CN106282434B - A kind of salt-free pickling technique of process hides - Google Patents
A kind of salt-free pickling technique of process hides Download PDFInfo
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- CN106282434B CN106282434B CN201610821395.0A CN201610821395A CN106282434B CN 106282434 B CN106282434 B CN 106282434B CN 201610821395 A CN201610821395 A CN 201610821395A CN 106282434 B CN106282434 B CN 106282434B
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- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C1/00—Chemical treatment prior to tanning
- C14C1/08—Deliming; Bating; Pickling; Degreasing
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- Treatment And Processing Of Natural Fur Or Leather (AREA)
Abstract
The invention provides a kind of salt-free pickling technique of process hides, the addition of unclassified stores is counted by 100 parts of graywall of parts by weight.Specifically comprise the following steps：（1）Graywall after washing, adds 70 parts of water, adds 24 parts of buffers, rotate 10 minutes through conventional deashing and softening；（2）0.2 0.4 parts of solid acids are added every time, 0.1 0.3 parts of buffers, are rotated 20 minutes, are repeated 3 times；（3）0.3 0.6 parts of solid acids are added, 0.1 0.3 parts of buffers, are rotated 60 minutes, survey pH value 2.7 2.8, immersion liquid is overnight, and next day surveys pH value 2.7 2.8, and routinely technique carries out tanning；Described buffer is sodium acetate, sulfamic acid sodium, adipic acid sodium, disodium hydrogen phosphate, the one or more of sodium dihydrogen phosphate.
Description
Technical field
The present invention relates to a kind of salt-free pickling technique of process hides, belong to leather industry technical field.
Background technology
Pickling is process most crucial together in tanning production, in traditional chrome tanning process, needs pickling to adjust before chrome tanning
The pH value of skin is saved, the pH value condition of tanning operations is made it suitable for, next to that collagen fiber structure can be made further loose.Pickling
When in order to prevent skin base acid swollen, it is necessary to using substantial amounts of sodium chloride, typically constitute from the 7-10% of tare weight, this had both been unfavorable for tanning initial stage
The infiltration of chrome tanning agent, and the intensity of serious infringement skin, if neutral salt dosage is excessive, it is flat thin, no to also result in skin dehydration, finished leather
Plentiful grade and influence the quality of finished leather.But without pickling procedure, leather internal pH-values are higher, do not reach pH value needed for chrome tanning,
Misoperation easily causes chrome tanning agent accumulation and becomes big, it is difficult to penetrates into inside leather, is deposited on leather surface and causes surface
Cross tan, it is coarse that skin base becomes grain, produces chromium spot etc., has a strong impact on the quality of leather.
In addition the chloride ion content of excessive concentrations can also cause drink water bitter saline taste, the salinization of soil in water quality so that plant
Grow difficult, easy corrosion pipeline and equipment and be detrimental to health, cause such as dehydration, hypertension, thyroid gland, nephrosis, the heart
Dirty disease, stomach cancer, osteoporosis diseases.But sodium chloride is difficult processing in waste water, and conventional mainly has following several processing
Method：1st, silver salt or cuprous salt precipitation method, but the cost recovery of silver salt difficulty is high, the control of cuprous salt easy-oxidizing hard.2nd, membrane separation technique,
Including electrodialysis and counter-infiltration, application is wide, but organic impurities easily cause irreversible membrane fouling to membrane module in waste water, limitation
Its application, cost are also high.3rd, evaporation concentration method, equipment is corrosion-resistant to require high, involves great expense.Several common methods above
Processing cost is all very high, is not well suited for leather-making enterprises.And according to newest discharge standard GB 30486-2013《Process hides and
Fur manufacturing industrial water pollution thing discharge standard》, chlorine ion concentration is defined to 3000mg/kg, traditional pickling work in leather-making waste water
Skill, for chlorine ion concentration up to 20000-30000mg/kg, it is very high to deal with cost, thus to control in leather-making waste water chlorine from
Son, sodium chloride can only be used by reducing.In leather-making technology sodium chloride for the use of mainly having two, when storage rawhide when
Carried out with sodium chloride salted to prevent from rotting, two be exactly that latter of which accounts for major part to prevent acid swollen in pickling procedure.Before
Person can be by using the processing recovery of desalination machine before production, and the latter then reaches few with or without chlorination by the adjustment of technique
Sodium.
And prepare pickling liquid, careless manipulation usually using formic acid and the concentrated sulfuric acid in pickling technique, it is easy to damage,
Because injury case can be found everywhere caused by operator's carelessness is off one's guard.
The content of the invention
The purpose of the present invention is the deficiency for existing pickling technology, there is provided a kind of salt-free pickling technique of process hides, should
Technique had both reduced the amount of sodium chloride neutral salt in waste water, and had been easily handled waste water, avoided again without using sodium chloride and the concentrated sulfuric acid
It is potentially hazardous during operation.Sodium chloride main function in pickling technique is that have cushioning effect to pickling liquid, makes the pH of skin base
Value will not produce during pickling drastically to be changed and causes acid swollen.It is bent by determining buffering of the sodium chloride during pickling
Line, and can reach same cushioning effect from the similar material of buffer curve accordingly.In the selection of acid, avoid using liquid
Strong acid, and the strong acid of solid is selected, easy-to-operate, artificial injury can be reduced to the full extent.
Technical scheme is used by the present invention realizes foregoing invention purpose：
A kind of salt-free pickling technique of process hides, the addition of unclassified stores are counted by 100 parts of graywall of parts by weight.Specific bag
Include following steps：
（1）Graywall after washing, adds 70 parts of water, adds 2-4 part buffers, rotate 10 minutes through conventional deashing and softening；
（2）0.2-0.4 part solid acids are added every time, 0.1-0.3 part buffers, are rotated 20 minutes, are repeated 3 times；
（3）0.3-0.6 part solid acids are added, 0.1-0.3 part buffers, are rotated 60 minutes, survey pH value 2.7-2.8, immersion liquid
Overnight, next day surveys pH value 2.7-2.8, and routinely technique carries out tanning；
In the above-mentioned salt-free pickling technique of process hides, described buffer is sodium acetate, sulfamic acid sodium, adipic acid sodium, phosphoric acid
The one or more of disodium hydrogen, sodium dihydrogen phosphate.
In the above-mentioned salt-free pickling technique of process hides, described solid acid is sulfamic acid and adipic acid, and its weight ratio is
100:5~10。
By this salt-free pickling technique, the shrinkage temperature of wet blue is more slightly higher than traditional process for tanning after tanning, and three in waste liquid
Two chromium contents are aoxidized to reduce than traditional process for tanning.
The addition of unclassified stores is counted by 100 parts of graywall of parts by weight, and traditional pickling technique is following steps：
（1）Graywall after washing, adds 70 parts of water, adds 7-10 part sodium chloride, rotate 10 points through conventional deashing and softening
Clock；
（2）0.2-0.4 part formic acid is added, is added after being diluted with water 2-4 parts, is rotated 20 minutes；
（3）Addition 0.9-1.1 part concentrated sulfuric acids, after being diluted with water 9-11 parts, point 5 additions, each rotation 20 minutes, finally
Rotated 60 minutes after once adding, survey pH value 2.5-2.8, immersion liquid is overnight, and next day surveys pH value 2.7-2.8, and routinely technique adds
Carry out tanning.
Embodiment
The present invention is specifically described below by embodiment.But not it will be understood that being the scope of the above-mentioned theme of the present invention
Following embodiment is only limitted to, it is all that the scope of the present invention is belonged to based on the technology that present invention is realized.
Embodiment 1
（1）Graywall after washing, adds 70 parts of water, adds 2.5 parts of buffers, rotate 10 minutes through conventional deashing and softening；
（2）0.2 part of solid acid is added every time, 0.15 part of buffer, is rotated 20 minutes, is repeated 3 times；
（3）0.4 part of solid acid is added, 0.3 part of buffer, is rotated 60 minutes, surveys pH value 2.79, immersion liquid is overnight, and next day surveys
PH value 2.80, routinely technique progress tanning.
After chrome tanning terminates, wet blue shrinkage temperature is measured as 92.3 DEG C, chromic oxide content is 1.47g/l in waste liquid.
Comparative example 1
（1）Graywall after washing, adds 70 parts of water, adds 7 parts of sodium chloride, rotate 10 minutes through conventional deashing and softening；
（2）0.2 part of formic acid is added, with being added after 2 parts of dilutions of water, is rotated 20 minutes；
（3）1.1 parts of concentrated sulfuric acids are added, after 11 parts of dilutions of water, divides 5 additions, rotates 20 minutes every time, last time adds
Rotated 60 minutes after entering, survey pH value 2.62, immersion liquid is overnight, and next day surveys pH value 2.71, and routinely technique carries out tanning.
After chrome tanning terminates, wet blue shrinkage temperature is measured as 91.5 DEG C, chromic oxide content is 2.04g/l in waste liquid.
Embodiment 2
（1）Graywall after washing, adds 70 parts of water, adds 4 parts of buffers, rotate 10 minutes through conventional deashing and softening；
（2）0.25 part of solid acid is added every time, 0.15 part of buffer, is rotated 20 minutes, is repeated 3 times；
（3）0.5 part of solid acid is added, 0.3 part of buffer, is rotated 60 minutes, surveys pH value 2.71, immersion liquid is overnight, and next day surveys
PH value 2.78, routinely technique progress tanning.
After chrome tanning terminates, wet blue shrinkage temperature is measured as 92.5 DEG C, chromic oxide content is 1.39g/l in waste liquid.
Embodiment 3
（1）Graywall after washing, adds 70 parts of water, adds 2 parts of buffers, rotate 10 minutes through conventional deashing and softening；
（2）0.2 part of solid acid is added every time, 0.3 part of buffer, is rotated 20 minutes, is repeated 3 times；
（3）0.5 part of solid acid is added, 0.2 part of buffer, is rotated 60 minutes, surveys pH value 2.70, immersion liquid is overnight, and next day surveys
PH value 2.75, routinely technique progress tanning.
After chrome tanning terminates, wet blue shrinkage temperature is measured as 91.9 DEG C, chromic oxide content is 1.46g/l in waste liquid.
Claims (2)
1. a kind of salt-free pickling technique of process hides, the addition of unclassified stores are counted by 100 parts of graywall of parts by weight, specifically included
Following steps：
（1）Graywall after washing, adds 70 parts of water, adds 2-4 part buffers, rotate 10 minutes through conventional deashing and softening；
（2）0.2-0.4 part solid acids are added every time, 0.1-0.3 part buffers, are rotated 20 minutes, are repeated 3 times；
（3）0.3-0.6 part solid acids are added, 0.1-0.3 part buffers, are rotated 60 minutes, survey pH value 2.7-2.8, immersion liquid is overnight,
Next day surveys pH value 2.7-2.8, and routinely technique carries out tanning；Described buffer is sodium acetate, sulfamic acid sodium, adipic acid
Sodium, disodium hydrogen phosphate, the one or more of sodium dihydrogen phosphate.
2. in the salt-free pickling technique of a kind of process hides according to claim 1, described solid acid be sulfamic acid and oneself two
Acid, its weight ratio are 100:5~10.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610821395.0A CN106282434B (en) | 2016-09-14 | 2016-09-14 | A kind of salt-free pickling technique of process hides |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610821395.0A CN106282434B (en) | 2016-09-14 | 2016-09-14 | A kind of salt-free pickling technique of process hides |
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| Publication Number | Publication Date |
|---|---|
| CN106282434A CN106282434A (en) | 2017-01-04 |
| CN106282434B true CN106282434B (en) | 2018-03-09 |
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| CN201610821395.0A Active CN106282434B (en) | 2016-09-14 | 2016-09-14 | A kind of salt-free pickling technique of process hides |
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Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115232891B (en) * | 2022-07-28 | 2023-07-18 | 四川大学 | Tanning ammonium-free de-ashing agent with grain surface protection function and de-ashing method |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB547129A (en) * | 1941-02-07 | 1942-08-14 | John Burchill | Improved tanning process |
| BRPI0203260B8 (en) * | 2002-08-09 | 2022-11-29 | Rhodia Poliamida E Especialidades Ltda | SKIN TANNING PROCESS. |
| EP2508626A1 (en) * | 2011-04-04 | 2012-10-10 | LANXESS Deutschland GmbH | Solid, particular tanning agent preparations |
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| CN106282434A (en) | 2017-01-04 |
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