CN1804044A - Clean production method of chromium-free automobile cushion leather - Google Patents
Clean production method of chromium-free automobile cushion leather Download PDFInfo
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- CN1804044A CN1804044A CN 200510022188 CN200510022188A CN1804044A CN 1804044 A CN1804044 A CN 1804044A CN 200510022188 CN200510022188 CN 200510022188 CN 200510022188 A CN200510022188 A CN 200510022188A CN 1804044 A CN1804044 A CN 1804044A
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Abstract
The clear production method for Cr-free vehicle seat cushion comprises: hair-saving, combing acid and base for expansion; ammonia-free deliming, dipping weak acid and low slat, Cr-free bating, composite batting, and adding strong-absorption fat for dyeing to treat skin from pig, cattle or sheep. The product has shrinkage temperature up to 110Deg, shows well hand feeling and resistance to thermal and age. This invention reduces material quantity and 30-50% sewage discharge, improves absorption rate, and brings a new way for Cr-free leather.
Description
Technical field
The present invention relates to a kind of clean method for producing of chromium-free automobile cushion leather, belong to the production field of leather tanning.Be fit to the requirement of the no chrome tanning automobile cushion leather of demand on the current market, the shrinkage temperature of finished leather, physical mechanical index reach the light industry chrome tanned leather standard of carrying out promulgated by the ministries or commissions of the Central Government in 1999.
Background technology
Eliminating hair is the operation of a nature of process hides with epidermis.Traditional Na
2S ruins hair and has caused the most serious S
2-, COD discharging.Substitute Na
2The thanomin of S, organic mercaptan or other organic amine chemical are as the many (Zhang Renquan of the report of special-purpose chemical reagent depilation, Sun Jiliang, Zhang Jingbin. print 1994 (12) during the development chemical industry of no sulphur trichogen: 21-23.), use but all be difficult to suitability for industrialized production.Nineteen eighty-three has solved Na by the SIROLIME guarantor hair depilation that Australian Union's science and industrial research institute (CSIRO) release
2S ruins the process of hair, has significantly reduced Na
2A large amount of ox hair albumen has been reclaimed in the discharging of S use and COD and BOD again.Domestic also test once (Chen Ding state .SIROLIME protects a hair liming technology. Chinese leather, 1992,21 (1): 14-17.), require the supporting of a kind of special auxiliary agent in implementing producing, all do not put into production always but problem is this technology.
The history in existing several thousand of process hides liming, and use till today always.Collegen filament disperse in the natural rawhide, the dissolving of interfibrillar substance is removed is to enter and obtain the softness of finished leather product, the necessary and sufficient condition of index such as plentiful to follow-up material.But the mud of process hides is one of pollutent of refractory reason, and the lime precipitation thing that wherein contains proteolysate, grease neutral salt the simplest method at present is to bury and burn.Although early stage " ashless liming " method research and more with the biomaterial patent of invention, thoroughly solve ashless problem also needs the time.Certainly, with regard to liming, the product of various auxiliary liming agents and the exploitation of utilisation technology over nearly 20 years, as assist lime dispersion, solubilising, infiltration etc., significantly reduced lime consumption, solved this operation partly clean (Peng Biyu. pre-treatment auxiliary agent one. auxiliary liming agent. leather science and engineering, 2000, (10) 3:23-27.).Once there was report to carry out the dispersion of fiber, but thisly existed than big difference with being dispersed on the quality product with lime to be hydrolyzed to main dispersion with enzyme.In fact, adopting novel " liming agent " or " auxiliary liming agent ", will be the important channel of cleaning tanning industry without lime or minute quantity lime.
Traditional method is used a large amount of salt (8wt%～10wt%), make the salt concn 1mol/L of pickling liquid.Pickling has become the second largest operation in neutral salt source in the waste water.The function of salt-free pickling auxiliary agent is to make pelt to be in low pH following time acid plumping does not take place.External BASF and TFL company use the pickling auxiliary agent can reduce by 40%～60% salt consumption from the beginning of the nineties in last century existing salt-free pickling auxiliary agent (naphthene sulfonic acid) production and application.The domestic salt-free pickling of also once studying chrome tanning, according to the screening of electric charge expansion principle and various materials development auxiliary agent (Dan Zhihua, Wang Qunzhi. the research of salt-free pickling and auxiliary agent. Chinese leather, 1998,27 (10): 5-7.).Result of study shows, does not also really use industrial.
In the our times scope, because chromium particularly has carinogenicity by the sexavalent chrome that trivalent chromium conversion forms to the mankind to the hazardness of human and environment, and international and domestic medium-to-high grade automobile requires to adopt the Chrome-free manufacturing with leather.Up to now, the automobile that does not have a kind of complete no chromic tanning to produce reaches with leather or near current chrome-tanned requirement, wherein shows moisture-proof thermostability 〉=110 ℃ of leather, and is all identical with the chrome tanned leather requirement on Ge feel, the physical mechanical strength simultaneously.
The method that requires the complete chrome tanning of elimination to pollute is to adopt no chrome tanning.Vegetable tanning, formaldehyde tanning, Al tan, oil tanning etc. continued to use in production a small amount of, specific leather always.The leather that these tannages obtain or strong or white and can wash, but the common shortcoming is Ts low (≤85 ℃), this is nonsensical to furniture, clothes, soft vamp and the technical leather that requires Ts 〉=90 ℃ now.Therefore, the no chrome tanning on the Modern Significance is and to make the Ts of leather reach 90 ℃ with the tanning of non-chromium material, and more the requirement is higher than 100 ℃, with the needs that satisfy leatherware processing and use.From the seventies in last century (abroad) and the nineties (in China), various no chrome tanning researchs have entered hot state.Only be the examination target, reach or to be higher than 90 ℃ tannage very many that are independent non-chromium metal-salt such as Zr with Ts
4+, Fe
3+, Ti
4+The combination that more is two kinds and two or more non-chromium material is tanned, and mainly contains that Al-plants, glutaraldehyde-Zhi, oxazolidines-plant, phosphonium salt-tannage such as plant.At present can basicly stable technically having: what abroad be used to produce be that Al-plants and glutaraldehyde-plants; Domestic to Al-plant, the tannage of glutaraldehyde-Zhi, oxazolidines-plant, phosphonium salt-plant begun industrialization and attempted.
Summary of the invention
Purpose of the present invention is realized that by following technical measures the umber of described raw material is parts by weight except that specified otherwise.The objective of the invention is provides a kind of clean method for producing that does not have the chrome tanning automobile cushion leather at the deficiencies in the prior art.
Chromium-free automobile cushion leather whole process clean preparation method, contain following steps:
(1) half circulation immersion
With 100 parts of wet salted hides, go into drum, with temperature 150～200 parts of vexed washing 30～60 minutes of water of 22～28 ℃, use 150～200 parts in the water of 22～28 ℃ of temperature then, add 0.1～0.3 part of sanitas, 0.02～0.1 part of soaking enzyme, soak, lead immersion in advance, the water that last batch wet salted hide soaks in advance, main soaking process is discharged is used for the pre-immersion of next batch wet salted hide;
(2) protect the hair depilation
With temperature 22～28 ℃ 50～100 parts in water, 1～2 part in sodium sulphite, 0.2～0.4 part of Sodium sulfhydrate, 1～3 part in lime, 0.5～1.5 part of auxiliary liming agent, pre-treatment 20～60 minutes, add 0.4～0.8 part in sodium sulphite again and handled 30～60 minutes, add temperature and be 18～22 ℃ 50～100 parts in water, stall was in conjunction with 12～18 hours, liquid effluent reclaims ox hair by filter hair device;
(3) the low ash of enzyme alkali is in conjunction with expanding
With temperature is 22～28 ℃ 50～100 parts in water, 0.2～0.5 part of Sumizyme MP, and 1～3 part in lime, 0.5～1.5 part of auxiliary liming agent rotated 120～150 minutes, changeed 10 minutes every 1 hour later on, totally 16～18 hours, sheet alkali skin then;
(4) no ammonia deliming, softening
Getting 100 parts of sheet alkali skins, is 30～33 ℃ 50～100 parts in water with temperature, 0.2～0.5 part in formic acid, and 2.5～3.5 parts of deliming auxiliary agents rotated 120～150 minutes, and regulating pH is 8～8.5, with 1～1.5 part of neutral protease, rotates 120～150 minutes;
(5) the weak pickling of less salt
Skin after softening is washed, and control water, added temperature and be 18～22 ℃ 60～80 parts in water, 2～4 parts in sodium sulfate rotated 20～30 minutes, added concentration again and be 0.3～0.6 part in the sulfuric acid of 85wt%, rotated 120～180 minutes, the pH that regulates acid solution is 3.5～3.6;
(6) tanning 1
Add 1～3 part of synthetic nitrogen phosphine tanning agent in the pickling drum, rotated 3～5 hours, add 1.0～2.0 parts in sodium bicarbonate then, the pH value of regulating acid solution is 4.5～5.0;
(7) tanning 2
In rousing, add 1～2 part of accessory syntan, rotate uniformly penetrating, then, add 10～15 parts of vegetable tanning agents, rotated 6～8 hours, after the tanning fully,, rotated again 60 minutes with pH value to 3.8～4.0 of acetate adjusting owse;
(8) rinsing
In drum, add temperature and be 40～50 ℃ 100～150 parts in water, guarantee that temperature is 30～35 ℃ in the drum, add 1.0～2.0 parts of accessory syntans, rotated 30～60 minutes, wash, rinsing liquid as pickling with in the liquid adding pickling;
(9) tanning 3
The adding temperature is 18～22 ℃ 100～200 parts in a water in drum, add 0.2～0.6 part of acetate again, rotated 20～60 minutes, regulate the pH value 3.2～3.5 of body lotion, add 4～8 parts of non-chromium metal-salt tanning agents, tanning 60～120 minutes is 3.8～4.2 with 1.0～3.0 parts of pH values of regulating body lotion of sodium bicarbonate then, and the liquid of discharge is used further to next batch tanning 3 operations fully;
(10) neutralization
The washing leather of being tanned adds temperature and is 18～22 ℃ 100～200 parts in water then in drum, 2.0～4.0 parts of 1.0～3.0 parts in sodium bicarbonate and neutralizing retanning agents, and the pH value of adjusting body lotion is 4.5～5.0;
(11) high absorption stuffing, dyeing
The adding temperature is 50～60 ℃ 100～200 parts in a water in drum, guarantee that temperature is 45～50 ℃ in the drum, adding 1～2 part of synthetic nitrogen phosphine tanning agent, rotated 20～60 minutes, add 2～4 parts of dyestuffs, 12～18 parts of highly sulfonated animal-plant oil rotated 60～120 minutes, and the pH value with acetate adjusting body lotion is 3.8～4.2 then;
(12) leaving standstill-wet toggling-vibration-buffing-covering with paint all carries out according to ordinary method.
Sanitas is for being salicylyl sodium or salicylic amide;
Auxiliary liming agent is C
6-C
10Carboxylic acid ammonium's mixture;
The deliming auxiliary agent is at least a in lactic acid, formic acid, acetate, the propionic acid;
Synthetic nitrogen phosphine tanning agent is phosphorus and C
2～C
6The condenses of alkyl ammonia sees Chinese patent 200410040212.9 for details;
The improved plant tanning agent is that wattle skin vegetable tanning agent or tower draw vegetable tanning agent;
Accessory syntan is any in sodium naphthalene sulfonate, benzene sulfonic acid sodium salt, the natrium phenolsulfonicum;
Neutralizing retanning agent is sodium naphthalene sulfonate or natrium phenolsulfonicum;
Non-chromium metal-salt is Tai-Ace S 150 or ferric sulfate tanning agent.
The shrinkage temperature of tanning of the present invention and dried finished leather can reach 110 ℃ with, outward appearance is near-white (under the situation of no dyeing), the tensile strength of finished leather is 10MPa, tear strength is 30N/mm, elongation at break less than 80%, pliability all reaches the chrome-tanned ministerial standard of leatherwear with leather, be applicable to pig, ox, sheepskin tanning are become automobile cushion leather, upholstery leather.
The present invention has following advantage:
1 the present invention adopts industrialization whole process clearer production technology.And produce high rerum natura chromium-free automobile cushion leather with this technology.
It is less that 2 chemical materialss use, and absorb and can reach more than 90%, and waste water, mud discharging be than traditional technology decreased average 30%～50%, the easy biochemical treatment of waste water.Contaminative to environment is little, is the oligosaprobic tanning technology of a kind of high benefit.
The compound combination tannage of 3 usefulness replaces traditional chromic tanning tanning.Not only eliminated the pollution of trivalent chromium in waste water and leather products, particularly got rid of of the pollution of the sexavalent chrome of generation, for medium-to-high grade time automobile cushion leather provides inner decoration material human and environment.
4 the present invention adopt the relatively low tanning agent of several flexibilities in conjunction with tanning, produce the leather of high heat-resistant stability by the synergy of the skeleton construction between them, and shrinkage temperature reaches more than 100 ℃.
Specific embodiments
Below by embodiment the present invention is carried out concrete description.Be necessary to be pointed out that at this following examples just are used for the present invention is further specified; can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field can make some nonessential improvement and adjustment to the present invention according to the content of foregoing invention.
Embodiment 1
(1) half circulation immersion
With the wet salted hide double centner, go into drum, with temperature 22～28 ℃ 150 kilograms in water, vexed washing 30 minutes, discharging, with temperature 22～28 ℃ 150 kilograms in water, 0.1 kilogram in adding salicylyl sodium, soaking enzyme are soaked for 0.02 kilogram in advance, and main immersion is used for the water that last batch wet salted hide soaks in advance, main soaking process is discharged the pre-immersion of next batch wet salted hide;
(2) protect the hair depilation
With temperature is 22～28 ℃ 50 kilograms in water, 1 kilogram in sodium sulphite, 0.2 kilogram of Sodium sulfhydrate, 1 kilogram in lime, C
6-C
70.5 kilogram in carboxylic acid ammonium's mixture, pre-treatment 20 minutes adds 0.4 kilogram in sodium sulphite again and handled 30 minutes, and additional temperature is 18～22 ℃ 50 kilograms in a water, and stall was in conjunction with 12 hours.Liquid effluent reclaims ox hair by filter hair device;
(3) the low ash of enzyme alkali is in conjunction with expanding
With temperature is 22～28 ℃ 50 kilograms in water, 0.2 kilogram of Sumizyme MP, 1 kilogram in lime, C
6-C
70.5 kilogram of carboxylic acid ammonium rotated 120 minutes, changeed 10 minutes every 1 hour later on, and totally 16 hours, sheet alkali skin then;
(4) no ammonia deliming, softening
Getting sheet alkali skin double centner, is 30～33 ℃ 50 kilograms in water with temperature, 0.2 kilogram in formic acid, and 1.5 kilograms of lactic acid, 1 kilogram of propionic acid rotated 120 minutes, and pH is 8, with 1 kilogram of neutral protease, rotates 120 minutes;
(5) the weak pickling of less salt
Skin after softening is washed, and control water, added temperature and be 18～22 ℃ 60 parts in water in drum, 2 kilograms in sodium sulfate rotated 20 minutes, added concentration again and be 0.3 kilogram in the sulfuric acid of 85wt%, rotated 120 minutes, and the pH of adjusting acid solution is 3.5;
(6) tanning 1
Add 1 kilogram of synthetic nitrogen phosphine tanning agent in the pickling drum, rotated 3 hours, add 1 kilogram in sodium bicarbonate then, the pH value of regulating acid solution is 4.5;
(7) tanning 2
In drum, add 1 kilogram of natrium phenolsulfonicum, rotate uniformly penetrating, then, add 10 kilograms of wattle skin vegetable tanning agents, rotated 6 hours, after the tanning fully,, rotated again 60 minutes with the pH value to 3.8 that acetate is regulated owse;
(8) rinsing
Tanned crust leather is a double centner, and the adding temperature is 40～50 ℃ a water double centner in drum, guarantees that temperature is 30～35 ℃ in the drum, and 1 kilogram of the natrium phenolsulfonicum of adding rotated 30 minutes, washing, and rinsing liquid joins in the pickling of next batch skin as pickling with liquid;
(9) tanning 3
The adding temperature is 18～22 ℃ a water double centner in drum, adding 0.2 kilogram of acetate, rotated 20 minutes, regulate the pH value 3.2 of body lotion, add 4 kilograms of Tai-Ace S 150 tanning agents, tanning 60 minutes is 3.8 with 1 kilogram of pH value of regulating body lotion of sodium bicarbonate then, and the liquid of discharge is used further in tanning 3 operations of next batch skin fully;
(10) neutralization
The washing leather of being tanned adds temperature and is 18～22 ℃ water double centner then in drum, 1 kilogram in sodium bicarbonate, and 2 kilograms of sodium naphthalene sulfonates, the pH value of adjusting body lotion is 4.5;
(11) high absorption stuffing, dyeing
The adding temperature is 50～60 ℃ a water double centner in drum, guarantees that temperature is 45～50 ℃ in the drum, adds 1 kilogram of synthetic nitrogen phosphine tanning agent, rotated 20 minutes, and added 2 kilograms of dyestuffs, 12 kilograms of sulfonating animal Vegetable oil lipoprotein, rotated 60 minutes, the pH value with acetate adjusting body lotion is 3.8 then;
(12) leaving standstill-wet toggling-vibration-buffing-covering with paint all carries out according to ordinary method.
Embodiment 2
(1) half circulation immersion
The wet salted hide double centner, go into drum, with temperature is vexed the washing 60 minutes of water of 22～28 ℃ 200 kilograms in water, discharging, with temperature 22～28 ℃ 200 kilograms in water, 0.3 part of adding salicylyl ammonium, soaking enzyme are soaked for 0.1 part in advance, and main immersion is used for the water that last batch wet salted hide soaks in advance, main soaking process is discharged the pre-immersion of next batch wet salted hide;
(2) depilation
With temperature is 22～28 ℃ water double centner, 2 kilograms in sodium sulphite, 0.4 kilogram of Sodium sulfhydrate, 3 kilograms in lime, C
7-C
81.5 kilograms in carboxylic acid ammonium's mixture, pre-treatment 60 minutes adds sodium sulphite again and handled 60 minutes for 0.8 kilogram, and additional temperature is 18～22 ℃ a water double centner, and stall was in conjunction with 18 hours, and liquid effluent reclaims ox hair by filter hair device;
(3) enzyme alkali is in conjunction with expansion
With temperature is 22～28 ℃ water double centner, 0.5 kilogram of Sumizyme MP, 3 kilograms in lime, C
8-C
91.5 parts of carboxylic acid ammoniums rotated 150 minutes, changeed 15 minutes every 1 hour later on, and totally 18 hours, sheet alkali skin then;
(4) no ammonia deliming, softening
Getting sheet alkali skin double centner, is 30～33 ℃ water double centner with temperature, 0.5 kilogram in formic acid, and 3.5 kilograms in formic acid rotated 150 minutes, and pH is 8.5, with 1.5 kilograms of neutral proteases, rotates 150 minutes;
(5) the weak pickling of less salt
Skin after softening is washed, and control water, added temperature and be 18～22 ℃ 80 kilograms in water in drum, 4 kilograms in sodium sulfate rotated 40 minutes, added concentration again and be 0.6 kilogram in the sulfuric acid of 85wt%, rotated 180 minutes, and the pH of adjusting acid solution is 3.6.
(6) tanning 1
Add 3 kilograms of synthetic nitrogen phosphine tanning agents in the pickling drum, rotated 5 hours, add 2 kilograms in sodium bicarbonate then, the pH value of regulating acid solution is 5.0;
(7) tanning 2
Add 2 kilograms of benzene sulfonic acid sodium salts in drum, rotate uniformly penetrating, then, add tower and draw 15 kilograms of vegetable tanning agents, rotated 8 hours, after the tanning fully, regulate with acetate about the pH value to 4.0 of owse, rotated again 60 minutes;
(8) rinsing
With tanned crust leather double centner, in drum, add temperature and be 40～50 ℃ 150 kilograms in water, guarantee that temperature is 30～35 ℃ in the drum, add 2 kilograms of benzene sulfonic acid sodium salts, rotated 60 minutes, to wash, rinsing liquid is used for the pickling of next batch skin.
(9) tanning 3
The adding temperature is 18～22 ℃ 200 kilograms in a water in drum, add 0.6 kilogram of acetate again, rotated 60 minutes, regulate the pH value 3.5 of body lotion, add 8 kilograms of ferric sulfate tanning agents, tanning 120 minutes is 3.8～4.2 with 3 kilograms of pH values of regulating body lotion of sodium bicarbonate then, and the liquid of discharge is used further to next batch tanning 3 operations fully;
(10) neutralization
The washing leather of being tanned adds temperature and is 18～22 ℃ 200 kilograms in water then in drum, 3 kilograms in sodium bicarbonate, and the pH values of 4 kilograms of adjustings of natrium phenolsulfonicum body lotion are 5.0;
(11) high absorption stuffing, dyeing
In drum, add temperature and be 50～60 ℃ 200 kilograms in water, guarantee that temperature is 45～50 ℃ in the drum, 2 kilograms of adding synthetic nitrogen phosphine tanning agents, rotated 60 minutes, and added 4 kilograms of dyestuffs, 8 kilograms of sulfonating animal Vegetable oil lipoprotein, rotated 120 minutes, the pH value with acetate adjusting body lotion is 4.2 then;
(12) leaving standstill-wet toggling-vibration-buffing-covering with paint all carries out according to ordinary method.
Embodiment 3
(1) immersion
The wet salted hide double centner, go into drum, with temperature 175 kilograms of vexed washing 60 minutes of water of 22～28 ℃, discharging, be 22～28 ℃ 175 kilograms in water then with temperature, add 0.2 kilogram in salicylyl sodium, 0.06 kilogram of soaking enzyme, soak in advance, main immersion is used for the water that last batch wet salted hide soaks in advance, main soaking process is discharged the pre-immersion of next batch wet salted hide;
(2) protect the hair depilation
With temperature is 22～28 ℃ 75 kilograms in water, 1.5 kilograms in sodium sulphite, 0.3 kilogram of Sodium sulfhydrate, 2 kilograms in lime, C
9-C
101 kilogram in carboxylic acid ammonium's mixture, pre-treatment 40 minutes adds 0.6 kilogram in sodium sulphite again and handled 45 minutes, and hair takes off most back, and to mend temperature be 18～22 ℃ 75 kilograms in water, and stall was in conjunction with 15 hours, and liquid effluent reclaims ox hair by a filter hair device;
(3) the low ash of enzyme alkali is in conjunction with expanding
With temperature is 22～28 ℃ 75 kilograms in water, 0.35 kilogram of Sumizyme MP, 2 kilograms in lime, C
9-C
101 kilogram of carboxylic acid ammonium rotated 125 minutes, changeed 12 minutes every 1 hour later on, and totally 17 hours, sheet alkali skin then;
(4) no ammonia deliming, softening
Getting sheet alkali skin double centner, is 30～33 ℃ 75 kilograms in water with temperature, 0.35 kilogram in formic acid, and 2 kilograms of lactic acid, 1 kilogram of acetate rotated 125 minutes, and pH is 8.2, with 1.25 kilograms of neutral proteases, rotates 125 minutes;
(5) the weak pickling of less salt
Skin after softening is washed, and control water, added temperature and be 18～22 ℃ 70 kilograms in water in drum, 3 kilograms in sodium sulfate rotated 25 minutes, added concentration again and be 0.45 kilogram in the sulfuric acid of 85wt%, rotated 150 minutes, and the pH of adjusting acid solution is 3.5;
(6) tanning 1
In the pickling drum, add 1.5 kilograms of synthetic nitrogen phosphine tanning agents, rotated 4 hours.Add 1.5 kilograms in sodium bicarbonate then, the pH value of regulating acid solution is 4.7;
(7) tanning 2
In drum, add 1.5 kilograms of sodium naphthalene sulfonates, rotate uniformly penetrating.Then, add 12.5 kilograms of wattle skin vegetable tanning agents, rotated 7 hours, after the tanning fully,, rotated again 60 minutes with the pH value to 3.9 that acetate is regulated owse;
(8) rinsing
Add temperature and be 40～50 ℃ 125 kilograms in water in drum, guarantee that temperature is 30～35 ℃ in the drum, add 1.5 kilograms of sodium naphthalene sulfonates, rotated 45 minutes, wash, rinsing liquid is used for the pickling of next batch skin;
(9) tanning 3
The adding temperature is 18～22 ℃ 150 kilograms in a water in drum, adding 0.4 kilogram of acetate, rotated 40 minutes, regulate the pH value 3.3 of body lotion, add 6 kilograms of Tai-Ace S 150 tanning agents, tanning 60～120 minutes is 4.0 with 2 kilograms of pH values of regulating body lotion of sodium bicarbonate then, and the liquid of discharge is used for tanning 3 operations of next batch skin fully;
(10) neutralization
The washing leather of being tanned adds temperature and is 18～22 ℃ 150 kilograms in water then in drum, 2 kilograms in sodium bicarbonate, and the pH values of 3 kilograms of adjustings of sodium naphthalene sulfonate body lotion are 4.7;
(11) dyeing, stuffing
In drum, add temperature and be 50～60 ℃ 150 kilograms in water, guarantee that temperature is 45～50 ℃ in the drum, 1.5 kilograms of adding synthetic nitrogen phosphine tanning agents, rotated 40 minutes, and added 3 kilograms of dyestuffs, 15 kilograms of sulfonating animal Vegetable oil lipoprotein, changeed 90 minutes, the pH value with acetate adjusting body lotion is 4.0 then;
(12) leaving standstill-wet toggling-vibration-buffing-covering with paint all carries out according to ordinary method.
Annotate: synthetic nitrogen phosphine tanning agent sees Chinese patent 200410040212.9 for details, and the improved plant tanning agent is that Italian Silva company produces; Accessory syntan is that Zhejiang Province Zhong Xiong enterprise-like corporation produces; Non-chromium metal-salt tanning agent is that your chemical company of Hunter, Sichuan produces; Other chemical materials can be bought on market.
Claims (9)
- The production method that 1 chromium-free automobile cushion leather cleans is characterized in that the described raw material of this method according to the weight part meter, contains following steps:(1) half circulation immersionWith 100 parts of wet salted hides, go into drum, with temperature 150～200 parts of vexed washing 30～60 minutes of water of 22～28 ℃, use 150～200 parts in the water of 22～28 ℃ of temperature then, add 0.1～0.3 part of sanitas, 0.02～0.1 part of soaking enzyme, soak, lead immersion in advance, the water that last batch wet salted hide soaks in advance, main soaking process is discharged is used for the pre-immersion of next batch wet salted hide;(2) protect the hair depilationWith temperature 22～28 ℃ 50～100 parts in water, 1～2 part in sodium sulphite, 0.2～0.4 part of Sodium sulfhydrate, 1～3 part in lime, 0.5～1.5 part of auxiliary liming agent, pre-treatment 20～60 minutes, add 0.4～0.8 part in sodium sulphite again and handled 30～60 minutes, add temperature and be 18～22 ℃ 50～100 parts in water, stall was in conjunction with 12～18 hours, filter, reclaim ox hair;(3) the low ash of enzyme alkali is in conjunction with expandingWith temperature is 22～28 ℃ 50～100 parts in water, 0.2～0.5 part of Sumizyme MP, and 1～3 part in lime, 0.5～1.5 part of auxiliary liming agent rotated 120～150 minutes, changeed 10 minutes every 1 hour later on, totally 16～18 hours, sheet alkali skin then;(4) no ammonia deliming, softeningGetting 100 parts of sheet alkali skins, is 30～33 ℃ 50～100 parts in water with temperature, 0.2～0.5 part in formic acid, and 2.5～3.5 parts of deliming auxiliary agents rotated 120～150 minutes, and regulating pH is 8～8.5, with 1～1.5 part of neutral protease, rotates 120～150 minutes;(5) the weak pickling of less saltSkin after softening is washed, and control water, added temperature and be 18～22 ℃ 60～80 parts in water, 2～4 parts in sodium sulfate rotated 20～30 minutes, added concentration again and be 0.3～0.6 part in the sulfuric acid of 85wt%, rotated 120～180 minutes, the pH that regulates acid solution is 3.5～3.6;(6) tanning 1Add 1～3 part of synthetic nitrogen phosphine tanning agent in the pickling drum, rotated 3～5 hours, add 1.0～2.0 parts in sodium bicarbonate then, the pH value of regulating acid solution is 4.5～5.0;(7) tanning 2In rousing, add 1～2 part of accessory syntan, rotate uniformly penetrating, then, add 10～15 parts of vegetable tanning agents, rotated 6～8 hours, after the tanning fully,, rotated again 60 minutes with pH value to 3.8～4.0 of acetate adjusting owse;(8) rinsingIn drum, add temperature and be 40～50 ℃ 100～150 parts in water, guarantee that temperature is 30～35 ℃ in the drum, add 1.0～2.0 parts of accessory syntans, rotated 30～60 minutes, wash, rinsing liquid as pickling with in the liquid adding pickling;(9) tanning 3The adding temperature is 18～22 ℃ 100～200 parts in a water in drum, add 0.2～0.6 part of acetate again, rotated 20～60 minutes, regulate the pH value 3.2～3.5 of body lotion, add 4～8 parts of non-chromium metal-salt tanning agents, tanning 60～120 minutes is 3.8～4.2 with 1.0～3.0 parts of pH values of regulating body lotion of sodium bicarbonate then, and the liquid of discharge is used further to next batch tanning 3 operations fully;(10) neutralizationThe washing leather of being tanned adds temperature and is 18～22 ℃ 100～200 parts in water then in drum, 2.0～4.0 parts of 1.0～3.0 parts in sodium bicarbonate and neutralizing retanning agents, and the pH value of adjusting body lotion is 4.5～5.0;(11) high absorption stuffing, dyeingThe adding temperature is 50～60 ℃ 100～200 parts in a water in drum, guarantee that temperature is 45～50 ℃ in the drum, adding 1～2 part of synthetic nitrogen phosphine tanning agent, rotated 20～60 minutes, add 2～4 parts of dyestuffs, 12～18 parts of highly sulfonated animal-plant oil rotated 60～120 minutes, and the pH value with acetate adjusting body lotion is 3.8～4.2 then;(12) leaving standstill-wet toggling-vibration-buffing-covering with paint all carries out according to ordinary method.
- 2 production methods that clean of chromium-free automobile cushion leather according to claim 1 is characterized in that sanitas is salicylyl sodium or salicylic amide.
- 3 production methods that clean of chromium-free automobile cushion leather according to claim 1 is characterized in that auxiliary liming agent is C 6-C 10Carboxylic acid ammonium's mixture.
- 4 production methods that clean of chromium-free automobile cushion leather according to claim 1 is characterized in that the deliming auxiliary agent is at least a in lactic acid, formic acid, acetate, the propionic acid.
- 5 production methods that clean of chromium-free automobile cushion leather according to claim 1 is characterized in that synthetic nitrogen phosphine tanning agent is phosphorus and C 2～C 6The condenses of alkyl ammonia.
- 6 production methods that clean of chromium-free automobile cushion leather according to claim 1 is characterized in that the improved plant tanning agent is that wattle skin vegetable tanning agent or tower draw vegetable tanning agent.
- 7 production methods that clean of chromium-free automobile cushion leather according to claim 1 is characterized in that accessory syntan is any in sodium naphthalene sulfonate, benzene sulfonic acid sodium salt, the natrium phenolsulfonicum.
- 8 production methods that clean of chromium-free automobile cushion leather according to claim 1 is characterized in that neutralizing retanning agent is sodium naphthalene sulfonate or natrium phenolsulfonicum.
- 9 according to claim 1, and the production method that chromium-free automobile cushion leather cleans is characterized in that non-chromium metal-salt is Tai-Ace S 150 or ferric sulfate tanning agent.
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| 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 |
| CN102559951A (en) * | 2012-01-19 | 2012-07-11 | 朗盛（无锡）化工有限公司 | Ammonium-free deliming agent and application thereof in leather deliming process |
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| CN101353707B (en) * | 2007-07-25 | 2013-05-01 | 余锦刚 | Improved method for solving all process defects before leather is pickled and use thereof |
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| JPH0488100A (en) * | 1990-08-01 | 1992-03-19 | Yoshikawa Seiyu Kk | Tanning agent and production thereof |
| GB9120652D0 (en) * | 1991-09-27 | 1991-11-06 | Albright & Wilson | Use of phosphonium compounds in the preparation of leather |
| CN1077227A (en) * | 1992-04-07 | 1993-10-13 | 湘潭大学 | Process of zirconic tanning leather |
| CH691062A5 (en) * | 1996-06-17 | 2001-04-12 | Tfl Ledertechnik Gmbh & Co Kg | An aqueous composition for pre-tanning of hide pelts or retanning leather. |
| EA001976B1 (en) * | 1997-10-30 | 2001-10-22 | Родиа Конзьюмер Спешиалтиз Лимитед | Tanning leather |
| US6685747B1 (en) * | 1999-02-03 | 2004-02-03 | Rhodia Consumer Specialties Limited | Mixture of THP and chrome as tanning agents |
| GB0013611D0 (en) * | 2000-06-06 | 2000-07-26 | Rhodia Cons Spec Ltd | Tanning leather |
| GB2384006A (en) * | 2002-01-11 | 2003-07-16 | Rhodia Cons Spec Ltd | Tanning leather |
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| CN107641668A (en) * | 2017-09-27 | 2018-01-30 | 兴业皮革科技股份有限公司 | One kind cleans environmental cattle hide upper leather water field production technology |
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| CN109628654A (en) * | 2018-12-17 | 2019-04-16 | 兴业皮革科技股份有限公司 | A kind of manufacture craft that water proof type is removed from office without chromed tanned leather |
| CN113528716A (en) * | 2021-08-02 | 2021-10-22 | 青岛永昌因特皮革有限公司 | Clean type tanning production system |
| CN114134259A (en) * | 2021-11-10 | 2022-03-04 | 中牛集团有限公司 | Production process of chrome-free tanning and plant-free tanning sofa leather |
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Assignee: Haining Mengnu Leatherware Co., Ltd. Assignor: Sichuan University Contract fulfillment period: 2008.7.29 to 2013.7.29 contract change Contract record no.: 2008990001198 Denomination of invention: Clean production method of chromium-free automobile cushion leather Granted publication date: 20080109 License type: Exclusive license Record date: 20081117 |
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