CN101993960B - Leatherworking retanning method using chromium leather scraps - Google Patents
Leatherworking retanning method using chromium leather scraps Download PDFInfo
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Abstract
The invention provides a leatherworking retanning method using chromium leather scraps. The method comprises the following steps of: extracting collagen in the chromium leather scraps by using an alkali method, drying the collagen, performing amidation reaction on the dried collagen and an acrylic monomer in the absence of water, then performing graft copolymerization reaction to prepare a collagen modified substance, and applying the collagen modified substance to retannage of leather. By applying the chromium leather scraps to the leather retannage, the defects of leather color loss and strong plastic feel caused by excessive use of a synthesized retannage material in the retannage can be improved by using the performance of the collagen.
Description
Technical field
The invention belongs to the leather production technical field, in particular to a kind of process hides retanning method, particularly is that main raw material prepares collagen-modified thing with the chrome shavinge, and this modifier is applied to method in the tanning production retanning.
Background technology
Leather industry is an ancient industry, it is that low output with the high investment of raw material and product is feature, according to Britain leather association statistical information, have only 20% raw material skin to change leather in the process hides, if count lining leather in, utilization ratio also only is 31.5%, and remaining is because operations such as split, shaving, circle limit and buffing have formed solid waste.China has developed into machining center and the trade center of world's leather industry at present, and a year processing leather reaches 5.3 hundred million square metres, accounts for more than 1/5 of world's leather output, and leatherware such as leather shoes, fur clothing, leatherware account for more than 1/2 of world wide production.Because the turnout of China's leather is very big, the utilization ratio to the raw material skin is also low than advanced international standard in process of production, produces the maximum country of leather solid waste in the world thereby China is also become simultaneously.The annual solid waste that produces up to a million tons of development of China leather industry, leather goods industries such as shoemaking and clothing also will produce the cutting tailing of hundreds of thousands of ton every year.In addition, leatherware also has only certain working life with other consumer's goods are the same, will be abandoned after shabby when becoming and become rubbish, thereby the leatherware of all production and sales the most all becomes waste.
These main components are that the organic waste of protein can rot after banking up for a long time, wherein chemical materials such as poisonous chromic salts and dyestuff can discharge, environment is polluted, protein also can discharge aldehyde-containing type in the process of rotting, nitrogenous, obnoxious flavoures such as sulfur-bearing, organism also can cause severe contamination to ecotope after entering water body, also be the significant wastage of resource simultaneously, thereby development and use tanning waste, pollutent is converted into useful resources, avoiding environment is polluted and endangers, has been that pendulum needs the important topic that solves in face of us.
The solid waste that produces in the leather production mainly contains following several:
1. the leather castoff that does not contain chromic salts: do not pass through the tanning effect of chromic salts, extract high-quality collagen protein easily;
2. contain the chromium leather castoff: mainly be shaving and the circle limit waste of wet blue leather, passed through the tanning effect of chromic salts, the high-quality collagen protein of difficult extraction;
3. with look crust leather waste: mainly be shaving and the circle limit waste of dyeing back crust leather, comprise the cutting clout that comes from clothing factory and one factory, not only contain chromic salts, and contain dyestuff, retanning agent and fatting agent, be difficult to extract high-quality collagen protein.
The annual up to a million tons of leather solid waste that produce of China all do not obtain effective and safe utilization at present basically.The leather castoff that part does not contain chromium is generally for the production of edible Gelatinum oxhide and collagen protein, and major part contains the leather castoff of chromium for the production of feed, and cutting tailing and waste and old leather substantially all do not obtain utilizing.The chromium leather castoff is produced edible Gelatinum oxhide and there is the shortcoming that utilization ratio is low, cost is high in collagen protein because production technology aspect, utilization do not contain; The edible Gelatinum oxhide and the collagen protein chrome content that utilize chrome leather scrap to produce are higher, do not meet food sanitation standard, can cause potential harm to human body.
Summary of the invention
The invention provides a kind of process hides retanning method of utilizing chrome shavinge, be that main raw material prepares collagen-modified thing with the chrome shavinge, and this modifier is applied to process hides retanning operation, this method comprises following step:
1. the preparation of collagen-modified thing:
The present invention adopts alkaline process to the chrome shavinge processing that is hydrolyzed, and obtains collagen hydrolysate after the filtration.Adopt alkali process hydrolysis can make the chromic salts in the chrome shavinge be in the precipitation state, after separating, can obtain purity than higher collagen hydrolysate.The collagen protein method is extracted in the hydrolysis of chrome shavinge: chrome shavinge is in over dry 200 weight parts, water 1000 weight parts, sodium hydroxide 10～20 weight parts, 85～100 ℃ of following hydrolysis 1～3 hour are filtered, and adjust about pH value of filtrate to 7 with sulfuric acid, through super-dry, obtain collagen protein powder again.
The present invention makes the purpose that powdery has two aspects with the collagen protein that extracts: the one, can be with collagen protein intermediate prolonged preservation, and the 2nd, can under anhydrous state, carry out amidate action with follow-up acrylic monomer after making anhydrous state.
The modification of collagen protein: collagen protein itself is more weak with the bonding properties of leather, and the retanning effect that directly applies to process hides is also bad, thereby needs carry out modification to collagen protein earlier, strengthens the bonding properties of collagen protein and leather.The preparation method of collagen modification thing is: 80 ℃ of following back flow reaction 1.5～2 hours, make amido and the carboxyl on the Acrylic Acid Monomer on the collagen protein carry out amidate action above 100 weight part collagen protein powders and 50 parts by weight of acrylic acid class monomers; Add 200 weight parts waters more therein, after 80 ℃ of following stirring and dissolving are complete, potassium persulfate solution 10 weight parts that add 20% concentration, cause the free radical grafting copolymerization reaction, react after 2～3 hours, cool to below 50 ℃, use sodium hydroxide to adjust pH value to 7～8 of modifier, obtain collagen-modified thing.
2. the application of collagen-modified thing in the process hides retanning:
The collagen-modified thing of the present invention's preparation is to use acrylic resin to carry out modification, thereby part has the performance of acrylic resin retanning agent, the present invention is engaged in itself and aminoresin and synthetic tanning agent in the process hides retanning and uses, comprehensively the advantage of protein, acrylic acid or the like, aminoresin class and synthetic tanning agent class retanning agent.Simultaneously, in the collagen-modified thing of the present invention protein ingredient can also with after the aminoresin that adds and synthetic tanning agent reaction, increase the bonding force of collagen-modified thing and leather.Use modified collagen hydrolyzate or collagen hydrolysate will not have this synergy separately.
The application method of the collagen-modified thing of the present invention is (following consumption in shaving after the weight of wet blue leather):
The ox-hide wet blue leather is weighed behind the shaving, as following consumption basic weight,
Return wet: 150%, 35 ℃ in water, to rotate 30 minutes, control is done, and washes 1 time;
Retanning: 100%, 40 ℃ in water, dyestuff 1～3%, fatting agent 2% rotated 30 minutes; Add sodium formiate 0.6%, rotated 15 minutes, add sodium bicarbonate 0.4%, rotated 45 minutes; The collagen-modified thing 4～6% that obtains in adding 1. rotated 30 minutes; Add aminoresin retanning agent 2～3%, rotated 20 minutes; Synthetic tanning agent 2～3% rotated 30 minutes, and control is done;
100%, 50 ℃ in water, fatting agent 6～13% rotated 45 minutes; 0.5% formic acid, 10 times of water dilution backs add, and rotate 15 minutes; 0.5% formic acid, 10 times of water dilution backs add, and rotate 30 minutes, and control is done, and washs 1 time.
Following drying, get damp again and do method such as soft with general technology.
Aminoresin retanning agent, synthetic tanning agent, dyestuff and the fatting agent that the present invention relates to all is the general purpose material during leather is produced, and the material that different company produces may be used to the inventive method, does not have special requirement except known general property.
Particular content of the present invention is as follows:
A kind of process hides retanning method of utilizing chrome shavinge is characterized in that extracting the collagen protein in the chrome shavinge, after the graft modification of use Acrylic Acid Monomer, is applied to the retanning operation of process hides again, specifically may further comprise the steps:
1. the preparation of collagen-modified thing:
Chrome shavinge is in over dry 200 weight parts, water 1000 weight parts, and sodium hydroxide 10～20 weight parts, 85～100 ℃ of following hydrolysis 1～3 hour are filtered, and adjust about pH value of filtrate to 7 with sulfuric acid, again through super-dry, obtain collagen protein powder.
With above 100 weight part collagen protein powders and 50 parts by weight of acrylic acid class monomers 80 ℃ of following back flow reaction 1.5～2 hours, add 200 weight parts waters again, after 80 ℃ of following stirring and dissolving are complete, potassium persulfate solution 10 weight parts that add 20% concentration, react after 2～3 hours, cool to below 50 ℃, use sodium hydroxide to adjust pH value to 7～8 of modifier, obtain collagen-modified thing.
2. the application of collagen-modified thing in the process hides retanning:
The ox-hide wet blue leather is weighed behind the shaving, as following consumption basic weight,
Return wet: 150%, 35 ℃ in water, to rotate 30 minutes, control is done, and washes 1 time;
Retanning: 100%, 40 ℃ in water, dyestuff 1～3%, fatting agent 2% rotated 30 minutes; Add sodium formiate 0.6%, rotated 15 minutes, add sodium bicarbonate 0.4%, rotated 30 minutes; The collagen-modified thing 4～6% that obtains in adding 1. rotated 30 minutes; Add aminoresin retanning agent 2～3%, rotated 20 minutes; Synthetic tanning agent 2～3% rotated 30 minutes, and control is done;
100%, 50 ℃ in water, fatting agent 6～13% rotated 45 minutes; 0.5% formic acid, 10 times of water dilution backs add, and rotate 15 minutes; 0.5% formic acid, 10 times of water dilution backs add, and rotate 30 minutes, and control is done, and washs 1 time.
Above-described acrylic monomer is vinylformic acid and/or methacrylic acid.
The process hides retanning method of utilizing chrome shavinge provided by the invention has the advantage of following three aspects:
1. the main component of chrome shavinge is collagen protein, with the constituent class of leather seemingly, the present invention makes retanning agent with collagen protein, be incorporated into the over-all properties that can improve leather products in the leather again, and collagen protein is that a kind of Amphoteric Materials can prevent " effect of losing colour ", can improve owing to too much using synthetic class retanning material to cause the strong problem of leather products plastic sense.
2. after the present invention becomes powdery with the collagen protein preparation, can under anhydrous condition, carry out amidate action with acrylic monomer, acrylic monomer is received on the collagen molecules, be dissolved in water again and carry out graft copolymerization, avoid the shortcoming that general graft copolymerization Acrylic Acid Monomer autohemagglutination is many, percentage of grafting is low, obtained the good collagen-modified thing of retanning performance.
3. the present invention uses collagen-modified thing and aminoresin retanning agent, synthetic tanning agent in the application process of retanning with bathing, collagen protein can react with aminoresin and synthetic tanning agent, improve the bonding force of collagen-modified thing in leather, produce synergy.
Specific implementation method
Embodiment 1
Chrome shavinge is in over dry 200 weight parts, water 1000 weight parts, and sodium hydroxide 12 weight parts 98 ℃ of following hydrolysis 3 hours, filter, and adjust about pH value of filtrate to 7 with sulfuric acid, again through super-dry, obtain collagen protein powder.
With above 100 weight part collagen protein powders and 50 parts by weight of acrylic acid monomers 80 ℃ of following back flow reaction 1.5 hours, add 200 weight parts waters again, after 80 ℃ of following stirring and dissolving are complete, potassium persulfate solution 10 weight parts that add 20% concentration, react after 3 hours, cool to below 50 ℃, use sodium hydroxide to adjust the pH value to 7.5 of modifier, obtain collagen-modified thing.
The ox-hide wet blue leather is weighed behind the shaving, as following consumption basic weight,
Return wet: 150%, 35 ℃ in water, to rotate 30 minutes, control is done, and washes 1 time;
Retanning: 100%, 40 ℃ in water, dyestuff 1.5%, fatting agent 2% rotated 30 minutes; Add sodium formiate 0.6%, rotated 15 minutes, add sodium bicarbonate 0.4%, rotated 45 minutes; The collagen-modified thing 4% for preparing in adding 1. rotated 30 minutes; Add aminoresin retanning agent 3%, rotated 20 minutes; Synthetic tanning agent 2% rotated 30 minutes, and control is done;
100%, 50 ℃ in water, fatting agent 8% rotated 45 minutes; 0.5% formic acid, 10 times of water dilution backs add, and rotate 15 minutes; 0.5% formic acid, 10 times of water dilution backs add, and rotate 30 minutes, and control is done, and washs 1 time.
Following drying, get damp again and do method such as soft with general technology.
Embodiment 2
Chrome shavinge is in over dry 200 weight parts, water 1000 weight parts, and sodium hydroxide 18 weight parts 88 ℃ of following hydrolysis 1.5 hours, filter, and adjust about pH value of filtrate to 7 with sulfuric acid, again through super-dry, obtain collagen protein powder.
With above 100 weight part collagen protein powders and 50 weight part methacrylic acid monomers 80 ℃ of following back flow reaction 2 hours, add 200 weight parts waters again, after 80 ℃ of following stirring and dissolving are complete, persulfuric acid clock solution 10 weight parts that add 20% concentration, react after 3 hours, cool to below 50 ℃, use sodium hydroxide to adjust the pH value to 7.5 of modifier, obtain collagen-modified thing.
The ox-hide wet blue leather is weighed behind the shaving, as following consumption basic weight,
Return wet: 150%, 35 ℃ in water, to rotate 30 minutes, control is done, and washes 1 time;
Retanning: 100%, 40 ℃ in water, dyestuff 2.5%, fatting agent 2% rotated 30 minutes; Add sodium formiate 0.6%, rotated 15 minutes, add sodium bicarbonate 0.4%, rotated 45 minutes; The collagen-modified thing 6% for preparing in adding 1. rotated 30 minutes; Add aminoresin retanning agent 2%, rotated 20 minutes; Synthetic tanning agent 3% rotated 30 minutes, and control is done;
100%, 50 ℃ in water, fatting agent 12% rotated 45 minutes; 0.5% formic acid, 10 times of water dilution backs add, and rotate 15 minutes; 0.5% formic acid, 10 times of water dilution backs add, and rotate 30 minutes, and control is done, and washs 1 time.
Following drying, get damp again and do method such as soft with general technology.
Claims (2)
1. a process hides retanning method of utilizing chrome shavinge is characterized in that extracting the collagen protein in the chrome shavinge, after the graft modification of use Acrylic Acid Monomer, is applied to the retanning operation of process hides again, and described method may further comprise the steps:
1. the preparation of collagen-modified thing:
Chrome shavinge is in over dry 200 weight parts, water 1000 weight parts, and sodium hydroxide 10～20 weight parts, 85～100 ℃ of following hydrolysis 1～3 hour are filtered, and adjust about pH value of filtrate to 7 with sulfuric acid, again through super-dry, obtain collagen protein powder;
With above 100 weight part collagen protein powders and 50 parts by weight of acrylic acid class monomers 80 ℃ of following back flow reaction 1.5～2 hours, add 200 weight parts waters again, after 80 ℃ of following stirring and dissolving are complete, potassium persulfate solution 10 weight parts that add 20% concentration, react after 2～3 hours, cool to below 50 ℃, use sodium hydroxide to adjust pH value to 7～8 of modifier, obtain collagen-modified thing;
2. the application of collagen-modified thing in the process hides retanning:
The ox-hide wet blue leather is weighed behind the shaving, as following consumption basic weight,
Return wet: 150%, 35 ℃ in water, to rotate 30 minutes, control is done, and washes 1 time;
Retanning: 100%, 40 ℃ in water, dyestuff 1～3%, fatting agent 2% rotated 30 minutes; Add sodium formiate 0.6%, rotated 15 minutes, add sodium bicarbonate 0.4%, rotated 45 minutes; The collagen-modified thing 4～6% for preparing in adding 1. rotated 30 minutes; Add aminoresin retanning agent 2～3%, rotated 20 minutes; Synthetic tanning agent 2～3% rotated 30 minutes, and control is done;
100%, 50 ℃ in water, fatting agent 6～13% rotated 45 minutes; 0.5% formic acid, 10 times of water dilution backs add, and rotate 15 minutes; 0.5% formic acid, 10 times of water dilution backs add, and rotate 30 minutes, and control is done, and washs 1 time.
2. the method for claim 1 is characterized in that described acrylic monomer is vinylformic acid and/or methacrylic acid.
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| CN 201010554958 CN101993960B (en) | 2010-11-23 | 2010-11-23 | Leatherworking retanning method using chromium leather scraps |
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| CN102978298B (en) * | 2012-11-27 | 2016-02-03 | 四川大学 | A kind of chrome-reduced leather totally enclosed circulation means coordinating tanning agent based on Zirconium-aluminum-titanium |
| CN104818355B (en) * | 2015-04-17 | 2016-10-26 | 四川大学 | A kind of containing chromium leather retanning filler and preparation method thereof |
| KR20200044002A (en) * | 2017-08-29 | 2020-04-28 | 란세스 도이치란트 게엠베하 | Method for transferring and administering a small damp leather piece to the reactor |
| CN109022634B (en) * | 2018-08-19 | 2021-03-12 | 广东紫翼鞋业有限公司 | Preparation method and application of mildew-proof leather-making protein filler |
| CN109022635B (en) * | 2018-08-19 | 2021-01-26 | 史密特(南京)皮革化学品有限公司 | Preparation method and application of leather-making protein filler modified by metal material |
| CN109852743B (en) * | 2019-01-31 | 2021-11-02 | 云南省陆良和平科技有限公司 | Method for preparing protein retanning filler by using aziridine cross-linking agent |
| CN110283949B (en) * | 2019-05-20 | 2022-03-01 | 齐鲁工业大学 | Method for preparing collagen-based leather retanning agent and chrome tanning agent |
| CN112574553B (en) * | 2020-12-18 | 2022-03-22 | 四川大学 | Preparation method of light-curable chrome-containing leather powder 3D printing slurry |
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Denomination of invention: A retanning method using chrome shavings Effective date of registration: 20200820 Granted publication date: 20130821 Pledgee: Bank of China Limited by Share Ltd. Shishi Branch Pledgor: FUJIAN GUANXING LEATHER Co.,Ltd. Registration number: Y2020980005202 |
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