CN102559949A - Novel leather producing process by pickling and chrome tanning by indefinitely circularly utilizing waste liquid without adding salt - Google Patents
Novel leather producing process by pickling and chrome tanning by indefinitely circularly utilizing waste liquid without adding salt Download PDFInfo
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- CN102559949A CN102559949A CN201110007757XA CN201110007757A CN102559949A CN 102559949 A CN102559949 A CN 102559949A CN 201110007757X A CN201110007757X A CN 201110007757XA CN 201110007757 A CN201110007757 A CN 201110007757A CN 102559949 A CN102559949 A CN 102559949A
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Abstract
The invention provides a novel leather producing process by pickling and chrome tanning by indefinitely circularly utilizing waste liquid without adding a salt. The leather producing process is characterized in that in the picking process, edible salt is not added, and all waste chrome liquids are completely used indefinitely circularly, so that chromium powder, an edible salt, an alkali extraction agent and other chemical materials are greatly saved; the shrinkage temperature, fullness, granularity quality and other indexes of the prepared wet blue leather are in accordance with the requirement of national standard; compared with the conventional invention (application number: 201010169944.3), the novel leather producing process has the advantages that: the control range of the pH value of the waste chrome liquid in the process is greatly widened from 0.2-1.2 to 0.3-2.5, so that the process is more convenient to operate and control, and excellent wet blue leather can be produced more easily; and the temperature control range in the process is widened, and the operation is facilitated.
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 here.
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; The wet blue leather quality is unstable, inconvenience tissue production etc.
Summary of the invention
The object of the invention: recycle useless chrome liquor indefinitely; Outside removing the normal volatilization under the state of nature and inevitably spilling; The 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 practiced thrift.Practice thrift 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.Finished product leather each item performance index of producing thus all reach requirement, and effectively reduce finished leather loose side rate, have improved the degree of packing of finished leather.
For realizing above-mentioned purpose, technical scheme of the present invention is following:
The solid substance in the useless chrome liquor of elimination at first; Transfer to 0.3-2.5 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 ℃-42 ℃ (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, running time, working order etc. all can be made adjustment significantly 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 used chemical materials is in the weight of graywall.
Embodiment
Through instance the present invention is carried out concrete description and further explanation below.
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 be with other form embodiment of the present invention, 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; Transfer to 0.3-2.5 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 ℃-42 ℃ (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 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, running time, working order etc. all can be made adjustment significantly according to user's particular case, 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.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110007757XA CN102559949A (en) | 2010-12-14 | 2011-01-05 | Novel leather producing process by pickling and chrome tanning by indefinitely circularly utilizing waste liquid without adding salt |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010592358.X | 2010-12-14 | ||
| CN201010592358 | 2010-12-14 | ||
| CN201110007757XA CN102559949A (en) | 2010-12-14 | 2011-01-05 | Novel leather producing process by pickling and chrome tanning by indefinitely circularly utilizing waste liquid without adding salt |
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| CN102559949A true CN102559949A (en) | 2012-07-11 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| HU186370B (en) * | 1979-11-11 | 1985-07-29 | Ts Naucsno Iszledovatelszkij I | Process for producing titane-containing tanning materials |
| US20090158530A1 (en) * | 2007-12-25 | 2009-06-25 | Soda Sanayi A.S. | Use of chromium complex in the leather industry |
| CN101921881A (en) * | 2010-04-22 | 2010-12-22 | 张壮斗 | Novel process for recycling waste leather-making liquid step by step |
-
2011
- 2011-01-05 CN CN201110007757XA patent/CN102559949A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| HU186370B (en) * | 1979-11-11 | 1985-07-29 | Ts Naucsno Iszledovatelszkij I | Process for producing titane-containing tanning materials |
| US20090158530A1 (en) * | 2007-12-25 | 2009-06-25 | Soda Sanayi A.S. | Use of chromium complex in the leather industry |
| CN101921881A (en) * | 2010-04-22 | 2010-12-22 | 张壮斗 | Novel process for recycling waste leather-making liquid step by step |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
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Application publication date: 20120711 |