CN1142293C - Tannin extract type neutralizing agent for leather and its preparing process - Google Patents
Tannin extract type neutralizing agent for leather and its preparing process Download PDFInfo
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- CN1142293C CN1142293C CNB021134111A CN02113411A CN1142293C CN 1142293 C CN1142293 C CN 1142293C CN B021134111 A CNB021134111 A CN B021134111A CN 02113411 A CN02113411 A CN 02113411A CN 1142293 C CN1142293 C CN 1142293C
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Abstract
The present invention discloses a tannin extract type neutralizing agent for leather and a preparing process thereof. The tannin extract type neutralizing agent for leather is technically characterized in that the tannin content in the tannin extract type neutralizing agent for leather is less than or equal to 35%, and the pH is greater than or equal to 6.0. The preparing process is technically characterized in that a natural tannin extract is used as a raw material in which a great amount of sulfite is added, the sulfitation reaction is carried out under the intense reaction conditions of high temperature, high pressure, etc. of an aluminum salt catalyst so that the tannin content in the tannin extract is reduced, the tannin extract has moderate astringency, and a leather tanning agent obtained by the usual sulfitation reaction of the tannin extract generates change in quality to form a leather neutralizing agent so that the tannin extract has a new purpose and fills the blank of the field of the leather neutralizing agent. The tannin extract type neutralizing agent of the present invention has the advantages of rich material source, cheap price, simple production process and has better economic benefit than that of an aromatic type neutralizing and retanning agent, and when used, the tannin extract type neutralizing agent for leather has moderate neutralization reaction without resulting in environment pollution and contains an amount of tannin, so the tannin extract type neutralizing agent for leather simultaneously has the function of a retanning agent.
Description
One, technical field
The invention belongs to forest chemical and leather chemical industry technical field, be specifically related to a kind of tannin extract type leather neutralizing agent and preparation method thereof.
Two, background technology
Tannin extract is important silvichemical, be to obtain through lixiviate processing by bark that can the regenerated natural phant, shell, leaf etc., because of its tannin that contains about 70% becomes natural tanning agent commonly used in the process hides, be mainly used in the tanning of bottom leather, belt leather, luggage leather and the retanning of upper leather.Because synthetic materials has been substituted most bottom leather and belt leather made from tannin extract at present, tannin extract is significantly reduced as the application of tanning agent, therefore open up the new purposes of tannin extract, enlarge the range of application of tannin extract, for making full use of renewable resources, has important economic and social benefit.
Neutralization is an important procedure of tanning production, its objective is the free acid that removes in the peeling, makes the corrosion of hide fiber acid and alkali after drying, and is the condition that provides certain of finishing of operations such as follow-up retanning, dyeing, stuffing.Widely used neutralizing agent has two classes in tanning production: a class is micromolecular strong base-weak acid salt, as NaHCO
3, NaAc etc., another kind of is neutralizing retanning agent, it belongs to accessory syntan, make its commercial neutralizing agent such as Tamol GA (BASF AG's product), Tanigan PAK-N (Bayer company product) etc. through condensation, sulfonation, neutralization by aromatics.Because last class neutralizing agent belongs to strong base-weak acid salt, pH value of solution value is higher, in and the time reaction fierce, so make easily grain side of leather coarse with the generation loose side.Then a class neutralizing agent is because of being to use the aromatics synthetic, so its price is more expensive, and residual aromatics easily causes environmental pollution in the residual solution.
Three, summary of the invention
Task of the present invention is to use the situation of atrophy greatly in the process hides field at tannin extract in the present prior art, provides a kind of tannin extract type leather neutralizing agent for opening up the new purposes of tannin extract, to fill up its blank in leather neutralizing agent technical field.Another task of the present invention provides the preparation method of this tannin extract type leather neutralizing agent.
Tannin extract type leather neutralizing agent provided by the invention, it is characterized in that consisting of of this leather neutralizing agent: 100 parts of tannin extracts, 40～80 parts in sulphite, 1.5～6.5 parts of aluminum compound catalyzer, 300 parts in water, its content of tannin≤35%, most preferably 20～30%, pH value 〉=6.0, preferred 6.0～8.0, most preferably 6.5～7.5.
Tannin extract type leather neutralizing agent provided by the invention is to be raw material with the tannin extract, through intensive sulfited reaction method of modifying preparation, processing step and condition that this method adopts are as follows:
1. tannin extract is earlier used water dissolution, add sulphite successively then and the aluminum compound catalyzer mixes; 2. reaction system is warming up under 115～135 ℃ of temperature, the pressure 0.165～0.30Mpa, reacted 5～10 hours, promptly obtain tannin extract type leather neutralizing agent liquiform product or the spray-dried again solid, powdery product that gets.
Used tannin extract is selected from least a in myrica extract, Ternstroemia gymnanthera tannin extract, larch extract, valonea extract, the shaddock mandarin orange tannin extract among the preparation method of the present invention, and they are the commodity tannin extract.Used sulphite is selected from S-WAT, Sodium Pyrosulfite, the sodium bisulfite at least a.Used aluminum compound catalyzer specifically is selected from Tai-Ace S 150, aluminum chloride and the metallic aluminium powder at least a.
According to above description to the inventive method as can be seen, adopted under high temperature and elevated pressures just because of preparation method provided by the invention, with the kickback conditions such as sulphite that surpass conventional heavy dose tannin extract is carried out modification, just may make content of tannin in the tannin extract from common about 70% drop to 35% and below, the pH value then by 4.5～5.0 be elevated to 6.0 and more than, thereby the generation qualitative change, the leather retanning agent that sulfited reaction obtained common by tannin extract become the leather neutralizing agent.This qualitative change is because the strong sulfited reaction of tannin extract at first can increase the water-soluble of tannin extract significantly, reduces molecule, and its convergency is descended; Secondly can make tannin extract divide sulfonic group on the subband, form R-SO
3The structure of Na, and have between different pH value buffer zones with the difference of R, and with on sulfonic group be electronegative, can with the chromium coordination in the tanning agent, reduce the positive polarity of chromic compound, play neutralizing effect.
In addition, the inventor also finds, also contains an amount of unreacted sulphite in the tannin extract type leather neutralizing agent that is obtained, and helps the carrying out of the sulfited reaction of tannin so on the one hand, also can produce the neutralization synergy on the other hand when using.
The present invention has the following advantages:
1. the present invention has broken through tannin extract and generally is no more than tannin extract less than 100 ℃, sulphite at normal pressure, temperature and weighs the restriction of carrying out sulfited reaction under 10% the condition, making it can to surpass tannin extract at pressure 0.165～0.30Mpa, 115～135 ℃ of temperature, sulphite consumption weigh under 30% the condition and carry out, the content of tannin is significantly descended, convergency relaxes, thereby obtained a kind of new product---leather neutralizing agent, opened up the new purposes of tannin extract, filled up its blank in leather neutralizing agent field.
2. adopt aluminium salt catalysis tannin extract sulfited reaction first, greater than 6.5 o'clock, the color of reaction product was light at pH, helped applying of product.
3. tannin extract type leather neutralizing agent provided by the invention and is that raw material synthetic neutralizing retanning agent is compared with phenol, and is inexpensive, pollution-free, belong to the green leather chemical materials, and compare with strong base weak acid salt neutralizing agent, in and time reaction comparatively relax, can not cause grain side of leather coarse and produce loose side.Also contain an amount of tannin in the tannin extract type leather neutralizing agent, so product also has the effect of retanning agent concurrently in addition.
4. prepare the leather neutralizing agent with tannin extract, raw material sources are abundant, and cheap, production process is simple, and economic benefit is better than fragrant same clan neutralizing retanning agent.
Four, 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 foregoing invention content.
Embodiment one:
100 parts of myrica extracts are dissolved in having the withstand voltage reactor of agitator and condenser with 300 parts of water, add 40 parts of S-WATs then successively, Tai-Ace S 150 mixes for 4 parts, and be warming up to 125 ℃, boost to 0.20Mpa, react with this understanding then and promptly obtained leather neutralizing agent liquiform product in 8 hours.
Embodiment two:
100 parts of myrica extracts are dissolved in having the withstand voltage reactor of agitator and condenser with 300 parts of water, add 24 parts of S-WATs and 20 parts of sodium bisulfites, 2 parts of metallic aluminium powders (150～200 order) then successively, mix, and be warming up to 129 ℃, boost to 0.26Mpa, react with this understanding then and promptly obtained leather neutralizing agent liquiform product in 6 hours.
Embodiment three:
100 parts of Ternstroemia gymnanthera tannin extracts are dissolved in having the withstand voltage reactor of agitator and condenser with 300 parts of water, add 25 parts of S-WATs then successively, 20 parts of sodium bisulfites, 2 parts of aluminum chlorides, 4 parts in Tai-Ace S 150, mix, and be warming up to 134 ℃, boost to 0.30Mpa, react with this understanding then and promptly obtained leather neutralizing agent liquiform product in 5 hours.
Embodiment four:
100 parts of valonea extracts are dissolved in having the withstand voltage reactor of agitator and condenser with 300 parts of water, add 20 parts of S-WATs, 10 parts of Sodium Pyrosulfites, 25 parts of sodium bisulfites then successively, 1 part of aluminum chloride, 2 parts in Tai-Ace S 150, mix, and be warming up to 116 ℃, boost to 0.17Mpa, react with this understanding then and promptly obtained leather neutralizing agent liquiform product in 8 hours.
Embodiment five:
100 parts of larch extracts are dissolved in having the withstand voltage reactor of agitator and condenser with 300 parts of water, add 35 parts of S-WATs, 40 parts of sodium bisulfites, 2 parts of metallic aluminium powders (150～200 order) then successively, mix, and be warming up to 127 ℃, boost to 0.25Mpa, react with this understanding then and promptly obtained leather neutralizing agent liquiform product in 10 hours.
Embodiment six:
100 parts of shaddock mandarin orange tannin extracts are dissolved in having the withstand voltage reactor of agitator and condenser with 300 parts of water, add 20 parts of S-WATs, 24 parts of sodium bisulfites, 2 parts of aluminum chlorides, 4 parts in Tai-Ace S 150 then successively, mix, and be warming up to 126 ℃, boost to 0.24Mpa, react with this understanding then and promptly obtained leather neutralizing agent liquiform product in 6 hours.
The performance index that product that above embodiment obtains is tested according to the described standard method of analysis of " leather physico-chemical analysis " (light industry press, in November, 1988 are compiled by Chengdu Univ. of Science ﹠ Technology, Xibei College of Light Industry) are seen attached list.
Leather neutralizing agent product performance table
Claims (9)
1. a tannin extract type leather neutralizing agent is characterized in that consisting of of this leather neutralizing agent: 100 parts of tannin extracts, 40～80 parts in sulphite, 1.5～6.5 parts of aluminum compound catalyzer, 300 parts in water, its content of tannin≤35%, pH value 〉=6.0.
2. tannin extract type leather neutralizing agent according to claim 1, the content of tannin that it is characterized in that this leather neutralizing agent is 20～30%.
3. tannin extract type leather neutralizing agent according to claim 1 and 2, the pH value that it is characterized in that this leather neutralizing agent is 6.0～8.0.
4. tannin extract type leather neutralizing agent according to claim 1 and 2, the pH value that it is characterized in that this leather neutralizing agent is 6.5～7.5.
5. method for preparing each described tannin extract type leather neutralizing agent in the claim 1～4 is characterized in that the processing step and the condition that adopt are as follows:
Tannin extract is used earlier water dissolution, add sulphite, aluminum compound catalyzer then successively, mix, and under 115～135 ℃ of temperature, pressure 0.165～0.30Mpa, react and promptly got tannin extract type leather neutralizing agent liquiform product or spray-dried again solid, powdery product in 5～10 hours.
6. the method for preparing tannin extract type leather neutralizing agent according to claim 5, it is at least a to it is characterized in that used tannin extract is selected from myrica extract, Ternstroemia gymnanthera tannin extract, larch extract, valonea extract, the shaddock mandarin orange tannin extract.
7. according to claim 5 or the 6 described methods that prepare tannin extract type leather neutralizing agent, it is at least a to it is characterized in that used sulphite is selected from S-WAT, Sodium Pyrosulfite, the sodium bisulfite.
8. according to claim 5 or the 6 described methods that prepare tannin extract type leather neutralizing agent, it is characterized in that used aluminum compound catalyzer specifically is selected from Tai-Ace S 150, aluminum chloride, the metallic aluminium powder at least a.
9. the method for preparing tannin extract type leather neutralizing agent according to claim 7 is characterized in that used aluminum compound catalyzer specifically is selected from least a of Tai-Ace S 150, aluminum chloride, metallic aluminium powder.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021134111A CN1142293C (en) | 2002-03-04 | 2002-03-04 | Tannin extract type neutralizing agent for leather and its preparing process |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021134111A CN1142293C (en) | 2002-03-04 | 2002-03-04 | Tannin extract type neutralizing agent for leather and its preparing process |
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| Publication Number | Publication Date |
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| CN1368556A CN1368556A (en) | 2002-09-11 |
| CN1142293C true CN1142293C (en) | 2004-03-17 |
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| CNB021134111A Expired - Fee Related CN1142293C (en) | 2002-03-04 | 2002-03-04 | Tannin extract type neutralizing agent for leather and its preparing process |
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| CN102839237B (en) * | 2012-09-28 | 2014-10-29 | 郑州科信化工有限公司 | Novel leather retanning method |
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