CN1142294C - Acid-free chromte tannage agent and its prepn - Google Patents
Acid-free chromte tannage agent and its prepn Download PDFInfo
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- CN1142294C CN1142294C CNB011084057A CN01108405A CN1142294C CN 1142294 C CN1142294 C CN 1142294C CN B011084057 A CNB011084057 A CN B011084057A CN 01108405 A CN01108405 A CN 01108405A CN 1142294 C CN1142294 C CN 1142294C
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- acid
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- chromte tannage
- free chromte
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Abstract
The present invention relates to an acid-free chrome tanning agent and a preparation method thereof. The pH value of the chrome tanning agent is no greater than 3.2, when the pH value of the environmental condition is no smaller than 8, precipitation can not occur within one hour. The present invention can not only make the chrome tanning agent smoothly infiltrate into a softening naked hide, the pH value of which is about 7.5, and the chrome tanning agent can not be untimely converted into large molecules. The permeated and combined contradiction of the traditional chrome tanning agent in the tanning process can be well solved, and the naked hide is not pickled before tanning. Accordingly, the present invention has the advantages of reduced cost, simplified process, shortened period, the avoidance of environmental pollution, simple preparation method and easy control.
Description
One, technical field
The invention belongs to the leather chemical industry technical field, be specifically related to a kind of pelt that can be used for and need not pickling after softening and can directly carry out chrome tanning agent of tanning and preparation method thereof.
Two, background technology
At present, the chrome tanning agent that uses in the tanning production must pickling be the tanning prerequisite after mostly softening with pelt.Pickled purpose one is to suppress the carboxyl disassociation of collagen, the 2nd, hinder chromic compound water deolation under the higher condition of pelt surface p H, and permeate to intracutaneous thereby help tanning agent, tanning is carried out smoothly.Thereby pelt is handled without pickling, the surface then can occur crosses and to tan or chromium skewness and cause serious quality problems in leather, see Zhang Mingrang, Chen Wuyong chief editor " tanning chemistry ", China Light Industry Press, in August, 1999, " tanning chemistry and the technology " that P88-91 and Chengdu Univ. of Science ﹠ Technology etc. compile, light industry press, October nineteen eighty-two, P183.Yet things often has duality, i.e. pickling also can bring following point:
1. because the general used acid of pickling can make pelt expand, and this both had been unfavorable for the infiltration of chrome tanning agent, the major injury materials with hide glue fibril descends strength of leather again, therefore also must add a large amount of neutral salt simultaneously at pickled, as the sodium-chlor repression of swelling.And neutral salt makes the pelt dehydration cause leather flat thin again, and the adding of simultaneously a large amount of salt will cause Cl
-The pollution of luxuriant environment.
2. traditional pickling, tanning technological operation complexity, influence factor is more, as because of pelt soaks peracid, just must carry alkali in the tanning later stage, and it is too fast to propose the alkali operation, can cause quality problems such as blue surface is thick, chromium flower.
3. in the pickling process, many solubility in acids and salt soluble protein can run off in the collagen, and particularly the loose side phenomenon appears in ox-hide, kid shoes upper leather easily to make finished leather.
4. pickling generally needs 2～24 hours, and whole pickling, tanning process cycle is increased.
Though pickling helps tanning agent infiltration and chrome uptake, but in the pickling chrome tanning process of routine, the chrome uptake rate also can only reach 65～75%, and nearly about 30% chromium will be discharged with waste water, this not only causes the significant wastage of chromium resource, also can cause serious pollution of chromium.
For fear of the problem that pickling brought, tanning smoothly again, Austrian Karl Heinz Munz adopts CO
2Pelt is carried out pre-treatment, carry out then tanning method (DAS LEDER, 1997, P617).Owing to use CO
2Pelt is carried out pre-treatment be similar to pickling, so its production technique is not still simplified.
Zelanian S.Das Gupta then with polymeric amide to the modification of the chrome tanning agent property advanced, making chrome tanning agent is cloudy neutral chromic compound at the tanning initial stage, can infiltration smoothly in the pelt after softening, thereby realized not pickling, tanning (JSLTC, 1998,82,15).But, this method of modifying reaction system complexity, production cost is higher, and only is suitable for the tanning than thin skin such as sheepskin.
Three, summary of the invention
Task of the present invention is to provide a kind of acid-free chromte tannage agent at the deficiencies in the prior art.
Another task of the present invention provides the method for this not pickling tanning agent of preparation.
The prescription (is benchmark in the hexavalent chromium compound umber) that acid-free chromte tannage agent provided by the invention adopts is: 100 parts of hexavalent chromium compounds; 70～120 parts of the vitriol oils; 20～25 parts of sugar; 300～400 parts in water; Aromatic sulfonic acid compounds: Cr
2O
3=0.3～2: 1 (moles/mole); Organic acid salt compound: Cr
2O
3=0.5～3: 1 (moles/mole), pH value≤3.2, preferred pH value is 2.0～3.0, and in the pH of envrionment conditions value 〉=8, Cr (OH) can not take place in 1 hour this chrome tanning agent
3Precipitation, its precipitation pH value curve is over time seen accompanying drawing, thereby chrome tanning agent provided by the invention successfully is about 7.5 softening intracutaneous infiltration on the one hand at pH because of the molecule I at the tanning initial stage, on the other hand pH value own is lower, after the adding at short notice the pH value because of the tanning system drop to 3～4 rapidly, make the unlikely macromole that becomes prematurely of chrome tanning agent in the solution again, thereby can continue to permeate to intracutaneous, and intracutaneous pH value is higher, at this moment just can promote small molecules the moon, the neutral chromic compound chromic compound that faces south changes, then by intracutaneous outside skin with collagen generation crosslinking reaction, solved traditional chrome tanning agent preferably and in tannery, permeated and the bonded contradictory problems, made the preceding pelt of tanning without pickling.
After chrome tanning agent of the present invention not only makes pelt softening without directly tanning smoothly of pickling, and specific absorption＞85% of chromium sesquioxide in the finished leather, distribution consistency degree＞90% of chromium sesquioxide in finished leather.
The method of the above-mentioned acid-free chromte tannage agent of preparation that another task of the present invention provides, on the basis of adopting above-mentioned prescription, its step of preparation process and condition are:
1. hexavalent chromium compound is used water dissolution earlier, add the vitriol oil, aromatic sulfonic acid compounds then successively, and stirring is warming up to little boiling;
2. drip and use water-soluble sugar, dropping time＞15 minute make reaction solution still keep slight boiling condition simultaneously;
3. drip again with water-soluble organic acid salt compound, 30～70 minutes dropping time, promptly got liquiform product in 1～4 hour in 30～90 ℃ of following reactions of temperature then.If consider the needs of convenient transportation and storage, can above-mentioned aqueous chrome tanning agent spray-dried again must the solid, powdery product, and control its water content＜10%.
The used hexavalent chromium compound of the present invention is known sodium dichromate 99 of prior art or potassium bichromate.Consider from economic angle as the vitriol oil and the reductive agent sugar of acid catalyst, select the inexpensive industrial vitriol oil and industrial white sugar, and preferred 80～110 parts of the add-on of the industrial vitriol oil.The aromatic sulfonic acid compounds can be selected from Phenylsulfonic acid, the naphthene sulfonic acid at least a.The organic acid salt compound can be selected from sodium formiate, sodium-acetate, phthalic acid sodium, the Soduxin at least a.Addition for aromatic sulfonic acid compounds and organic acid salt compound is by Cr contained in the hexavalent chromium compound
2O
3Mol ratio is that benchmark calculates, and these method of calculation are known to a person of ordinary skill in the art.
Preferred 30～60 minutes of the dropping time of sugar in preparation method's of the present invention processing step and the condition; Preferred 50～90 ℃ of temperature of reaction behind the adding organic acid salt compound.
The present invention has the following advantages:
1. because chrome tanning agent tanning of the present invention without pickling, just can not used a large amount of sodium-chlor yet, thereby both eliminated the flat thin and Cl of leather of pelt dehydration
-To the pollution of environment, avoid again very difficulty, cost very high contain Cl
-Sewage disposal.
2. owing to use chrome tanning agent of the present invention need not pass through pickling, also need not carry alkali, therefore simplify technology, shorten process cycle, also avoid the disadvantageous effect of bringing because of manual operation leather quality in the tanning later stage.
3. owing to use chrome tanning agent of the present invention can eliminate the effect of acid, salt pair materials with hide glue fibril, therefore reduced the possibility of finished leather loose side, make finished leather tear strength (＞80N/mm) be higher than the chrome-tanned tear strength of pickling (＜70N/mm), tensile strength (＞45N/mm
2) also be higher than chrome-tanned the tensile strength (＜25N/mm of pickling
2).
4. the cost of acid-free chromte tannage agent provided by the invention is than low approximately 500 yuan/ton of conventional chrome tanning agent cost, and its consumption is identical with conventional chrome tanning agent, in addition, has saved pickling on the technology, has put forward the alkali operation, need not sour, salt, thus the tanning production total cost is descended greatly.
5. because chrome tanning agent of the present invention can effectively solve infiltration and bonded contradiction, significantly the chrome uptake rate has been brought up to about 90%.Both save chromium resource, alleviated Cr again
3+Environmental pollution caused by discharge.Moreover, find also that after tested chromium also more becomes evenly in the distribution of intracutaneous, uniformity coefficient is greater than 90% (seeing attached list).
6. simple, the control easily of preparation method's technology provided by the invention.
Four, description of drawings
Accompanying drawing is the precipitation pH value of product of the present invention curve over time.
Five, embodiment
Provide embodiment below so that the present invention will be described in more detail; it is important to point out that following examples can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field can make some nonessential improvement and adjustment to the present invention according to the invention described above content.
Embodiment one:
100 parts of sodium dichromate 99s are dissolved in the reactor that has agitator, thermometer and condenser with 200 parts of water earlier, add 90 parts of vitriol oils and naphthene sulfonic acid then successively, naphthene sulfonic acid consumption and Cr
2O
3Mol ratio be 0.4: 1, and stir and to be warming up to little boiling; Sugared with 25 parts again with 50 parts of water dissolution, in 30 minutes, drip the reduction chromium cpd, make reaction solution still keep slight boiling condition simultaneously; At last with phthalic acid sodium with 80 parts of water dissolution, phthalic acid sodium consumption and Cr
2O
3Mol ratio be 1.5: 1, and dropwised in 40 minutes, then 50 ℃ of temperature down reaction promptly obtained the acid-free chromte tannage agent liquiform product in 4 hours.
Embodiment two:
100 parts of potassium bichromate are dissolved in the reactor that has agitator, thermometer and condenser with 200 parts of water, add 100 parts of vitriol oils and Phenylsulfonic acid then successively, Phenylsulfonic acid consumption and Cr
2O
3Mol ratio be 0.8: 1, and stir and to be warming up to little boiling; Sugared with 20 parts again with 40 parts of water dissolution, in 40 minutes, drip the reduction chromium cpd, make reaction solution still keep slight boiling condition simultaneously; At last with sodium-acetate with 120 parts of water dissolution, sodium-acetate consumption and Cr
2O
3Mol ratio be 1.0: 1, and dropwised in 30 minutes, then 60 ℃ of temperature down reaction promptly obtained the acid-free chromte tannage agent liquiform product in 3 hours.
Embodiment three:
100 parts of sodium dichromate 99s are dissolved in the reactor that has agitator, thermometer and condenser with 200 parts of water earlier, add 110 parts of vitriol oils and naphthene sulfonic acid then successively, naphthene sulfonic acid consumption and Cr
2O
3Mol ratio be 1.6: 1, and stir and to be warming up to little boiling; Sugared with 25 parts again with 50 parts of water dissolution, in 50 minutes, drip the reduction chromium cpd, make reaction solution still keep slight boiling condition simultaneously; At last with sodium formiate with 160 parts of water dissolution, sodium formiate consumption and Cr
2O
3Mol ratio be 0.5: 1, and dropwised in 50 minutes, then 70 ℃ of temperature down reaction promptly obtained the acid-free chromte tannage agent liquiform product in 2 hours.
Embodiment four:
100 parts of sodium dichromate 99s are dissolved in the reactor that has agitator, thermometer and condenser with 200 parts of water earlier, add 105 parts the vitriol oil and naphthene sulfonic acid then successively, naphthene sulfonic acid consumption and Cr
2O
3Mol ratio be 1.0: 1, and stir and to be warming up to little boiling; Sugared with 25 parts again with 50 parts of water dissolution, in 55 minutes, drip the reduction chromium cpd, make reaction solution still keep slight boiling condition simultaneously; At last with Soduxin with 100 parts of water dissolution, its consumption and Cr
2O
3Mol ratio be 1.0: 1, and dropwised in 60 minutes, then 80 ℃ of temperature down reaction promptly obtained the acid-free chromte tannage agent liquiform product in 1.5 hours.
Embodiment five:
100 parts of sodium dichromate 99s are dissolved in the reactor that has agitator, thermometer and condenser with 200 parts of water, add 85 parts of vitriol oils and Phenylsulfonic acid then successively, Phenylsulfonic acid consumption and Cr
2O
3Mol ratio be 1.0: 1, and stir and to be warming up to little boiling; Sugared with 25 parts again with 50 parts of water dissolution, in 60 minutes, drip the reduction chromium cpd, make reaction solution still keep slight boiling condition simultaneously; At last with sodium formiate with 60 parts of water dissolution, its consumption and Cr
2O
3Mol ratio be 2.5: 1, and dropwised in 70 minutes, then 90 ℃ down reaction promptly obtained the acid-free chromte tannage agent liquiform product in 1 hour.
(compile by Chengdu Univ. of Science ﹠ Technology, Xibei College of Light Industry according to " leather physico-chemical analysis " for product that above embodiment obtains, light industry press, in November, 1988) performance index that described standard method of analysis is tested and the performance index of existing pickling chrome tanning agent product K MC tanning agent relatively sees attached list.Embodiment and Comparative Examples product performance table
Claims (10)
1. an acid-free chromte tannage agent is characterized in that the prescription (is benchmark in the hexavalent chromium compound umber) that this chrome tanning agent adopts is: 100 parts of hexavalent chromium compounds; 70～120 parts of the vitriol oils; 20～25 parts of sugar; 300～400 parts in water; Aromatic sulfonic acid compounds: Cr
2O
3=0.3～2: 1 (moles/mole); Organic acid salt compound: Cr
2O
3=0.5～3: 1 (moles/mole), its pH value≤3.2 under the condition of pH value 〉=8, can not produce precipitation in 1 hour, and before the tanning pelt without pickling.
2. acid-free chromte tannage agent according to claim 1, the pH value that it is characterized in that this chrome tanning agent is 2.0～3.0.
3. acid-free chromte tannage agent according to claim 1 and 2 is characterized in that the finished leather with this chrome tanning agent tanning, the specific absorption of its chromium sesquioxide＞85%, chromium sesquioxide distribution consistency degree＞90% in leather.
4. method for preparing each described acid-free chromte tannage agent of claim 1 to 3 is characterized in that the step of preparation process of this chrome tanning agent and condition are:
1. hexavalent chromium compound is used water dissolution earlier, add the vitriol oil, aromatic sulfonic acid compounds then successively, and stirring is warming up to little boiling;
2. drip and use water-soluble sugar, dropping time＞15 minute make reaction solution still keep slight boiling condition simultaneously;
3. drip again with water-soluble organic acid salt compound, 30～70 minutes dropping time, promptly got liquiform product in 1～4 hour in 30～90 ℃ of following reactions of temperature then.
5. the method for preparing acid-free chromte tannage agent according to claim 4, it is at least a to it is characterized in that the aromatic sulfonic acid compounds is selected from Phenylsulfonic acid, the naphthene sulfonic acid.
6. according to claim 4 or the 5 described methods that prepare acid-free chromte tannage agent, it is at least a to it is characterized in that the organic acid salt compound is selected from sodium formiate, sodium-acetate, phthalic acid sodium, the Soduxin.
7. according to claim 4 or the 5 described methods that prepare acid-free chromte tannage agent, it is characterized in that preferred 80～110 parts of the add-on of the vitriol oil.
8. the method for preparing acid-free chromte tannage agent according to claim 6 is characterized in that preferred 80～110 parts of the add-on of the vitriol oil.
9. according to claim 4 or the 5 described methods that prepare acid-free chromte tannage agent, it is characterized in that preferred 30～60 minutes of the dropping time of sugar, preferred 50～90 ℃ of the temperature of reaction behind the adding organic acid salt compound.
10. the method for preparing acid-free chromte tannage agent according to claim 6 is characterized in that preferred 30～60 minutes sugared of the dropping time, preferred 50～90 ℃ of the temperature of reaction behind the adding organic acid salt compound.
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| CNB011084057A CN1142294C (en) | 2001-05-08 | 2001-05-08 | Acid-free chromte tannage agent and its prepn |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011084057A CN1142294C (en) | 2001-05-08 | 2001-05-08 | Acid-free chromte tannage agent and its prepn |
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| CN1142294C true CN1142294C (en) | 2004-03-17 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100376693C (en) * | 2002-10-23 | 2008-03-26 | 戢祖健 | Process for producing pigskin garment leather |
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| CN101948938A (en) * | 2010-09-01 | 2011-01-19 | 桐乡市鑫诺皮草有限公司 | Fur tanning process without salt and acid |
| CN101974655B (en) * | 2010-10-15 | 2013-05-15 | 陕西科技大学 | Method for tanning non-pickling high-pH chrome leather by using chrome formate |
| CN103773908B (en) * | 2014-01-21 | 2016-03-23 | 中国皮革和制鞋工业研究院 | Ox-hide leather produces tanning without pickling method |
| CN104450991B (en) * | 2014-09-26 | 2017-02-22 | 山东力厚轻工新材料有限公司 | No-pickling chromium powder and preparation method thereof |
| CN104593528A (en) * | 2014-12-30 | 2015-05-06 | 海宁瑞星皮革有限公司 | High pH value fast leather tanning method |
| CN105671222A (en) * | 2016-01-20 | 2016-06-15 | 意帝皮毛科技(上海)有限公司 | Tanning method for sheep healthcare leather capable of resisting to high-temperature washing |
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| CN109880942B (en) * | 2019-03-13 | 2021-10-22 | 广东盛方化工有限公司 | Acid-free chrome tanning agent |
| CN109852741A (en) * | 2019-04-03 | 2019-06-07 | 四川大学 | A kind of preparation method of acid-free chromte tannage agent |
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2001
- 2001-05-08 CN CNB011084057A patent/CN1142294C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100376693C (en) * | 2002-10-23 | 2008-03-26 | 戢祖健 | Process for producing pigskin garment leather |
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| CN1348994A (en) | 2002-05-15 |
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