CN101497929B - Hair protecting, dehairing and liming method for cattle hide tanning - Google Patents
Hair protecting, dehairing and liming method for cattle hide tanning Download PDFInfo
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- CN101497929B CN101497929B CN2009100959968A CN200910095996A CN101497929B CN 101497929 B CN101497929 B CN 101497929B CN 2009100959968 A CN2009100959968 A CN 2009100959968A CN 200910095996 A CN200910095996 A CN 200910095996A CN 101497929 B CN101497929 B CN 101497929B
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Abstract
The invention discloses a method of hair-protecting, unhairing and liming of cattle hide, which solves the problems that the three pollutants of sulfide, organic matter and solid lime have high content with the conventional sulfide unhairing and liming method. The method comprises the a first step of adopting a hair-protecting agent to protect hair, a second step of adding sulfide and neutral salt to unhair and a third step of liming. The method is characterized in that the amount of used sulfide is small, hair shafts are mainly protected when protecting hair, and the sulfide mainly acts on hair roots when unhairing; in addition, the method has obvious unhairing effect, uses short time, needs no special liquid circulation and hair filtering device, has stable product quality and, low technology cost, and is easy to control; meanwhile, the recovered hair shafts are better protected and has high strength and utilization value. The method can replace the traditional sulfide unhairing and liming method and significantly reduce the indexes of pollutants in wastewater, wherein the total emission of COD, BOD5 and suspended matter is reduced by more than 55 percent, and the total emission of sulfide is reduced by more than 75 percent; and the method creates a new way for the clean production of leather-making enterprises.
Description
Technical field
The invention belongs to the leather processing field, particularly a kind of cleaning depilation liming technology of ox-hide process hides.
Background technology
Ash alkaline process depilation is a kind of ancient depilating method, have that raw material is easy to get, cost is low, simple to operate, control easily, advantage such as resultant leather quality is stable, applied widely, at present both at home and abroad tanning production still to lose hair or feathers with grey alkaline process be main.But there are some fatal shortcomings in grey alkaline process depilation, mainly shows the following aspects: the pollution of sulfide; Organic pollution; The pollution of solid lime.
Change this present situation, preferably adopt no sulphur method depilation, like enzyme unhairing, oxidative unhairing etc., but these methods itself also come with some shortcomings, and from the present situation of China's tanning industry, fully phase out grey alkaline process and lose hair or feathers also unrealistic.Therefore from reducing the angle of polluting, protect hair depilation a kind of more feasible way of can yet be regarded as.
Protecting the hair epilation mainly is through controlling alkali and the reductive agent action condition to hair, is that the depilation condition only acts on hair root and stays complete hair, re-use the recycle system hair is recycled, rather than with discharge of wastewater.Can reduce suspended substance and organism in the waste water effectively like this, reduce the value of BOD and COD.The common coloured promise method of guarantor's hair depilating method (Sirolime), HS protect hair liming system, Blair's method (Blair) etc.
Its primary process of Se Nuofa (Sirolime) is to flood with Sodium sulfhydrate earlier, and relatively low pH value can guarantee HS
-1The hair effect is protected in generation, and can any damage not arranged to hair.Then through Ca (ClO)
2Short period of time handles, and the NaHS oxidation that is attached on the fleece is removed, and avoids hair shaft in ensuing highly basic is handled, to be damaged, to keep the intensity of hair.NaHS in the hair root can be not oxidized, in the relaxation of hair, adds Ca (OH)
2Make PH greater than 12, this part NaHS will produce strong reducing action, and weakening and destruction hair are got in touch with hair follicle, and hair is come off.In case hair is loosening, depilatory solution is filtered, circulates, separate hair.The waste water of dipping waste water, the waste water that makes mao relaxation and liming can recycle through post precipitation.The advantage of this method is not need special chemical materials, and economical with materials and water are difficult for protecting hair excessively, the grain cleaning, and the loose side rate is low, the recyclable utilization of hair, its shortcoming is a complex process, once throws skin and possibly have the inadequate situation of depilation more for a long time; The sulfide consumption is higher, if use organosulfur can increase cost again as reductive agent; Need special filter hair device to remove unhairing, increased investment.
It is that a kind of few sulphur is protected hair depilation technology that HS protects a hair liming system, can cooperate sodium sulphite to use, and also can not use sodium sulphite, is divided into immersion, hides, protects hair, activates, loses hair or feathers, stage such as ash again.Need keep during immersion between pH9～10, add soaking enzyme, wetting agent and grease-removing agent, need 4～5h altogether.In the process of hiding, liquor ratio 0.7～0.8 adds 0.8%～1.2%Erhait HS, changes and stops 1h.Protect between hair, active period, add 1%～2% lime, pH value of solution is controlled at 12～13.The Sodium sulfhydrate of depilation operation adding 0.7%～1.2% loses hair or feathers, and is circulation body lotion filtering separation hair when hair begins to become flexible.Add a small amount of sodium sulphite or Sodium sulfhydrate and lime during multiple at last ash, go out residual hair and loose fiber.This method complex procedures needs special material, needs special filter hair device to remove unhairing simultaneously, has increased investment.
Blair (Blair) epilation principal feature is that hair shaft is handled through suitable alkali (lime) and the hair effect is protected in generation, adds Sodium sulfhydrate then, and hair root is not damaged because be protected, and hair is become flexible, and relends and helps mechanical effect that hair is removed.The hair taken off after with the hair filtering separation, the waste liquid recycle.Use lime, Sodium sulfhydrate and auxiliary liming agent FR-62 (a kind of fatty amine material helps to remove residual hair and prevents to protect the generation of the excessive and hydrogen sulfide of hair through improving pH value) in the multiple grey process subsequently.This method does not need special rotary drum circulation and filter hair device, but the depilation time is long, and multiple ash of later stage also need add sulfide again.Strictness all compare in control to the temperature and time of technology in addition, careless slightlyly a mao over-drastic situation will occur protecting.
Summary of the invention
The objective of the invention is in order to overcome the shortcoming and defect that prior art exists, and a kind of pollutent index in the waste water that can significantly reduce is provided, the ox-hide hair protecting, dehairing that hair removal effect is obvious, the time is short and the method for liming.
For realizing above-mentioned purpose, technical scheme of the present invention is may further comprise the steps:
(1) protect hair: the routine ox-hide that soaks behind the fleshing is put into rotary drum, and add the water of tare weight 150～250%, attemperation is 18～25 ℃, adds tare weight 1～2% and protects a mao agent, and 0.05～0.2% grease-removing agent rotates and stopped 15 minutes in 15 minutes, lasting 90～150 minutes;
(2) depilation: the water of control liquid to tare weight 50～100%, 18～25 ℃ of holding temperatures add trichogen, and the addition of this trichogen satisfies its S that contains
2-Quality is 0.14～0.24% of a tare weight, rotates 10-15 minute, adds neutral salt 1～2%, rotates 10-30 minute, and hair comes off more than 95%;
(3) liming: continue during depilation is bathed to add tare weight 0.3～1.0% auxiliary liming agent, 2～4% lime rotated 15～30 minutes, further depilation; Add tare weight 50～100% water, rotated 15～30 minutes; At least again add tare weight 50～100% water one time, and rotate 15～30 minutes (gradation of this step adds entry and enlarges the quality that liquor ratio helps to improve leather, maybe be at twice, three times even more times, three times is good in general); And then stop the mode of combining and continue at least 10 hours per hour to change the commentaries on classics that stopped in 5 minutes 55 minutes.
(4) control water and clean hair ball: add tare weight 200～300% water, 20～27 ℃ of attemperation add tare weight 0.1～0.3% oxygenant, rotate 20～30 minutes, go out drum, clean the ground hair ball.
Improve and replenish as the further of such scheme, technical characterictic of the present invention also includes: mao agent of adding in the described step (1) of protecting is a lime, and this is to consider lime economy and practicality, and can effectively reduce cost.The grease-removing agent that step (1) is added mainly refers to some tensio-active agents, and purpose is to remove a lot of greases that fresh hide self has, and avoids grease to influence the quality of leather.Specifically can arrive on the market and purchase, such as the grease-removing agent AN of Bayer company.Saying in the step (3) that in addition adding auxiliary liming agent is special assistant in a kind of liming process in the leather processing procedure, is the general name of one type of material.Specifically can arrive on the market and purchase, such as the auxiliary liming agent 4005 of Bayer company.The product code name of these two types of material different companys can be different, the difference that effect can be to some extent, and those skilled in the art can require to select Different products according to different process.
Further be provided with is that the trichogen that adds in described rapid (2) is sodium sulphite or Sodium sulfhydrate.
Further being provided with is that described neutral salt is a sodium-chlor.This sodium-chlor can adopt and pickle the salt that reclaims behind the hide in the leather production process.
Further being provided with is that described oxygenant is ydrogen peroxide 50 or sodium sulfite anhy 96.This oxygenant can with the remaining S in depilation back
2-Attack but to the hide non-evident effect.Consider environmental factors, preferred ydrogen peroxide 50.
The invention has the advantages that:
(1) can need not exotic materials, technological operation is simple and easy to control, is fit to industrialization promotion;
(2) S
2-Consumption can be low to moderate below 0.24% (reduces to conventional hair-destroying process S
2-Below 40% of consumption), depilation rapidly and efficiently can be accomplished in 20～70 minutes, reclaimed hair intensity and can utilize well again, had avoided conventional guarantor's hair depilation S
2-Consumption is high, and reclaiming hair is pulpous state, the defective that utility value is few;
(3) leather quality and routine are ruined the no significant difference of hair depilation;
(4) reduce pollutent index in the waste water, wherein COD, BOD5, suspended substance total emission volumn reduce more than 55%, and the sulfide emission total amount reduces more than 75%.
Below in conjunction with embodiment the present invention is done further introduction.
Embodiment
Through embodiment the present invention is carried out concrete description below; Only be used for the present invention is further specified; Can not be interpreted as the qualification to protection domain of the present invention, the technician in this field can make some nonessential improvement and adjustment to the present invention according to the content of foregoing invention.The wherein raw materials used meter of mark by weight.
Embodiment 1
(1) protect hair: ox-hide behind the conventional immersion fleshing, weigh.The water that adds tare weight 150%, 18 ℃ of attemperation add tare weight 1% and protect a mao agent, and 0.05% grease-removing agent changes and stopped 15 minutes in 15 minutes, 90 minutes total times;
(2) depilation: the water of control liquid to 50%, 18 ℃ of temperature add tare weight 0.14%S
2-, rotated 10 minutes, add salt 1%, rotated 10 minutes, hair comes off 95% or more, and bulk is insoluble separates for one-tenth mao in drum;
(3) liming: continue during depilation is bathed to add tare weight 0.3% auxiliary liming agent, 2% lime rotated 15 minutes, and hair has fallen basically; Add tare weight 50% water, rotated 15 minutes; Add tare weight 50% water, rotated 15 minutes; Add tare weight 50% water, rotated 15 minutes; Change and stop combining (per hour change and stopped in 5 minutes 55 minutes) to spend the night.
Control water next day, add tare weight 200% water, 20 ℃ of temperature add tare weight 0.1% ydrogen peroxide 50, rotate 20 minutes.Go out drum, the cleaning hair ball is recycled, and gets into subsequent processing behind the hide fleshing.
Embodiment 2
(1) protect hair: ox-hide behind the conventional immersion fleshing, weigh.The water that adds tare weight 150%, 18 ℃ of temperature, add-on are that a mao agent is protected in the conduct of tare weight 1% lime, and 0.05% grease-removing agent changes and stopped 15 minutes in 15 minutes, 90 minutes total times;
(2) depilation: the water of control liquid to 75%, 22 ℃ of temperature add tare weight 0.2%S
2-Trichogen, this trichogen of this embodiment is a sodium sulphite, rotates 12 minutes, adds neutral salt 1.5%, rotates 20 minutes, hair comes off 95% or more, bulk is insoluble separates for one-tenth mao in drum;
(3) liming: continue during depilation is bathed to add tare weight 0.6% auxiliary liming agent, 3% lime rotated 20 minutes, and hair has fallen basically; Add tare weight 80% water, rotated 20 minutes; Add tare weight 80% water, rotated 20 minutes; Add tare weight 80% water, rotated 20 minutes; Change and stop combining (per hour change and stopped in 5 minutes 55 minutes) to spend the night.
Control water next day, add tare weight 250% water, 24 ℃ of temperature add tare weight 0.2% ydrogen peroxide 50, rotate 25 minutes.Go out drum, the cleaning hair ball is recycled, and gets into subsequent processing behind the hide fleshing.
Embodiment 3
(1) protect hair: ox-hide behind the conventional immersion fleshing, weigh.The water that adds tare weight 150%, 18 ℃ of temperature add tare weight 1% and protect a mao agent, and 0.05% grease-removing agent changes and stopped 15 minutes in 15 minutes, 90 minutes total times;
(2) depilation: the water of control liquid to 100%, 25 ℃ of temperature add tare weight 0.24%S
2-, rotated 15 minutes, add neutral salt 2%, rotated 30 minutes, hair comes off 95% or more, and bulk is insoluble separates for one-tenth mao in drum;
(3) liming: continue during depilation is bathed to add tare weight 1.0% auxiliary liming agent, 4% lime rotated 30 minutes, and hair has fallen basically; Add tare weight 100% water, rotated 30 minutes; Add tare weight 100% water, rotated 30 minutes; Add tare weight 100% water, rotated 30 minutes; Change and stop combining (per hour change and stopped in 5 minutes 55 minutes) to spend the night.
Control water next day, add tare weight 300% water, 27 ℃ of temperature add tare weight 0.3% ydrogen peroxide 50, rotate 30 minutes.Go out drum, the cleaning hair ball is recycled, and gets into subsequent processing behind the hide fleshing.
Embodiment 4
(1) protect hair: ox-hide behind the conventional immersion fleshing, weigh.The water that adds tare weight 200%, 22 ℃ of temperature add tare weight 1.5% and protect a mao agent, and 0.1% grease-removing agent changes and stopped 15 minutes in 15 minutes, 120 minutes total times;
(2) depilation: the water of control liquid to 50%, 18 ℃ of temperature add tare weight 0.14%S
2-, rotated 10 minutes, add neutral salt 1%, rotated 10 minutes, hair comes off 95% or more, and bulk is insoluble separates for one-tenth mao in drum;
(3) liming: continue during depilation is bathed to add tare weight 0.6% auxiliary liming agent, 3% lime rotated 20 minutes, and hair has fallen basically; Add tare weight 80% water, rotated 20 minutes; Add tare weight 80% water, rotated 20 minutes; Add tare weight 80% water, rotated 20 minutes; Change and stop combining (per hour change and stopped in 5 minutes 55 minutes) to spend the night.
Control water next day, add tare weight 300% water, 27 ℃ of temperature add tare weight 0.3% ydrogen peroxide 50, rotate 30 minutes.Go out drum, the cleaning hair ball is recycled, and gets into subsequent processing behind the hide fleshing.
Embodiment 5
(1) protect hair: ox-hide behind the conventional immersion fleshing, weigh.The water that adds tare weight 200%, 22 ℃ of temperature add tare weight 1.5% and protect a mao agent, and 0.1% grease-removing agent changes and stopped 15 minutes in 15 minutes, 120 minutes total times;
(2) depilation: the water of control liquid to 75%, 22 ℃ of temperature add tare weight 0.2%S
2-, rotated 12 minutes, add neutral salt 1.5%, rotated 20 minutes, hair comes off 95% or more, and bulk is insoluble separates for one-tenth mao in drum;
(3) liming: continue during depilation is bathed to add tare weight 1.0% auxiliary liming agent, 4% lime rotated 30 minutes, and hair has fallen basically; Add tare weight 100% water, rotated 30 minutes; Add tare weight 100% water, rotated 30 minutes; Add tare weight 100% water, rotated 30 minutes; Change and stop combining (per hour change and stopped in 5 minutes 55 minutes) to spend the night.
Control water next day, add tare weight 200% water, 20 ℃ of temperature add tare weight 0.1% ydrogen peroxide 50, rotate 20 minutes.Go out drum, the cleaning hair ball is recycled, and gets into subsequent processing behind the hide fleshing.
Embodiment 6
(1) protect hair: ox-hide behind the conventional immersion fleshing, weigh.The water that adds tare weight 200%, 22 ℃ of temperature add tare weight 1.5% and protect a mao agent, and 0.1% grease-removing agent changes and stopped 15 minutes in 15 minutes, 120 minutes total times;
(2) depilation: the water of control liquid to 100%, 25 ℃ of temperature add tare weight 0.24%S
2-, rotated 15 minutes, add neutral salt 2%, rotated 30 minutes, hair comes off 95% or more, and bulk is insoluble separates for one-tenth mao in drum;
(3) liming: continue during depilation is bathed to add tare weight 0.3% auxiliary liming agent, 2% lime rotated 15 minutes, and hair has fallen basically; Add tare weight 50% water, rotated 15 minutes; Add tare weight 50% water, rotated 15 minutes; Add tare weight 50% water, rotated 15 minutes; Change and stop combining (per hour change and stopped in 5 minutes 55 minutes) to spend the night.
Control water next day, add tare weight 250% water, 24 ℃ of temperature add tare weight 0.2% ydrogen peroxide 50, rotate 25 minutes.Go out drum, the cleaning hair ball is recycled, and gets into subsequent processing behind the hide fleshing.
Embodiment 7
(1) protect hair: ox-hide behind the conventional immersion fleshing, weigh.The water that adds tare weight 250%, 25 ℃ of temperature add tare weight 2% and protect a mao agent, and 0.2% grease-removing agent changes and stopped 15 minutes in 15 minutes, 150 minutes total times;
(2) depilation: the water of control liquid to 50%, 18 ℃ of temperature add tare weight 0.14%S
2-, rotated 10 minutes, add neutral salt 1%, rotated 10 minutes, hair comes off 95% or more, and bulk is insoluble separates for one-tenth mao in drum;
(3) liming: continue during depilation is bathed to add tare weight 1.0% auxiliary liming agent, 4% lime rotated 30 minutes, and hair has fallen basically; Add tare weight 100% water, rotated 30 minutes; Add tare weight 100% water, rotated 30 minutes; Add tare weight 100% water, rotated 30 minutes; Change and stop combining (per hour change and stopped in 5 minutes 55 minutes) to spend the night.
Control water next day, add tare weight 250% water, 24 ℃ of temperature add tare weight 0.2% ydrogen peroxide 50, rotate 25 minutes.Go out drum, the cleaning hair ball is recycled, and gets into subsequent processing behind the hide fleshing.
Embodiment 8
(1) protect hair: ox-hide behind the conventional immersion fleshing, weigh.The water that adds tare weight 250%, 25 ℃ of temperature add tare weight 2% and protect a mao agent, and 0.2% grease-removing agent changes and stopped 15 minutes in 15 minutes, 150 minutes total times;
(2) depilation: the water of control liquid to 75%, 22 ℃ of temperature add tare weight 0.2%S
2-, rotated 12 minutes, add neutral salt 1.5%, rotated 20 minutes, hair comes off 95% or more, and bulk is insoluble separates for one-tenth mao in drum;
(3) liming: continue during depilation is bathed to add tare weight 0.3% auxiliary liming agent, 2% lime rotated 15 minutes, and hair has fallen basically; Add tare weight 50% water, rotated 15 minutes; Add tare weight 50% water, rotated 15 minutes; Add tare weight 50% water, rotated 15 minutes; Change and stop combining (per hour change and stopped in 5 minutes 55 minutes) to spend the night.
Control water next day, add tare weight 300% water, 27 ℃ of temperature add tare weight 0.3% ydrogen peroxide 50, rotate 30 minutes.Go out drum, the cleaning hair ball is recycled, and gets into subsequent processing behind the hide fleshing.
Embodiment 9
(1) protect hair: ox-hide behind the conventional immersion fleshing, weigh.The water that adds tare weight 250%, 25 ℃ of temperature add tare weight 2% and protect a mao agent, and 0.2% grease-removing agent changes and stopped 15 minutes in 15 minutes, 150 minutes total times;
(2) depilation: the water of control liquid to 100%, 25 ℃ of temperature add tare weight 0.24%S
2-, rotated 15 minutes, add neutral salt 2%, rotated 30 minutes, hair comes off 95% or more, and bulk is insoluble separates for one-tenth mao in drum;
(3) liming: continue during depilation is bathed to add tare weight 0.6% auxiliary liming agent, 3% lime rotated 20 minutes, and hair has fallen basically; Add tare weight 80% water, rotated 20 minutes; Add tare weight 80% water, rotated 20 minutes; Add tare weight 80% water, rotated 20 minutes; Change and stop combining (per hour change and stopped in 5 minutes 55 minutes) to spend the night.
Control water next day, add tare weight 200% water, 20 ℃ of temperature add tare weight 0.1% ydrogen peroxide 50, rotate 20 minutes.Go out drum, the cleaning hair ball is recycled, and gets into subsequent processing behind the hide fleshing.
Embodiment 10
(1) protect hair: ox-hide behind the conventional immersion fleshing, weigh.The water that adds tare weight 200%, 22 ℃ of temperature add tare weight 2% and protect a mao agent, and 0.1% grease-removing agent changes and stopped 15 minutes in 15 minutes, 120 minutes total times;
(2) depilation: the water of control liquid to 50%, 22 ℃ of temperature add tare weight 0.18%S
2-, rotated 10 minutes, add neutral salt 1%, rotated 30 minutes, hair comes off 95% or more, and bulk is insoluble separates for one-tenth mao in drum;
(3) liming: continue during depilation is bathed to add tare weight 0.5% auxiliary liming agent, 3% lime rotated 20 minutes, and hair has fallen basically; Add tare weight 50% water, rotated 30 minutes; Add tare weight 80% water, rotated 30 minutes; Add tare weight 100% water, rotated 30 minutes; Change and stop combining (per hour change and stopped in 5 minutes 55 minutes) to spend the night.
Control water next day, add tare weight 200% water, 25 ℃ of temperature add tare weight 0.3% ydrogen peroxide 50, rotate 20 minutes.Go out drum, the cleaning hair ball is recycled, and gets into subsequent processing behind the hide fleshing.
Claims (1)
1. the hair protecting, dehairing liming method of an ox-hide process hides is characterized in that may further comprise the steps:
(1) protect hair: the routine ox-hide that soaks behind the fleshing is put into rotary drum, and add the water of tare weight 150～250%, attemperation is 18～25 ℃; Add tare weight 1～2% and protect a mao agent, 0.05～0.2% grease-removing agent rotates and stopped 15 minutes in 15 minutes; Continue 90～150 minutes, said to protect mao agent be lime;
(2) depilation: the water of control liquid to tare weight 50～100%, 18～25 ℃ of holding temperatures add trichogen; The addition of this trichogen satisfies its S2-that contains amount for 0.14～0.24% of tare weight, rotates 10-15 minute, adds neutral salt 1～2%; Rotated 10-30 minute; Hair comes off more than 95%, and described neutral salt is a sodium-chlor, and described trichogen is sodium sulphite or Sodium sulfhydrate;
(3) liming: continue during depilation is bathed to add tare weight 0.3～1.0% auxiliary liming agent, 2～4% lime rotated 15～30 minutes, further depilation; Add tare weight 50～100% water, rotated 15～30 minutes; At least again add tare weight 50～100% water one time, and rotated 15～30 minutes; And then stop the mode of combining and continue at least 10 hours per hour to change the commentaries on classics that stopped in 5 minutes 55 minutes;
(4) control water and clean hair ball: add tare weight 200～300% water, 20～27 ℃ of attemperation add tare weight 0.1～0.3% oxygenant, rotate 20～30 minutes, go out drum, clean the ground hair ball, and said oxygenant is ydrogen peroxide 50 or sodium sulfite anhy 96.
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| CN101798604B (en) * | 2010-02-10 | 2012-10-03 | 广东省石油化工研究院 | Method for preparing leather through hair-saving unhairing |
| CN109554510B (en) * | 2018-10-19 | 2021-09-14 | 海宁森德皮革有限公司 | Method for producing low-odor clean automobile interior leather by using bio-enzyme technology |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1730669A (en) * | 2004-08-04 | 2006-02-08 | 中国皮革和制鞋工业研究院 | Cleaning depilation method |
| CN101319254A (en) * | 2008-07-22 | 2008-12-10 | 淄博大桓九宝恩皮革集团有限公司 | Cleaning treatment process for cow leather |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1730669A (en) * | 2004-08-04 | 2006-02-08 | 中国皮革和制鞋工业研究院 | Cleaning depilation method |
| CN101319254A (en) * | 2008-07-22 | 2008-12-10 | 淄博大桓九宝恩皮革集团有限公司 | Cleaning treatment process for cow leather |
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