CN105671219B - A kind of tanning production technique - Google Patents

A kind of tanning production technique Download PDF

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Publication number
CN105671219B
CN105671219B CN201610122809.0A CN201610122809A CN105671219B CN 105671219 B CN105671219 B CN 105671219B CN 201610122809 A CN201610122809 A CN 201610122809A CN 105671219 B CN105671219 B CN 105671219B
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China
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minutes
tanning
water
turn
agent
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Expired - Fee Related
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CN201610122809.0A
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Chinese (zh)
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CN105671219A (en
Inventor
许建新
柯瑞华
余建明
李振宁
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HAINING SHANGYUAN LEATHER CO Ltd
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HAINING SHANGYUAN LEATHER CO Ltd
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Priority to CN201610122809.0A priority Critical patent/CN105671219B/en
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Classifications

    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C14—SKINS; HIDES; PELTS; LEATHER
    • C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
    • C14C1/00—Chemical treatment prior to tanning
    • C14C1/06—Facilitating unhairing, e.g. by painting, by liming
    • 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
    • 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
    • C14C3/06—Mineral tanning using chromium compounds
    • 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
    • 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
    • C14C9/00—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes
    • C14C9/02—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes using fatty or oily materials, e.g. fat liquoring

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Treatment And Processing Of Natural Fur Or Leather (AREA)

Abstract

The present invention relates to a kind of tanning production technique, including order below step：Immersion-fleshing-is lost hair or feathers-pushed away hair-alkali swelling-split-dealkalize-softening-pickling-tanning, then chrome tanning subsequent technique routinely is carried out, in preparatory process, using it is ashless, without sulphur new technology, solves the generation of sulfide, solve with pulverized limestone and caused sludge, solve the problems, such as enterprise's mud discharging.No ammonia dealkalize and less salt technique are employed in tanning processes, greatly reduces ammonia nitrogen discharge and Nacl exhaust emission.The present invention using without sulphur, it is ashless, without ammonia, less salt new technology, the leather hand feeling of production is soft, richness is good, and indices reach EU criteria, outlet Europe, obtain the consistent favorable comment of user.

Description

A kind of tanning production technique
Technical field：
The present invention relates to a kind of tanning production technique, particularly a kind of leather processing field without sulphur, ashless, nothing Ammonia, less salt production technology.
Background technology：
Leather-making mud is current leather-making enterprises, the problem of the headache generally faced in production.Country is to whole society at present It is more and more stronger that the environment of meeting payes attention to dynamics.Sewage, sludge, waste gas, the environmental protection index of ammonia nitrogen discharged to leather-making enterprises is more next It is higher.Many small enterprises are handled because having no ability to, and are closed down in succession.To medium-and-large-sized leather-making enterprises sludge treatment capacity and work Process it is also proposed higher requirement and challenge.
Chrome tanning come out over more than 100 years, with its superior tanning performance always in occupation of dominant position, and use vulcanize Sodium（Or NaHS）Unhairing, vulcanization soda lime are expanded, and this production technology is also that the most frequently used one kind of chrome tanning is raw Production. art link.Vulcanized sodium（Or NaHS）Because its is cheap, unhairing and expansion effect are outstanding always by leather-making enterprises Used extensively.Lime is also that its price is low and the effect of expansion relaxes and is widely used.The use band of this identical material The consequence come is that substantial amounts of sulfide is exceeded and lime produces substantial amounts of leather-making mud, while to substantial amounts of sewage, waste gas, sludge Carrying out processing needs huge cost, greatly reduces the profit margin of enterprise.
Therefore research uses to human body fanout free region to new tanning production technique of the environment without destruction, new system in production It is imperative to remove from office material.From now on, people-oriented Leather Chemicals and technology harmonious with environment are used in leather production Increasingly attract attention and support.And it is ashless in technique is cleaned, without sulphur, without ammonia, less salt be that leather nesting will be sustainable from now on The trend of development.
The content of the invention
Present invention solves the technical problem that be, in the prior art, vulcanized sodium（Or NaHS）Because its is cheap, go Hair and expansion effect is outstanding is used extensively by leather-making enterprises always, lime be also that its price is low and the effect of expansion relaxes and It is widely used, and the consequence that the use of this identical material is brought is that substantial amounts of sulfide is exceeded and lime produces substantial amounts of process hides Sludge, while the huge cost of processing needs is carried out to substantial amounts of sewage, waste gas, sludge, greatly reduce the profit of enterprise The problem of space, and then provide a kind of tanning production technique of optimization.
The technical solution adopted in the present invention is a kind of tanning production technique, including order below step：Soak-go Meat-depilation-pushes away hair-alkali swelling-split-dealkalize-softening-pickling-tanning, then carries out chrome tanning subsequent technique, with Percentage composition in lower each operation is to operate before the process on the basis of the weight of skin；
Depilation：Depilatory solution is uniformly applied to the flesh noodles of skin, carries out doubling, 20 a piles are placed, bank up 4~6 hours it is laggard Row pushes away hair；
Alkali swelling：Carried out in rotary drum, the ratio of liquor ratio 100%, wherein skin and water is 1:1, addition UHB 2%~2.5%, UHA 1.5%, rotate 40 minutes after check unhairing situation, if unhairing not to the utmost if extend 10 minutes；2 times are added water to, 30 DEG C of holding is even Temperature, add sodium hydroxide 1.5%, ashless expanding agent CAS 2%, dispersing agent for fibre OPF 1%, each hour turn 5 after turning 40 minutes Minute, turn to stop combining after 16~18 hours, frizing split；
Split：To carry out split without ammonia salt deliming agent LAB；
Dealkalize：With the water of liquor ratio 100% it is vexed wash it is secondary after, add LAB 1.5%, turn 40 minutes, cut with phenolphthalein indicator inspection Mouthful, it on red, side is colourless that titration open center, which is, and dealkalize is completed；
Softening：Added in rotary drum without ammonium macerating enzyme 2~1.5%, pH controls 8~8.2, liquor ratio 150%, 35 DEG C of water temperature~ 38 DEG C, turn 40 minutes, check that the laggard water-filling of softening degree is washed, vexed washing is twice；
Pickling：Skin is placed in pickling liquid, aqueous 150% in pickling liquid, neutral salt 1~1.5%, water temperature is 22 DEG C~24 DEG C, turn 10 minutes, add the formic acid 0.5% of concentration 85%, turn 20 minutes, add salt-free auxiliary pickling agent FSP, turn 10 minutes, add The sulfuric acid 1.2% opened with 10 times of aquations, is added at twice, is turned 30 points again after addition once in every 20 minutes, is then controlled the pickling liquid to be 100%, add chromium powder 6%, turn 60/after chrome tanning subsequent technique routinely.
Preferably, described depilatory solution is formed by the component proportion of following parts by weight：1.5 parts of 2.5 parts of UHB, UHA, UHE0.3 parts, 0.3 part of sodium hydroxide, 3 parts of water, thickened with rice bran.
Preferably, during the alkali swelling, auxiliary agent UHE, UHE 0.3% is additionally added in rotary drum.
Preferably, in described tanning processes, chromium powder is concentration 24%, the chrome green of basicity 33, and alkali includes little Su Beat and sodium acetate, pH value are 3.8~3.9.
Preferably, the chrome tanning subsequent technique is followed successively by retanning-washing again-neutralization washing-dyeing-stuffing.
Preferably, in the neutralization washing step, added with 250%~300% water, 0.5~1% degreasing agent and formic acid 0.5%, water temperature is 40~45 DEG C, turns 40 minutes, is washed in the environment of pH3.6~3.7.
Preferably, in stuffing process, addition 150%, then 55 DEG C of water adds 8% phosphatide fatting agent, 8% synthesis adds Fat agent, 3% nonionic fatting agent, turn 60 minutes, add the formic acid 1.6% that concentration is more than or equal to 85%, turn 30 minutes, pH3.7~ 3.8。
The beneficial effects of the present invention are：For the present invention in preparatory process, use is ashless, without sulphur new technology, solves sulphur The generation of compound, is solved with pulverized limestone and caused sludge, solves the problems, such as enterprise's mud discharging.Employed in tanning processes Without ammonia dealkalize and less salt technique, ammonia nitrogen discharge and Nacl exhaust emission are greatly reduced.The present invention is using without sulphur, ashless, nothing Ammonia, less salt new technology, the leather hand feeling softness of production, richness are good, and indices reach EU criteria, outlet Europe, obtain The consistent favorable comment of user.
Embodiment
The present invention is described in further detail with reference to embodiment, but protection scope of the present invention is not limited to This.
The present invention relates to a kind of tanning production technique, including order below step：Immersion-fleshing-lose hair or feathers-push away hair- Alkali swelling-split-dealkalize-softening-pickling-tanning, chrome tanning subsequent technique is then carried out, the percentage in following each operation Content is to operate before the process on the basis of the weight of skin；
Wherein, immersion and the step of fleshing according to the processing of conventional treatment means；
Depilation：Depilatory solution is uniformly applied to the flesh noodles of skin, carries out doubling, 20 a piles are placed, bank up 4~6 hours it is laggard Row pushes away hair；
Alkali swelling：Carried out in rotary drum, liquor ratio 100%, i.e., wherein the ratio of skin and water is 1:1, addition UHB 2%~ 2.5%th, UHA 1.5%, unhairing situation is checked after rotating 40 minutes, hair removes can, if unhairing not to the utmost if extend 10 minutes；Add Water is to 2 times, i.e. the 2 of raw water amount times, keeps 30 DEG C of even temperature, adds sodium hydroxide 1.5%, ashless expanding agent CAS 2%, fiber disperses Agent OPF 1%, 5 minutes each hours turn after turning 40 minutes, turn to stop combining after 16~18 hours, frizing split；
Split：To carry out split without ammonia salt deliming agent LAB；Wherein, LAB is that the gas chromatography that can be directly obtained is answered Compound, it is free of dimethylamine sulfide；
Dealkalize：With the water of liquor ratio 100% it is vexed wash it is secondary after, add LAB 1.5%, turn 40 minutes, cut with phenolphthalein indicator inspection Mouthful, it on red, side is colourless that titration open center, which is, and dealkalize is completed；
Softening：Added in rotary drum without ammonium macerating enzyme 2~1.5%, pH controls 8~8.2, liquor ratio 150%, 35 DEG C of water temperature~ 38 DEG C, turn 40 minutes, check that the laggard water-filling of softening degree is washed, vexed washing is twice；
Pickling：Skin is placed in pickling liquid, aqueous 150% in pickling liquid, neutral salt 1~1.5%, water temperature is 22 DEG C~24 DEG C, turn 10 minutes, add the formic acid 0.5% of concentration 85%, turn 20 minutes, add salt-free auxiliary pickling agent FSP, turn 10 minutes, add The sulfuric acid 1.2% opened with 10 times of aquations, is added, generally added at twice at twice, turns 30 again after addition once in every 20 minutes Point, it is 100% then control pickling liquid, adds chromium powder 6%, turns 60/after chrome tanning subsequent technique routinely.
Described depilatory solution is formed by the component proportion of following parts by weight：1.5 parts of 2.5 parts of UHB, UHA, UHE0.3 parts, 0.3 part of sodium hydroxide, 3 parts of water, is thickened with rice bran.Generally, be thickened to rice bran can stir it is semi-fluid.Its In, UHB is mainly hair remover, and UHA is mainly the hair remover without vulcanized sodium；UHA has the performance lost hair or feathers and adjust skin expansion, UHB has the function that depilation and scattered collagenous fibres, and both can fully ensure that the diastole of pore and disperseing for fiber, be easy to take off The progress of hair operation；UHE is then a kind of depilation enzyme preparation, is that excellent hair remover and fiber disperse enzyme preparation, can loosen hair Root, epidermis and scurf, and there is preferable peptizaiton to collagenous fibres, in the present invention, mainly application is hair remover to UHE Auxiliary agent.
Auxiliary agent UHE, UHE 0.3% is additionally added during the alkali swelling, in rotary drum.
In described tanning processes, chromium powder is concentration 24%, the chrome green of basicity 33, and alkali includes sodium bicarbonate and vinegar Sour sodium, pH value are 3.8~3.9.
The chrome tanning subsequent technique is followed successively by retanning-washing again-neutralization washing-dyeing-stuffing.
In the neutralization washing step, the water, 0.5~1% degreasing agent and formic acid 0.5%, water temperature that add 250%~300% are 40~45 DEG C, turn 40 minutes, washed in the environment of pH3.6~3.7.Wherein, degreasing agent is free of APEO.
In stuffing process, then 150%, 55 DEG C of water of addition adds 8% phosphatide fatting agent, 8% synthetic fat liquor, and 3% Nonionic fatting agent, turn 60 minutes, add the formic acid 1.6% that concentration is more than or equal to 85%, turn 30 minutes, pH3.7~3.8.
The reagent not illustrated in the present invention can be selected according to understanding of the those skilled in the art to the technology of the present invention It is preferred that select.
The present invention solves in the prior art, vulcanized sodium（Or NaHS）Because its is cheap, unhairing and expansion effect Fruit is outstanding to be used extensively by leather-making enterprises always, and lime is also that its price is low and the effect of expansion relaxes and extensively should With, and the consequence that the use of this identical material is brought is that substantial amounts of sulfide is exceeded and lime produces substantial amounts of leather-making mud, together When processing carried out to substantial amounts of sewage, waste gas, sludge need huge cost, the profit margin for greatly reducing enterprise is asked Topic, in preparatory process, use is ashless, without sulphur new technology, solves the generation of sulfide, solves with pulverized limestone and caused Sludge, solves the problems, such as enterprise's mud discharging.No ammonia dealkalize and less salt technique are employed in tanning processes, greatly reduces ammonia nitrogen Discharge and Nacl exhaust emission.The present invention using without sulphur, it is ashless, without ammonia, less salt new technology, the leather hand feeling of production is soft, Richness is good, and indices reach EU criteria, outlet Europe, obtain the consistent favorable comment of user.

Claims (7)

  1. A kind of 1. tanning production technique, it is characterised in that：Including order below step：Immersion-fleshing-is lost hair or feathers-pushed away hair-alkali Expansion-split-dealkalize-softening-pickling-tanning, chrome tanning subsequent technique is then carried out, the percentage in following each operation contains Amount is to operate before the process on the basis of the weight of skin；
    Depilation：Depilatory solution is uniformly applied to the flesh noodles of skin, carries out doubling, 20 a piles are placed, pushed away after banking up 4~6 hours Hair；
    Alkali swelling：Carried out in rotary drum, the ratio of liquor ratio 100%, wherein skin and water is 1:1, add UHB 2%~2.5%, UHA 1.5%, rotate 40 minutes after check unhairing situation, if unhairing not to the utmost if extend 10 minutes；2 times are added water to, keeps 30 DEG C of even temperature, Add sodium hydroxide 1.5%, ashless expanding agent CAS 2%, dispersing agent for fibre OPF 1%, 5 points of each hour turn after turning 40 minutes Clock, turn to stop combining after 16~18 hours, frizing split；
    Split：To carry out split without ammonia salt deliming agent LAB；
    Dealkalize：With the water of liquor ratio 100% it is vexed wash it is secondary after, add LAB 1.5%, turn 40 minutes, with phenolphthalein indicator check otch, drop It on red, side is colourless to determine open center to be, dealkalize is completed；
    Softening：Added in rotary drum without ammonium macerating enzyme 2~1.5%, pH controls 8~8.2, liquor ratio 150%, water temperature 35 DEG C~38 DEG C, turn 40 minutes, check that the laggard water-filling of softening degree is washed, vexed washing is twice；
    Pickling：Skin is placed in pickling liquid, aqueous 150% in pickling liquid, neutral salt 1~1.5%, water temperature is 22 DEG C~24 DEG C, is turned 10 minutes, the formic acid 0.5% of concentration 85% is added, turns 20 minutes, adds salt-free auxiliary pickling agent FSP, turns 10 minutes, adds with 10 times The sulfuric acid 1.2% that aquation is opened, is added at twice, turns 30 points again after addition once in every 20 minutes, and it is 100% then to control pickling liquid, Add chromium powder 6%, turn 60/after chrome tanning subsequent technique routinely.
  2. A kind of 2. tanning production technique according to claim 1, it is characterised in that：Described depilatory solution is by following parts by weight Component proportion form：1.5 parts of 2.5 parts of UHB, UHA, UHE0.3 parts, 0.3 part of sodium hydroxide, 3 parts of water, thickened with rice bran.
  3. A kind of 3. tanning production technique according to claim 1, it is characterised in that：During the alkali swelling, rotary drum Inside it is additionally added auxiliary agent UHE, UHE 0.3%.
  4. A kind of 4. tanning production technique according to claim 1, it is characterised in that：In described tanning processes, chromium powder is The chrome green of concentration 24%, basicity 33, alkali include sodium bicarbonate and sodium acetate, and pH value is 3.8~3.9.
  5. A kind of 5. tanning production technique according to claim 1, it is characterised in that：The chrome tanning subsequent technique is followed successively by again Retanning-washing-neutralization washing-dyeing-stuffing.
  6. A kind of 6. tanning production technique according to claim 5, it is characterised in that：In the neutralization washing step, addition 250%~300% water, 0.5~1% degreasing agent and formic acid 0.5%, water temperature are 40~45 DEG C, are turned 40 minutes, in pH3.6~3.7 Washed under environment.
  7. A kind of 7. tanning production technique according to claim 5, it is characterised in that：In stuffing process, addition 150%, 55 DEG C water, then add 8% phosphatide fatting agent, 8% synthetic fat liquor, 3% nonionic fatting agent, turn 60 minutes, it is big to add concentration In or equal to 85% formic acid 1.6%, turn 30 minutes, pH3.7~3.8.
CN201610122809.0A 2016-03-04 2016-03-04 A kind of tanning production technique Expired - Fee Related CN105671219B (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105936948A (en) * 2016-06-24 2016-09-14 安徽创荣服装辅料有限公司 Soft leather processing process
CN106319104B (en) * 2016-08-18 2019-12-13 明新旭腾新材料股份有限公司 production process of high-absorption chrome tanned leather
CN110144424B (en) * 2019-05-23 2021-10-26 漳州香洲皮革有限公司 Processing technology for preparing retainable wet blue leather by using low-grade grey fur
CN110129489B (en) * 2019-05-23 2021-10-01 漳州香洲皮革有限公司 Method for preparing chrome-free pickled skin

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US4762522A (en) * 1987-03-02 1988-08-09 Gaf Corporation Agent for treatment of hides and pelts
US6777219B2 (en) * 2002-03-13 2004-08-17 Council Of Scientific And Industrial Research Process for the preparation of alkaline protease
CN100381582C (en) * 2006-07-27 2008-04-16 四川大学 Method for ash-free and no-sulfurizing alkaline liming treatment for making pigskin leather
CN101260443A (en) * 2008-04-29 2008-09-10 四川大学 Ashless and alkali sulfide free liming treatment method for preparing leather from cowskin
CN101265505A (en) * 2008-05-08 2008-09-17 四川大学 Ashless and alkali sulfide free depilation liming treatment method for preparing leather from raw sheep skin
CN101265506B (en) * 2008-05-08 2012-09-05 四川大学 Ashless and alkali sulfide free depilation liming treatment method for preparing leather from goatskin
CN101445843B (en) * 2008-12-30 2012-08-08 国家皮革质量监督检验中心（浙江） Method for carrying out unhairing and liming treatment without dust and akali sulphide during buffalo hide tanning

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