CN102041321A - Leather manufacturing process by pickling and tanning salt-free and chrome-free recycled waste liquid - Google Patents
Leather manufacturing process by pickling and tanning salt-free and chrome-free recycled waste liquid Download PDFInfo
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- CN102041321A CN102041321A CN2010106165442A CN201010616544A CN102041321A CN 102041321 A CN102041321 A CN 102041321A CN 2010106165442 A CN2010106165442 A CN 2010106165442A CN 201010616544 A CN201010616544 A CN 201010616544A CN 102041321 A CN102041321 A CN 102041321A
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- waste liquid
- tanning
- changeed
- pickling
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- 239000007788 liquid Substances 0.000 title claims abstract description 53
- 239000002699 waste material Substances 0.000 title claims abstract description 49
- 238000005554 pickling Methods 0.000 title claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 8
- 239000010985 leather Substances 0.000 title abstract description 14
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 28
- 150000003839 salts Chemical class 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 16
- 239000000126 substance Substances 0.000 claims abstract description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 22
- 239000011651 chromium Substances 0.000 claims description 16
- 238000005516 engineering process Methods 0.000 claims description 16
- 229910052804 chromium Inorganic materials 0.000 claims description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 239000003112 inhibitor Substances 0.000 claims description 7
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 6
- 235000019253 formic acid Nutrition 0.000 claims description 6
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 6
- 239000011707 mineral Substances 0.000 claims description 6
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 150000007524 organic acids Chemical class 0.000 claims description 4
- 239000001648 tannin Substances 0.000 claims description 4
- 235000018553 tannin Nutrition 0.000 claims description 4
- 229920001864 tannin Polymers 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- 240000007594 Oryza sativa Species 0.000 claims description 2
- 235000007164 Oryza sativa Nutrition 0.000 claims description 2
- 230000009286 beneficial effect Effects 0.000 claims description 2
- 230000000694 effects Effects 0.000 claims description 2
- 230000008030 elimination Effects 0.000 claims description 2
- 238000003379 elimination reaction Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 235000009566 rice Nutrition 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000002474 experimental method Methods 0.000 claims 1
- 238000001914 filtration Methods 0.000 claims 1
- 230000005764 inhibitory process Effects 0.000 claims 1
- 230000003247 decreasing effect Effects 0.000 abstract 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 240000005373 Panax quinquefolius Species 0.000 description 1
- QRRWWGNBSQSBAM-UHFFFAOYSA-N alumane;chromium Chemical compound [AlH3].[Cr] QRRWWGNBSQSBAM-UHFFFAOYSA-N 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Landscapes
- Treatment And Processing Of Natural Fur Or Leather (AREA)
Abstract
The invention provides a leather manufacturing process by pickling and tanning a salt-free and chrome-free recycled waste liquid. The process is characterized in that no chrome is used in the tanning process, thus the problem of chrome pollution is solved thoroughly; all the chrome tanning-free waste liquid is recycled, thus zero discharge of chrome tanning-free waste liquid is realized; and the process is suitable for the existing large production process of leather factories. In addition, no salt is added in the pickling process, a large amount of salt and other related chemical materials can be saved, wherein the salt can be saved by 100%, and the other related chemical materials can be saved by 40%-60%, and the energy can be saved by 25% approximately. Each performance index of the finished leather manufactured by the process meets the requirements, the rate of loose surface of the finished leather is decreased effectively, and the compactness of the finished leather is improved.
Description
Technical field
The invention belongs to and make full use of the green circulation technology that starting material reduce disposal of pollutants in the leather production technical field, release the leather-making technology that a kind of recycle in indefinitely waste liquid that does not have salt chromium carries out pickling, tanning herein.
Background technology
Chrome tanning is in dominant position because of its remarkable performance always in the process hides tannery, chromic salts is used for the history in existing more than 100 year of leather production as tanning agent.Because the leather that it is tanned has many good qualities, as finished leather shrinkage temperature height, anti-storage, chemical stability is good, flexibility, good-extensibility, so chromic salts is a preferred materials of making light leather, in tanning industry, be widely adopted, be used for the chrome tanning agent of process hides every year above 400,000 tons at present.But Cr
6+Be strong carcinogen, Cr
3+Biology is caused bigger toxicity, and therefore, along with the attention of countries in the world to environmental protection work, many countries have all progressively formulated the emission standard of strict industrial wastewater pollution thing, and strict restriction has been done in the discharging of chromium cpd.And chromium is non-renewable scarce resource, and chromium metal is maximum at the reserves in South Africa, also only enough exploit the centuries, and chromium is used in the course of processing of process hides and accounts for 1/3 of turnout, and have 1/3 along with sewage has been discharged in the process hides course of processing.
Because chromium resource lacks, and environmental pollution is serious, people are seeking not have chromic tanning always, therefore, reduce the chromic salts consumption, replace chromic salts with other materials, no chrome tanning technology, no chrome tanning waste liquid cycling and reutilization technology etc. has become the problem of various countries' leather industry primary study.
Generally adopt few chromium in conjunction with tanning in many developed countries at present, in conjunction with tanning, rare earth-chromium is in conjunction with tanning as aluminium chromium, and resin-chromium is in conjunction with tanning etc.These methods all can obviously reduce the consumption of chromium, but thoroughly do not solve pollution of chromium, also do not solve pollution, the emission problem of tanning waste water.
Summary of the invention
Purpose of the present invention: recycle no chrome tanning waste liquid indefinitely; outside removing the normal volatilization under the state of nature and inevitably spilling; the rate of recovery of no chrome tanning waste liquid can reach 100%; thoroughly eradicated the pollution of chromium problem; and the existing big technological process of production of suitable process hides producer, a large amount of simultaneously salt and other relevant chemical materials saved are saved salt 100%; save other associated materials 40%-60%, save energy about 25%.The finished product of Sheng Chaning is removed from office every performance index and is all reached requirement thus, and effectively reduces finished leather loose side rate, has improved the degree of packing of finished leather.
For achieving the above object, technical scheme of the present invention is as follows:
On pickling, tanning rotary drum side pickling, tanning waste liquid liquid storage tank is set, this pond preferably is deep to underground 2-8 rice and is beneficial to temperature control, and preferably standby pool is arranged.From entering the waste liquid liquid storage tank behind the solid substance in the waste liquid elimination waste liquid of pickling, tanning operation, after cooling, to 0.3-5.0, stir, to be ready for use on down the pickling, tanning of batch skin with sour pH value of regulating waste liquid.Utilize no chrome tanning waste liquid to carry out pickled technology to be: in graywall weight, the add-on of salt is zero, also can add a small amount of (0%-5%) salt or other has the material that suppresses the swollen effect of acid, 0%-5% salt, the 3%-100% waste liquid, the 0.05%-0.3% mould inhibitor changeed 5-30 minute; 0%-2.0% formic acid or acetic acid or other organic acid changeed 5-40 minute; 0%-3.5% sulfuric acid or hydrochloric acid or other mineral acid are divided two to ten addings equally, each 5-15 minute at interval, change 40-120 minute; The 0%-1.0% fatting agent changeed about 30 minutes, stopped 0.5-2 hour.Also but adjusting process is: 0%-5% salt, and the 0.05%-0.3% mould inhibitor changeed 5-30 minute; 0%-2.0% sulfuric acid or hydrochloric acid or other mineral acid changeed 5-20 minute; The 3%-100% waste liquid changeed 5-20 minute; 0%-2.0% formic acid or acetic acid or other organic acid changeed 5-40 minute; 0%-2.0% sulfuric acid or hydrochloric acid or other mineral acid are divided two to ten addings equally, each 5-15 minute at interval, change 40-120 minute; The 0%-1.0% fatting agent changeed about 30 minutes, stopped 0.5-2 hour.Carry out tanning then, technology is: the 3%-100% waste liquid, be warming up in the drum 25 ℃-50 ℃ (add rotary drum after waste liquid heated again or earlier waste liquid is added in the rotary drum whole again heat up all can), the 0.1%-3.0% glutaraldehyde, the white tannin of 1.0%-8.0% changeed 3-4 hour, stopped drum and spent the night, or per hour changeed 1-5 minute, spend the night.
This such scheme, waste liquid divide two portions to use, and a part is used in the pickling initial stage, and a part is used in the tanning temperature rise period.The consumption of various chemical materials and kind, waste liquid consumption, heating and cooling amplitude, operating time, working order etc. all can be made significantly according to user's particular case and adjusting.Also can select other chemical material to substitute above-mentioned materials according to user's particular case.The percentage ratio of used chemical materials is in the weight of graywall.
Embodiment
Below by example the present invention is carried out concrete description and further instruction.
Embodiment 1
With sulfuric acid the pH value of waste liquid is transferred to 0.9, carry out pickling, tanning then, the consumption of salt is zero in the pickling process, and technology is: 90% waste liquid, and 0.2% mould inhibitor changeed 10 minutes; 0.4% formic acid changeed 20 minutes; 0.5% sulfuric acid is divided three addings equally, each 10 minutes at interval, changes 90 minutes; 0.2% fatting agent changeed 30 minutes, stopped 2 hours; 60% waste liquid is warming up to 30 ℃, 1.0% glutaraldehyde, and 5.0% white tannin changeed 3 hours, stopped drum and spent the night.
Embodiment 2
With sulfuric acid the pH value of waste liquid is transferred to 1.2, carry out pickling, tanning then, technology is: 4% salt, and 0.15% mould inhibitor changeed 10 minutes; 0.3% sulfuric acid changeed 10 minutes; 70% waste liquid changeed 10 minutes; 0.5% formic acid changeed 20 minutes; 0.3% sulfuric acid is divided three addings equally, each 10 minutes at interval, changes 90 minutes; Stopped 2 hours; 60% waste liquid is warming up to 30 ℃, 1.0% glutaraldehyde, and 5.0% white tannin changeed 3 hours, stopped drum and spent the night.
Under the situation that does not break away from spirit of the present invention or substantive features, can implement the present invention with other form, with reference to claim but not above-mentioned specification sheets, as indication scope of the present invention.
Claims (10)
- A kind of recycle in indefinitely waste liquid that does not have salt chromium carries out the leather-making technology of pickling, tanning, and its feature is as follows:1. on pickling, tanning rotary drum side pickling, tanning waste liquid liquid storage tank is set, this pond preferably is deep to underground 2-8 rice and is beneficial to temperature control, and preferably standby pool is arranged.From entering the waste liquid liquid storage tank behind the solid substance in the waste liquid elimination waste liquid of pickling, tanning operation, after cooling, to 0.3-5.0, stir, to be ready for use on down the pickling, tanning of batch skin with sour pH value of regulating waste liquid.Utilize no chrome tanning waste liquid to carry out pickled technology to be: in graywall weight, the add-on of salt is zero, also can add a small amount of (0%-5%) salt or other has the material that suppresses the swollen effect of acid, 0%-5% salt, the 3%-100% waste liquid, the 0.05%-0.3% mould inhibitor changeed 5-30 minute; 0%-2.0% formic acid or acetic acid or other organic acid changeed 5-40 minute; 0%-3.5% sulfuric acid or hydrochloric acid or other mineral acid are divided two to ten addings equally, each 5-15 minute at interval, change 40-120 minute; The 0%-1.0% fatting agent changeed about 30 minutes, stopped 0.5-2 hour.Also but adjusting process is: 0%-5% salt, and the 0.05%-0.3% mould inhibitor changeed 5-30 minute; 0%-2.0% sulfuric acid or hydrochloric acid or other mineral acid changeed 5-20 minute; The 3%-100% waste liquid changeed 5-20 minute; 0%-2.0% formic acid or acetic acid or other organic acid changeed 5-40 minute; 0%-2.0% sulfuric acid or hydrochloric acid or other mineral acid are divided two to ten addings equally, each 5-15 minute at interval, change 40-120 minute; The 0%-1.0% fatting agent changeed about 30 minutes, stopped 0.5-2 hour.Carry out tanning then, technology is: the 3%-100% waste liquid, be warming up in the drum 25 ℃-50 ℃ (add rotary drum after waste liquid heated again or earlier waste liquid is added in the rotary drum whole again heat up all can), the 0.1%-3.0% glutaraldehyde, the white tannin of 1.0%-8.0% changeed 3-4 hour, stopped drum and spent the night, or per hour changeed 1-5 minute, spend the night.
- 2. experiment showed, that through nearly 1 year big production this waste liquid circulating technology is fit to the existing big technological process of production of tannery.
- 3. recycle no chrome tanning waste liquid indefinitely and carry out pickling, tanning, when carrying out continuing to recycle behind press filtration, the slagging-off supervisor after circulation for some time.
- 4. should regularly detect the microbe population in the waste liquid, generally circulate and detect once for three to five times, mainly detect mould quantity, determine the consumption of mould inhibitor according to detected result.
- 5. waste liquid divides two portions to use, and a part is used in the pickling initial stage in the right 1, a part be used in tanning temperature rise period in the right 1 (add rotary drum again after waste liquid heated or earlier waste liquid is added in the drum whole again heat up all can).
- 6. in the pickling process, the add-on of salt is 0, also can add a small amount of (0%-5%) salt or other material that has inhibition acid to swell and act on.
- 7. tannery is without chromium, and this technology is a kind of no chrome tanning waste liquid circulating technology.
- 8. the consumption of the various chemical materials in the right 1 and kind, waste liquid consumption, heating and cooling amplitude, operating time, working order etc. all can be made significantly according to user's particular case and adjusting, and also can select other chemical material to substitute above-mentioned materials according to user's particular case.
- 9. the percentage ratio in the right 1 is in the weight of graywall.
- 10. the pH value that recycles no chrome tanning waste liquid can be controlled between the 0.3-5.0.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010616544.2A CN102041321B (en) | 2010-12-24 | 2010-12-24 | Leather manufacturing process by pickling and tanning salt-free and chrome-free recycled waste liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010616544.2A CN102041321B (en) | 2010-12-24 | 2010-12-24 | Leather manufacturing process by pickling and tanning salt-free and chrome-free recycled waste liquid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102041321A true CN102041321A (en) | 2011-05-04 |
| CN102041321B CN102041321B (en) | 2014-05-28 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201010616544.2A Active CN102041321B (en) | 2010-12-24 | 2010-12-24 | Leather manufacturing process by pickling and tanning salt-free and chrome-free recycled waste liquid |
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| Country | Link |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102312023A (en) * | 2011-08-11 | 2012-01-11 | 温州伟硕皮业有限公司 | Secondary recycling method of pigskin chrome-free combination tannage waste liquid |
| CN102505057A (en) * | 2011-10-21 | 2012-06-20 | 中国皮革和制鞋工业研究院 | Cyclic utilization method of chrome tanning waste liquid |
| CN103525955A (en) * | 2013-04-18 | 2014-01-22 | 张壮斗 | Tanning waste liquor stepwise recycling process with good effects |
| CN103981301A (en) * | 2014-06-06 | 2014-08-13 | 张壮斗 | Tanning technique for regularly filtering pickling and tanning circulating wastewater |
| WO2015081624A1 (en) * | 2013-12-04 | 2015-06-11 | 张壮斗 | Tanning process |
| CN104962667A (en) * | 2015-06-23 | 2015-10-07 | 兴业皮革科技股份有限公司 | Quick producing process for pure vegetable tanning cattle leather |
| CN114231673A (en) * | 2021-11-10 | 2022-03-25 | 中牛集团有限公司 | Salt-free and chromium-free tanning process for pickling and tanning by utilizing waste liquid |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4217104A (en) * | 1977-02-04 | 1980-08-12 | Dr. Th. Bohme, Chem. Fabrik GmbH & Co. | Process for the production of fur skins |
| RU2147611C1 (en) * | 1998-07-08 | 2000-04-20 | Гармашов Валерий Иванович | Method of manufacturing fur and skin stocks |
| CN1302909A (en) * | 2000-08-15 | 2001-07-11 | 肖体平 | Process for tanning skin of highland schizothoracin and grass carp |
| KR100719481B1 (en) * | 2006-02-06 | 2007-05-18 | 한국신발피혁연구소 | Preparation method of anion degreasing agent using the lard oil |
-
2010
- 2010-12-24 CN CN201010616544.2A patent/CN102041321B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4217104A (en) * | 1977-02-04 | 1980-08-12 | Dr. Th. Bohme, Chem. Fabrik GmbH & Co. | Process for the production of fur skins |
| RU2147611C1 (en) * | 1998-07-08 | 2000-04-20 | Гармашов Валерий Иванович | Method of manufacturing fur and skin stocks |
| CN1302909A (en) * | 2000-08-15 | 2001-07-11 | 肖体平 | Process for tanning skin of highland schizothoracin and grass carp |
| KR100719481B1 (en) * | 2006-02-06 | 2007-05-18 | 한국신발피혁연구소 | Preparation method of anion degreasing agent using the lard oil |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102312023A (en) * | 2011-08-11 | 2012-01-11 | 温州伟硕皮业有限公司 | Secondary recycling method of pigskin chrome-free combination tannage waste liquid |
| CN102505057A (en) * | 2011-10-21 | 2012-06-20 | 中国皮革和制鞋工业研究院 | Cyclic utilization method of chrome tanning waste liquid |
| CN103525955A (en) * | 2013-04-18 | 2014-01-22 | 张壮斗 | Tanning waste liquor stepwise recycling process with good effects |
| WO2014169564A1 (en) * | 2013-04-18 | 2014-10-23 | Zhang Zhuangdou | Tannery waste liquid step-by-step recycling process having improved effect |
| WO2015081624A1 (en) * | 2013-12-04 | 2015-06-11 | 张壮斗 | Tanning process |
| CN103981301A (en) * | 2014-06-06 | 2014-08-13 | 张壮斗 | Tanning technique for regularly filtering pickling and tanning circulating wastewater |
| CN104962667A (en) * | 2015-06-23 | 2015-10-07 | 兴业皮革科技股份有限公司 | Quick producing process for pure vegetable tanning cattle leather |
| CN114231673A (en) * | 2021-11-10 | 2022-03-25 | 中牛集团有限公司 | Salt-free and chromium-free tanning process for pickling and tanning by utilizing waste liquid |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102041321B (en) | 2014-05-28 |
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Effective date of registration: 20160525 Address after: 476000 No. 6 Changjiang East Road, Shangqiu Development Zone, Henan Patentee after: Baosika (Shangqiu) Chemical Co.,Ltd. Address before: 476000 development zones in Henan province Shangqiu City Star Road and Changjiang Road intersection Patentee before: Zhang Zhuangdou |