CN102234694A - Salt-free leather-making process capable of carrying out acid-picking chrome tannage by indefinitely recycling waste liquid - Google Patents
Salt-free leather-making process capable of carrying out acid-picking chrome tannage by indefinitely recycling waste liquid Download PDFInfo
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- CN102234694A CN102234694A CN2011100093591A CN201110009359A CN102234694A CN 102234694 A CN102234694 A CN 102234694A CN 2011100093591 A CN2011100093591 A CN 2011100093591A CN 201110009359 A CN201110009359 A CN 201110009359A CN 102234694 A CN102234694 A CN 102234694A
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- salt
- chrome
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- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 238000000034 method Methods 0.000 title claims abstract description 20
- 239000002699 waste material Substances 0.000 title claims abstract description 10
- 239000007788 liquid Substances 0.000 title claims abstract description 8
- 238000004064 recycling Methods 0.000 title abstract 2
- 150000003839 salts Chemical class 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 11
- 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 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- 238000005554 pickling Methods 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 12
- 238000005516 engineering process Methods 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 10
- 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
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000003112 inhibitor Substances 0.000 claims description 6
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 6
- 239000011707 mineral Substances 0.000 claims description 6
- 150000007524 organic acids Chemical class 0.000 claims description 4
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 2
- 230000008030 elimination Effects 0.000 claims description 2
- 238000003379 elimination reaction Methods 0.000 claims description 2
- 239000012530 fluid Substances 0.000 claims description 2
- 238000001802 infusion Methods 0.000 claims description 2
- 230000005764 inhibitory process Effects 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 239000011651 chromium Substances 0.000 abstract description 5
- 229910052804 chromium Inorganic materials 0.000 abstract description 3
- 239000003513 alkali Substances 0.000 abstract 1
- 238000000605 extraction Methods 0.000 abstract 1
- 239000000843 powder Substances 0.000 abstract 1
- 239000010985 leather Substances 0.000 description 10
- 239000002351 wastewater Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 241000502561 Acacia irrorata Species 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 240000005373 Panax quinquefolius Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000031018 biological processes and functions Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000012528 membrane 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
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
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- Treatment And Processing Of Natural Fur Or Leather (AREA)
Abstract
The invention provides a salt-free leather-making process capable of carrying out acid-picking chrome tannage by indefinitely recycling a waste liquid. The process is characterized in that salt is not added in the acid-picking process, and all of waste chromium liquids are indefinitely recycled, thereby massively saving chemical materials such as chromium powders, salts, alkali extraction agents and the like; and the indexes, such as shrinkage temperature, fullness and grain surface quality, of prepared wet blue meet national standard requirement.
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 no salt added recycle in indefinitely waste liquid carries out the pickling chrome tanning herein.
Background technology
Now, China has become the leather big producing country that generally acknowledges in the world, and still, developing rapidly of leather industry also caused serious environmental pollution, the wasting of resources and ecological damage.Chrome Tanning Wastewater is that tannery pollutes one of the most serious waste water, be wherein unique heavy metal contamination, but chrome tanning can give leather good performance, is the mainstream technology of leather tanning always, almost can't shake.In the chrome tanning process, the effective rate of utilization of chromium generally has only 60%-70%, and the chromic salts of all the other 30%-40% remains in the waste water, Cr in its useless chrome liquor
2O
3Content is up to 2000mg/L-5000mg/L.The Cr of composite wastewater
2O
3Concentration is also more than 30mg/L.So discharge, not only can cause great pollution, and can produce the great wasting of resources environment with the useless chrome liquor of high-content.
At present, the method of both at home and abroad chromate waste water being handled mainly contains: chemical reduction method, electrolytic process, membrane separation process, absorption method, ion exchange method, biological process etc., height, efficient are low, weak effect can't reach real pollution treatment purpose but its operational process often spends.
Once also the someone utilized useless chrome liquor to recycle in the chrome tanning process, but often because the wherein existence of excessive impurity such as organism causes tannery slow, tanning is inhomogeneous, and crust leather floating etc. have a strong impact on its chrome tanning effect, wet blue leather quality instability, inconvenience tissue production etc.
Summary of the invention
Purpose of the present invention: recycle useless chrome liquor indefinitely; outside removing the normal volatilization under the state of nature and inevitably spilling; the rate of recovery of useless chrome liquor can reach 100%; thoroughly eradicated the right problem of serious dirt that the discharging of useless chrome liquor and salt brings, a large amount of simultaneously chromium powder and other relevant chemical materials saved.Save salt 100%, chromium powder 35%-55%, save energy about 25%, and the quality of assurance wet blue, the shrinkage temperature of wet blue improves more than 1 ℃, the yield of leather increase (is compared with common process) more than 1%, has obtained the blue skin of high-quality.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: the solid substance in the useless chrome liquor of elimination at first, transfer to 0.2-1.2 with will the give up pH value of chrome liquor of hydrochloric acid or sulfuric acid or other acid, carry out pickling then, the add-on of salt is zero in the pickling process, also can add a small amount of (0%-5%) salt or other material that has inhibition acid to swell and act on.Utilize chroming waste liquor to carry out pickled technology to be: in graywall weight, the 3%-100% chrome liquor that gives up, 0%-5% salt, 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% chrome liquor that gives up 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.The pH value requires 0.7-4.5.Carry out chrome tanning then, technology is: the 0.5%-2% chromium powder, changeed 10-40 minute; The 0.5%-3.5% chromium powder changeed 30-90 minute; The 0.2%-1.2% sodium formiate changeed about 30 minutes; 0.10%-0.55% carries alkaline agent, changes 2.0-4.5 hour; The 3%-80% chrome liquor that gives up, be warming up in the drum 28 ℃-38 ℃ (chrome liquor that will give up add rotary drum again after heating or the chrome liquor that will give up earlier add in the rotary drum whole again heat up all can), changeed 2-4 hour.The pH value requires 1.3-5.0.
This such scheme, useless chrome liquor divide two portions to use, and a part is used in the pickling initial stage, and a part is used in the fluid infusion temperature rise period in chrome tanning later stage.Total consumption of chromium powder is 2.0%-5.0%.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, and 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 skin.
Embodiment
Below by example the present invention is carried out concrete description and further instruction.
Embodiment 1
Transfer to 0.9 with will the give up pH value of chrome liquor of sulfuric acid, carry out the pickling chrome tanning then, the consumption of salt is zero in the pickling process, and technology is: 90% useless chrome liquor, 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; 2% chromium powder changeed 30 minutes; 2.0% chromium powder changeed 1 hour; 0.5% sodium formiate changeed 30 minutes; 0.3% carries alkaline agent, changes 4 hours; Add the useless chrome liquor 60% (being warming up to 65 ℃) after heating up, changeed 3 hours.
Embodiment 2
Transfer to 0.7 with will the give up pH value of chrome liquor of sulfuric acid, carry out the pickling chrome tanning then, the add-on of salt is zero in the pickling process, and technology is: 90% useless chrome liquor, and 0.25% mould inhibitor 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; 0.2% fatting agent changeed 30 minutes, stopped 1.5 hours; 1.8% chromium powder changeed 30 minutes; 2.2% chromium powder changeed 1 hour; 0.5% sodium formiate changeed 30 minutes; 0.25% carries alkaline agent, changes 4 hours; 80% useless chrome liquor is warming up to 35 ℃, changes 3 hours.
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 (6)
1. the solid substance in the useless chrome liquor of elimination at first transfers to 0.2-1.2 with will the give up pH value of chrome liquor of hydrochloric acid or sulfuric acid, carries out pickling then, and the add-on of salt is zero in the pickling process, and also can add a small amount of (0%-5%) salt or other has and suppress the swollen material that acts on of acid.Utilize chroming waste liquor to carry out pickled technology to be: in graywall weight, the 3%-100% chrome liquor that gives up, 0%-5% salt, 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.The pH value requires 0.7-4.5.Carry out chrome tanning then, technology is: the 0.5%-2% chromium powder, changeed 10-40 minute; The 0.5%-3.5% chromium powder changeed 30-90 minute; The 0.2%-1.2% sodium formiate changeed about 30 minutes; 0.10%-0.55% carries alkaline agent, changes 2.0-4.5 hour; The 3%-80% chrome liquor that gives up, be warming up in the drum 28 ℃-38 ℃ (chrome liquor that will give up add rotary drum again after heating or the chrome liquor that will give up earlier add in the rotary drum whole again heat up all can), changeed 2-4 hour.The pH value requires 1.3-5.0.
2. useless chrome liquor divides two portions to use, and a part is used in the pickling initial stage in the right 1, a part be used in the chrome tanning later stage in the right 1 the fluid infusion temperature rise period (chrome liquor that will give up add rotary drum again after heating or the chrome liquor that will give up earlier add in the rotary drum whole again heat up all can).
3. in the pickling chrome tanning 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.
4. total consumption of chromium powder is 2.0%-5.0% in the right 1.
5. 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.
6. the percentage ratio in the right 1 is in the weight of graywall.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100093591A CN102234694A (en) | 2010-04-21 | 2011-01-05 | Salt-free leather-making process capable of carrying out acid-picking chrome tannage by indefinitely recycling waste liquid |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010169944 | 2010-04-21 | ||
| CN201010169944.3 | 2010-04-21 | ||
| CN2011100093591A CN102234694A (en) | 2010-04-21 | 2011-01-05 | Salt-free leather-making process capable of carrying out acid-picking chrome tannage by indefinitely recycling waste liquid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102234694A true CN102234694A (en) | 2011-11-09 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011100093591A Pending CN102234694A (en) | 2010-04-21 | 2011-01-05 | Salt-free leather-making process capable of carrying out acid-picking chrome tannage by indefinitely recycling waste liquid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102234694A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103088168A (en) * | 2013-01-25 | 2013-05-08 | 陕西科技大学 | Process for circularly tanning cowhide sofa leather by using waste liquor for pickling without bath salt |
| CN103757148A (en) * | 2014-01-22 | 2014-04-30 | 烟台昊煜标本有限公司 | Tanning process for making fur-bearing animal specimen |
| WO2014169564A1 (en) * | 2013-04-18 | 2014-10-23 | Zhang Zhuangdou | Tannery waste liquid step-by-step recycling process having improved effect |
| CN104586231A (en) * | 2014-12-23 | 2015-05-06 | 廖玉连 | Residue and juice separation device for food processor |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101921881A (en) * | 2010-04-22 | 2010-12-22 | 张壮斗 | Novel process for recycling waste leather-making liquid step by step |
| CN101928791A (en) * | 2010-05-04 | 2010-12-29 | 张壮斗 | Tanning process for deashing and softening by indefinitely recycling waste liquor |
-
2011
- 2011-01-05 CN CN2011100093591A patent/CN102234694A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101921881A (en) * | 2010-04-22 | 2010-12-22 | 张壮斗 | Novel process for recycling waste leather-making liquid step by step |
| CN101928791A (en) * | 2010-05-04 | 2010-12-29 | 张壮斗 | Tanning process for deashing and softening by indefinitely recycling waste liquor |
Non-Patent Citations (1)
| Title |
|---|
| 邓维钧: "循环经济在制革准备工段生态问题中的应用（续）", 《中国皮革》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103088168A (en) * | 2013-01-25 | 2013-05-08 | 陕西科技大学 | Process for circularly tanning cowhide sofa leather by using waste liquor for pickling without bath salt |
| WO2014169564A1 (en) * | 2013-04-18 | 2014-10-23 | Zhang Zhuangdou | Tannery waste liquid step-by-step recycling process having improved effect |
| CN103757148A (en) * | 2014-01-22 | 2014-04-30 | 烟台昊煜标本有限公司 | Tanning process for making fur-bearing animal specimen |
| CN104586231A (en) * | 2014-12-23 | 2015-05-06 | 廖玉连 | Residue and juice separation device for food processor |
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Application publication date: 20111109 |