CN102041321B - 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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- CN102041321B CN102041321B CN201010616544.2A CN201010616544A CN102041321B CN 102041321 B CN102041321 B CN 102041321B CN 201010616544 A CN201010616544 A CN 201010616544A CN 102041321 B CN102041321 B CN 102041321B
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- waste liquid
- tanning
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- pickling
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- 239000002699 waste material Substances 0.000 title claims abstract description 44
- 239000007788 liquid Substances 0.000 title claims abstract description 42
- 238000005554 pickling Methods 0.000 title claims abstract description 21
- 239000010985 leather Substances 0.000 title abstract description 15
- 238000004519 manufacturing process Methods 0.000 title abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 22
- 150000003839 salts Chemical class 0.000 claims abstract description 18
- 239000000126 substance Substances 0.000 claims abstract description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 22
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 238000005516 engineering process Methods 0.000 claims description 8
- 239000003795 chemical substances by application 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
- 239000002253 acid Substances 0.000 claims description 6
- 235000019253 formic acid Nutrition 0.000 claims description 6
- 239000003112 inhibitor Substances 0.000 claims description 6
- 238000003860 storage Methods 0.000 claims description 5
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 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
- 238000001816 cooling Methods 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 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
- 230000008030 elimination Effects 0.000 claims description 2
- 238000003379 elimination reaction Methods 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
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 abstract description 17
- 239000000463 material Substances 0.000 abstract description 11
- 230000003247 decreasing effect Effects 0.000 abstract 1
- 239000011651 chromium Substances 0.000 description 13
- 229910052804 chromium Inorganic materials 0.000 description 11
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 2
- 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
- 230000000694 effects Effects 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
- 238000010438 heat treatment 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
- 230000001105 regulatory effect Effects 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 the green circulatory technique that makes full use of starting material minimizing disposal of pollutants in leather production technical field, release a kind of infinite circulating without salt chromium herein and utilize waste liquid to carry out the leather-making technology of pickling, tanning.
Background technology
Chrome tanning because of its remarkable performance in process hides tannery always in dominant position, chromic salts is produced the history of existing more than 100 year for leather as tanning agent.The leather of tanning due to it has many good qualities, as high in finished leather shrinkage temperature, resistance to storage, chemical stability is good, flexibility, good-extensibility, and therefore chromic salts is the preferred materials of manufacturing light leather, in tanning industry, be widely adopted, exceed 400,000 tons for the chrome tanning agent of process hides every year at present.But Cr
6+strong carcinogen, Cr
3+biology is caused to larger 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 the discharge of chromium cpd has been done to strict restriction.And chromium is non-renewable scarce resource, 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 in the process hides course of processing, have 1/3 along with sewage has been discharged.
Because chromium resource lacks, and environmental pollution is serious, and people are seeking without chromic tanning always, therefore, reduce chromic salts consumption, replace chromic salts with other materials, without chrome tanning technology, become the problem of various countries' leather industry primary study without chroming waste liquor cycling and reutilization technology etc.
Generally adopt few chromium in conjunction with tanning in many developed countries at present, if aluminium chromium is in conjunction with tanning, rare earth-chromium is in conjunction with tanning, 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
Object of the present invention: infinite circulating uses without chroming waste liquor; outside removing the normal volatilization under state of nature and inevitably spilling; the rate of recovery without chroming waste liquor can reach 100%; thoroughly eradicate pollution of chromium problem; and the existing large technological process of production of applicable process hides producer, a large amount of salt and other relevant chemical materials saved, save salt 100% simultaneously; save other associated materials 40%-60%, save energy 25% left and right.The finished product leather property indices of producing thus all reaches requirement, 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 is preferably deep to underground 2-8 rice and is beneficial to temperature control, and preferably has standby pool.From entering waste liquid liquid storage tank after solid substance in the waste liquid elimination waste liquid of pickling, tanning operation, after cooling,, stir, to be ready for use on down the pickling, tanning of batch skin to 0.3-5.0 by the pH value of acid adjusting waste liquid.Utilize the technique of carrying out pickling without chroming waste liquor to be: with graywall weighing scale, the add-on of salt is zero, also can add a small amount of (0%-5%) salt or other to have the material that suppresses the swollen effect of acid, 0%-5% salt, 3%-100% waste liquid, 0.05%-0.3% mould inhibitor, turns 5-30 minute; 0%-2.0% formic acid or acetic acid or other organic acid, turn 5-40 minute; 0%-3.5% sulfuric acid or hydrochloric acid or other mineral acid, divide two to ten times equally and add, and every minor tick 5-15 minute, turns 40-120 minute; 0%-1.0% fatting agent, turned about 30 minutes, stopped 0.5-2 hour.Also capable of regulating technique is: 0%-5% salt, and 0.05%-0.3% mould inhibitor, turns 5-30 minute; 0%-2.0% sulfuric acid or hydrochloric acid or other mineral acid, turn 5-20 minute; 3%-100% waste liquid, turns 5-20 minute; 0%-2.0% formic acid or acetic acid or other organic acid, turn 5-40 minute; 0%-2.0% sulfuric acid or hydrochloric acid or other mineral acid, divide two to ten times equally and add, and every minor tick 5-15 minute, turns 40-120 minute; 0%-1.0% fatting agent, turned about 30 minutes, stopped 0.5-2 hour.Then carry out tanning, technique is: 3%-100% waste liquid, in drum, be warming up to 25 ℃-50 ℃ (after waste liquid is heated, add again rotary drum or first waste liquid is added in rotary drum again entirety heat up all can), 0.1%-3.0% glutaraldehyde, the white tannin of 1.0%-8.0%, turns 3-4 hour, stops drum and spends the night, or the 1-5 minute that turns per hour, spend the night.
This such scheme, waste liquid divides 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 and adjusting according to user's particular case.Also can select other chemical material to substitute above-mentioned materials according to user's particular case.The percentage ratio of chemical materials used is with the weighing scale of graywall.
Embodiment
Below by example, the present invention is specifically described and further instruction.
Embodiment 1
The pH value of waste liquid is adjusted to 0.9 with sulfuric acid, then carries out pickling, tanning, in pickling process, the consumption of salt is zero, and technique is: 90% waste liquid, and 0.2% mould inhibitor, turns 10 minutes; 0.4% formic acid, turns 20 minutes; 0.5% sulfuric acid, divides three times equally and adds, and every minor tick 10 minutes, turns 90 minutes; 0.2% fatting agent, turns 30 minutes, stops 2 hours; 60% waste liquid, is warming up to 30 ℃, 1.0% glutaraldehyde, and 5.0% white tannin, turns 3 hours, stops drum and spends the night.
Embodiment 2
The pH value of waste liquid is adjusted to 1.2 with sulfuric acid, then carries out pickling, tanning, technique is: 4% salt, and 0.15% mould inhibitor, turns 10 minutes; 0.3% sulfuric acid, turns 10 minutes; 70% waste liquid, turns 10 minutes; 0.5% formic acid, turns 20 minutes; 0.3% sulfuric acid, divides three times equally and adds, and every minor tick 10 minutes, turns 90 minutes; Stop 2 hours; 60% waste liquid, is warming up to 30 ℃, 1.0% glutaraldehyde, and 5.0% white tannin, turns 3 hours, stops drum and spends the night.
In the situation that not departing 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 (3)
1. the recycle waste liquid of a Chrome-free carries out the leather-making technology of pickling, tanning, its feature is as follows: at the other pickling, tanning waste liquid liquid storage tank that arranges of pickling, tanning rotary drum, this pond is deep to underground 2-8 rice and is beneficial to temperature control, and there is standby pool, from entering waste liquid liquid storage tank after solid substance in the waste liquid elimination waste liquid of pickling, tanning operation, after cooling, regulate the pH value of waste liquid to 0.3-5.0 with acid, stir, to be ready for use on down the pickling, tanning of batch skin, the technique that utilization is carried out pickling without chroming waste liquor is: with graywall weighing scale, 0%-5% salt, 3%-100% waste liquid, 0.05%-0.3% mould inhibitor, turn 5-30 minute, 0.4%-2.0% formic acid, turns 5-40 minute, 0%-3.5% sulfuric acid or hydrochloric acid, divide two to ten times equally and add, and every minor tick 5-15 minute, turns 40-120 minute, 0%-1.0% fatting agent, turns 30 minutes, stops 0.5-2 hour, or adjusting process is: 0%-5% salt, and 0.05%-0.3% mould inhibitor, turns 5-30 minute, 0.3%-2.0% sulfuric acid, turns 5-20 minute, 3%-100% waste liquid, turns 5-20 minute, 0%-2.0% formic acid or acetic acid, turn 5-40 minute, 0.3%-2.0% sulfuric acid, divides two to ten times equally and adds, and every minor tick 5-15 minute, turns 40-120 minute, 0%-1.0% fatting agent, turns 30 minutes, stops 0.5-2 hour, then carry out tanning, technique is: 3%-100% waste liquid, waste liquid is heated and add rotary drum again after 25 ℃-50 ℃, or first waste liquid is added in rotary drum entirety to be again warming up to 25 ℃-50 ℃, 0.1%-3.0% glutaraldehyde, the white tannin of 1.0%-8.0%, turn 3-4 hour, stop drum and spend the night, or the 1-5 minute that turns per hour, spend the night.
2. leather-making technology according to claim 1, is characterized in that: waste liquid divide two portions use, a part is used in the pickling initial stage, a part is used in the tanning temperature rise period, after waste liquid is heated, add again rotary drum or first waste liquid is added drum in again entirety heat up all can.
3. leather-making technology according to claim 1, is characterized in that: recycle without the pH value of chroming waste liquor and be controlled between 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 |
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| 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 |
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| Publication Number | Publication Date |
|---|---|
| CN102041321A CN102041321A (en) | 2011-05-04 |
| CN102041321B true CN102041321B (en) | 2014-05-28 |
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|---|---|---|---|
| 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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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102312023B (en) * | 2011-08-11 | 2013-06-12 | 温州伟硕皮业有限公司 | Secondary recycling method of pigskin chrome-free combination tannage waste liquid |
| CN102505057B (en) * | 2011-10-21 | 2013-10-16 | 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 |
| CN104694675A (en) * | 2013-12-04 | 2015-06-10 | 张壮斗 | Novel process for manufacturing leather with simple procedures and equipment |
| CN103981301A (en) * | 2014-06-06 | 2014-08-13 | 张壮斗 | Tanning technique for regularly filtering pickling and tanning circulating wastewater |
| CN104962667B (en) * | 2015-06-23 | 2017-03-08 | 兴业皮革科技股份有限公司 | A kind of quickly pure vegetable tanning cow hide production technology |
| 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 | Manufacturing method of anion degreasing agent using waste pig paper |
-
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 | Manufacturing method of anion degreasing agent using waste pig paper |
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| CN102041321A (en) | 2011-05-04 |
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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 |