CN102505056B - Hair-protection unhairing and liming waste liquor recycling method - Google Patents
Hair-protection unhairing and liming waste liquor recycling method Download PDFInfo
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- CN102505056B CN102505056B CN2011103218527A CN201110321852A CN102505056B CN 102505056 B CN102505056 B CN 102505056B CN 2011103218527 A CN2011103218527 A CN 2011103218527A CN 201110321852 A CN201110321852 A CN 201110321852A CN 102505056 B CN102505056 B CN 102505056B
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Abstract
The invention provides a hair-protection unhairing and liming waste liquor recycling method in the tanning industry. In the method, an organic sulfur unhairing material is used to carry out hair-protection unhairing; sodium sulfide and lime are used to carry out liming processing; after solid impurities in liming waste liquor are removed, the liming waste liquor replaces water to be reused in theliming processing; after being circulated for 1 to 5 times, the liming waste liquor is processed by acid, so that sodium sulfide in the waste liquor is converted into hydrogen sulfide and proteins also generate precipitates; the generated sodium sulfide is adsorbed by using sodium hydroxide and is reused in the liming processing; after the proteins in the processed waste liquor are filtered, the processed waste liquor is reused for pre-soaking, so that the complete circulation of the liming waste liquor is realized.
Description
The method field
The invention belongs to the tanning production method that cleans of leather production technical field, specially refer to the depilation of a kind of guarantor's hair and liming waste liquor recycling method.
Background technology
The pollution of leather industry mainly comes from prepares workshop section, and the pollution of preparing workshop section mainly comes from the depilation operation, in the pollution that leather production produces except sulphide staining fully from the sulfide depilation liming operation, also has the pervaporation residue more than 65%, organism more than 61%, the total nitrogen more than 40% and 70% above chemical oxygen demand (COD
Cr) also from the depilation liming operation.
In occupation of absolute dominant position, reason is that the sulfide depilation method has the unrivaled advantage of other epilation to the sulfide depilation method in the depilating method that current leather is produced: 1. depilation is clean and speed is fast; 2. the material that loses hair or feathers easily obtains and is with low cost; 3. easy, the easy control of epilation operation can realize protecting the hair depilation or ruin the hair depilation; 4. good product quality and more stable, applicable leather kind is wide.
But also there is heavy-polluted fatal shortcoming in the sulfide depilation method simultaneously, and it pollutes pollution and the organic pollution that mainly comprises sulfide.Sulfide residual in the depilation waste liquor can cause severe contamination to environment, the waste water of sulfur compound enters can make the smelly blackening of water quality in the rivers, many fresh-water fishes sulfide content be in the water of 1.0-25mg/l 1-3 days will be dead, containing a large amount of sulfide in the soil can make the old root blackout of plant rot, new root is long bad, causes farm crop withered.Another the most serious harm of sulfide, be exactly that it can be converted into the stronger hydrogen sulfide of toxicity, hydrogen sulfide has the intense stimulus effect to eyes and respiratory tract, be subjected to for a long time low concentration hydrogen sulphide effect meeting to make people's dizziness, general weakness, easily tired, hidrosis, pleasantly sweet in mouthful, feel sick, concentration of hydrogen sulfide Gao Shihui make people's dim eyesight, dizzy until lose consciousness, death.When airborne concentration of hydrogen sulfide reaches 0.015mg/l, will cause toxicity symptom, concentration then can cause death when surpassing 1mg/l.Expensive very large to the processing of sulfur compound sewage in addition, the energy of its consumption is without sulphur sewage three times except equipment, and if sewage medium sulphide content content above 50mg/l, sludge bacteria can be died, and has reduced water treatment effect.
Hair on the process hides raw material skin and epidermis will be removed by chemical process in the depilation operation, these main components be the process hides dud of keratoprotein account for raw material skin dry weight 5～10%, in the depilation operation, after degrading, basically all enter in the depilation waste liquor, become the principal pollutant of leather-making waste water.In addition, the most of interfibrillar substance in the process hides raw material skin also will be removed by the depilation operation, and the main component of interfibrillar substance is some ball-type albumen, and this has also improved the organic content in the depilation waste liquor to a certain extent greatly.A large amount of protein in the depilation waste liquor make it become greatest contamination source in the leather-making waste water, COD
CrContent is up to more than the 20000mg/l, and general chemical oxygen demand can make the microorganism in the water when 500-3000mg/l, comprises that disease carrying germ obtains enough nutrition and rapidly breeding, causes pollution of waterhead, is detrimental to health.When containing large amount of organic in the water in addition, the dissolved oxygen in the water is consumed in a large number, when oxygen in water less than 4 the time, the hydrocoles such as the fish expiratory dyspnea that can become gradually, so be choked to death and die.
In order to improve the with serious pollution shortcoming of sulfide depilation method, the scientific worker has developed some depilating methods that clean both at home and abroad, as protect a mao epilation, Lime Liquor circulation method, oxidation style depilation and enzyme unhairing etc., but these methods since separately shortcoming basically all be not applied aborning.
Protecting the hair depilating method is by controlling the condition of alkali and reductive agent, make the depilation material only act on hair root and stay complete hair, reduced suspended solid and organism, reduced the value of BOD and COD, also having reduced the consumption of sulfide.Protect the hair epilation and can be divided into two classes: first sulfide removal is the method for alkaline purification and the method that first alkaline purification postcure thing is processed again, the former Typical Representative is the HS guarantor hair liming system that the successful Sirolime of Australian Union's science and industrial research institute (CSIRO) research protects hair liming system and Romo Co.,Ltd's exploitation, Blair's epilation of Blair's research and development that the typical representative of the latter is rom Haars Co., Ltd.But the shortcoming of protecting the hair epilation is to still have the dissolving of part hair to enter in the waste liquid, cleans effect more limited, generally can only be with the COD content about 30% in the waste liquid, and also waste liquid contains a large amount of sulfide, still can cause larger pollution to environment.
Depilation liming liquid direct circulation method is that direct reuse is in the depilation operation after the depilation liming waste liquid being reclaimed and replenishes the depilation material, and the advantage of the method is that sulfide and lime can be utilized effectively, can be to environment.Can constantly increase but the shortcoming of the method is salt and the protein content of depilatory solution in circulation, thereby make the process stabilizing performance poor, quality product is affected, so cycle index is very limited, needs regularly discharging, still can cause larger pollution to environment.
Depilation liming liquid indirect cycle method is to use acid that the sulfide in the depilation waste liquor is transformed into hydrogen sulfide, after absorbing, stink damp body and function alkali generates sulfide, be used further to the operation of losing hair or feathers, can make protein precipitation out, the COD content in the decrease waste liquid simultaneously.The advantage of the method is that the sulfide purity that reclaims is high, be back to production and can not impact quality product, and can reduce organic pollution when reclaiming sulfide, but that shortcoming is protein content in the waste liquid is lower, and processing cost is higher.
Summary of the invention
The purpose of this invention is to provide the depilation of a kind of guarantor's hair and liming waste liquor recycling method, the method combines protects a hair epilation, Lime Liquor direct circulation method and indirect cycle method, has given full play to protect advantage, the Lime Liquor direct circulation method that the hair epilation can reduce Organic pollutants and can save the advantage of depilation material and the advantage that Lime Liquor indirect cycle method can reclaim sodium sulphite and protein.
In the method for the invention, after wet salted hide is processed through pre-immersion, fleshing, immersion first, protect hair depilation and a liming, collect the depilation liming waste liquid, be back to a liming stage of protecting the hair depilation after removing solid substance, waste liquid after the reuse 1～5 time re-uses acid and processes, generate hydrogen sulfide and use the sodium hydroxide absorption to obtain sodium sulphite, be back to and protect the hair depilation, and the waste liquid that will reclaim behind the sodium sulphite filters, the clear liquid behind the protein precipitation is removed in collection, and it is back to pre-soaking process.
Method of the present invention comprises following four-stage:
Pre-immersion, fleshing and immersion stage: contain a large amount of salt in the wet salted hide, and sanitas and dirt, the purpose of pre-immersion is to remove salt, sanitas and dirt, and makes the rawhide suction, tentatively returns to the fresh hide state.Fleshing is in the meat of removing on the rawhide, and rawhide is eased back.Immersion is further to make the rawhide suction, returns to the fresh hide state, is convenient to the infiltration of follow-up depilation liming material.
Protect the hair depilation stage: use first organosulfur depilation material that rawhide is processed, because the depilation ability of organosulfur depilation material is more limited, therefore can only act on the hair root position, poor to the destructiveness of hair shaft.Add again the pH value that improves body lotion behind the lime, hair root is damaged and hair is come off, remove hair by filter method, replenish again sodium sulphite and lime, with the hair removal of remnants, and carry out liming.
The depilation liming waste liquid direct circulation stage: collect the depilation liming waste liquid, after use air supporting or intermediate processing are removed throw out, waste liquid is back to the moisturizing liming stage of depilation liming.
The depilation liming waste liquid indirect cycle stage: collect the waste liquid behind the direct circulation 1～5 time, add about acid for adjusting pH value to 3～6, make sodium sulphite be converted into hydrogen sulfide, and use pneumatic blending and take hydrogen sulfide out of, re-using sodium hydroxide absorbs, regenerate sodium sulphite, be back to depilation liming after the purity of analysis recovery sodium sulphite.To reclaim the waste liquid press filtration of sodium sulphite, the clear liquid that will remove again behind the protein precipitation is back to the pre-immersion stage.
Particularly, the present invention includes the content of the following aspects:
1, the depilation of a kind of guarantor's hair and liming waste liquor recycling method is characterized in that may further comprise the steps:
(1) pre-immersion, fleshing and immersion: water is soaked in advance to the ox wet salted hide, and fleshing after control is done re-uses water rawhide is soaked, and control is done;
(2) protect the hair depilation: in rotary drum, use first organosulfur depilation material that rawhide is processed, add again lime treatment hair is come off, and remove hair by filter method;
(3) liming: add sodium sulphite, lime and water and carry out the liming processing;
(4) Lime Liquor direct circulation: collect Lime Liquor in (3), replace water to be back in the step (3) behind the removal solid substance impurity;
(5) Lime Liquor indirect cycle: collect the waste liquid behind the direct circulation 1～5 time, after removing solid substance impurity, adding acid makes the sodium sulphite in the waste liquid be converted into hydrogen sulfide and makes simultaneously protein precipitation out, use the sodium hydroxide absorbing hydrogen sulphide, regenerate sodium sulphite and be back in the step (3), remaining waste liquid replaces water to be back in the pre-immersion of step (1) after removing protein precipitation.
2, such as 1 depilation of described guarantor's hair and liming waste liquor recycling method, it is characterized in that may further comprise the steps:
(1) weigh: the ox wet salted hide is weighed, as following materials foundation;
(2) pre-immersion: skin is added in the rotary drum, add entry 200～300wt%, rotary drum turns and stops in conjunction with 6～12 hours, and control is done;
(3) fleshing: remove in the meat;
(4) immersion: skin is added in the rotary drum, add entry 200～300wt%, rotary drum turns and stops in conjunction with 12～24 hours, and control is done;
(5) protect the hair depilation: add entry 100～200wt%, organosulfur depilation material 1～3wt%, rotated 1 hour, add lime 1～2wt%, rotate beginning body lotion circulating filtration defeathering after 30 minutes, defeathering stops the body lotion circulation after 1 hour;
(6) liming: add 1.5～3.0wt% sodium sulphite, 1～2wt% lime and 100～200wt% water and carry out the liming processing, turn and stop totally 15～20 hours;
(7) Lime Liquor direct circulation: collect the Lime Liquor in the step (6), replace water to be back in the step (6) behind the removal solid substance impurity;
(8) Lime Liquor indirect cycle: collect the waste liquid behind the direct circulation 1～5 time, acid adding behind the removal solid substance impurity, regulating body lotion pH value is 3～6, make sodium sulphite in the waste liquid be converted into hydrogen sulfide and make simultaneously protein precipitation out, absorb the hydrogen sulfide that generates with sodium hydroxide, regenerate sodium sulphite and be back in the step (6), remaining waste liquid replaces water to be back in the pre-immersion of step (2) after removing protein precipitation.
3, such as 1 or 2 method, one or more in described organosulfur depilation material selected from mercapto ethanol, Thioglycolic acid sodium salt and the formamidine sulfinic acid.
4, such as 1 or 2 method, described acid is selected from one or more in sulfuric acid, hydrochloric acid and the nitric acid.
Use first the organosulfur depilation material with week reduction energy to replace the sulfide of strong reducing property that rawhide is processed in present method, can prevent that hair shaft is damaged, after organosulfur depilation material penetrates sufficiently into hair root, add lime and improve the pH value, depilation occurs in high pH value in organosulfur depilation material, destroy hair root, whole of hair is come off, realize protecting the hair depilation.Use organosulfur depilation material to replace having the sodium sulphite of strong depilation ability or the destruction that Sodium sulfhydrate can effectively prevent hair, improve the rate of recovery of hair, further reduce the organic content in the waste liquid.
The hair rear use filter plant that comes off in the rotary drum, then the hair in the filtering water adds depilation material sodium sulphite and lime, makes remaining mao thoroughly to take off, and finishes the liming effect.
Contain a large amount of sodium sulphite and lime in the waste liquid after liming finishes, present method is back to the liming stage with after its collection and removing solid substance impurity, on the one hand can Partial Replacement water, and water saving; Can take full advantage of on the other hand residual sodium sulphite and lime in the waste liquid, save chemical materials, and can prevent that pollutent from entering in the waste water.
Behind the Lime Liquor direct circulation 1～5 time, because the impurity such as calcium ion increase, can affect the depilation liming effect if circulate again, therefore present method will circulate and carry out the acid adding processing after Lime Liquor after 1～5 time is collected, make sodium sulphite wherein be converted into the hydrogen sulfide effusion, re-use sodium hydroxide and absorb, regenerate sodium sulfide solution, can replace that employed sodium sulphite is back to production in the liming process.The body lotion pH value of controlling simultaneously after the acid adding is 3～6, makes protein precipitation out, uses plate-and-frame filter press filtering protein precipitation, filtrate is replaced water to be back to the pre-immersion stage again, can save the process hides water, realizes the recycle to extinction of waste water.
Present method is to process recovery sodium sulphite after Lime Liquor circulation 1～5 time again, this is because if all carry out each time manipulation of regeneration, protein mass in the waste liquid is few on the one hand, the cost that reclaims on the other hand can be higher, therefore first direct circulation is 1～5 time, add again acid recovery sodium sulphite, can realize higher economic worth, and it is also very thorough to clean effect.The concrete number of times of direct circulation depends on Lime Liquor direct circulation process to the impact of quality product, if impact is few, cycle index can be more, if circulating effect is large, cycle index can be lacked.
Present method has been combined with protects hair epilation, Lime Liquor direct circulation method and Lime Liquor indirect cycle method, has the following advantages:
1, uses organosulfur depilation material to protect the hair depilation, compare with using sulfide, have advantages of that the hair shape that comes off is complete, organic content is low in the waste liquid;
2, the direct circulation number of times of Lime Liquor is 1～5 time, can prevent that traditional direct circulation method is on the impact of quality product;
3, behind the Lime Liquor direct circulation 1～5 time, add acid treatment, the sodium sulphite that reclaims wherein is used for the liming stage, and after filtering the protein precipitation of removing in the waste liquid, is back to the pre-immersion stage.The sodium sulphite that reclaims is purer, is back to liming and can impact quality product; Although contain a large amount of calcium ions in the clear liquid after the processing, be used for pre-soaking process, can not impact production, can realize the recycle to extinction of depilation liming waste liquid.
4, present method had both kept the advantage of protecting hair depilating method, Lime Liquor direct circulation method and liming liquid indirect cycle method, had overcome simultaneously guarantor's hair epilation and had cleaned the shortcoming that effect is limited, the direct circulation method affects quality product, indirect cycle method cost is high.
Description of drawings
Fig. 1 provides the schema that specifically utilizes method of the present invention.
Specific implementation method
The present invention is further illustrated below in conjunction with embodiment.
Embodiment 1
(1) weigh: the ox wet salted hide is weighed, as following materials foundation;
(2) pre-immersion: water 300wt%, rotary drum turn and stop in conjunction with 8 hours, and control is done;
(3) fleshing: remove in the meat;
(4) immersion: water 200wt%, rotary drum turn and stop in conjunction with 18 hours, and control is done;
(5) protect hair depilation, liming: water 150wt%, Thioglycolic acid sodium salt 2%, rotated 1 hour, and added lime 1%, rotate beginning body lotion circulating filtration defeathering after 30 minutes, defeathering stops the body lotion circulation after 1 hour, add 2% sodium sulphite, 2% lime and 100% water and carry out the liming processing, turn and stop totally 15 hours, graywall goes out drum, collect Lime Liquor, remove by filter solid substance impurity, stand-by.
Embodiment 2
(1) weigh: the ox wet salted hide is weighed, as following materials foundation;
(2) pre-immersion: water 250wt%, rotary drum turn and stop in conjunction with 10 hours, and control is done;
(3) fleshing: remove in the meat;
(4) immersion: water 250wt%, rotary drum turn and stop in conjunction with 20 hours, and control is done;
(5) protect hair depilation, liming: water 150wt%, mercaptoethanol 1.5%, rotated 1 hour, and added lime 1.5%, rotate beginning body lotion circulating filtration defeathering after 30 minutes, defeathering stops the body lotion circulation after 1 hour, the Lime Liquor that adds among 1% sodium sulphite, 1% lime and 100% embodiment 1 carries out the liming processing, turns and stops totally 18 hours, and graywall goes out drum, collect Lime Liquor, remove by filter solid substance impurity, stand-by.
Embodiment 3
(1) weigh: the ox wet salted hide is weighed, as following materials foundation;
(2) pre-immersion: water 250wt%, rotary drum turn and stop in conjunction with 10 hours, and control is done;
(3) fleshing: remove in the meat;
(4) immersion: water 250wt%, rotary drum turn and stop in conjunction with 20 hours, and control is done;
(5) protect hair depilation, liming: water 150wt%, mercaptoethanol 1.5%, rotated 1 hour, and added lime 1.5%, rotate beginning body lotion circulating filtration defeathering after 30 minutes, defeathering stops the body lotion circulation after 1 hour, the Lime Liquor that adds among 1% sodium sulphite, 1% lime and 100% embodiment 1 carries out the liming processing, turns and stops totally 18 hours, and graywall goes out drum, collect Lime Liquor, remove by filter solid substance impurity.
(6) the moisturizing stage during the liming that Lime Liquor of collecting in (5) is back to the next batch skin for the 2nd time is processed regathers Lime Liquor, removes by filter solid substance impurity.
(7) the moisturizing stage during the liming that Lime Liquor of collecting in (6) is back to the next batch skin for the 3rd time is processed regathers Lime Liquor, removes by filter solid substance impurity, stand-by.
Embodiment 4
The Lime Liquor of the recycle in embodiment 2 and 3 is added in the encloses container, pump into sulfuric acid, regulate the pH value to 4 in the waste liquid, and pass into air and stir, the hydrogen sulfide of generation is overflowed, in spray column, use again sodium hydroxide to absorb, regenerate sodium sulfide solution, after analyzing content, stand-by.
Use plate-and-frame filter press that the waste liquid after processing is carried out press filtration, collect filtrate, stand-by.
Embodiment 5
(1) weigh: the ox wet salted hide is weighed, as following materials foundation;
(2) pre-immersion: the filtrate 300wt% of embodiment 4, rotary drum turn and stop in conjunction with 12 hours, and control is done;
(3) fleshing: remove in the meat;
(4) immersion: water 200wt%, rotary drum turn and stop in conjunction with 16 hours, and control is done;
(5) protect hair depilation, liming: water 150wt%, formamidine sulfinic acid 2.5% was rotated 1 hour, added lime 2%, rotate beginning body lotion circulating filtration defeathering after 30 minutes, defeathering stops the body lotion circulation after 1 hour, the Lime Liquor that adds among 1% sodium sulphite, 1% lime and 100% embodiment 1 carries out the liming processing, turns and stops totally 18 hours, graywall goes out drum, collect Lime Liquor, filter, be used for the recovery sodium sulphite of embodiment 4.
Claims (4)
1. protect hair depilation and liming waste liquor recycling method for one kind, it is characterized in that may further comprise the steps:
(1) pre-immersion, fleshing and immersion: water is soaked in advance to the ox wet salted hide, and fleshing after control is done re-uses water rawhide is soaked, and control is done;
(2) protect the hair depilation: in rotary drum, use first organosulfur depilation material that rawhide is processed, add again lime treatment hair is come off, and remove hair by filter method;
(3) liming: add sodium sulphite, lime and water and carry out the liming processing;
(4) Lime Liquor direct circulation: collect Lime Liquor in (3), replace water to be back in the step (3) behind the removal solid substance impurity;
(5) Lime Liquor indirect cycle: collect the waste liquid behind the direct circulation 1～5 time, after removing solid substance impurity, adding acid makes the sodium sulphite in the waste liquid be converted into hydrogen sulfide and makes simultaneously protein precipitation out, use the sodium hydroxide absorbing hydrogen sulphide, regenerate sodium sulphite and be back in the step (3), remaining waste liquid replaces water to be back in the pre-immersion of step (1) after removing protein precipitation.
2. guarantor's hair as claimed in claim 1 loses hair or feathers and liming waste liquor recycling method, it is characterized in that may further comprise the steps:
(1) weigh: the ox wet salted hide is weighed, as following materials foundation;
(2) pre-immersion: skin is added in the rotary drum, add entry 200～300wt%, rotary drum turns and stops in conjunction with 6～12 hours, and control is done;
(3) fleshing: remove in the meat;
(4) immersion: skin is added in the rotary drum, add entry 200～300wt%, rotary drum turns and stops in conjunction with 12～24 hours, and control is done;
(5) protect the hair depilation: add entry 100～200wt%, organosulfur depilation material 1～3wt%, rotated 1 hour, add lime 1～2wt%, rotate beginning body lotion circulating filtration defeathering after 30 minutes, defeathering stops the body lotion circulation after 1 hour;
(6) liming: add 1.5～3.0wt% sodium sulphite, 1～2wt% lime and 100～200wt% water and carry out the liming processing, turn and stop totally 15～20 hours;
(7) Lime Liquor direct circulation: collect the Lime Liquor in the step (6), replace water to be back in the step (6) behind the removal solid substance impurity;
(8) Lime Liquor indirect cycle: collect the waste liquid behind the direct circulation 1～5 time, acid adding behind the removal solid substance impurity, regulating body lotion pH value is 3～6, make sodium sulphite in the waste liquid be converted into hydrogen sulfide and make simultaneously protein precipitation out, absorb the hydrogen sulfide that generates with sodium hydroxide, regenerate sodium sulphite and be back in the step (6), remaining waste liquid replaces water to be back in the pre-immersion of step (2) after removing protein precipitation.
3. such as the method for claim 1 or 2, one or more in described organosulfur depilation material selected from mercapto ethanol, Thioglycolic acid sodium salt and the formamidine sulfinic acid.
4. such as the method for claim 1 or 2, described acid is selected from one or more in sulfuric acid, hydrochloric acid and the nitric acid.
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| CN2011103218527A CN102505056B (en) | 2011-10-21 | 2011-10-21 | Hair-protection unhairing and liming waste liquor recycling method |
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| CN2011103218527A CN102505056B (en) | 2011-10-21 | 2011-10-21 | Hair-protection unhairing and liming waste liquor recycling method |
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| CN102505056A CN102505056A (en) | 2012-06-20 |
| CN102505056B true CN102505056B (en) | 2013-10-16 |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104611480A (en) * | 2015-01-16 | 2015-05-13 | 峰安皮业股份有限公司 | Method for recycling tanning liming liquid waste |
| CN107619887A (en) * | 2017-11-06 | 2018-01-23 | 宁夏金海皮业有限责任公司 | A kind of method for leather-making for protecting hair depilation |
| CN110358874A (en) * | 2018-04-09 | 2019-10-22 | 徐州鸿丰高分子材料有限公司 | Hair-protection and hair-removing composition preparation and its guarantor's hair depilating method |
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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 |
| CN101445843A (en) * | 2008-12-30 | 2009-06-03 | 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 |
| WO2010070571A2 (en) * | 2008-12-17 | 2010-06-24 | Asociacion De Investigacion De Las Industrias Del Curtido Y Anexas | Procedure for the tanning of skins, material obtained during said procedure and device |
| CN101798604A (en) * | 2010-02-10 | 2010-08-11 | 广东省石油化工研究院 | Method for preparing leather through hair-saving unhairing |
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2011
- 2011-10-21 CN CN2011103218527A patent/CN102505056B/en not_active Expired - Fee Related
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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 |
| WO2010070571A2 (en) * | 2008-12-17 | 2010-06-24 | Asociacion De Investigacion De Las Industrias Del Curtido Y Anexas | Procedure for the tanning of skins, material obtained during said procedure and device |
| CN101445843A (en) * | 2008-12-30 | 2009-06-03 | 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 |
| CN101798604A (en) * | 2010-02-10 | 2010-08-11 | 广东省石油化工研究院 | Method for preparing leather through hair-saving unhairing |
Non-Patent Citations (2)
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| 朱荣基等.制革废液中硫化物处理的实验研究.《皮革科技动态》.1979,(第06期),第1-6、58页. |
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