum rotated 30 minutes again.
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| CN102517408A (en) * | 2011-11-17 | 2012-06-27 | 烟台大学 | Sheepskin tanning process capable of replacing enzyme softening with excessive deliming |
| CN102952907A (en) * | 2011-08-26 | 2013-03-06 | 约泰实业股份有限公司 | Method for depilating animal skin |
| TWI427205B (en) * | 2011-08-22 | 2014-02-21 | ||
| CN103627825A (en) * | 2013-11-20 | 2014-03-12 | 邱占伟 | Method for carrying out softening treatment on leather |
| CN105053144A (en) * | 2015-07-24 | 2015-11-18 | 淄博黄河龙生物工程有限公司 | Leather pickling technology |
| CN105132596A (en) * | 2015-07-30 | 2015-12-09 | 兴业皮革科技股份有限公司 | Production technology of cow skin nappa leather |
| CN105624339A (en) * | 2015-12-23 | 2016-06-01 | 天津科技大学 | Method for shortening leather making soaking time |
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| CN102952907B (en) * | 2011-08-26 | 2015-05-13 | 约泰实业股份有限公司 | Method for depilating animal skin |
| CN102517408A (en) * | 2011-11-17 | 2012-06-27 | 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 |
| CN105053144A (en) * | 2015-07-24 | 2015-11-18 | 淄博黄河龙生物工程有限公司 | Leather pickling technology |
| CN105132596A (en) * | 2015-07-30 | 2015-12-09 | 兴业皮革科技股份有限公司 | Production technology of cow skin nappa leather |
| CN105624339A (en) * | 2015-12-23 | 2016-06-01 | 天津科技大学 | Method for shortening leather making soaking time |
| CN105624339B (en) * | 2015-12-23 | 2018-05-18 | 天津科技大学 | A kind of method for shortening process hides soaking time |
| CN105734182A (en) * | 2016-01-29 | 2016-07-06 | 佛山市聚成生化技术研发有限公司 | Treatment process applied before tanning of pigskin and untanned pigskin obtained by same |
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| CN106350619A (en) * | 2016-09-29 | 2017-01-25 | 天津科技大学 | Chrome-reduced combination tanning method of compound enzyme preparation after soaking |
| 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 |
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| CN109609484A (en) * | 2018-12-06 | 2019-04-12 | 河北省微生物研究所 | The preparation method of compound depilation enzyme preparation and its application in losing hair or feathers containing small Mao import cattle hide |
| 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 |
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